Semiconductive 2D arrays of pancake-bonded oligomers of partially charged TCNQ radicals

Dedicated to the memory of Professor Stanko Popović, who passed away on 18 December 2020.

Multicentre two-electron (mc/2e or `pancake bonding') bonding between 7,7,8,8-tetra­cyano­quinodi­methane (TCNQ) radical anions was studied on its 14 novel salts with planar organic cations. The formal charges of the TCNQ^δ− moieties are −1/2 and −2/3, and they form mc/2e bonded dimers, trimers and tetramers which are further stacked into extended arrays. Multicentre bonding within these oligomers is characterized by short interplanar separations of 2.9–3.2 Å; distances between the oligomers are larger, typically >3.3 Å. The stacks are laterally connected by C—H⋯N hydrogen bonding, forming 2D arrays. The nature of mc/2e bonding is characterized by structural, magnetic and electrical data. The compounds are found to be semiconductors, and high conductivity [10⁻² (Ω cm)⁻¹] correlates with short interplanar distances between pancake-bonded oligomers.

1. Introduction

π-Stacking of planar organic radicals is known to involve spin pairing of contiguous radicals (Preuss, 2014; Kertesz, 2019; Molčanov & Kojić-Prodić, 2019; Molčanov et al., 2019c), as shown by the diamagnetic or antiferromagnetic properties of bulk samples (Molčanov & Kojić-Prodić, 2019; Molčanov et al., 2019c). This implies the formation of a weak covalent interaction (Huang & Kertesz, 2007; Huang et al., 2008; Novoa et al., 2009; Tian & Kertesz, 2011; Preuss, 2014; Cui et al., 2014a,b,c; Mou & Kertesz, 2017; Kertesz, 2019; Molčanov & Kojić-Prodić, 2019; Molčanov et al., 2019c) with a non-localized electron pair distributed between two rings (Kertesz, 2019; Molčanov & Kojić-Prodić, 2019). Commonly used terms for this type of interaction are two-electron multicentre (mc/2e) bonding and pancake bonding (Preuss, 2014; Kertesz, 2019). According to quantum chemical models, an HOMO spanning both rings is formed (Kertesz, 2019) and the covalent contribution to the total interaction may exceed −15 kcal mol⁻¹, which is comparable to strong hydrogen bonding (Steiner, 2002; Kojić-Prodić & Molčanov, 2008). Therefore, pancake bonding may be regarded as both a strong intermolecular interaction and a weak covalent bond. It is interesting from both fundamental (the nature of chemical bonding) and practical (design of organic magnets and conductive materials) aspects (Podzorov, 2010; Hicks, 2011; Sanvito, 2011a,b; Veciana, 2011; Ratera & Veciana, 2011; Morita et al., 2013; Murata et al., 2013).

The most important factors for designing functional materials are stability and a low HOMO–LUMO energy barrier, which limits conductivity. It is known that electrons can easily jump between two rings in a pancake-bonded dimer, whereas non-bonding stacking contacts (between the dimers) prevent electron jumping due to high energy barriers (Molčanov et al., 2019a). Thus, conductivity can be enhanced if pancake bonding is extended throughout a crystal. We have shown that, in infinite stacks of equidistant radicals, pancake bonding extends not only between a pair of radicals, but throughout a stack (Molčanov et al., 2019a,c; Molčanov & Kojić-Prodić, 2019), and such crystals are semiconductive (Molčanov et al., 2016; 2018a). For ionic radical systems, conductivity rarely exceeds 10⁻⁶ S cm⁻¹ (Itkis et al., 2002; Lekin et al., 2010; Podzorov, 2010; Mercuri et al., 2010; Sanvito, 2011b; Yu et al., 2011, 2012; Morita et al., 2013; Murata et al., 2013; Nakano, 2014; Chen et al., 2016; Molčanov et al., 2016; 2018a), but neutral radicals tend to be better conductors, with conductivity reaching 10⁻¹ S cm⁻¹ (Itkis et al., 2002; Podzorov, 2010; Mercuri et al., 2010; Lekin et al., 2010; Sanvito, 2011b; Yu et al., 2011, 2012; Morita et al., 2013; Murata et al., 2013; Nakano, 2014; Alemany et al., 2015; Chen et al., 2016).

The stability of a solid-state radical system depends mostly on the stability of the radical. Therefore, planar radicals with extensive delocalization of π-electrons are most widely used in crystal engineering, for example, derivatives of tetra­thia- and tetraselena­fulvalene (Ganesan et al., 2003; Bendikov et al., 2004; Rosokha & Kochi, 2007; Mercuri et al., 2010; Morita et al., 2013; Murata et al., 2013), and semi­quinones (Rosokha & Kochi, 2007; Rosokha et al., 2009; Molčanov et al., 2016; 2018a, 2019b).

One of the most stable and extensively studied organic radicals is 7,7,8,8-tetra­cyano­quinodi­methane (TCNQ, neutral and radical forms are shown below), a strong electron

acceptor suitable for the formation of salts. It comprises a six-membered ring similar to the quinones (Hünig, 1990) and is stabilized by four electron-withdrawing cyano groups. It also readily forms pancake bonds. However, unlike the semi­quinones, which usually form negatively charged radicals with a total charge of −1 (Molčanov et al., 2012, 2016, 2018a, 2019a,c; Molčanov & Kojić-Prodić, 2019), TCNQ is, in its salts, often only partially charged (its formal charge being −1/2 or −2/3), implying a partial radical character of the TCNQ^δ− moiety. Increasing negative charge enhances the delocalization of the π electrons; formally double bonds (a and c in Fig. 1) are elongated, whereas formally single bonds (b and d in Fig. 1) are shortened compared with the neutral compound. To estimate the charge of the TCNQ^δ− moiety, correlations of these bond lengths have been proposed, for example c/(b+d) (Kistenmacher et al., 1982). In a review of a larger number of compounds containing TCNQ, Herbstein & Kapon (2008) used differences in bond lengths b–a and c–d. Their respective values for the neutral compound are 0.096 and −0.052 Å and for a negatively charged (−1) anion radical are 0.068 and −0.012 Å. However, owing to a variety of reasons, these are of limited reliability (see the Results and discussion).

Figure 1 Lettering denotes the different types of C—C bonds in the TCNQ^δ− radical used for geometric correlation between the bond lengths and charge of the ring. With increasing negative charge and radical character, bonds a and c are elongated, whereas bonds b and d are shortened.

To date, over 1000 crystal structures containing TCNQ in various oxidation states, ranging from 0 to −1, have been published (Groom et al., 2016). A detailed review was published by Harms et al.(1982). Thus, a systematic analysis of crystal packing and molecular interactions is beyond the scope of this paper; here we discuss only structures with π-interactions between the TCNQ moieties, but not mixed stacks involving electron donors and acceptors, represented by a well known molecular complex of TCNQ with tetra­thia­fulvalene (TTF) (Schultz et al., 1976).

Unlike semi­quinones, which usually form stacks of pancake-bonded dimers (or, more rarely, stacks of equidistant radicals) (Molčanov et al., 2018a; 2019a,b; Molčanov & Kojić-Prodić, 2019), TCNQ^δ− radicals form different types of pancake-bonded oligomers and a wide variety of long-range ordering. In many structures, isolated pancake-bonded dimers (which form no stacking interaction with neighbouring molecules) are present (Keller et al., 1981; Harms et al., 1982; Abashev et al., 1987; Miller et al., 1987; O'Hare et al., 1990; Stein et al., 1991; Grossel & Weston, 1992; Chen et al., 2008; Sutton et al., 2016; Park et al., 2018). Sometimes the dimers form 1D stacks similar to those of semi­quinones (Hoekstra et al., 1972; Ashwell et al., 1975a, 1977a; Bosch & Bodegom, 1977; Endres et al., 1978,b; Diezt et al., 1981; Konno & Saito, 1981; Waclawek et al., 1983; Visser et al., 1990a,b,c,d,e; Magonov et al., 1991; Ballester et al., 1997; Moore et al., 2001; Mukai et al., 2001; Nishimura et al., 2002; Chen et al., 2008; Qu et al., 2011; Martin et al., 2012; Lu et al., 2017; Üngör et al., 2021a), but also planar 2D arrays have been described (Ashwell et al., 1982, 1983; Bryce et al., 1988; Brook & Koch, 1997; Radváková et al., 2010; Qu et al., 2011); in some of these structures the formal charge (i.e. charge derived from stoichiometry) of TCNQ is −1/2 (Ashwell et al., 1977a, 1982). Pancake-bonded trimers, which often form stacks, are quite common, with a formal charge on the TCNQ^δ− moiety of −2/3 (Ashwell et al., 1977b; Endres et al., 1978a,b; Ashwell & Wallwork, 1979; Sandman et al., 1980; Lau et al., 1982; Bell et al., 1991; Usov et al., 1991; Akutagawa et al., 1996, 2004; Bigoli et al., 1996; Ballester et al., 2000; Nishijo et al., 2004; Chen et al., 2007; Liu et al., 2008; Mochida et al., 2008; Martin et al., 2012; Kubota et al., 2014; Phan et al., 2015). However, different bond lengths in the central and lateral rings of a trimer indicate different total charge of the rings, which can be estimated using geometric correlations (see above). For example, in the compound (MT)₂(TCNQ)₃·2H₂O (MT = S-methilthio­uronium) the charges on the central ring and the lateral rings were estimated to be −0.9 and −0.4, respectively; the total charge of a trimer is thus −1.7 (Usov et al., 1991). In a 2:3 salt of N,N-di­methyl-D-proline-methyl­ester and TCNQ^δ− the rings form a trimer stack in the sequence ...ABB... with the charge of A being −0.30 and of B being −0.94 [thus, the charge of the trimer is −2.18 (Martin et al., 2012)]. The trimers are usually centrosymmetric, and the central ring is usually more negatively charged than the lateral rings. In our previous studies we noted a similar distribution of charge in trimers of semi­quinone radicals (Molčanov et al., 2018b; 2019b).

There are also tetramers, usually composed of TCNQ^δ− moieties with a formal charge of −1/2 [therefore, a tetramer has a charge of −2, implying paired spins (Ashwell & Nowell, 1984; Ashwell & Wallwork, 1985; Rindorf et al., 1988; Takagi et al., 1994; Malatesta et al., 1995)]. These tetramers can stack, forming 1D (Ashwell et al., 1977c,d; Filhol et al., 1980; Filhol & Thomas, 1984; Üngör et al., 2021b) or 2D arrays (Kubota et al., 2014). Stacks of equidistant radicals, which involve long-range antiferromagnetic ordering and semiconductive properties have also been described for a number of compounds (Shirotani & Kobayashi, 1973; Kistenmacher et al., 1974; van Bodegom et al., 1977; Endres, 1982; Bryce et al., 1990; Visser et al., 1990f; Murata et al., 2007; Chen et al., 2008; Liu et al., 2011). Less common are stacked pentamers (Ashwell et al., 1977c,d, 1978; Lu et al., 2011) and structures comprising two different types of stacks (Ashwell et al., 1978; Murata et al., 2006).

Studying the nature of multicentre covalent bonding between TCNQ^δ− radicals requires correlation of the crystal structures with magnetic and electric properties. Analogous to the detailed studies of stacked semi­quinones, it can be established with certainty that structures of pancake-bonded dimers and trimers with a total charge of −2 are diamagnetic and insulators, and that those of equidistant radicals are semiconductors with long-range magnetic order [most likely antiferromagnetic (Molčanov et al., 2012, 2016, 2018a,b, 2019c; Molčanov & Kojić-Prodić, 2019]. However, little can be said of the magnetic and electric properties of 2D arrays of dimers (TCNQ)₂⁻ with a total charge of −1 (these contain a single unpaired electron) and tetramers of radicals, which do not have a well studied quinoid analogue. To determine properties of multicentre bonding in such systems, we prepared and characterized a series of fourteen novel salts of the TCNQ^δ− radical anion with planar organic cations.

2. Results and discussion

A series of salts of the partially charged TCNQ^δ− radical anion with the following organic cations was prepared: 2-bromo-N-methyl­pyridinium (1), 2-methyl-N-methyl­pyridinium (2), 3-iodo-N-methyl­pyridinium (3), 4-benzoyl-N-methyl­pyridinium (4), 4-di­methyl­amino-N-methyl­pyridinium (5), 4-iodo-N-methyl­pyridinium (6), 4-methyl-N-methyl­pyridinium (7), 3,5-di­bromo-N-ethyl­pyridinium (8), N,N′-di­ethyl-4,4′-bipyrid­inium (9), N,N′-di­methyl-4,4′-bipyridinium (10), 3-bromo-N-methyl­pyridinium (11), 3,5-di­bromo-N-methyl­pyridinium (12), N-methyl­pyridinium (13) and N-methyl-1,10-phenanthrolinium (14) (see below).

In the majority of the compounds there are two TCNQ^δ− moieties per one cation (or four in the case of the divalent N,N′-di­ethyl-4,4′-bipyridinium cation), so the stoichiometries are 2·(TCNQ)₂, 3·(TCNQ)₂, 4·(TCNQ)₂, 5·(TCNQ)₂, 6·(TCNQ)₂, 7·(TCNQ)₂, 8·(TCNQ)₂, 9·(TCNQ)₄, 12·(TCNQ)₂, 13·(TCNQ)₂ and 14·(TCNQ)₂. Two compounds include halide anions: 1₂·Br·(TCNQ)₂ and 11₂·I·(TCNQ)₂, and one crystallized with a stoichiometry of 1:3, 10·(TCNQ)₃.

2.1. Structure and charge of the TCNQ^δ− radical

Stoichiometries of the studied compounds indicate that the charge of TCNQ^δ− is −1/2, except in 10·(TCNQ)₃ where it is −2/3. Molecular geometry (Table S1 of the supporting information) and IR spectra (Table 1) are in agreement with the partial charge and partial radical character of the TCNQ^δ− moieties. It is known that with increasing negative charge and radical character, the molecular structure of TCNQ^δ− and related quinones change from quinoid towards semiquinoid: formally double bonds (a and c in Fig. 1) are elongated whereas formally single bonds (b and d in Fig. 1) are shortened. The geometric correlation by Kistenmacher et al. (1982) is 0.476 for neutral TCNQ, whereas for a negative radical with a total charge of −1 it is 0.500. For the salts studied in this work with a formal charge on TCNQ of −1/2 it is 0.487 (4), corresponding to a charge of 0.44 (17) (Table 2). Although the average value is close to the expected one, large variance makes this geometric correlation quite unreliable. Similar results are obtained if the correlation is expanded to (a + c)/(b + d). Average values of differences in bond lengths b–a and c–d for compounds with a formal charge on TCNQ of −1/2 studied in this work are 0.080 (10) and −0.034 (11) Å, respectively (Table 2). Again, the variances are too large to be reliable. Therefore, all these geometric correlations should be taken cum grano salis; as noted by Herbstein & Kapon (2008), `it would be haza­rdous to base a distinction (for a single determination) on bond lengths alone'. Our conclusions for related semi­quinone radicals were similar (Molčanov et al., 2019b). The reason for this variance of molecular geometry can be attributed to the effect of crystal field and especially the strong, partially covalent pancake bonding between the radicals.

Table 1
Selected absorption bands (cm^–1) of TCNQ^δ− in the infrared spectra of compounds 1–14

Assignment according to Lunelli & Pecile (1970). Overlapping bands, which could not be well resolved, are italic; w – weak; sh – shoulder.

Compound	C—H stretch	C—N stretch	C=C ethyl stretch	C—H bend	C—CN stretch	NC—C—CN bend
12·Br·(TCNQ)2	3053	2202, 2157	1555, 1520	1297, 852	1113	482
2·(TCNQ)2	3057	2202, 2177	1563, 1516	1336, 859sh	1114	480
3·(TCNQ)2	3047	2202, 2158	1555, 1513	1341sh, 837	1115	480
4·(TCNQ)2	3047	2196, 2160	1557, 1522	1323, 859	1115	480
5·(TCNQ)2	3053	2200, 2171sh	1563, 1515	1330, 822	1113	470
6·(TCNQ)2	3057	2202, 2158	1553, 1515	1332sh, 860	1113	483
7·(TCNQ)2	3055	2202, 2167	1557, 1517	1332, 856sh	1114	487
8·(TCNQ)2	3059, 3035	2223w	1549	1338, 874	1121w	474
9·(TCNQ)4	3062	2198, 2176	1561, 1526	1344, 841	1115	478
10·(TCNQ)3	3051	2190, 2169	1564, 1516	1353, 862	1113sh	474
112·I·(TCNQ)2	3053	2202, 2171	1555, 1503	1347sh, 851	1104	480
12·(TCNQ)2	3051	2200, 2178	1553, 1520	1295, 859sh	1113	480
13·(TCNQ)2	3057	2202, 2169	1557, 1518	1334, 852w	1111	481
14·(TCNQ)2	3057	2204, 2169	1561, 1525	1359, 843	1117sh	482

Table 2
Estimated charge by geometric correlations

Chemical bonds (labelled a, b, c and d) correspond to those in Fig. 1. RT – room temperature.

Ring	b–a	c–d	c/(b + d)	(a + c)/(b + d)	Est. charge†
12·Br·(TCNQ)2	0.091	−0.044	0.483	0.988	0.31
2·(TCNQ)2, 100 K	0.103	−0.055	0.478	0.993	0.10
2·(TCNQ)2, RT	0.080	−0.031	0.488	0.989	0.48
3·(TCNQ)2, A	0.083	−0.050	0.483	0.988	0.27
3·(TCNQ)2, B	0.070	−0.024	0.490	0.989	0.59
4·(TCNQ)2, A	0.088	−0.037	0.485	0.988	0.39
4·(TCNQ)2, B	0.073	−0.018	0.492	0.986	0.68
5·(TCNQ)2	0.088	−0.038	0.485	0.990	0.37
6·(TCNQ)2, A	0.073	−0.029	0.488	0.992	0.50
6·(TCNQ)2, B	0.087	−0.032	0.487	0.989	0.45
7·(TCNQ)2, 100 K	0.085	−0.040	0.484	0.991	0.35
7·(TCNQ)2, RT	0.082	−0.033	0.487	0.990	0.44
8·(TCNQ)2, A	0.082	−0.030	0.488	0.987	0.50
8·(TCNQ)2, B	0.080	−0.032	0.487	0.989	0.47
9·(TCNQ)4, A	0.083	−0.036	0.486	0.990	0.41
9·(TCNQ)4, B	0.075	−0.023	0.491	0.987	0.60
112·I·(TCNQ)2, A	0.072	−0.024	0.490	0.989	0.58
112·I·(TCNQ)2, B	0.066	−0.027	0.489	0.991	0.55
12·(TCNQ)2, A	0.070	−0.028	0.489	0.989	0.55
12·(TCNQ)2, B	0.053	−0.010	0.497	0.984	0.86
12·(TCNQ)2, C	0.088	−0.050	0.481	0.992	0.22
13·(TCNQ)2, 100 K, A	0.091	−0.054	0.480	0.991	0.17
13·(TCNQ)2, 100 K, B	0.093	−0.051	0.481	0.991	0.20
13·(TCNQ)2, RT	0.077	−0.027	0.489	0.989	0.54
14·(TCNQ)2, 100 K	0.078	−0.034	0.487	0.987	0.48
14·(TCNQ)2, RT	0.077	−0.027	0.488	0.991	0.52
10·(TCNQ)3, A‡	0.084	−0.032	0.487	0.989	0.45
10·(TCNQ)3, B‡	0.065	−0.008	0.496	0.986	0.82
Average	0.08 (1)	−0.03 (1)	0.487 (4)	0.989 (2)	0.4 (2)
TCNQ neutral§	0.096	−0.052	0.480	0.990	0
TCNQ^−§	0.068	−0.012	0.495	0.983	−1

†From c/(b+d).
‡Data for the trimer were not used to calculate the average.
§Data obtained from the work by Herbstein & Kapon (2008).

In the case of 10·(TCNQ)₃, which comprises a pancake-bonded trimer with a formal charge of −2/3 [i.e. (TCNQ)₃²⁻], the geometry indicates that the total charge of the central ring B is higher, −0.82, whereas the lateral rings A have a lower total charge of −0.45 (Table 2). Thus, the total charge of a trimer is −1.72, fairly close to the formal value of −2. Similar values have been found for similar trimers (Usov et al., 1991). A more reliable assessment of total charge based on X-ray charge density was recently used in a study of a trimer of tetra­chloro­semi­quinone radicals with a formal charge of −2 (Molčanov et al., 2018b), and it revealed similarly uneven distribution of the negative charge: the central ring has a higher total charge of −0.76, whereas the two lateral rings have a charge of −0.59. The total charge of that trimer was −1.94 (Molčanov et al., 2018b). Accordingly, we may conclude that charge distribution in 10·(TCNQ)₃ is similar.

Assignment of IR spectra in salts of TCNQ^δ− radicals is not straightforward owing to the presence of cation vibrations, which often overlap with bands of the TCNQ^δ− radical. However, stretching of the cyano group does not overlap with other bands, so it can be used as a rough estimate for the ionization state of TCNQ^δ− (Herbstein & Kapon, 2008): in the neutral molecule it is 2228 cm⁻¹, whereas in its mono anion there are two bands at 2194 and 2177 cm⁻¹. In the studied salts, there are two bands at about 2200 and 2160−2170 cm⁻¹ (Table 1), of which the first is blue-shifted and the second is red-shifted compared with the fully negatively charged radical anion, indicating a partial radical nature. The ethyl C=C stretching band is red-shifted compared with the neutral TCNQ^δ− by 20−25 cm⁻¹, indicating weaker C=C bonds due to enhanced delocalization of π-electrons (Table 1).

2.2. Crystal packing and multicentre bonding

In all the studied crystal structures the dominant motif is the stacking of TCNQ^δ− radical anions, with a secondary motif of weak C—H⋯N hydrogen bonding between dimers (or oligomers) of the radicals. These two motifs create 2D-layered arrays of TCNQ^δ− radicals, which we discuss below. In all cases there are separate layers of radicals and cations, connected by C—H⋯N hydrogen bonds. Geometric parameters of π-stacking contacts are given in Table 3; note that interplanar distances corresponding to pancake bonding (i.e. those within the oligomers) are rather short (typically <3.25 Å), whereas those between the oligomers are longer (mostly exceeding 3.3 Å). However, these differences are much less pronounced than in semi­quinones, where inter-dimer distances usually exceed 3.4 Å (Molčanov et al., 2016; 2018a; 2019b,c).

Table 3
Geometric parameters of π interactions

π⋯π	Cg†⋯Cg (Å)	α‡	β§	Cg⋯plane(Cg2) (Å)	Offset (Å)	Symmetry operations on Cg2
12·Br·(TCNQ)2
C3→C11⋯C3→C11	5.166 (4)	0.0 (3)	52.1	3.176 (3)	4.075	2 − x, −2 − y, 2 − z
C3→C11⋯C3→C11	4.974 (4)	0.0 (3)	48.1	3.324 (3)	3.701	2 − x, −1 − y, 2 − z
C3→C11⋯C3→C11	3.720 (4)	0.0 (3)	32.7	3.129 (3)	2.011	3 − x, −2 − y, 2 − z
N5→C17⋯C5→C17	4.906 (6)	0.0 (5)	41.0	3.700 (4)	3.222	3 − x, −1 − y, 1 − z
2·(TCNQ)2, 100 K
C3→C11⋯C3→C11	3.680 (2)	0.00 (18)	32.9	3.090 (1)	1.998	1 − x, 1 − y, 1 − z
C3→C11⋯C3→C11	5.014 (3)	6.63 (18)	48.0	3.013 (1)	3.728	x, 1/2 − y, −1/2 + z
C3→C11⋯C3→C11	5.014 (3)	6.63 (18)	53.1	3.353 (1)	4.008	x, 1/2 − y, 1/2 + z
2·(TCNQ)2Q, RT
C3→C11⋯C3→C11	3.719 (1)	0.02 (9)	32.5	3.1379 (8)	1.997	1 − x, 1 − y, 1 − z
C3→C11⋯C3→C11	5.071 (1)	7.01 (9)	47.6	3.0665 (8)	3.744	x, 1/2 − y, −1/2 + z
C3→C11⋯C3→C11	5.071 (1)	7.01 (9)	52.8	3.4207 (8)	4.039	x, 1/2 − y, 1/2 + z
3·(TCNQ)2
C3A→C11A⋯C3B→C11B	3.759 (4)	1.3 (3)	32.5	3.157 (3)	2.022	x, y, 1 + z
C3A→C11A⋯C3B→C11B	5.341 (4)	1.3 (3)	53.2	3.265 (3)	4.278	1 + x, −1 + y, 1 + z
C3A→C11A⋯C3B→C11B	4.770 (4)	1.3 (3)	44.6	3.343 (3)	3.349	1 + x, y, 1 + z
C3B→C11B⋯C3A→C11A	4.770 (4)	1.3 (3)	45.5	3.397 (2)	3.402	−1 + x, y, −1 + z
C3B→C11B⋯C3A→C11A	5.340 (4)	1.3 (3)	52.3	3.197 (2)	4.226	−1 + x, 1 + y, −1 + z
C3B→C11B⋯C3A→C11A	3.759 (4)	1.3 (3)	32.9	3.168 (2)	2.041	x, y, −1 + z
4·(TCNQ)2, 100 K
C3A→C11A⋯C3A→C11A	3.8501 (7)	0.00 (5)	28.8	3.3732 (5)	1.856	−x, 1 − y, 1 − z
C3A→C11A⋯C3B→C11B	3.7472 (7)	2.57 (5)	33.2	3.1824 (5)	2.050	x, y, z
C3B→C11B⋯C3A→C11A	3.7471 (7)	2.57 (5)	31.9	3.1367 (4)	1.978	x, y, z
C3B→C11B⋯C3B→C11B	3.3476 (6)	0.03 (5)	20.8	3.1292 (4)	1.189	1 − x, 2 − y, 1 − z
N5→C17⋯N5→C17	4.4886 (7)	0.00 (5)	31.8	3.8140 (4)	2.367	1 − x, 3 − y, 2 − z
N5→C17⋯C20→C25	5.2401 (7)	61.04 (6)	47.0	3.8846 (4)	−	−x, 3 − y, 2 − z
C20→C25⋯N5→C17	5.2401 (7)	61.04 (6)	42.2	3.5715 (5)	−	−x, 3 − y, 2 − z
C20→C25⋯C20→C25	5.1280 (8)	0.00 (7)	50.8	3.240 (6)	3.975	−x, 2 − y, 2 − z
4·(TCNQ)2, RT
C3A→C11A⋯C3A→C11A	3.9170 (8)	0.00 (7)	29.5	3.4101 (6)	1.927	−x, 1 − y, 1 − z
C3A→C11A⋯C3B→C11B	3.8016 (8)	2.04 (6)	32.8	3.2338 (6)	2.058	x, y, z
C3B→C11B⋯C3A→C11A	3.8017 (8)	2.04 (6)	31.7	3.1968(5)	1.999	x, y, z
C3B→C11B⋯C3B→C11B	3.4907 (7)	0.03 (6)	22.5	3.2250 (5)	1.336	1 − x, 2 − y, 1 − z
N5→C17⋯N5→C17	4.5411 (8)	0.00 (7)	30.9	3.8977 (6)	2.330	1 − x, 3 − y, 2 − z
N5→C17⋯C20→C25	5.255 (1)	61.99 (9)	46.5	4.0163 (5)		−x, 3 − y, 2 − z
C20→C25⋯N5→C17	5.255 (1)	61.99 (9)	40.2	3.6197 (9)		−x, 3 − y, 2 − z
C20→C25⋯C20→C25	5.364 (1)	0.0 (1)	51.9	3.3067 (9)	4.224	−x, 2 − y, 2 − z
5·(TCNQ)2
C3→C11⋯C3→C11	3.798 (1)	0.02 (9)	32.1	3.2167 (8)	2.020	1 − x, 1 − y, 2 − z
6·(TCNQ)2
C3A→C11A⋯C3B→C11B	5.033 (4)	0.5 (3)	51.0	3.145 (3)	3.910	x, y, z
C3A→C11A⋯C3B→C11B	5.082 (4)	0.5 (3)	50.3	3.271 (3)	3.908	x, 1 + y, z
C3A→C11A⋯C3B→C11B	3.727 (4)	0.5 (3)	33.0	3.124 (3)	2.030	1 + x, y, z
C3B→C11B⋯C3A→C11A	3.726 (4)	0.5 (3)	33.1	3.125 (3)	2.032	−1 + x, y, z
C3B→C11B⋯C3A→C11A	5.082 (4)	0.5 (3)	49.9	3.249 (3)	3.889	x, −1 + y, z
C3B→C11B⋯C3A→C11A	5.034 (4)	0.5 (3)	51.3	3.169 (3)	3.930	x, y, z
7·(TCNQ)2, 100 K
C3→C11⋯C3→C11	3.6872 (9)	0.03 (7)	33.2	3.0866 (6)	2.017	−x, 2 − y, −z
C3→C11⋯C3→C11	5.1357 (9)	0.03 (7)	52.2	3.1470 (6)	4.059	1 − x, 1 − y, −z
C3→C11⋯C3→C11	4.9180 (9)	0.03 (7)	49.9	3.1696 (6)	3.760	1 − x, 2 − y, −z
7·(TCNQ)2, RT
C3→C11⋯C3→C11	3.7390 (9)	0.02 (7)	32.7	3.1455 (6)	2.021	−x, −y, 1 − z
C3→C11⋯C3→C11	5.0008 (9)	0.02 (7)	49.7	3.2335 (6)	3.815	1 − x, −y, 1−z
C3→C11⋯C3→C11	5.1723 (9)	0.02 (7)	51.3	3.2310 (6)	4.039	1 − x, 1 − y, 1 − z
8·(TCNQ)2
C3A→C11A⋯C3A→C11A	3.771 (1)	0.(1)	24.9	3.4198 (9)	1.590	2 − x, 1 − y, 2 − z
C3A→C11A⋯C3B→C11B	3.685 (1)	1.6 (1)	32.5	3.1408 (9)	1.978	x, y, 1 + z
C3B→C11B⋯C3A→C11A	3.685 (1)	1.6 (1)	31.5	3.1089 (9)	1.927	x, y, −1 + z
C3B→C11B⋯C3B→C11B	3.718 (1)	0.0 (1)	28.0	3.2831 (9)	1.744	1 − x, −y, −z
9·(TCNQ)2
C3A→C11A⋯C3A→C11A	5.1343 (7)	16.73 (6)	43.1	2.8125 (5)	3.509	x, 1/2 − y, 1/2 + z
C3A→C11A⋯C3B→C11B	3.7304 (7)	2.08 (6)	31.6	3.1874 (5)	1.956	x, y, z
C3B→C11B⋯C3A→C11A	3.7304 (7)	2.08 (6)	31.3	3.1765 (5)	1.938	x, y, z
C3B→C11B⋯C3B→C11B	3.7423 (7)	0.00 (6)	31.9	3.1785 (5)	1.975	1 − x, 1 − y, −z
10·(TCNQ)3
C3A→C11A⋯C3A→C11A	4.907 (1)	0.03 (9)	47.0	3.3459 (7)	3.590	−x, 3 − y, 1 − z
C3A→C11A⋯C3A→C11A	5.181 (1)	0.03 (9)	54.6	3.0009 (7)	4.224	1 − x, 3 − y, 1 − z
C3A→C11A⋯C3B→C5B_a	3.646 (1)	1.23 (8)	33.9	3.0362 (7)	2.036	x, y, z
C3B→C5B_a⋯C3A→C11A	3.646 (1)	1.23 (8)	33.6	3.0251 (7)	2.019	x, y, z
112·I·(TCNQ)2
C3A→C11A⋯C3A→C11A	3.638 (2)	0.0 (2)	31.4	3.105 (1)	1.896	1 − x, 2 − y, 2 − z
C3A→C11A⋯C3B→C11B	5.255 (2)	7.2 (2)	59.2	3.173 (1)	4.515	x, y, z
C3A→C11A⋯C3B→C11B	4.592 (2)	7.2 (2)	41.5	3.104 (1)	3.043	1 + x, y, z
C3B→C11B⋯C3A→C11A	4.592 (2)	7.2 (2)	47.5	3.438 (1)	3.383	−1 + x, y, z
C3B→C11B⋯C3A→C11A	5.255 (2)	7.2 (2)	52.9	2.689 (1)	4.189	x, y, z
C3B→C11B⋯C3B→C11B	3.688 (2)	0.0 (2)	33.4	3.079 (1)	2.029	−x, 3 − y, 2 − z
N5→C17⋯N5→C17	4.622 (2)	0.0 (2)	36.3	3.725 (1)	2.736	−x, 2 − y, 1 − z
12·(TCNQ)2
C3A→C11A⋯C3A→C11A	4.017 (2)	0.0 (1)	33.3	3.357 (1)	2.207	1 − x, 1 − y, 1 − z
C3A→C11A⋯C3A→C11A	3.694 (2)	0.0 (1)	33.0	3.098 (1)	2.012	2 − x, 1 − y, 1 − z
C3B→C10B_a⋯C3C→C10C_b	4.240 (2)	1.1 (1)	39.9	3.307 (1)	2.718	−1 + x, −1 + y, z
C3C→C10C_b⋯C3B→C10B_a	4.240 (2)	1.1 (1)	38.7	3.254 (1)	2.653	x, y, z
13·(TCNQ)2, 100 K
C3A→C11A⋯C3A→C11A	3.689 (1)	0.02 (9)	33.0	3.0946 (8)	2.008	1 − x, 2 − y, 2 − z
C3A→C11A⋯C3B→C11B	5.064 (1)	8.23 (9)	47.3	2.9296 (8)	3.719	−x, 1 − y, 1 − z
C3A→C11A⋯C3B→C11B	4.935 (1)	8.23 (9)	53.9	3.3783 (8)	3.990	1 − x, 1 − y, 1 − z
C3B→C11B⋯C3A→C11A	5.064 (1)	8.23 (9)	54.7	3.4366 (8)	4.130	−x, 1 − y, 1 − z
C3B→C11B⋯C3A→C11A	4.935 (1)	8.23 (9)	46.8	2.9043 (8)	3.597	1 − x, 1 − y, 1 − z
C3B→C11B⋯C3B→C11B	3.689 (1)	0.02 (9)	33.1	3.0914 (8)	2.013	−x, 1 − y, −z
13·(TCNQ)2, RT
C1→C6⋯C1→C6	3.723 (2)	0.0 (1)	32.5	3.139 (1)	2.002	−x, −y, 1 − z
C1→C6⋯C1→C6	5.017 (2)	0.0 (1)	49.2	3.277 (1)	3.798	1 − x, −y, 1 − z
C1→C6⋯C1→C6	5.082 (2)	0.0 (1)	51.2	3.186 (1)	3.959	1 − x, 1 − y, 1 − z
14·(TCNQ)2, 100 K
C3→C11⋯C3→C11	4.771 (2)	0.0 (2)	46.3	3.297 (1)	3.449	−x, 1 − y, 1 − z
C3→C11⋯C3→C11	5.265 (2)	0.0 (2)	53.1	3.162 (1)	4.210	−x, 2 − y, 1 − z
C3→C11⋯C3→C11	3.687 (2)	0.0 (2)	32.9	3.097 (1)	2.000	1 − x, 1 − y, 1 − z
14·(TCNQ)2, RT
C3→C11⋯C3→C11	4.742 (2)	0.0 (1)	44.4	3.390 (1)	3.316	−x, 1 − y, 1 − z
C3→C11⋯C3→C11	5.423 (2)	0.0 (1)	53.7	3.207 (1)	4.373	−x, 2 − y, 1 − z
C3→C11⋯C3→C11	3.738 (2)	0.0 (1)	32.4	3.155 (1)	2.004	1−x, 1 − y, 1 − z

†Cg – centroid of the aromatic ring.
‡α – angle between planes of two interacting rings.
§β – angle between Cg⋯Cg line and normal to the plane of the first interacting ring.

A pancake-bonded dimer of partially charged TCNQ^δ− moieties, (TCNQ)₂⁻, as a main unit is present in 1₂·Br·(TCNQ)₂, 2·(TCNQ)₂, 3·(TCNQ)₂, 5·(TCNQ)₂, 6·(TCNQ)₂, 7·(TCNQ)₂, 8·(TCNQ)_2, 11₂·I·(TCNQ)₂, 12·(TCNQ)_2, 13·(TCNQ)₂ and 14·(TCNQ)₂. In 10·(TCNQ)₃ it is the trimer (TCNQ)₃²⁻, and in 4·(TCNQ)₂ and 9·(TCNQ)₄ it is the tetramer (TCNQ)₄²⁻. Dimers are common in almost all planar radicals, semi­quinones (Molčanov et al., 2018a; 2019b,c; Molčanov & Kojić-Prodić, 2019), various diazo­lyls (Lekin et al., 2010; Yu et al., 2011, 2012; Melen et al., 2016; Nikolayenko et al., 2017; Beldjoudi et al., 2019) etc. They typically involve a pair of radicals, each having a single unpaired electron; thus the intermolecular HOMO is filled by a pair of electrons and the multicentre bond order is 1 (Mou & Kertesz, 2017; Molčanov et al., 2018b, 2019a). Such structures are therefore diamagnetic. However, in the present case of TCNQ^δ−, stoichiometry (and molecular geometry, see above) indicates that their charge is −1/2, so a dimer contains a single unpaired electron, (TCNQ)₂⁻. Thus, the muticentre bond order is 1/2 (Mou & Kertesz, 2017; Molčanov et al., 2018b) and the single electron remains unpaired.

Trimers in 10·(TCNQ)₃ are similar to those observed in semi­quinones (Molčanov et al., 2018b, 2019c; Molčanov & Kojić-Prodić, 2019), sharing two electrons per three radicals, implying a multicentre bond order of <0.71 (Molčanov et al., 2018b). The two electrons occupying the HOMO of the (TCNQ)₃²⁻ group are paired and the ground state is antiferromagnetic.

Tetramers (TCNQ)₄²⁻ in 4·(TCNQ)₂ and 9·(TCNQ)₄ involve four TCNQ^δ− radicals with a formal charge of −1/2, meaning two electrons occupy the HOMO. Therefore, the multicentre bond order is about 1/2 (Mou & Kertesz, 2017; Molčanov et al., 2018b), since a pair of electrons is shared by four TCNQ rings.

The dimers, trimers and tetramers are stacked by somewhat weaker π-interactions (Molčanov & Kojić-Prodić, 2019; Molčanov et al., 2019c) and laterally connected by C—H⋯N hydrogen bonds (Table 4, Fig. 2) into 2D arrays. The cyano group of the TCNQ^δ− radical is a strong acceptor, and the proton-donating capability of the C−H group is barely affected by a partial negative charge. In addition, a lateral contact between two radicals involves two hydrogen bonds, so the interaction is fairly strong. Therefore, the motif shown in Fig. 2 is observed in all structures. All the studied structures involve alternating layers of anions and cations (Fig. 3), and these layers are connected by C−H⋯N hydrogen bonds with the cation acting as a weak donor and the cyano groups of TCNQ^δ− acting as acceptors (Fig. 4). Typically, there are only dispersion interactions between the cations. Stacking between aromatic cations was observed in the compounds 1₂·Br·(TCNQ)₂, 4·(TCNQ)₂ and 11₂·I·(TCNQ)₂, but it is a much weaker interaction with interplanar distances exceeding 3.6 Å. Such geometry is common for aromatic π-interactions (Molčanov & Kojić-Prodić, 2019; Molčanov et al., 2019c).

Table 4
Geometric parameters of hydrogen bonds

	D—H (Å)	H⋯A (Å)	D⋯A (Å)	D—H⋯A (°)	Symmetry operations on A
12·Br·(TCNQ)2
C16—H16⋯N4	0.93	2.48	3.39 (2)	167	x, 1 + y, z
C18—H18A⋯N4	0.96	2.59	3.12 (1)	115	1 + x, y, z
2·(TCNQ)2, 100 K
C4—H4⋯N3	0.93	2.59	3.266 (7)	130	x, y, −1 + z
C11—H11⋯N2	0.93	2.57	3.248 (7)	130	x, y, 1 + z
C16—H16⋯N1	0.93	2.53	3.42 (1)	161	−1 + x, −1/2 − y, 1/2 + z
3·(TCNQ)2
C4A—H4A⋯N3A	0.93	2.59	3.30 (1)	134	x, 1 + y, z
C4B—H4B⋯N3B	0.93	2.54	3.28 (1)	136	x, 1 + y, z
C11A—H11A⋯N2A	0.93	2.56	3.29 (1)	135	x, −1 + y, z
C11B—H11B⋯N2B	0.93	2.61	3.36 (1)	138	x, −1 + y, z
C13—H13⋯N1A	0.93	2.31	3.24 (1)	177	−1 + x, 1 + y, −1 + z
C15—H15⋯N4B	0.93	2.61	3.35 (2)	136	1 + x, y, 1 + z
C18—H18A⋯N4B	0.96	2.59	3.55 (2)	179	x, 1 + y, 1 + z
4·(TCNQ)2
C5A—H5A⋯N2B	0.93	2.60	3.331 (2)	136	−x, 2 − y, 1 − z
C11A—H11A⋯N3B	0.93	2.48	3.282 (2)	145	1 − x, 1 − y, 1 − z
C14A—H14A⋯N1B	0.93	2.45	3.170 (2)	134	x, 1 + y, 1 + z
C16—H16⋯N2B	0.93	2.54	3.457 (2)	168	x, y, z
C18—H18C⋯N4A	0.96	2.49	3.305 (2)	143	x, 1 + y, z
C22—H22⋯N1B	0.93	2.52	3.374 (3)	153	−x, 2 − y, 1 − z
6·(TCNQ)2
C13—H13⋯N4A	0.93	2.55	3.27 (1)	135	x, y, 1 + z
C16—H16⋯N1B	0.93	2.50	3.29 (1)	143	x, y, z
C17—H17⋯N1A	0.93	2.59	3.48 (2)	143	−1 + x, y, z
7·(TCNQ)2, 100 K
C13—H13⋯N1	0.93	2.54	3.242 (2)	133	1 − x, 1 − y, 1 − z
7·(TCNQ)2, RT
N6—H16A⋯N1	1.00 (4)	2.56 (4)	3.316 (4)	133 (3)	−1 + x, y, z
C13—H13⋯N1	0.93	2.56	3.302 (3)	137	1 − x, 1 − y, 2 − z
8·(TCNQ)2
C11A—H11A⋯N1A	0.93	2.57	3.250 (3)	130	−1 + x, y, z
C13—H13⋯N2B	0.93	2.46	3.220 (3)	139	x, 1 + y, 1 + z
C17—H17⋯N3A	0.93	2.53	3.284 (3)	139	−1 + x, y, −1 + z
C18—H18B⋯N4B	0.97	2.62	3.366 (3)	134	−x, 1 − y, −z
9·(TCNQ)4
C13—H13⋯N2A	0.93	2.43	3.353 (2)	172	1 − x, 1 − y, 1 − z
C1—H1⋯N2B	0.93	2.42	3.332 (2)	167	1 − x, 1 − y, 1 − z
C17—H17⋯N3B	0.93	2.40	3.239 (2)	150	−x, 1 − y, −z
10·(TCNQ)3
C13—H13⋯N3A	0.93	2.54	3.447 (3)	165	−x, 2 − y, 2 − z
C14—H14⋯N3B	0.93	2.34	3.116 (2)	140	−1 + x, y, 1 + z
C17—H17⋯N2A	0.93	2.55	3.250 (2)	132	1 − x, 3 − y, 1 − z
112·I·(TCNQ)2
C5A—H5A⋯N4A	0.93	2.60	3.341 (4)	137	1 + x, y, z
C5B—H5B⋯N4B	0.93	2.51	3.267 (4)	139	1 + x, y, z
C10A—H10A⋯N1A	0.93	2.57	3.277 (4)	133	−1 + x, y, z
C10B—H10B⋯N1B	0.93	2.53	3.285 (4)	139	−1 + x, y, z
C13B—H13B⋯I1	0.93	2.95	3.848 (4)	164	2 − x, 1 − y, 1 − z
C15B—H15B⋯N2A	0.93	2.60	3.332 (6)	136	2 − x, 2 − y, 1 − z
C17A—H17A⋯N2A	0.93	2.59	3.495 (5)	164	−1 + x, y, z
C17B—H17B⋯N2B	0.93	2.54	3.225 (5)	131	2 − x, 2 − y, 1 − z
C18B—H18B⋯I1	0.96	3.05	3.784 (4)	134	−1 + x, y, z
C18B—H18D⋯N3B	0.96	2.54	3.484 (5)	166	2 + x, −1 + y, −1 + z
12·(TCNQ)2
C4C—H4C⋯N1C	0.93	2.62	3.244 (3)	125	2 − x, −y, −z
C13—H13⋯N3C	0.93	2.51	3.375 (4)	155	x, −1 + y, z
13·(TCNQ)2, 100 K
C4A—H4A⋯N3A	0.93	2.62	3.318 (3)	132	1 + x, y, z
C4B—H4B⋯N3B	0.93	2.60	3.272 (3)	130	1 + x, y, z
C11B—H11B⋯N2B	0.93	2.60	3.271 (3)	129	−1 + x, y, z
C13—H13⋯N1B	0.93	2.44	3.356 (3)	170	x, y, z
C14—H14⋯N4B	0.93	2.49	3.316 (3)	148	−x, 1 − y, −z
C15—H15⋯N4B	0.93	2.56	3.305 (4)	137	1 + x, 1 + y, 1 + z
C16—H16⋯N1A	0.93	2.60	3.362 (4)	139	2 − x, 2 − y, 2 − z
C17—H17⋯N4A	0.93	2.61	3.446 (3)	150	1 + x, y, z
14·(TCNQ)2, 100 K
C5—H5⋯N4	0.93	2.56	3.270 (5)	134	x, 1 + y, z
C10—H10⋯N1	0.93	2.60	3.317 (5)	134	x, −1 + y, z
C15—H15⋯N3	0.93	2.60	3.338 (6)	137	1 + x, y, z
14·(TCNQ)2, RT
C5—H5⋯N4	0.93	2.59	3.299 (4)	134	x, 1 + y, z

Figure 2 Typical lateral connection between pancake-bonded pairs in 12·Br·(TCNQ)2, involving two pairs of C—H⋯N hydrogen bonds.

Figure 3 Crystal packings showing layers of TCNQ^δ− moieties (red) and cations (blue) of (a) 7·(TCNQ)2, (b) 8·(TCNQ)2, (c) 10·(TCNQ)3, (d) 4·(TCNQ)2, (e) 9·(TCNQ)4 and (f) 12·(TCNQ)2. Symmetry-independent moieties are shown in lighter and darker shades.

Figure 4 Different types of layers of TCNQ^δ− radicals observed in the compounds studied: (a) `brick wall' array of pancake-bonded dimers in 7·(TCNQ)2, (b) stacking of parallel hydrogen-bonded chains in 8·(TCNQ)2, (c) brick-wall array of pancake-bonded trimers in 10·(TCNQ)3 (A are red and B are blue), (d) brick wall array of pancake-bonded tetramers in 4·(TCNQ)2 (A are red and B are blue), (e) herringbone-like array of pancake-bonded tetramers in 9·(TCNQ)4 (A are red and B are blue) and (f) 2D array formed by stacks of equidistant radicals in 12·(TCNQ)2 (B are red and C are blue). Individual dimers, trimers and tetramers are highlighted in green; hydrogen bonds are shown as black dotted lines.

The most common type of 2D arrangement is a `brick wall' pattern of pancake-bonded dimers, which is found in 1₂·Br·(TCNQ)₂, 2·(TCNQ)₂, 3·(TCNQ)₂, 6·(TCNQ)₂, 7·(TCNQ)₂ 11₂·I·(TCNQ)₂, 12·(TCNQ)₂, 13·(TCNQ)₂ and 14·(TCNQ)₂ [Figs. 4(a) and S4–S17]. A similar pattern, although with fewer hydrogen bonds, is also present in 5·(TCNQ)₂. In 8·(TCNQ)₂ the pancake-bonded dimers form hydrogen-bonded chains parallel to [001], which are stacked on top of one another [Fig. 4(b)]. Brick-wall patterns are also formed by trimers in 10·(TCNQ)₃ [Fig. 4(c)] and tetramers in 4·(TCNQ)₂ [Fig. 4(d)]. Tetramers in 9·(TCNQ)₄ are laterally connected into chains parallel to [001], and are inclined by ca 20° towards the b axis. The contiguous chains are inclined in opposite directions, resulting in a herringbone-like pattern [Fig. 4(e)]. Interactions between the chains are very weak.

The unique crystal packing in the series studied is the structure of 12·(TCNQ)₂ which comprises three symmetry-independent TCNQ^δ− radicals (labelled A, B and C), each with a formal charge of −1/2. Molecule A, which is located in a general position, forms a 2D brick-wall pattern of pancake bonded dimers, identical to those described above [Fig. 4(a)]. Centrosymmetric anions B and C form equidistant stacks with alternating rings (...BCBC...) extending in the direction [100]. Hydrogen bonds (C−H⋯N) between the C rings connect the stacks into layers parallel to (001) [Fig. 4(f)]. The overall crystal packing exhibits alternating layers: anions A...cations...anions B/C...cations...anions A... (Fig. S15 of the supporting information).

In some structures intermolecular halogen bonding is present. The crystal packing of 1₂·Br·(TCNQ)₂ involves a bromide anion located at an inversion centre (p.p. 0.5) which is connected to two cations of 1 by a pair of symmetry-related Br⋯Br halogen bonds of 3.356 Å (Fig. 5). Similarly, in 11₂·I·(TCNQ)₂, an iodide anion forms a pair of Br⋯I halogen bonds of 3.556 and 3.662 Å. In both structures the halogen bonds are (approximately) collinear [180° in 1₂·Br·(TCNQ)₂ and at ca 161° in 11₂·I·(TCNQ)₂]. In addition, the halide also acts as an acceptor of several C—H⋯Br (C—H⋯I) hydrogen bonding contacts, as is usually observed in halogeno­pyridine halogenides (Grebe et al., 1999; Logothetis et al., 2004; Caballero et al., 2012; Fotović & Stilinović, 2020). Halogen bonding is also present in 3·(TCNQ)₂, 6·(TCNQ)₂, 8·(TCNQ)₂ and 12·(TCNQ)₂ where cyano groups of TCNQ^δ− anions act as halogen bond acceptors. However, there is a significant difference between the halogen bonds formed by the iodo­pyridinium cations [in 3·(TCNQ)₂ and 6·(TCNQ)₂] and the di­bromo­pyridinium cations [in 8·(TCNQ)₂ and 12·(TCNQ)₂]. The iodo­pyridinium cations form I⋯N halogen bonds [of 3.322 Å in 3·(TCNQ)₂ and 3.172 Å in 6·(TCNQ)₂] with the cyano nitro­gen lone pair, whereas the di­bromo­pyridinium cations form halogen bonds orthogonal to the cyano group (i.e. with the π-electrons of the cyano group). Note that both bond geometries have been observed in halogen-bonded structures of coordination complexes of cyanide ligands (Mínguez Espallargas et al., 2009; Ormond-Prout et al., 2012; Jakupec et al., 2020) with a formal negative charge.

Figure 5 Bromide anion held by a pair of symmetry-related halogen bonds Br⋯Br in 12·Br·(TCNQ)2.

In 4·(TCNQ)₂ the cations form a dimer through a pair of π–hole interactions involving a carbonyl group and pyridinium ring; in addition the pyridinium rings stack, and this interaction is enhanced by antiparallel local dipoles (Fig. 6). π–Hole interactions are also present in 8·(TCNQ)₂, between a cyano group from the TCNQ^δ− molecule B and the pyridinium ring of the cation, and also in 12·(TCNQ)₂ between the iodide anion and pyridinium ring of the cation.

Figure 6 Dimer of cations of 4 in 4·(TCNQ)2 formed by π–hole interactions (shown as dashed lines) and π-stacking of pyridyl rings enhanced by antiparallel local dipoles.

2.3. Correlation of electrical conductivity and crystal packing

Impedance spectroscopy measurements of selected compounds: 1₂·Br·(TCNQ)₂, 4·(TCNQ)₂, 6·(TCNQ)₂, 8·(TCNQ)₂, 9·(TCNQ)₄, 10·(TCNQ)₃ and 12·(TCNQ)₂ showed that conductivity isotherms of all samples are frequency-independent (corresponding to DC conductivity) over a wide range of frequencies. Fig. 7 shows the conductivity spectra of 10·(TCNQ)₃ as typical spectra for all measured compounds. The observed behaviour is typical for electronically conducting materials and indicates fast electron transport (Austin, 1970; Morimoto et al., 2019; Renka et al., 2020).

Figure 7 Electrical conductivity spectra of 10·(TCNQ)3 at different temperatures.

For all measured compounds, the DC conductivity exhibits Arrhenius temperature dependence and hence has a characteristic activation energy, see Fig. 8. The activation energy for DC conductivity (E_DC) for each compound was determined from the slope log(σ_DC) versus 1000/T using the equation σ_DCT = σ₀exp(−E_DC/k_BT), where σ_DC is the conductivity, σ₀ is the pre-exponential factor, E_DC is the activation energy, k_B is the Boltzmann constant and T is the temperature (K). The DC conductivities at 293 K and the determined activation energies (E_DC) for all compounds are listed in Table 5.

Table 5
Electrical conductivity (σ_DC) and activation energy for conductivity (E_DC) of selected compounds

Compound	σDC (Ω cm) ^−1 at 20°C		EDC (eV)
12·Br·(TCNQ)2	2.36 × 10^−7		0.22
4·(TCNQ)2	4.15 × 10^−6		0.26
6·(TCNQ)2	3.35 × 10^−6		0.12
8·(TCNQ)2	5.29 × 10^−5		0.21
9·(TCNQ)4	2.44 × 10^−2		0.05
10·(TCNQ)3	1.91 × 10^−4		0.22
12·(TCNQ)2	5.07 × 10^−5		0.19

Figure 8 Electrical conductivity as a function of reciprocal temperature for all measured compounds. Solid lines represent the least-squares linear fit to the experimental data (full symbols).

The electrical conductivities are higher than those observed for similar salts of semi­quinones (Molčanov et al., 2016; 2018a), whose conductivities are below 10⁻⁶ (Ω cm⁻¹) and are among the highest for ionic radicals. The phenomenon can be attributed to the shorter interplanar distance between oligomers (Table 3) and probably with a partial radical character of TCNQ^δ−. The lowest-conducting compound 1₂·Br·(TCNQ)₂ contains bromide anions as well as TCNQ^δ−. The radical dimers are arranged in a 2D brick wall-like array (Fig. S4), but the interplanar distances between the dimers are only 0.05 and 0.10 Å longer than the distances within the dimer. These small differences imply that the electrons can jump between the dimers.

The next-lowest conducting compound is 4·(TCNQ)₂, which comprises a `brick wall' pattern of tetramers; a relatively large inter-tetramer separation of 3.3732 (5) Å indicates a relatively high energy barrier for electrons jumping between the tetramers. The following four salts 6·(TCNQ)<sub>2</sub>, 8·(TCNQ)<sub>2</sub>, 9·(TCNQ)<sub>4</sub> and 10·(TCNQ)<sub>3</sub>, and 12·(TCNQ)<sub>2</sub> possess different 2D packing motifs of dimers, trimers and tetramers (see above). In all of them the interplanar distances between the oligomers are shorter than 3.3 Å, which can explain conductivities of 10<sup>−5</sup>–10<sup>−6</sup> (Ω cm)<sup>−1</sup>, as the energy barrier is lower than in the two previous compounds. In 12·(TCNQ)<sub>2</sub> there are two motifs, one with stacks of equidistant radicals which are known to be good conductors (Molčanov & Kojić-Prodić, 2019; Molčanov et al., 2019c). The other is a 2D `brick wall' and is likely to be a very poor conductor since the interplanar distances between the dimers are >3.35 Å.

The highest conducting compound 9·(TCNQ)₄ reveals a herringbone-like array of pancake-bonded tetramers, where contiguous tetramers are not parallel, but inclined by 16.7° [Table 3, Fig. 4(e)]. Therefore, interplanar distances between tetramers cannot be defined; however, close contacts between them are indicated by perpendicular distances of only 2.81 Å. Such short contacts enable electron transfer throughout a herringbone-like layer, resulting in very high conductivity of 10⁻² (Ω cm)⁻¹, which can be compared to neutral radicals such as phenalenyls and di­thia­zolyls (Lekin et al., 2010; Yu et al., 2011, 2012; Morita et al., 2013), and hybrid salts of TCNQ^δ− with Fe(II) complexes (Üngör et al., 2021b).

2.4. Electron paramagnetic resonance study

In the first step, the total spin concentrations were determined from the powder electron paramagnetic resonance (EPR) spectra of the samples at room temperature. The results are shown in Table 6. All powder samples have spin concentrations comparable to N_mol except for 8·(TCNQ)₂, whose spin concentration is 1% of N_mol. From Table 6 it can be observed that the number of spins regarding the number of molecules differs from sample to sample. 6·(TCNQ)₂ and 12·(TCNQ)₂ have one electron spin per molecule, whereas 9·(TCNQ)₄ has two spins per molecule. These results agree very well with the charge calculations. 1₂·Br·(TCNQ)₂ and 4·(TCNQ)₂ have about half an electron spin per single molecule. For the rest of the sample one can say the EPR signal is not a property of every molecule, specifically for 8·(TCNQ)₂. Regarding 4·(TCNQ)₂ and 10·(TCNQ)₃, we observed a magnetic transition that is not constant at room temperature and therefore the results show deviation from charge calculations. Further study at higher temperatures is needed to validate the agreement of N_spin/N_mol with the calculated charges. On the other hand, the recorded single-crystal spectra of 8·(TCNQ)₂ show reasonable intensity, so the low powder spin concentration cannot be assigned to the defects of the structure. The temperature dependence of the EPR spectra studied in the temperature range 100–350 K for the powder samples of 1₂·Br·(TCNQ)₂, 6·(TCNQ)₂, 9·(TCNQ)₄ and 12·(TCNQ)₂ shows that, by lowering the temperature, the EPR intensity increases (Figs. S19, S20 and S23), and the samples are paramagnetic in the range studied. In these cases of non-cooperative phenomena, electron spins associated with the TCNQ^δ− anions do not interact with each other (non-coupling spins), and the line intensities follow the Curie law which can be calculated using Equation (1),

where T is the absolute temperature (in K), C is the material-specific Curie constant and χ_EPR is the magnetic susceptibility obtained by double integration of the EPR spectra.

Table 6
Spin counting results

Sample	Mr	Nmol	Nspin	Nspin/Nmol	Formal charge
12·Br·(TCNQ)2	461.15	5.2584e+18	2.4524e+18	0.46±0.09	1
4·(TCNQ)2	606.61	1.8107e+18	5.6066e+17	0.31±0.06	1
6·(TCNQ)2	746.39	2.3884e+18	2.2957e+18	0.96±0.19	1
8·(TCNQ)2	746.39	2.3884e+18	9.6413e+14	0.0004±0.00008	1
9·(TCNQ)4	662.68	1.0416e+18	1.9589e+18	1.88±0.38	2
10·(TCNQ)3	594.63	1.2618e+18	7.2700e+16	0.06±0.01	2
12·(TCNQ)2	660.30	1.1908e+18	1.0446e+18	0.87±0.18	1

4·(TCNQ)₂ and 10·(TCNQ)₃ are paramagnetic at room temperature, but they do not follow the Curie law. Instead, EPR intensities show continuous decrease by lowering the temperature, indicating an antiferromagnetic transition.

For a deeper insight into the structure, orientation-dependent measurements of the single crystals at room temperature were performed and the changes of the g-value, intensity, linewidth and asymmetry were monitored. The g-factor is a second-rank tensor whose anisotropy arises from coupling of the spin angular momentum with the orbital angular momentum. The single crystal is rotated in the EPR cavity around a crystallographic axis and the measured g-value is a function of the orientation of the crystal with respect to the field. Presuming a molecular axis, u, v and w are the eigendirections of the g-tensor, the second rank tensor is given by (Wertz & Bolton, 1986)

where φ, χ and ψ are the angles between the static magnetic field B and the u, v and w axes, respectively.

The EPR lines of the investigated samples 1₂·Br·(TCNQ)₂, 4·(TCNQ)₂, 6·(TCNQ)₂, 9·(TCNQ)₂, 10·(TCNQ)₃ and 12·(TCNQ)₂ have a symmetric Lorentzian shape as a result of averaging out both the fine structure and the hyperfine splittings by spin carrier dynamics in the crystal lattices. Nevertheless, for some orientations of the crystals with respect to the static magnetic field, and for highly conducting large samples, an asymmetric line shape known as a Dysonian line was detected (Dyson, 1955). The physical origin of the Dysonian lineshape can be attributed to the fact that the incident microwave field only penetrates a conductive sample to a certain depth, the skin depth (δ), given by the relation

where σ is the electrical conductivity of the material, μ₀ is the permeability of a vacuum (4π × 10⁻⁷ H m⁻¹) and f is the microwave frequency.

Despite the averaging effects produced by dynamical spin delocalization and exchange and dipolar coupling, the g-factor and EPR linewidth of the 10·(TCNQ)₃ EPR spectra exhibited overly complicated spectra in the single-crystal study so no analysis was carried out. Looking at the complicated spectral shape of 10·(TCNQ)₃ (see Fig. S22), it seems justifiable that there are spectral components regarding a spin crossover, as expected for a triplet excited signal, but they are poorly resolved. It may be interpreted as a triplet with rather small zero-field splitting. Further investigations at high field or lower temperature are necessary.

Angular-dependent peak-to-peak linewidth (Γ) follows the general formula for dipolar broadening (Cheung & Soos, 1978),

where A, B and C are temperature-dependent, experimentally determined parameters. The angle θ at θ = 0° marks the position with the largest linewidth, which occurs when the magnetic field is perpendicular to the plane.

Results obtained for 1₂·Br·(TCNQ)₂, 4·(TCNQ)₂, 6·(TCNQ)₂, 9·(TCNQ)₄, 10·(TCNQ)₃ and 12·(TCNQ)₂ are shown in Fig. S24–S29 for all three crystal orientations (red, green, blue). Typically, variation of linewidth showing two peaks (one larger and one smaller, separated by approximately 90°) in two rotations about two axes suggest a 2D magnetic ordering and conductivity.

For 1₂·Br·(TCNQ)₂, which has a 2D brick wall pattern of pancake-bonded dimers (Fig. S4) parallel to the plane (001), rotations around axes a and b show two maxima, 90° apart, with considerable variation of linewidth. This is consistent with strong interactions between spins and conductivity in two dimensions, parallel to the plane (001).

4·(TCNQ)₂ exhibits the largest linewidth variations (0.05–0.3 mT) among all samples measured. The results support a 2D brick wall arrangement of pancake-bonded tetramers in the plane (001) and the strongest interaction in the direction [110] (i.e. direction of stacking). For 6·(TCNQ)₂ a single linewidth peak was observed in each rotation.

Crystals of 8·(TCNQ)₂ were mostly splinters, so it was difficult to establish habitus of the crystals and determine the main crystallographic directions. However, in one of the rotations (Fig. S27) two maxima of linewidth (one smaller, one larger) can be seen. This direction is likely to correspond to the strongest interactions (i.e. crystallographic b axis).

Since the crystals of 9·(TCNQ)₄ are monoclinic with β ≃ 93°, three orthogonal directions of rotation can be approximated with crystallographic axes a, b and c. Rotation about the a axis showed two maxima of linewidth, whereas the other two rotations had only one maximum.

12·(TCNQ)₂ displayed rather narrow lines (<0.1 mT) at all orientations. However, variation of linewidths is in accordance with a 2D spin system: 2D arrangement (brick wall dimers and equidistant stacks) in the plane (001); stacking in two directions, one in the direction of the a axis, the other in the [110] direction (i.e. along the bis­ector of the a and b axes). The repeatable line asymmetries in rotations 1 and 3 of 12·(TCNQ)₂ have been observed which are unique among all samples studied. Taking into account that the conductivity is low, the asymmetry of other samples is more likely to be induced by imperfections. EPR parameters obtained by simulation are presented in Table 6.

In general, as can be seen from Table 7, the extracted g-values for the single-crystal measurements are in good agreement with those extracted from the powder samples. A degree of difference in the average g-value occurs due to the conductivity and difference in sample size regarding single-crystal and powder samples. The most unreliable parameter for all samples is the asymmetry as it depends on many different factors, see Equation (3). The parameters extracted from Equation (4) are shown in Table S3.

Table 7
Summary of the effective g-factor global fitting results for single-crystal and powder samples

Sample	{g1, g2, g3} (g1 ≥ g2 ≥ g3)	gaverage	Eigenvectors
12·Br·(TCNQ)2	{2.0039, 2.0031, 20.0028}	2.0032
4·(TCNQ)2	{2.0039, 2.0032, 2.0027}	2.0033
6·(TCNQ)2	{2.0040, 2.0035, 2.0026}	2.0034
8·(TCNQ)2	{2.0041, 2.0031, 2.0028}	2.0033
9·(TCNQ)4	{2.0039, 2.0032, 2.0028}	2.0033
12·(TCNQ)2	{2.0035, 2.0032, 2.0027}	2.0031

3. Conclusions

We prepared and structurally characterized 14 novel salts of the TCNQ^δ− radical anion with planar organic cations. All of them involve pancake-bonded oligomers (dimers, trimers or tetramers) arranged in extended 2D stacked arrays. Alternating anion and cation layers are held together by C—H⋯N hydrogen bonds. The most typical array is the brick wall pattern. Owing to the close contacts between the oligomers, the crystals are semiconductors with magnetic interactions and conductivity extending in the plane of stacking.

For a selected seven samples representing each type of stacking pattern (Fig. 4) we have determined the magnetic (EPR) and electric (impedance spectroscopy) properties and correlated them with crystal packing. Single-crystal EPR measurements confirmed that 2D stacked arrays of TCNQ^δ− radicals lead to long-range spin ordering and conductivity in two dimensions, corresponding to the plane of stacking. The most important factor for electrical conductivity is the distance between oligomers within a 2D array, as it facilitates electron transfer from one oligomer to another. Thus the electrical conductivity of 9·(TCNQ)₄ [2.44 × 10⁻² (Ω cm)⁻¹] is one of the highest among ionic radicals (Morita et al., 2013; Murata et al., 2013). This can be attributed the close contact between the pancake-bonded tetramers which are as short as 2.81 Å.

Though pancake bonding has been considered undesirable for the design of novel conductive materials, it is also energetically favourable and therefore difficult to avoid. However, the present work suggests to reverse the problem: 2D arrays with short distances between radical oligomers are both stable and good conductors. Therefore, this work offers a possible novel strategy for the design of organic conductors.

4. Experimental

4.1. Preparation and IR spectroscopy

All chemicals and solvents used were purchased from commercial sources (Merck, Alfa Aesar, Kemika), were of p.a. or reagent grade and used without additional purification.

The compounds were prepared by a modification of our method for the preparation of salts of semi­quinone radicals with organic cations (Molčanov et al., 2011, 2012, 2016, 2018a, 2019b). Powdered TCNQ (20.0 mg) was dissolved in cold acetone (5 ml, at 5°C) until the solution was approximately saturated. Into the solution an excess of solid iodide salt of the appropriate organic cation was added [in the case of 1₂·Br·(TCNQ)₂ it was bromide]. The beaker was sealed with paraffin and left overnight at room temperature; the next day the acetone solution was decanted and black crystals of the TCNQ^δ− salt were washed with acetone and dried.

Infrared spectra were recorded with KBr pellets using a Bruker Alpha-T spectrometer in the 4000–350 cm⁻¹ range.

4.2. X-ray diffraction

Single-crystal measurements were performed on an Oxford Diffraction Xcalibur Nova R (microfocus Cu tube) equipped with an Oxford Instruments CryoJet liquid nitro­gen cooling device. The CrysAlisPRO package (Rigaku OD, 2018) was used for data reduction and numerical absorption correction.

The structures were solved using SHELXS97 (Sheldrick, 2015a) and refined with SHELXL-2017 (Sheldrick, 2015b). Models were refined using the full-matrix least squares refinement; all non-hydrogen atoms were refined anisotropically. Hydrogen atoms were located in a difference Fourier map and refined either as riding entities or a mixture of free restrained and riding entities.

In the crystals of 2·(TCNQ)₂, 5·(TCNQ)₂, 7·(TCNQ)₂, 13·(TCNQ)₂ and 14·(TCNQ)₂ the cation is disordered about an inversion centre. Thus, two positions of the cation with a p.p. of 0.5 are present, as shown in Fig. S3. To better resolve the structures, the crystals were measured at 100 K; however, in some cases low-temperature data showed no improvement over room temperature. Interestingly, crystals of 13·(TCNQ)₂ at 100 K showed no disorder and the b axis doubled compared with the room-temperature structure. It is probable that two phases exist in the same sample, one with ordered and one with disordered cations, since a temperature-driven phase transformation is unlikely here (it would require rotation of an entire N-methyl­pyridinium cation by 180°).

Note that two salts with the iodine-substituted cation 3·(TCNQ)₂ and 6·(TCNQ)₂ crystallize in the rare non-centrosymmetric space group P1. The crystal packing of 3·(TCNQ)₂ obviously lacks any symmetry (other than translation), whereas 6·(TCNQ)₂ is pseudocentric with a pseudo-inversion centre coinciding with the centroid of the aromatic ring of the 4-iodo-N-methyl­pyridinium cation. Therefore, the structure can be solved in the space group P1 with orientational disorder of the cation, similar to those described above. However, refinement of such a structure did not converge, and the disagreement factor R remained above 0.20. Refinement in the space group P1 proceeded smoothly; however, a small degree of orientational disorder of the cation is nevertheless present. This could be inferred from the unrealistically elongated N5—C18 bond [which was restrained to 1.40 (1) Å] and unusually small displacement ellipsoid of C18 (Fig. S2). This disorder was too small to be modelled.

Molecular geometry calculations were performed using PLATON (Spek, 2003; 2020) and molecular graphics were prepared with ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2020). Crystallographic and refinement data for the structures reported in this paper are provided in Table 8. CCDC entries 2105173–2105191 contain the supplementary crystallographic data for this paper.

Table 8
Crystallographic data collection and refinement parameters for variable-temperature X-ray diffraction

Compound	12·(TCNQ)2·Br	2·(TCNQ)2 100 K	2·(TCNQ)2 RT	3·(TCNQ)2
Empirical formula	C18H11Br1.50N5	C31H10N9	C31H10N9	C30H15IN9
Formula weight (g mol^−1)	417.18	508.48	508.48	628.41
Colour	Black	Black	Black	Black
Crystal dimensions (mm)	0.18 × 0.06 × 0.04	0.25 × 0.13 × 0.10	0.25 × 0.13 × 0.10	0.12 × 0.10 × 0.05
Space group	P1	P21/c	P21/c	P1
a (Å)	7.2378 (4)	13.2712 (6)	13.3766 (2)	7.1680 (4)
b (Å)	7.7475 (4)	12.5807 (5)	12.8023 (2)	7.6291 (4)
c (Å)	17.8746 (12)	7.7388 (5)	7.78610 (10)	13.6797 (8)
α (°)	83.578 (5)	90	90	78.422 (5)
β (°)	83.241 (5)	90.466 (4)	90.3960 (10)	83.441 (5)
γ (°)	67.104 (5)	90	90	69.680 (5)
Z	2	2	2	1
V (Å^3)	914.53 (10)	1292.04 (11)	1333.35 (3)	686.44 (7)
Dcalc (g cm^−3)	1.515	1.266	1.266	1.518
λ (Å)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)
μ (mm^−1)	4.415	0.653	0.653	9.464
Θ range (°)	4.99–73.47	4.84–75.70	4.75–75.91	3.30–75.99
T (K)	293 (2)	100 (2)	293 (2)	293 (2)
Diffractometer type	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova
Range of hkl	−9 < h < 8; −9 < k < 8; −19 < l < 22	−15 < h < 16; −15 < k < 14; −9 < l < 9	−16 < h < 13; −15 < k < 13; −9 < l < 9	−7 < h < 8; −7 < k < 9; −15 < l < 17
Reflections collected	7195	5148	7175	5556
Independent reflections	3677	2569	2655	3390
Observed reflections (I ≥ 2σ)	3245	1751	2368	3380
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin, Tmax	0.2258, 1.0000	0.4314, 1.0000	0.7402, 1.0000	0.5928, 1.0000
Rint	0.0267	0.0797	0.0155	0.0367
R(F)	0.0659	0.1360	0.0801	0.0421
Rw(F^2)	0.2150	0.3914	0.2436	0.1145
Goodness of fit	1.055	1.064	1.063	1.032
H atom treatment	Constrained	Constrained	Constrained	Constrained
No. of parameters	224	190	190	361
No. of restraints	0	58	59	3
Δρmax, Δρmin, Δρr.m.s. (eÅ^–3)	1.054, −0.608, 0.127	1.088, −0.690, 0.132	0.495, −0.466, 0.057	0.536, −1.182, 0.079

Compound	4·(TCNQ)2	5·(TCNQ)2	6·(TCNQ)2	7·(TCNQ)2 100 K
Empirical formula	C37H20N9O	C16H8N5	C30H15IN9	C15H9N5
Formula weight (g mol^−1)	606.62	270.27	628.41	259.27
Colour	Black	Black	Black	Black
Crystal dimensions (mm)	0.40 × 0.15 × 0.12	0.22 × 0.20 × 0.03	0.15 × 0.09 × 0.05	0.38 × 0.32 × 0.05
Space group	P1	P1	P1	P1
a (Å)	9.1474 (2)	7.5381 (5)	7.0735 (5)	7.0634 (4)
b (Å)	11.3666 (5)	8.0130 (7)	7.8171 (4)	7.8154 (5)
c (Å)	15.9321 (6)	13.3368 (12)	13.8419 (4)	13.4680 (8)
α (°)	106.234 (4)	103.618 (8)	74.353 (4)	73.628 (5)
β (°)	91.277 (3)	90.811 (6)	88.928 (4)	89.550 (5)
γ (°)	99.804 (3)	115.727 (8)	67.934 (6)	67.258 (6)
Z	2	2	1	2
V (Å^3)	1562.98 (10)	699.07 (11)	680.10 (7)	653.56 (7)
Dcalc (g cm^−3)	1.289	1.267	1.534	1.317
λ (Å)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)
μ (mm^−1)	0.665	0.648	9.552	0.679
Θ range (°)	4.11–75.96	3.44–76.34	6.28–75.70	3.42–75.92
T (K)	293 (2)	293 (2)	293 (2)	100 (2)
Diffractometer type	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova
Range of hkl	−7 < h < 11; −13 < k < 14; −18 < l < 20	−9 < h < 8; −9 < k < 9; −16 < l < 15	−8 < h < 8; −9 < k < 9; −11 < l < 17	−7 < h < 8; −6 < k < 9; −14 < l < 16
Reflections collected	13967	4489	5812	4851
Independent reflections	6405	2612	3377	2657
Observed reflections (I ≥ 2σ)	5339	2083	3335	2343
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin, Tmax	0.6377, 1.0000	0.5524, 1.0000	0.4396, 1.0000	0.6578, 1.0000
Rint	0.0226	0.0320	0.0317	0.0455
R(F)	0.0458	0.0725	0.0625	0.0592
Rw(F^2)	0.1796	0.2367	0.1460	0.1813
Goodness of fit	0.712	1.066	1.099	0.996
H atom treatment	Constrained	Constrained	Constrained	Constrained
No. of parameters	424	217	362	190
No. of restraints	0	0	5	6
Δρmax, Δρmin, Δρr.m.s. (eÅ^–3)	0.161, −0.146, 0.030	0.359, −0.235, 0.061	2.770, −0.802, 0.143	0.332, −0.313, 0.065

Compound	7·(TCNQ)2 RT	8·(TCNQ)2	9·(TCNQ)4	10·(TCNQ)3
Empirical formula	C15H9N5	C31H16Br2N9	C31H17N9	C48H26N14
Formula weight (g mol^−1)	259.27	674.35	515.53	798.83
Colour	Black	Black	Black	Black
Crystal dimensions (mm)	0.30 × 0.28 × 0.05	0.41 × 0.28 × 0.04	0.20 × 0.18 × 0.08	0.31 × 0.12 × 0.10
Space group	P1	P1	P21/c	P1
a (Å)	7.1924(3)	8.0361 (3)	13.0864 (2)	7.8212 (5)
b (Å)	7.8489 (5)	13.0398 (3)	25.3377 (4)	9.7542 (7)
c (Å)	13.6170 (9)	14.2071(4)	7.84030 (10)	13.2653 (7)
α (°)	106.174 (6)	92.624 (2)	90	78.103 (5)
β (°)	90.739 (4)	98.576 (2)	92.6510 (10)	75.829 (5)
γ (°)	112.525 (5)	104.767 (3)	90	82.246 (5)
Z	2	2	4	1
V (Å^3)	675.74 (7)	1418.00 (7)	2596.90 (7)	956.32 (11)
Dcalc (g cm^−3)	1.274	1.579	1.319	1.387
λ (Å)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)
μ (mm^−1)	0.657	3.943	0.671	0.706
Θ range (°)	6.27–75.85	3.15–75.81	3.77–75.75	3.49–76.47
T (K)	293 (2)	293 (2)	293 (2)	100 (2)
Diffractometer type	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova
Range of hkl	−8 < h < 5; −9 < k < 9; −16 < l < 16	−10 < h < 10; −16 < k < 15; −14 < l < 17	−15 < h < 16; −25 < k < 31; −9 < l < 9	−9 < h < 9; −12 < k < 12; −16 < l < 13
Reflections collected	5385	12861	13505	8051
Independent reflections	2719	5835	5368	3944
Observed reflections (I ≥ 2σ)	2333	5366	4600	3294
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin, Tmax	0.4767, 1.0000	0.5426, 1.0000	0.6352, 1.0000	0.6772, 1.0000
Rint	0.0279	0.0451	0.0180	0.0484
R(F)	0.0589	0.0416	0.0468	0.0686
Rw(F^2)	0.1930	0.1124	0.1416	0.2069
Goodness of fit	1.018	0.778	0.929	0.928
H atom treatment	Constrained	Constrained	Constrained	Constrained
No. of parameters	190	379	371	280
No. of restraints	6	0	2	0
Δρmax, Δρmin, Δρr.m.s. (eÅ^–3)	0.231, −0.287, 0.044	0.836, −1.020, 0.095	0.257, −0.252, 0.032	0.465, −0.326, 0.083

Compound	112·I·(TCNQ)2	12·(TCNQ)2	13·(TCNQ)2 100 K	13·(TCNQ)2 RT
Empirical formula	C36H22Br2IN10	C30H14Br2N9	C30H16N9	C30H16N9
Formula weight (g mol^−1)	881.35	660.32	502.52	502.52
Colour	Black	Black	Black	Black
Crystal dimensions (mm)	0.31 × 0.14 × 0.12	0.33 × 0.19 × 0.04	0.35 × 0.32 × 0.20	0.20 × 0.17 × 0.07
Space group	P1	P1	P1	P1
a (Å)	7.5693 (3)	6.6911 (2)	7.7274 (4)	7.2867 (5)
b (Å)	13.0300 (3)	7.8201 (3)	13.1422 (6)	7.7545 (4)
c (Å)	18.5239 (5)	27.6491 (6)	13.3145 (6)	13.1305 (7)
α (°)	105.159 (2)	97.673 (2)	99.902 (4)	92.616 (5)
β (°)	90.971 (3)	90.168 (2)	106.251 (5)	103.414 (5)
γ (°)	98.382 (3)	108.973 (3)	97.225 (4)	113.979 (6)
Z	2	2	2	1
V (Å^3)	1741.67 (9)	1354.24 (8)	1257.00 (11)	651.18 (7)
Dcalc (g cm^−3)	1.681	1.619	1.328	1.230
λ (Å)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)	1.54184 (Cu Kα)
μ (mm^−1)	10.252	4.115	0.679	0.640
Θ range (°)	3.55–76.25	3.21–76.29	3.47–75.21	6.31–76.07
T (K)	100 (2)	293 (2)	100 (2)	293 (2)
Diffractometer type	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova	Xcalibur Nova
Range of hkl	−9 < h < 9; −15 < k < 16; −23 < l < 21	−8 < h < 8; −9 < k < 9; −23 < l < 34	−8 < h < 9; −15 < k < 16; −16 < l < 15	−8 < h < 9; −9 < k < 7; −16 < l < 14
Reflections collected	15827	11901	8993	4998
Independent reflections	7163	5582	4926	2624
Observed reflections (I ≥ 2σ)	6810	5100	4067	1975
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin, Tmax	0.3460, 1.0000	0.5628, 1.0000	0.3544, 1.0000	0.7450, 1.0000
Rint	0.0504	0.0433	0.0708	0.0210
R(F)	0.0381	0.0434	0.0815	0.1198
Rw(F^2)	0.1125	0.1177	0.2380	0.3926
Goodness of fit	0.898	1.042	1.699	1.558
H atom treatment	Constrained	Constrained	Constrained	Constrained
No. of parameters	442	370	352	190
No. of restraints	0	0	0	90
Δρmax, Δρmin, Δρr.m.s. (eÅ^–3)	1.313, −1.421, 0.132	0.873, −0.679, 0.107	0.434, −0.351, 0.085	0.853, −0.783, 0.098

Compound	14·(TCNQ)2 100 K	14·(TCNQ)2 RT
Empirical formula	C36H16N10	C36H16N10
Formula weight (g mol^−1)	588.59	588.59
Colour	Black	Black
Crystal dimensions (mm)	0.21 × 0.09 × 0.08	0.32 × 0.11 × 0.09
Space group	P1	P1
a (Å)	7.1249 (13)	7.2179 (10)
b (Å)	7.6572 (13)	7.6887 (14)
c (Å)	14.4249 (10)	14.5445 (13)
α (°)	89.017 (10)	89.176 (10)
β (°)	83.589 (12)	82.570 (9)
γ (°)	68.340 (17)	69.284 (14)
Z	1	1
V (Å^3)	726.6 (2)	748.2 (2)
Dcalc (g cm^−3)	1.345	1.306
λ (Å)	1.54184 (Cu Kα)	1.54184 (Cu Kα)
μ (mm^−1)	0.685	0.665
Θ range (°)	6.17–75.55	6.15–74.72
T (K)	100 (2)	293 (2)
Diffractometer type	Xcalibur Nova	Xcalibur Nova
Range of hkl	−8 < h < 6; −9 < k < 9; −18 < l < 18	−9 < h < 8; −9 < k < 9; −17 < l < 18
Reflections collected	5931	6183
Independent reflections	2996	3038
Observed reflections (I ≥ 2σ)	2391	2470
Absorption correction	Multi-scan	Multi-scan
Tmin, Tmax	0.6330, 1.0000	0.6757, 1.0000
Rint	0.0572	0.0374
R(F)	0.1281	0.1078
Rw(F^2)	0.3816	0.3477
Goodness of fit	1.481	1.400
H atom treatment	Constrained	Constrained
No. of parameters	217	217
No. of restraints	0	0
Δρmax, Δρmin, Δρr.m.s. (eÅ^–3)	1.251, −0.400, 0.120	0.918, −0.236, 0.080

4.3. Electron paramagnetic resonance spectroscopy

EPR spectroscopy was used to determine the magnetic properties of the studied compounds. The single-crystal and powder measurements were carried out on a standard Bruker Elexsys 580 X-band EPR spectrometer, equipped with an Oxford continuous-flow cryostat with a flow of cold N₂ gas, in the range 80–300 K. EPR spectra in the range 300–360 K were recorded on a Varian E-109 X-band spectrometer using a Bruker ER 4111VT variable-temperature unit with a flow of cold N₂ gas. For the powder samples, Suprasil Quartz EPR Sample Tubes were used. The single crystal was evaluated first under a microscope and then by X-ray diffraction. It was aligned with a crystal axis on the EPR holder to ensure the EPR measurements were carried out on single crystals and to avoid twinning or multiple crystals that would affect our EPR measurements. The single crystals were mounted on the quartz rod with a goniometer and EPR spectra were recorded in three mutually perpendicular planes by rotating the crystals around the a, b and c axes at 5° intervals from 0 to 180°. The manganese standard reference Mn²⁺ in MgO was used to calibrate the magnetic field of the EPR spectrometer and consequently the g-value. The radical concentration in each sample was determined by dividing the value of the double integral of the EPR signal by the mass of the sample. Varian strong pitch was used as a standard to calculate the number of radicals. Spectral simulations were carried out using the Easyspin (Stoll & Schweiger, 2006) software working on the MATLAB platform (The Mathworks, 2011), and the in-house-made Mathematica program was used for the single-crystal spectra (Wolfram Research, 2019).

4.4. Electrical measurements

The electrical conductivities of 1₂·Br·(TCNQ)₂, 4·(TCNQ)₂, 6·(TCNQ)₂, 8·(TCNQ)₂, 9·(TCNQ)₄, 10·(TCNQ)₃ and 12·(TCNQ)₂ were measured by impedance spectroscopy (Novocontrol Alpha-AN dielectric analyser) from 0.01 to 1 MHz at temperatures from −80 to 80°C (in steps of 20°C). The measurements were performed on polycrystalline samples pressed into pellets approximately 1 mm-thick. For the electrical contacts, gold electrodes (3.8 mm in diameter) were sputtered on the opposite surfaces of the pellets, except for the 4·(TCNQ)₂ sample, which was measured with Ag electrodes due to difficulties with Au deposition.

Supporting information

Computing details

For all structures, data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); cell refinement: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); data reduction: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2017).

(tcnq_2br_1)

Crystal data

2(C12H4N4)·2(C6H7BrN)·Br	Z = 2
Mr = 417.18	F(000) = 413
Triclinic, P1	Dx = 1.515 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.2378 (4) Å	Cell parameters from 3587 reflections
b = 7.7475 (4) Å	θ = 5.0–73.5°
c = 17.8746 (12) Å	µ = 4.42 mm^−1
α = 83.578 (5)°	T = 293 K
β = 83.241 (5)°	Prism, black
γ = 67.104 (5)°	0.18 × 0.06 × 0.04 mm
V = 914.53 (10) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	3677 independent reflections
Radiation source: micro-focus sealed X-ray tube	3245 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.4°, θmin = 5.0°
ω scans	h = −9→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→8
Tmin = 0.226, Tmax = 1	l = −19→22
7195 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.066	w = 1/[σ^2(Fo^2) + (0.1293P)^2 + 1.2355P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.215	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 1.05 e Å^−3
3677 reflections	Δρmin = −0.61 e Å^−3
224 parameters	Extinction correction: SHELXL-2017/1 (Sheldrick 2017)
0 restraints	Extinction coefficient: 0.0072 (11)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	1.3798 (15)	−0.9710 (15)	1.2365 (5)	0.122 (3)
N2	1.1716 (14)	−0.2500 (11)	0.8461 (5)	0.111 (2)
N3	1.3164 (12)	−1.4027 (11)	1.1189 (5)	0.104 (2)
N4	1.0722 (14)	−0.6714 (13)	0.7303 (4)	0.108 (2)
C1	1.3545 (13)	−1.0158 (11)	1.1815 (4)	0.0871 (19)
C2	1.3173 (10)	−1.0695 (9)	1.1119 (4)	0.0736 (14)
C3	1.2834 (9)	−0.9506 (9)	1.0477 (4)	0.0726 (14)
C4	1.2863 (10)	−0.7663 (9)	1.0460 (4)	0.0738 (14)
H4	1.314242	−0.726878	1.089143	0.089*
C5	1.2493 (10)	−0.6490 (9)	0.9831 (4)	0.0756 (15)
H5	1.252363	−0.530291	0.983856	0.091*
C6	1.2060 (9)	−0.7009 (9)	0.9158 (4)	0.0723 (14)
C7	1.1644 (10)	−0.5780 (9)	0.8513 (4)	0.0772 (15)
C8	1.1672 (11)	−0.3953 (10)	0.8486 (4)	0.0819 (17)
C9	1.3151 (10)	−1.2530 (9)	1.1152 (4)	0.0767 (15)
C10	1.2384 (9)	−1.0035 (9)	0.9789 (4)	0.0716 (14)
H10	1.234772	−1.121832	0.97771	0.086*
C11	1.2019 (9)	−0.8850 (9)	0.9171 (4)	0.0720 (14)
H11	1.17304	−0.922789	0.87378	0.086*
C12	1.1133 (11)	−0.6278 (10)	0.7848 (4)	0.0838 (17)
Br1	0.95267 (8)	−0.22453 (8)	0.56792 (3)	0.0659 (3)
N5	1.3072 (11)	−0.2688 (10)	0.6516 (4)	0.0916 (17)
C13	1.2384 (13)	−0.3548 (12)	0.6084 (5)	0.0881 (19)
C14	1.3573 (14)	−0.5398 (13)	0.5923 (5)	0.101 (2)
H14	1.307418	−0.604044	0.564388	0.122*
C15	1.5436 (14)	−0.6272 (14)	0.6167 (7)	0.119 (3)
H15	1.624638	−0.747987	0.603569	0.143*
C16	1.6132 (16)	−0.5300 (17)	0.6630 (7)	0.126 (4)
H16	1.737548	−0.588678	0.68297	0.152*
C17	1.4972 (17)	−0.3551 (15)	0.6769 (6)	0.115 (3)
H17	1.544734	−0.288263	0.704471	0.138*
C18	1.1750 (19)	−0.0659 (14)	0.6716 (6)	0.123 (3)
H18A	1.244889	−0.023061	0.703086	0.184*
H18B	1.147084	0.014938	0.626107	0.184*
H18C	1.050818	−0.063571	0.698163	0.184*
Br2	0.5	0	0.5	0.0706 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.142 (7)	0.154 (8)	0.092 (5)	−0.071 (6)	−0.017 (5)	−0.029 (5)
N2	0.131 (6)	0.082 (4)	0.119 (6)	−0.041 (4)	−0.017 (5)	0.000 (4)
N3	0.113 (5)	0.093 (5)	0.118 (5)	−0.054 (4)	−0.020 (4)	0.005 (4)
N4	0.121 (6)	0.123 (6)	0.089 (4)	−0.052 (5)	−0.026 (4)	−0.006 (4)
C1	0.100 (5)	0.082 (4)	0.082 (4)	−0.038 (4)	−0.004 (4)	−0.011 (3)
C2	0.067 (3)	0.071 (3)	0.081 (4)	−0.024 (3)	−0.006 (3)	−0.008 (3)
C3	0.059 (3)	0.071 (3)	0.086 (4)	−0.022 (3)	−0.004 (3)	−0.012 (3)
C4	0.072 (3)	0.077 (4)	0.075 (3)	−0.029 (3)	−0.008 (3)	−0.013 (3)
C5	0.073 (3)	0.064 (3)	0.089 (4)	−0.025 (3)	−0.006 (3)	−0.009 (3)
C6	0.058 (3)	0.068 (3)	0.087 (4)	−0.019 (2)	−0.004 (3)	−0.012 (3)
C7	0.076 (4)	0.067 (3)	0.081 (4)	−0.018 (3)	−0.009 (3)	−0.002 (3)
C8	0.083 (4)	0.066 (4)	0.093 (4)	−0.025 (3)	−0.003 (3)	−0.006 (3)
C9	0.073 (4)	0.072 (4)	0.088 (4)	−0.030 (3)	−0.003 (3)	−0.010 (3)
C10	0.067 (3)	0.064 (3)	0.087 (4)	−0.029 (3)	−0.003 (3)	−0.010 (3)
C11	0.065 (3)	0.073 (3)	0.078 (4)	−0.025 (3)	−0.012 (3)	−0.006 (3)
C12	0.083 (4)	0.077 (4)	0.088 (4)	−0.028 (3)	−0.011 (3)	0.000 (3)
Br1	0.0609 (4)	0.0605 (4)	0.0730 (4)	−0.0191 (3)	−0.0129 (3)	0.0011 (3)
N5	0.102 (4)	0.093 (4)	0.087 (4)	−0.044 (4)	−0.013 (3)	−0.008 (3)
C13	0.098 (5)	0.087 (5)	0.086 (4)	−0.043 (4)	−0.007 (4)	−0.005 (4)
C14	0.102 (6)	0.096 (5)	0.103 (6)	−0.032 (4)	−0.014 (4)	−0.014 (4)
C15	0.091 (6)	0.100 (6)	0.152 (9)	−0.013 (5)	−0.018 (6)	−0.032 (6)
C16	0.090 (6)	0.131 (9)	0.152 (9)	−0.025 (6)	−0.026 (6)	−0.032 (7)
C17	0.122 (7)	0.106 (6)	0.127 (7)	−0.048 (6)	−0.028 (6)	−0.014 (5)
C18	0.168 (10)	0.106 (6)	0.102 (6)	−0.056 (7)	−0.008 (6)	−0.024 (5)
Br2	0.0635 (5)	0.0658 (5)	0.0751 (5)	−0.0135 (4)	−0.0144 (4)	−0.0077 (4)

Geometric parameters (Å, º)

N1—C1	1.134 (11)	C10—H10	0.93
N2—C8	1.135 (10)	C11—H11	0.93
N3—C9	1.150 (9)	Br1—C13	2.093 (9)
N4—C12	1.172 (11)	N5—C13	1.325 (10)
C1—C2	1.441 (10)	N5—C17	1.380 (13)
C2—C3	1.370 (9)	N5—C18	1.546 (12)
C2—C9	1.423 (9)	C13—C14	1.397 (12)
C3—C4	1.434 (9)	C14—C15	1.352 (13)
C3—C10	1.448 (9)	C14—H14	0.93
C4—C5	1.348 (10)	C15—C16	1.428 (14)
C4—H4	0.93	C15—H15	0.93
C5—C6	1.415 (9)	C16—C17	1.321 (14)
C5—H5	0.93	C16—H16	0.93
C6—C7	1.392 (10)	C17—H17	0.93
C6—C11	1.435 (9)	C18—H18A	0.96
C7—C8	1.418 (10)	C18—H18B	0.96
C7—C12	1.420 (10)	C18—H18C	0.96
C10—C11	1.337 (9)
N1—C1—C2	178.6 (10)	C6—C11—H11	119.1
C3—C2—C9	122.7 (6)	N4—C12—C7	179.1 (9)
C3—C2—C1	122.2 (6)	C13—N5—C17	121.1 (8)
C9—C2—C1	115.1 (6)	C13—N5—C18	119.3 (8)
C2—C3—C4	121.5 (6)	C17—N5—C18	119.6 (8)
C2—C3—C10	121.6 (6)	N5—C13—C14	118.6 (8)
C4—C3—C10	116.8 (6)	N5—C13—Br1	121.6 (6)
C5—C4—C3	121.2 (6)	C14—C13—Br1	119.7 (6)
C5—C4—H4	119.4	C15—C14—C13	121.2 (9)
C3—C4—H4	119.4	C15—C14—H14	119.4
C4—C5—C6	122.0 (6)	C13—C14—H14	119.4
C4—C5—H5	119	C14—C15—C16	118.6 (9)
C6—C5—H5	119	C14—C15—H15	120.7
C7—C6—C5	121.7 (6)	C16—C15—H15	120.7
C7—C6—C11	121.1 (6)	C17—C16—C15	118.6 (10)
C5—C6—C11	117.2 (6)	C17—C16—H16	120.7
C6—C7—C8	122.2 (7)	C15—C16—H16	120.7
C6—C7—C12	121.6 (6)	C16—C17—N5	121.7 (10)
C8—C7—C12	116.2 (6)	C16—C17—H17	119.1
N2—C8—C7	179.2 (10)	N5—C17—H17	119.1
N3—C9—C2	178.6 (9)	N5—C18—H18A	109.5
C11—C10—C3	121.1 (6)	N5—C18—H18B	109.5
C11—C10—H10	119.5	H18A—C18—H18B	109.5
C3—C10—H10	119.5	N5—C18—H18C	109.5
C10—C11—C6	121.8 (6)	H18A—C18—H18C	109.5
C10—C11—H11	119.1	H18B—C18—H18C	109.5
C9—C2—C3—C4	180.0 (6)	C3—C10—C11—C6	0.2 (10)
C1—C2—C3—C4	1.0 (10)	C7—C6—C11—C10	−178.9 (6)
C9—C2—C3—C10	1.4 (10)	C5—C6—C11—C10	−0.4 (9)
C1—C2—C3—C10	−177.5 (6)	C17—N5—C13—C14	3.8 (13)
C2—C3—C4—C5	−178.8 (6)	C18—N5—C13—C14	−178.4 (8)
C10—C3—C4—C5	−0.2 (9)	C17—N5—C13—Br1	−178.9 (7)
C3—C4—C5—C6	0.0 (10)	C18—N5—C13—Br1	−1.1 (11)
C4—C5—C6—C7	178.8 (6)	N5—C13—C14—C15	−3.6 (15)
C4—C5—C6—C11	0.3 (9)	Br1—C13—C14—C15	179.1 (8)
C5—C6—C7—C8	1.4 (10)	C13—C14—C15—C16	3.4 (17)
C11—C6—C7—C8	179.9 (6)	C14—C15—C16—C17	−4 (2)
C5—C6—C7—C12	−177.5 (6)	C15—C16—C17—N5	4 (2)
C11—C6—C7—C12	1.0 (10)	C13—N5—C17—C16	−4.1 (16)
C2—C3—C10—C11	178.7 (6)	C18—N5—C17—C16	178.0 (11)
C4—C3—C10—C11	0.1 (9)

(tcnq_2pic_100k_3)

Crystal data

2(C12H4N4)·C7H2N	F(000) = 546
Mr = 508.48	Dx = 1.266 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 2404 reflections
a = 13.2712 (6) Å	θ = 4.8–75.7°
b = 12.5807 (5) Å	µ = 0.65 mm^−1
c = 7.7388 (5) Å	T = 100 K
β = 90.466 (4)°	Prism, black
V = 1292.04 (11) Å^3	0.25 × 0.13 × 0.10 mm
Z = 2

Data collection

Xcalibur, Ruby, Nova diffractometer	2569 independent reflections
Radiation source: micro-focus sealed X-ray tube	1751 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.080
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.6°, θmin = 3.3°
ω scans	h = −15→16
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −15→14
Tmin = 0.431, Tmax = 1	l = −9→9
5148 measured reflections

Refinement

Refinement on F^2	58 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.136	H-atom parameters constrained
wR(F^2) = 0.391	w = 1/[σ^2(Fo^2) + (0.161P)^2 + 5.3177P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2569 reflections	Δρmax = 1.09 e Å^−3
190 parameters	Δρmin = −0.70 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.7958 (3)	0.3820 (4)	0.4640 (7)	0.0488 (12)
N2	0.2551 (3)	0.3839 (4)	−0.1017 (7)	0.0473 (12)
N3	0.6298 (3)	0.3691 (3)	0.9462 (7)	0.0466 (11)
N4	0.0885 (3)	0.3407 (4)	0.3824 (6)	0.0499 (12)
C1	0.7185 (4)	0.3802 (4)	0.5283 (7)	0.0392 (12)
C2	0.6220 (4)	0.3776 (3)	0.6099 (7)	0.0343 (11)
C3	0.5326 (3)	0.3776 (3)	0.5196 (6)	0.0312 (10)
C4	0.5319 (4)	0.3827 (3)	0.3314 (7)	0.0348 (11)
H4	0.592604	0.386207	0.272514	0.042*
C5	0.4447 (3)	0.3823 (3)	0.2418 (7)	0.0366 (11)
H5	0.44682	0.386946	0.121993	0.044*
C6	0.3487 (3)	0.3749 (3)	0.3242 (6)	0.0344 (11)
C7	0.2590 (4)	0.3701 (3)	0.2332 (6)	0.0344 (11)
C8	0.2570 (3)	0.3778 (3)	0.0485 (7)	0.0375 (11)
C9	0.6252 (3)	0.3735 (3)	0.7948 (7)	0.0357 (11)
C10	0.4366 (4)	0.3716 (3)	0.6011 (7)	0.0368 (11)
H10	0.434616	0.367936	0.721064	0.044*
C11	0.3493 (3)	0.3711 (3)	0.5128 (6)	0.0327 (10)
H11	0.288657	0.368283	0.572077	0.039*
C12	0.1643 (4)	0.3552 (4)	0.3149 (7)	0.0413 (12)
N5	0.0278 (5)	0.5157 (8)	0.9296 (9)	0.098 (3)	0.5
C13	0.0278 (5)	0.5157 (8)	0.9296 (9)	0.098 (3)	0.5
C14	0.0320 (6)	0.4602 (10)	0.7738 (11)	0.108 (3)
C15	−0.0247 (10)	0.3832 (12)	0.7700 (19)	0.091 (3)	0.5
H15	−0.030181	0.342766	0.669813	0.109*	0.5
C16	−0.0818 (8)	0.3555 (8)	0.9167 (17)	0.062 (3)	0.5
H16	−0.122484	0.295674	0.904845	0.074*	0.5
C17	−0.0847 (7)	0.4009 (12)	1.0607 (13)	0.125 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.032 (2)	0.048 (3)	0.066 (3)	0.0032 (18)	0.000 (2)	0.003 (2)
N2	0.042 (2)	0.042 (2)	0.058 (3)	0.0015 (18)	−0.013 (2)	−0.003 (2)
N3	0.044 (2)	0.036 (2)	0.060 (3)	−0.0005 (18)	−0.007 (2)	0.006 (2)
N4	0.036 (2)	0.050 (3)	0.064 (3)	−0.0039 (19)	−0.001 (2)	0.002 (2)
C1	0.036 (2)	0.024 (2)	0.058 (3)	0.0033 (17)	−0.009 (2)	0.001 (2)
C2	0.037 (2)	0.0179 (19)	0.048 (3)	0.0005 (16)	0.0014 (19)	0.0004 (17)
C3	0.039 (2)	0.0156 (19)	0.039 (2)	0.0002 (15)	0.0004 (19)	−0.0011 (16)
C4	0.035 (2)	0.0169 (19)	0.053 (3)	0.0013 (16)	0.0047 (19)	0.0002 (18)
C5	0.033 (2)	0.024 (2)	0.052 (3)	−0.0003 (17)	0.000 (2)	−0.0028 (19)
C6	0.036 (2)	0.018 (2)	0.048 (3)	−0.0003 (16)	0.0011 (19)	0.0008 (17)
C7	0.038 (2)	0.023 (2)	0.042 (3)	0.0008 (17)	0.0006 (19)	−0.0008 (17)
C8	0.031 (2)	0.026 (2)	0.056 (3)	0.0022 (16)	−0.011 (2)	−0.002 (2)
C9	0.032 (2)	0.018 (2)	0.057 (3)	−0.0020 (15)	−0.007 (2)	0.0059 (18)
C10	0.035 (2)	0.0167 (19)	0.059 (3)	−0.0004 (16)	0.001 (2)	0.0038 (18)
C11	0.036 (2)	0.0186 (19)	0.044 (3)	−0.0019 (16)	0.0046 (18)	0.0006 (17)
C12	0.036 (2)	0.031 (2)	0.057 (3)	−0.0002 (19)	−0.009 (2)	−0.001 (2)
N5	0.040 (3)	0.159 (8)	0.094 (5)	0.038 (4)	0.020 (3)	0.056 (5)
C13	0.040 (3)	0.159 (8)	0.094 (5)	0.038 (4)	0.020 (3)	0.056 (5)
C14	0.064 (4)	0.171 (9)	0.090 (5)	0.052 (5)	0.025 (4)	0.062 (5)
C15	0.070 (8)	0.112 (9)	0.090 (8)	0.069 (6)	0.023 (6)	0.045 (6)
C16	0.041 (5)	0.028 (5)	0.116 (8)	−0.005 (4)	−0.014 (5)	0.002 (5)
C17	0.069 (6)	0.213 (13)	0.093 (6)	0.069 (7)	0.015 (5)	0.029 (7)

Geometric parameters (Å, º)

N1—C1	1.143 (7)	C6—C11	1.460 (7)
N2—C8	1.165 (7)	C7—C12	1.424 (7)
N3—C9	1.174 (7)	C7—C8	1.432 (7)
N4—C12	1.151 (7)	C10—C11	1.341 (7)
C1—C2	1.433 (7)	C10—H10	0.93
C2—C3	1.372 (7)	C11—H11	0.93
C2—C9	1.432 (7)	C13—C17^i	1.295 (17)
C3—C10	1.428 (7)	C13—C13^i	1.378 (11)
C3—C4	1.458 (7)	C13—C14	1.395 (12)
C4—C5	1.344 (7)	C14—C15	1.226 (15)
C4—H4	0.93	C15—C16	1.414 (14)
C5—C6	1.433 (7)	C15—H15	0.93
C5—H5	0.93	C16—C17	1.253 (13)
C6—C7	1.380 (7)	C16—H16	0.93
N1—C1—C2	179.6 (6)	N3—C9—C2	178.5 (5)
C3—C2—C9	121.8 (4)	C11—C10—C3	123.1 (5)
C3—C2—C1	123.2 (5)	C11—C10—H10	118.5
C9—C2—C1	115.0 (4)	C3—C10—H10	118.5
C2—C3—C10	123.1 (5)	C10—C11—C6	120.4 (4)
C2—C3—C4	120.5 (4)	C10—C11—H11	119.8
C10—C3—C4	116.4 (4)	C6—C11—H11	119.8
C5—C4—C3	120.9 (4)	N4—C12—C7	178.3 (5)
C5—C4—H4	119.5	C17^i—C13—C13^i	120.1 (12)
C3—C4—H4	119.5	C17^i—C13—C14	115.3 (7)
C4—C5—C6	122.4 (5)	C13^i—C13—C14	124.4 (12)
C4—C5—H5	118.8	C15—C14—C13	112.8 (10)
C6—C5—H5	118.8	C14—C15—C16	120.6 (13)
C7—C6—C5	122.9 (5)	C14—C15—H15	119.7
C7—C6—C11	120.4 (4)	C16—C15—H15	119.7
C5—C6—C11	116.7 (4)	C17—C16—C15	128.5 (12)
C6—C7—C12	122.7 (5)	C17—C16—H16	115.8
C6—C7—C8	121.0 (4)	C15—C16—H16	115.8
C12—C7—C8	116.3 (4)	C16—C17—C13^i	113.5 (10)
N2—C8—C7	179.8 (6)
C9—C2—C3—C10	−1.1 (6)	C11—C6—C7—C8	177.6 (4)
C1—C2—C3—C10	178.0 (4)	C2—C3—C10—C11	−179.7 (4)
C9—C2—C3—C4	179.5 (4)	C4—C3—C10—C11	−0.3 (6)
C1—C2—C3—C4	−1.3 (6)	C3—C10—C11—C6	1.1 (6)
C2—C3—C4—C5	179.7 (4)	C7—C6—C11—C10	177.4 (4)
C10—C3—C4—C5	0.4 (6)	C5—C6—C11—C10	−1.8 (6)
C3—C4—C5—C6	−1.2 (6)	C17^i—C13—C14—C15	−178.6 (10)
C4—C5—C6—C7	−177.3 (4)	C13^i—C13—C14—C15	4.6 (14)
C4—C5—C6—C11	1.9 (6)	C13—C14—C15—C16	−3.2 (15)
C5—C6—C7—C12	175.4 (4)	C14—C15—C16—C17	1 (2)
C11—C6—C7—C12	−3.7 (6)	C15—C16—C17—C13^i	0.8 (18)
C5—C6—C7—C8	−3.3 (6)

Symmetry code: (i) −x, −y+1, −z+2.

(tcnq_2pic_2)

Crystal data

2(C12H4N4)·C7H2N	F(000) = 554
Mr = 508.48	Dx = 1.266 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4296 reflections
a = 13.3766 (2) Å	θ = 4.8–75.9°
b = 12.8023 (2) Å	µ = 0.65 mm^−1
c = 7.7861 (1) Å	T = 293 K
β = 90.396 (1)°	Prism, black
V = 1333.35 (3) Å^3	0.25 × 0.13 × 0.10 mm
Z = 2

Data collection

Xcalibur, Ruby, Nova diffractometer	2655 independent reflections
Radiation source: micro-focus sealed X-ray tube	2368 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.016
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.0°, θmin = 3.3°
ω scans	h = −16→13
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −15→13
Tmin = 0.740, Tmax = 1	l = −9→9
7175 measured reflections

Refinement

Refinement on F^2	59 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.080	H-atom parameters constrained
wR(F^2) = 0.244	w = 1/[σ^2(Fo^2) + (0.127P)^2 + 0.7163P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2655 reflections	Δρmax = 0.50 e Å^−3
190 parameters	Δρmin = −0.47 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.79412 (17)	0.3804 (2)	0.4643 (4)	0.0786 (8)
N2	0.25924 (19)	0.3835 (2)	−0.0970 (3)	0.0752 (7)
N3	0.62860 (19)	0.36881 (19)	0.9386 (3)	0.0696 (7)
N4	0.09276 (18)	0.3418 (3)	0.3785 (4)	0.0843 (8)
C1	0.71694 (17)	0.37920 (18)	0.5278 (3)	0.0530 (6)
C2	0.62222 (16)	0.37756 (15)	0.6091 (3)	0.0445 (5)
C3	0.53293 (15)	0.37771 (14)	0.5162 (3)	0.0411 (5)
C4	0.53252 (16)	0.38336 (16)	0.3324 (3)	0.0441 (5)
H4	0.592932	0.387704	0.274452	0.053*
C5	0.44604 (16)	0.38249 (16)	0.2417 (3)	0.0446 (5)
H5	0.448037	0.386771	0.12255	0.054*
C6	0.35108 (16)	0.37507 (15)	0.3258 (3)	0.0433 (5)
C7	0.26228 (17)	0.37032 (16)	0.2318 (3)	0.0484 (6)
C8	0.26028 (18)	0.37778 (19)	0.0499 (3)	0.0546 (6)
C9	0.62503 (17)	0.37243 (16)	0.7917 (3)	0.0485 (5)
C10	0.43804 (16)	0.37212 (15)	0.5998 (3)	0.0434 (5)
H10	0.435939	0.369351	0.71905	0.052*
C11	0.35137 (16)	0.37077 (15)	0.5091 (3)	0.0439 (5)
H11	0.290957	0.366966	0.567191	0.053*
C12	0.16802 (18)	0.3552 (2)	0.3133 (3)	0.0582 (6)
N5	0.0283 (3)	0.5130 (4)	0.9314 (6)	0.1145 (14)	0.5
C13	0.0283 (3)	0.5130 (4)	0.9314 (6)	0.1145 (14)	0.5
C14	0.0353 (4)	0.4620 (6)	0.7794 (8)	0.144 (2)
C15	−0.0182 (6)	0.3943 (6)	0.7836 (9)	0.0871 (18)	0.5
H15	−0.023482	0.354855	0.683739	0.105*	0.5
C16	−0.0806 (5)	0.3607 (5)	0.9277 (11)	0.0852 (18)	0.5
H16	−0.119588	0.301335	0.912059	0.102*	0.5
C17	−0.0850 (5)	0.4025 (7)	1.0591 (8)	0.159 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0476 (13)	0.102 (2)	0.0867 (18)	0.0044 (11)	0.0116 (11)	0.0033 (13)
N2	0.0720 (15)	0.0977 (19)	0.0558 (13)	0.0051 (12)	−0.0113 (11)	−0.0046 (11)
N3	0.0765 (16)	0.0808 (16)	0.0513 (12)	−0.0050 (11)	−0.0069 (10)	0.0093 (10)
N4	0.0483 (13)	0.108 (2)	0.0964 (19)	−0.0037 (12)	0.0049 (12)	−0.0006 (15)
C1	0.0447 (12)	0.0576 (14)	0.0568 (13)	0.0027 (9)	−0.0033 (10)	−0.0002 (10)
C2	0.0435 (11)	0.0427 (11)	0.0473 (11)	0.0006 (8)	0.0002 (8)	0.0012 (8)
C3	0.0423 (11)	0.0367 (10)	0.0442 (11)	0.0000 (7)	0.0006 (8)	−0.0011 (7)
C4	0.0429 (11)	0.0466 (11)	0.0427 (11)	0.0005 (8)	0.0045 (8)	−0.0032 (8)
C5	0.0460 (11)	0.0476 (11)	0.0403 (10)	0.0002 (8)	0.0013 (8)	−0.0032 (8)
C6	0.0430 (11)	0.0399 (11)	0.0470 (11)	−0.0004 (7)	−0.0005 (8)	−0.0010 (8)
C7	0.0446 (12)	0.0488 (12)	0.0518 (12)	0.0006 (8)	−0.0040 (9)	−0.0024 (9)
C8	0.0491 (13)	0.0595 (14)	0.0551 (14)	0.0028 (9)	−0.0108 (10)	−0.0056 (10)
C9	0.0469 (12)	0.0479 (12)	0.0507 (13)	−0.0012 (8)	−0.0040 (9)	0.0049 (9)
C10	0.0449 (11)	0.0436 (11)	0.0416 (10)	−0.0027 (8)	0.0028 (8)	0.0027 (8)
C11	0.0418 (11)	0.0442 (11)	0.0458 (11)	−0.0032 (8)	0.0038 (8)	0.0012 (8)
C12	0.0440 (13)	0.0650 (14)	0.0655 (15)	0.0018 (10)	−0.0062 (10)	−0.0030 (11)
N5	0.0594 (18)	0.161 (3)	0.123 (3)	0.0318 (19)	0.0183 (17)	0.075 (3)
C13	0.0594 (18)	0.161 (3)	0.123 (3)	0.0318 (19)	0.0183 (17)	0.075 (3)
C14	0.084 (3)	0.209 (6)	0.139 (4)	0.038 (3)	0.017 (3)	0.084 (4)
C15	0.085 (5)	0.110 (5)	0.066 (3)	0.036 (4)	−0.003 (3)	−0.002 (3)
C16	0.069 (4)	0.064 (3)	0.123 (5)	−0.010 (3)	−0.014 (3)	−0.014 (3)
C17	0.118 (4)	0.242 (8)	0.117 (4)	0.068 (5)	0.030 (3)	0.053 (4)

Geometric parameters (Å, º)

N1—C1	1.148 (3)	C7—C8	1.420 (3)
N2—C8	1.146 (3)	C7—C12	1.428 (3)
N3—C9	1.145 (3)	C10—C11	1.353 (3)
N4—C12	1.144 (3)	C10—H10	0.93
C1—C2	1.420 (3)	C11—H11	0.93
C2—C3	1.392 (3)	C13—C17^i	1.323 (9)
C2—C9	1.423 (3)	C13—C14	1.355 (8)
C3—C10	1.432 (3)	C13—C13^i	1.356 (7)
C3—C4	1.433 (3)	C13—C15	2.002 (10)
C4—C5	1.351 (3)	C14—C15	1.124 (8)
C4—H4	0.93	C15—C16	1.467 (10)
C5—C6	1.436 (3)	C15—H15	0.93
C5—H5	0.93	C16—C17	1.157 (8)
C6—C7	1.392 (3)	C16—H16	0.93
C6—C11	1.428 (3)
N1—C1—C2	179.0 (3)	C3—C10—H10	119.3
C3—C2—C1	122.2 (2)	C10—C11—C6	121.14 (19)
C3—C2—C9	122.4 (2)	C10—C11—H11	119.4
C1—C2—C9	115.36 (19)	C6—C11—H11	119.4
C2—C3—C10	121.58 (19)	N4—C12—C7	179.1 (3)
C2—C3—C4	121.09 (19)	C17^i—C13—C14	113.6 (5)
C10—C3—C4	117.32 (19)	C17^i—C13—C13^i	118.7 (7)
C5—C4—C3	121.26 (19)	C14—C13—C13^i	127.8 (7)
C5—C4—H4	119.4	C17^i—C13—C15	145.9 (5)
C3—C4—H4	119.4	C14—C13—C15	32.4 (3)
C4—C5—C6	121.25 (19)	C13^i—C13—C15	95.4 (6)
C4—C5—H5	119.4	C15—C14—C13	107.3 (6)
C6—C5—H5	119.4	C14—C15—C16	127.9 (7)
C7—C6—C11	121.3 (2)	C14—C15—C13	40.3 (4)
C7—C6—C5	121.1 (2)	C16—C15—C13	87.7 (4)
C11—C6—C5	117.51 (19)	C14—C15—H15	116.1
C6—C7—C8	122.1 (2)	C16—C15—H15	116.1
C6—C7—C12	121.7 (2)	C13—C15—H15	156.2
C8—C7—C12	116.2 (2)	C17—C16—C15	125.0 (8)
N2—C8—C7	179.6 (3)	C17—C16—H16	117.5
N3—C9—C2	179.1 (3)	C15—C16—H16	117.5
C11—C10—C3	121.50 (19)	C16—C17—C13^i	113.3 (7)
C11—C10—H10	119.3
C1—C2—C3—C10	177.64 (19)	C5—C6—C7—C12	175.3 (2)
C9—C2—C3—C10	−0.3 (3)	C2—C3—C10—C11	−179.04 (18)
C1—C2—C3—C4	−2.3 (3)	C4—C3—C10—C11	0.9 (3)
C9—C2—C3—C4	179.75 (18)	C3—C10—C11—C6	−0.1 (3)
C2—C3—C4—C5	179.34 (18)	C7—C6—C11—C10	177.91 (18)
C10—C3—C4—C5	−0.6 (3)	C5—C6—C11—C10	−0.9 (3)
C3—C4—C5—C6	−0.5 (3)	C17^i—C13—C14—C15	−177.4 (5)
C4—C5—C6—C7	−177.61 (19)	C13^i—C13—C14—C15	2.6 (8)
C4—C5—C6—C11	1.2 (3)	C13—C14—C15—C16	−3.5 (10)
C11—C6—C7—C8	178.0 (2)	C14—C15—C16—C17	2.1 (13)
C5—C6—C7—C8	−3.2 (3)	C13—C15—C16—C17	−0.2 (8)
C11—C6—C7—C12	−3.5 (3)	C15—C16—C17—C13^i	1.1 (10)

Symmetry code: (i) −x, −y+1, −z+2.

(tcnq_3i_1)

Crystal data

2(C12H4N4)·C6H7IN	Z = 1
Mr = 628.41	F(000) = 310
Triclinic, P1	Dx = 1.518 Mg m^−3
Hall symbol: P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.1680 (4) Å	Cell parameters from 4584 reflections
b = 7.6291 (4) Å	θ = 3.3–76.0°
c = 13.6797 (8) Å	µ = 9.46 mm^−1
α = 78.422 (5)°	T = 293 K
β = 83.441 (5)°	Prism, black
γ = 69.680 (5)°	0.12 × 0.10 × 0.05 mm
V = 686.44 (7) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	3390 independent reflections
Radiation source: micro-focus sealed X-ray tube	3380 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.037
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.2°, θmin = 3.3°
ω scans	h = −7→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −7→9
Tmin = 0.593, Tmax = 1	l = −15→17
5556 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0822P)^2 + 0.1275P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.115	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.54 e Å^−3
3390 reflections	Δρmin = −1.18 e Å^−3
361 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower.
3 restraints	Absolute structure parameter: 0.161 (8)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.49222 (7)	0.81611 (7)	0.80898 (6)	0.07149 (16)
N5	0.2664 (9)	1.3474 (9)	0.9132 (4)	0.0590 (12)
C13	0.2900 (10)	1.1960 (10)	0.8724 (5)	0.0546 (12)
H13	0.187283	1.192059	0.837958	0.066*
C14	0.4652 (10)	1.0457 (10)	0.8810 (5)	0.0580 (14)
C15	0.6191 (13)	1.0503 (16)	0.9338 (8)	0.072 (2)
H15	0.73826	0.949331	0.941521	0.087*
C16	0.5862 (19)	1.212 (2)	0.9741 (10)	0.081 (3)
H16	0.686125	1.22122	1.008446	0.097*
C17	0.4114 (13)	1.3560 (12)	0.9641 (5)	0.0653 (16)
H17	0.391229	1.462153	0.992851	0.078*
C18	0.075 (2)	1.5110 (19)	0.8972 (13)	0.092 (4)
H18A	0.076958	1.610165	0.93017	0.137*
H18B	0.060876	1.558278	0.826936	0.137*
H18C	−0.03497	1.469137	0.924211	0.137*
N1A	0.9199 (15)	0.1876 (17)	1.7595 (7)	0.083 (2)
N2A	0.6916 (12)	0.9852 (11)	1.2322 (6)	0.0733 (17)
N3A	0.8984 (18)	−0.2446 (17)	1.6026 (10)	0.079 (3)
N4A	0.6467 (19)	0.554 (2)	1.0803 (8)	0.078 (3)
C1A	0.8996 (12)	0.1469 (14)	1.6881 (6)	0.061 (2)
C2A	0.8657 (8)	0.1005 (10)	1.5953 (5)	0.0535 (12)
C3A	0.8239 (8)	0.2344 (9)	1.5091 (4)	0.0470 (11)
C4A	0.8166 (9)	0.4265 (10)	1.5060 (5)	0.0492 (12)
H4A	0.839163	0.461309	1.563783	0.059*
C5A	0.7784 (9)	0.5564 (11)	1.4226 (5)	0.0488 (12)
H5A	0.774387	0.679183	1.423589	0.059*
C6A	0.7435 (7)	0.5087 (8)	1.3312 (4)	0.0435 (10)
C7A	0.7039 (8)	0.6412 (9)	1.2435 (4)	0.0480 (11)
C8A	0.6975 (11)	0.8328 (12)	1.2377 (6)	0.0526 (15)
C9A	0.8859 (10)	−0.0934 (11)	1.5989 (5)	0.0583 (15)
C10A	0.7890 (8)	0.1861 (9)	1.4188 (5)	0.0495 (11)
H10A	0.794032	0.062861	1.41807	0.059*
C11A	0.7482 (8)	0.3187 (9)	1.3333 (4)	0.0470 (11)
H11A	0.723239	0.28489	1.275759	0.056*
C12A	0.6731 (10)	0.5936 (10)	1.1530 (5)	0.0550 (13)
N1B	0.4121 (14)	0.5040 (13)	0.6957 (6)	0.0726 (19)
N2B	0.1531 (13)	1.3048 (10)	0.1631 (6)	0.0746 (17)
N3B	0.3523 (19)	0.0780 (16)	0.5411 (9)	0.074 (3)
N4B	0.0766 (16)	0.8757 (19)	0.0219 (9)	0.076 (3)
C1B	0.3833 (11)	0.4661 (11)	0.6236 (6)	0.0505 (15)
C2B	0.3455 (8)	0.4216 (8)	0.5327 (4)	0.0466 (10)
C3B	0.3059 (7)	0.5532 (8)	0.4447 (4)	0.0416 (9)
C4B	0.3019 (8)	0.7436 (8)	0.4398 (5)	0.0440 (10)
H4B	0.326588	0.779559	0.496749	0.053*
C5B	0.2631 (9)	0.8727 (9)	0.3546 (5)	0.0453 (12)
H5B	0.26368	0.994688	0.353864	0.054*
C6B	0.2212 (7)	0.8249 (8)	0.2658 (4)	0.0431 (10)
C7B	0.1738 (8)	0.9580 (8)	0.1771 (4)	0.0473 (11)
C8B	0.1627 (11)	1.1502 (11)	0.1718 (6)	0.0534 (15)
C9B	0.3484 (9)	0.2325 (9)	0.5380 (5)	0.0517 (12)
C10B	0.2674 (8)	0.5040 (8)	0.3553 (4)	0.0452 (10)
H10B	0.27017	0.381045	0.355808	0.054*
C11B	0.2265 (8)	0.6343 (8)	0.2693 (4)	0.0462 (10)
H11B	0.201838	0.598743	0.21221	0.055*
C12B	0.1238 (9)	0.9109 (10)	0.0916 (5)	0.0549 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0881 (3)	0.0634 (2)	0.0560 (2)	−0.01547 (16)	−0.00058 (15)	−0.01402 (14)
N5	0.062 (3)	0.069 (3)	0.051 (3)	−0.029 (2)	−0.003 (2)	−0.009 (2)
C13	0.059 (3)	0.062 (3)	0.048 (3)	−0.025 (3)	−0.005 (2)	−0.012 (2)
C14	0.055 (3)	0.065 (4)	0.049 (3)	−0.019 (3)	−0.004 (2)	−0.001 (3)
C15	0.063 (4)	0.085 (6)	0.068 (5)	−0.025 (4)	−0.010 (3)	−0.011 (5)
C16	0.082 (6)	0.100 (8)	0.076 (6)	−0.048 (6)	−0.024 (5)	−0.007 (5)
C17	0.081 (4)	0.078 (4)	0.051 (3)	−0.042 (4)	−0.008 (3)	−0.012 (3)
C18	0.095 (7)	0.068 (6)	0.104 (11)	−0.010 (5)	0.013 (7)	−0.036 (6)
N1A	0.092 (5)	0.098 (7)	0.063 (4)	−0.033 (5)	−0.022 (4)	−0.009 (4)
N2A	0.084 (4)	0.063 (4)	0.084 (5)	−0.037 (3)	−0.008 (3)	−0.013 (4)
N3A	0.089 (6)	0.067 (6)	0.081 (7)	−0.030 (5)	0.002 (5)	−0.004 (5)
N4A	0.096 (6)	0.100 (8)	0.050 (5)	−0.044 (6)	−0.019 (4)	−0.010 (5)
C1A	0.056 (3)	0.078 (5)	0.052 (4)	−0.029 (3)	−0.015 (3)	0.000 (3)
C2A	0.047 (2)	0.064 (3)	0.052 (3)	−0.020 (2)	−0.007 (2)	−0.009 (3)
C3A	0.042 (2)	0.058 (3)	0.045 (3)	−0.021 (2)	−0.0065 (18)	−0.008 (2)
C4A	0.050 (3)	0.058 (3)	0.048 (3)	−0.025 (2)	−0.010 (2)	−0.012 (3)
C5A	0.049 (3)	0.058 (4)	0.050 (3)	−0.027 (3)	−0.007 (2)	−0.013 (3)
C6A	0.040 (2)	0.054 (3)	0.043 (2)	−0.0217 (19)	−0.0047 (17)	−0.008 (2)
C7A	0.048 (2)	0.059 (3)	0.043 (3)	−0.025 (2)	−0.0026 (19)	−0.009 (2)
C8A	0.057 (3)	0.059 (4)	0.050 (4)	−0.029 (3)	−0.008 (3)	−0.005 (3)
C9A	0.055 (3)	0.063 (4)	0.051 (3)	−0.015 (3)	0.001 (2)	−0.008 (3)
C10A	0.046 (2)	0.051 (3)	0.056 (3)	−0.017 (2)	−0.003 (2)	−0.014 (2)
C11A	0.051 (2)	0.055 (3)	0.040 (2)	−0.021 (2)	−0.0010 (19)	−0.014 (2)
C12A	0.061 (3)	0.065 (4)	0.045 (3)	−0.026 (3)	−0.009 (2)	−0.008 (3)
N1B	0.092 (5)	0.076 (5)	0.050 (3)	−0.024 (4)	−0.007 (3)	−0.016 (4)
N2B	0.094 (5)	0.054 (3)	0.073 (4)	−0.025 (3)	0.000 (3)	−0.006 (3)
N3B	0.099 (6)	0.057 (5)	0.076 (7)	−0.039 (4)	−0.009 (5)	−0.007 (4)
N4B	0.072 (5)	0.100 (8)	0.057 (5)	−0.019 (5)	−0.015 (4)	−0.023 (5)
C1B	0.054 (3)	0.051 (3)	0.042 (3)	−0.016 (2)	0.001 (2)	−0.003 (3)
C2B	0.047 (2)	0.049 (3)	0.046 (3)	−0.020 (2)	0.0001 (19)	−0.009 (2)
C3B	0.038 (2)	0.044 (3)	0.044 (2)	−0.0155 (17)	−0.0014 (17)	−0.007 (2)
C4B	0.048 (2)	0.044 (3)	0.043 (3)	−0.0162 (19)	−0.001 (2)	−0.012 (2)
C5B	0.048 (3)	0.043 (3)	0.046 (3)	−0.017 (2)	−0.003 (2)	−0.008 (2)
C6B	0.039 (2)	0.048 (3)	0.044 (2)	−0.0172 (18)	−0.0023 (17)	−0.007 (2)
C7B	0.046 (2)	0.051 (3)	0.044 (3)	−0.017 (2)	−0.0029 (19)	−0.004 (2)
C8B	0.057 (3)	0.050 (4)	0.048 (4)	−0.016 (3)	−0.003 (3)	0.002 (3)
C9B	0.057 (3)	0.050 (3)	0.052 (3)	−0.026 (2)	−0.007 (2)	−0.001 (2)
C10B	0.047 (2)	0.044 (2)	0.050 (3)	−0.0200 (19)	−0.0045 (19)	−0.010 (2)
C11B	0.048 (2)	0.051 (3)	0.046 (3)	−0.023 (2)	−0.0057 (19)	−0.007 (2)
C12B	0.052 (3)	0.059 (3)	0.052 (3)	−0.018 (2)	−0.008 (2)	−0.004 (3)

Geometric parameters (Å, º)

I1—C14	2.119 (8)	C6A—C7A	1.390 (8)
N5—C13	1.333 (10)	C6A—C11A	1.433 (8)
N5—C17	1.342 (9)	C7A—C12A	1.420 (9)
N5—C18	1.502 (15)	C7A—C8A	1.432 (10)
C13—C14	1.373 (10)	C10A—C11A	1.368 (9)
C13—H13	0.93	C10A—H10A	0.93
C14—C15	1.400 (12)	C11A—H11A	0.93
C15—C16	1.39 (2)	N1B—C1B	1.141 (13)
C15—H15	0.93	N2B—C8B	1.139 (12)
C16—C17	1.348 (18)	N3B—C9B	1.162 (13)
C16—H16	0.93	N4B—C12B	1.155 (15)
C17—H17	0.93	C1B—C2B	1.430 (11)
C18—H18A	0.96	C2B—C3B	1.390 (8)
C18—H18B	0.96	C2B—C9B	1.423 (8)
C18—H18C	0.96	C3B—C10B	1.430 (8)
N1A—C1A	1.122 (14)	C3B—C4B	1.431 (8)
N2A—C8A	1.136 (12)	C4B—C5B	1.352 (9)
N3A—C9A	1.117 (15)	C4B—H4B	0.93
N4A—C12A	1.147 (14)	C5B—C6B	1.426 (9)
C1A—C2A	1.450 (11)	C5B—H5B	0.93
C2A—C3A	1.382 (9)	C6B—C7B	1.407 (8)
C2A—C9A	1.427 (11)	C6B—C11B	1.433 (8)
C3A—C10A	1.430 (8)	C7B—C12B	1.407 (9)
C3A—C4A	1.440 (9)	C7B—C8B	1.428 (10)
C4A—C5A	1.337 (10)	C10B—C11B	1.366 (8)
C4A—H4A	0.93	C10B—H10B	0.93
C5A—C6A	1.441 (8)	C11B—H11B	0.93
C5A—H5A	0.93
C13—N5—C17	121.1 (7)	C6A—C7A—C12A	122.0 (6)
C13—N5—C18	117.8 (8)	C6A—C7A—C8A	122.4 (6)
C17—N5—C18	121.1 (9)	C12A—C7A—C8A	115.5 (6)
N5—C13—C14	120.3 (6)	N2A—C8A—C7A	179.4 (9)
N5—C13—H13	119.8	N3A—C9A—C2A	178.7 (9)
C14—C13—H13	119.8	C11A—C10A—C3A	120.9 (6)
C13—C14—C15	119.9 (8)	C11A—C10A—H10A	119.6
C13—C14—I1	117.5 (5)	C3A—C10A—H10A	119.6
C15—C14—I1	122.6 (6)	C10A—C11A—C6A	121.0 (5)
C16—C15—C14	117.1 (9)	C10A—C11A—H11A	119.5
C16—C15—H15	121.5	C6A—C11A—H11A	119.5
C14—C15—H15	121.5	N4A—C12A—C7A	179.2 (9)
C17—C16—C15	121.0 (9)	N1B—C1B—C2B	179.2 (9)
C17—C16—H16	119.5	C3B—C2B—C9B	121.5 (5)
C15—C16—H16	119.5	C3B—C2B—C1B	122.9 (6)
N5—C17—C16	120.6 (9)	C9B—C2B—C1B	115.6 (6)
N5—C17—H17	119.7	C2B—C3B—C10B	121.4 (5)
C16—C17—H17	119.7	C2B—C3B—C4B	121.4 (5)
N5—C18—H18A	109.5	C10B—C3B—C4B	117.2 (5)
N5—C18—H18B	109.5	C5B—C4B—C3B	121.8 (6)
H18A—C18—H18B	109.5	C5B—C4B—H4B	119.1
N5—C18—H18C	109.5	C3B—C4B—H4B	119.1
H18A—C18—H18C	109.5	C4B—C5B—C6B	121.1 (6)
H18B—C18—H18C	109.5	C4B—C5B—H5B	119.5
N1A—C1A—C2A	177.7 (11)	C6B—C5B—H5B	119.5
C3A—C2A—C9A	122.8 (6)	C7B—C6B—C5B	122.3 (5)
C3A—C2A—C1A	121.9 (7)	C7B—C6B—C11B	119.9 (5)
C9A—C2A—C1A	115.3 (7)	C5B—C6B—C11B	117.8 (5)
C2A—C3A—C10A	120.9 (6)	C6B—C7B—C12B	121.6 (5)
C2A—C3A—C4A	121.7 (6)	C6B—C7B—C8B	121.4 (6)
C10A—C3A—C4A	117.4 (6)	C12B—C7B—C8B	117.0 (6)
C5A—C4A—C3A	122.1 (6)	N2B—C8B—C7B	177.0 (9)
C5A—C4A—H4A	119	N3B—C9B—C2B	179.1 (10)
C3A—C4A—H4A	119	C11B—C10B—C3B	121.2 (5)
C4A—C5A—C6A	120.9 (6)	C11B—C10B—H10B	119.4
C4A—C5A—H5A	119.6	C3B—C10B—H10B	119.4
C6A—C5A—H5A	119.6	C10B—C11B—C6B	120.9 (5)
C7A—C6A—C11A	120.4 (5)	C10B—C11B—H11B	119.5
C7A—C6A—C5A	121.9 (6)	C6B—C11B—H11B	119.5
C11A—C6A—C5A	117.7 (5)	N4B—C12B—C7B	177.9 (8)
C17—N5—C13—C14	−0.6 (10)	C2A—C3A—C10A—C11A	−179.8 (5)
C18—N5—C13—C14	177.2 (9)	C4A—C3A—C10A—C11A	−0.7 (8)
N5—C13—C14—C15	0.7 (10)	C3A—C10A—C11A—C6A	1.3 (8)
N5—C13—C14—I1	−177.7 (5)	C7A—C6A—C11A—C10A	179.3 (5)
C13—C14—C15—C16	−1.0 (13)	C5A—C6A—C11A—C10A	−1.4 (8)
I1—C14—C15—C16	177.3 (8)	C9B—C2B—C3B—C10B	−0.3 (8)
C14—C15—C16—C17	1.3 (16)	C1B—C2B—C3B—C10B	−179.6 (6)
C13—N5—C17—C16	0.9 (12)	C9B—C2B—C3B—C4B	179.6 (5)
C18—N5—C17—C16	−176.9 (10)	C1B—C2B—C3B—C4B	0.3 (8)
C15—C16—C17—N5	−1.3 (16)	C2B—C3B—C4B—C5B	−179.8 (5)
C9A—C2A—C3A—C10A	3.0 (8)	C10B—C3B—C4B—C5B	0.1 (8)
C1A—C2A—C3A—C10A	−179.3 (6)	C3B—C4B—C5B—C6B	1.0 (9)
C9A—C2A—C3A—C4A	−176.0 (6)	C4B—C5B—C6B—C7B	177.8 (5)
C1A—C2A—C3A—C4A	1.6 (9)	C4B—C5B—C6B—C11B	−1.5 (8)
C2A—C3A—C4A—C5A	179.2 (6)	C5B—C6B—C7B—C12B	−177.0 (5)
C10A—C3A—C4A—C5A	0.1 (8)	C11B—C6B—C7B—C12B	2.4 (8)
C3A—C4A—C5A—C6A	−0.3 (9)	C5B—C6B—C7B—C8B	−0.8 (8)
C4A—C5A—C6A—C7A	−179.8 (6)	C11B—C6B—C7B—C8B	178.6 (5)
C4A—C5A—C6A—C11A	0.9 (8)	C2B—C3B—C10B—C11B	179.3 (5)
C11A—C6A—C7A—C12A	−1.9 (8)	C4B—C3B—C10B—C11B	−0.6 (7)
C5A—C6A—C7A—C12A	178.8 (6)	C3B—C10B—C11B—C6B	0.1 (8)
C11A—C6A—C7A—C8A	180.0 (6)	C7B—C6B—C11B—C10B	−178.4 (5)
C5A—C6A—C7A—C8A	0.7 (9)	C5B—C6B—C11B—C10B	1.0 (8)

(tcnq_35bret)

Crystal data

2(C12H4N4)·C7H8Br2N	Z = 2
Mr = 674.35	F(000) = 670
Triclinic, P1	Dx = 1.579 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 8.0361 (3) Å	Cell parameters from 8501 reflections
b = 13.0398 (3) Å	θ = 3.2–75.8°
c = 14.2071 (4) Å	µ = 3.94 mm^−1
α = 92.624 (2)°	T = 293 K
β = 98.576 (2)°	Plate, black
γ = 104.767 (3)°	0.41 × 0.28 × 0.04 mm
V = 1418.00 (7) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	5835 independent reflections
Radiation source: micro-focus sealed X-ray tube	5366 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.045
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.2°, θmin = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −16→15
Tmin = 0.543, Tmax = 1	l = −14→17
12861 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0855P)^2 + 2.5012P] where P = (Fo^2 + 2Fc^2)/3
S = 0.78	(Δ/σ)max = 0.001
5835 reflections	Δρmax = 0.84 e Å^−3
379 parameters	Δρmin = −1.02 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.72222 (3)	0.91221 (2)	0.65465 (2)	0.03351 (10)
Br2	0.37038 (5)	0.47266 (2)	0.60162 (2)	0.04291 (11)
N5	0.2578 (3)	0.73913 (16)	0.50303 (13)	0.0209 (4)
C13	0.3980 (3)	0.81944 (18)	0.53890 (16)	0.0217 (4)
H13	0.401378	0.888992	0.525412	0.026*
C14	0.5367 (3)	0.79733 (19)	0.59598 (16)	0.0238 (4)
C15	0.5342 (3)	0.6946 (2)	0.61479 (17)	0.0270 (5)
H15	0.629022	0.67907	0.65166	0.032*
C16	0.3858 (4)	0.61503 (19)	0.57698 (17)	0.0266 (5)
C17	0.2476 (3)	0.63849 (18)	0.52078 (16)	0.0235 (4)
H17	0.148204	0.584671	0.495499	0.028*
C18	0.1071 (3)	0.7638 (2)	0.44254 (18)	0.0304 (5)
H18A	0.046245	0.703038	0.397363	0.036*
H18B	0.149171	0.823823	0.406607	0.036*
C19	−0.0173 (4)	0.7899 (3)	0.5039 (2)	0.0381 (6)
H19A	−0.113529	0.805543	0.463991	0.057*
H19B	−0.060124	0.73004	0.538776	0.057*
H19C	0.042615	0.850605	0.548003	0.057*
N1A	1.3909 (3)	0.3800 (2)	1.16972 (16)	0.0339 (5)
N2A	0.6354 (3)	0.30165 (19)	0.67969 (15)	0.0333 (5)
N3A	1.0343 (3)	0.4558 (2)	1.34768 (16)	0.0364 (5)
N4A	0.2662 (3)	0.36503 (17)	0.84928 (16)	0.0288 (4)
C1A	1.2534 (3)	0.3903 (2)	1.17385 (16)	0.0264 (5)
C2A	1.0847 (3)	0.40287 (18)	1.17936 (16)	0.0234 (4)
C3A	0.9566 (3)	0.38753 (17)	1.09751 (16)	0.0201 (4)
C4A	0.9953 (3)	0.36020 (17)	1.00553 (16)	0.0209 (4)
H4A	1.105021	0.351063	1.000988	0.025*
C5A	0.8748 (3)	0.34753 (17)	0.92537 (15)	0.0203 (4)
H5A	0.90291	0.330006	0.866618	0.024*
C6A	0.7038 (3)	0.36087 (16)	0.93008 (15)	0.0195 (4)
C7A	0.5784 (3)	0.34737 (17)	0.84837 (16)	0.0207 (4)
C8A	0.6127 (3)	0.32187 (18)	0.75550 (16)	0.0233 (5)
C9A	1.0541 (3)	0.4318 (2)	1.27230 (17)	0.0269 (5)
C10A	0.7867 (3)	0.40079 (17)	1.10215 (16)	0.0214 (4)
H10A	0.758838	0.418312	1.160959	0.026*
C11A	0.6657 (3)	0.38822 (17)	1.02217 (16)	0.0213 (4)
H11A	0.556208	0.397461	1.026956	0.026*
C12A	0.4067 (3)	0.35878 (17)	0.85021 (16)	0.0222 (4)
N1B	1.0697 (3)	0.10913 (19)	0.08899 (16)	0.0317 (5)
N2B	0.3339 (3)	0.04668 (18)	−0.40494 (15)	0.0324 (5)
N3B	0.7238 (3)	0.19482 (18)	0.26325 (15)	0.0303 (5)
N4B	−0.0399 (3)	0.12220 (18)	−0.23740 (15)	0.0299 (4)
C1B	0.9343 (3)	0.12297 (18)	0.08992 (15)	0.0228 (4)
C2B	0.7665 (3)	0.14082 (17)	0.09337 (15)	0.0194 (4)
C3B	0.6413 (3)	0.12847 (16)	0.01180 (15)	0.0182 (4)
C4B	0.6779 (3)	0.09883 (17)	−0.08011 (15)	0.0194 (4)
H4B	0.785583	0.086542	−0.084682	0.023*
C5B	0.5575 (3)	0.08855 (17)	−0.16033 (15)	0.0203 (4)
H5B	0.584762	0.070264	−0.219096	0.024*
C6B	0.3894 (3)	0.10529 (16)	−0.15617 (15)	0.0194 (4)
C7B	0.2656 (3)	0.09403 (17)	−0.23919 (16)	0.0214 (4)
C8B	0.3032 (3)	0.06748 (18)	−0.33081 (16)	0.0238 (5)
C9B	0.7389 (3)	0.17077 (18)	0.18681 (16)	0.0213 (4)
C10B	0.4713 (3)	0.14434 (16)	0.01618 (15)	0.0187 (4)
H10B	0.443735	0.162627	0.074868	0.022*
C11B	0.3512 (3)	0.13296 (17)	−0.06413 (16)	0.0196 (4)
H11B	0.242172	0.143222	−0.059609	0.023*
C12B	0.0971 (3)	0.10971 (18)	−0.23758 (16)	0.0238 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02673 (16)	0.03944 (17)	0.02903 (16)	0.00083 (11)	0.00443 (11)	−0.00574 (11)
Br2	0.0641 (2)	0.02718 (16)	0.04202 (19)	0.01762 (14)	0.01058 (15)	0.01267 (12)
N5	0.0231 (9)	0.0278 (9)	0.0146 (8)	0.0090 (7)	0.0074 (7)	0.0034 (7)
C13	0.0265 (11)	0.0221 (10)	0.0191 (10)	0.0071 (8)	0.0106 (8)	0.0031 (8)
C14	0.0233 (11)	0.0301 (11)	0.0175 (10)	0.0047 (9)	0.0067 (8)	−0.0012 (8)
C15	0.0285 (12)	0.0357 (13)	0.0203 (10)	0.0139 (10)	0.0046 (9)	0.0049 (9)
C16	0.0373 (13)	0.0244 (11)	0.0220 (11)	0.0122 (10)	0.0091 (9)	0.0060 (9)
C17	0.0266 (11)	0.0254 (11)	0.0188 (10)	0.0054 (9)	0.0078 (9)	0.0020 (8)
C18	0.0272 (12)	0.0429 (14)	0.0248 (11)	0.0159 (10)	0.0032 (9)	0.0081 (10)
C19	0.0291 (14)	0.0474 (16)	0.0426 (15)	0.0187 (12)	0.0071 (11)	0.0009 (12)
N1A	0.0273 (11)	0.0482 (13)	0.0259 (10)	0.0071 (9)	0.0076 (8)	0.0061 (9)
N2A	0.0416 (13)	0.0425 (12)	0.0220 (10)	0.0175 (10)	0.0121 (9)	0.0075 (9)
N3A	0.0349 (12)	0.0448 (13)	0.0243 (11)	0.0009 (10)	0.0083 (9)	−0.0046 (9)
N4A	0.0297 (11)	0.0279 (10)	0.0323 (11)	0.0111 (8)	0.0094 (9)	0.0043 (8)
C1A	0.0282 (13)	0.0299 (12)	0.0189 (10)	0.0022 (9)	0.0055 (9)	0.0048 (9)
C2A	0.0250 (11)	0.0231 (10)	0.0209 (10)	0.0014 (8)	0.0085 (9)	0.0025 (8)
C3A	0.0237 (11)	0.0171 (9)	0.0204 (10)	0.0035 (8)	0.0087 (8)	0.0041 (8)
C4A	0.0221 (11)	0.0204 (10)	0.0225 (10)	0.0052 (8)	0.0106 (8)	0.0047 (8)
C5A	0.0255 (11)	0.0198 (10)	0.0191 (10)	0.0080 (8)	0.0106 (8)	0.0047 (8)
C6A	0.0246 (11)	0.0164 (9)	0.0197 (10)	0.0059 (8)	0.0087 (8)	0.0053 (7)
C7A	0.0255 (11)	0.0197 (10)	0.0208 (10)	0.0086 (8)	0.0103 (8)	0.0058 (8)
C8A	0.0262 (11)	0.0258 (11)	0.0216 (11)	0.0109 (9)	0.0067 (9)	0.0082 (8)
C9A	0.0238 (11)	0.0291 (12)	0.0244 (12)	0.0000 (9)	0.0053 (9)	0.0019 (9)
C10A	0.0270 (11)	0.0185 (10)	0.0200 (10)	0.0041 (8)	0.0112 (8)	0.0027 (8)
C11A	0.0247 (11)	0.0187 (10)	0.0239 (11)	0.0076 (8)	0.0106 (9)	0.0041 (8)
C12A	0.0280 (12)	0.0197 (10)	0.0210 (10)	0.0076 (8)	0.0076 (9)	0.0045 (8)
N1B	0.0293 (11)	0.0434 (12)	0.0267 (10)	0.0157 (9)	0.0071 (8)	0.0047 (9)
N2B	0.0436 (13)	0.0334 (11)	0.0226 (10)	0.0146 (10)	0.0049 (9)	0.0027 (8)
N3B	0.0325 (11)	0.0372 (11)	0.0217 (10)	0.0077 (9)	0.0082 (8)	0.0035 (8)
N4B	0.0257 (11)	0.0376 (11)	0.0254 (10)	0.0067 (9)	0.0037 (8)	0.0042 (8)
C1B	0.0266 (12)	0.0258 (11)	0.0171 (10)	0.0075 (9)	0.0052 (8)	0.0043 (8)
C2B	0.0222 (10)	0.0200 (10)	0.0182 (10)	0.0067 (8)	0.0078 (8)	0.0050 (8)
C3B	0.0220 (10)	0.0170 (9)	0.0176 (10)	0.0058 (8)	0.0072 (8)	0.0051 (7)
C4B	0.0220 (10)	0.0183 (10)	0.0206 (10)	0.0077 (8)	0.0073 (8)	0.0041 (8)
C5B	0.0254 (11)	0.0209 (10)	0.0176 (10)	0.0085 (8)	0.0085 (8)	0.0049 (8)
C6B	0.0224 (11)	0.0166 (9)	0.0203 (10)	0.0049 (8)	0.0064 (8)	0.0044 (7)
C7B	0.0250 (11)	0.0203 (10)	0.0202 (10)	0.0070 (8)	0.0054 (8)	0.0044 (8)
C8B	0.0283 (12)	0.0227 (10)	0.0213 (11)	0.0091 (9)	0.0022 (9)	0.0043 (8)
C9B	0.0225 (11)	0.0233 (10)	0.0193 (11)	0.0065 (8)	0.0049 (8)	0.0054 (8)
C10B	0.0222 (10)	0.0176 (9)	0.0184 (10)	0.0053 (8)	0.0090 (8)	0.0041 (7)
C11B	0.0199 (10)	0.0197 (10)	0.0218 (10)	0.0067 (8)	0.0083 (8)	0.0050 (8)
C12B	0.0257 (12)	0.0249 (11)	0.0193 (10)	0.0041 (9)	0.0027 (8)	0.0049 (8)

Geometric parameters (Å, º)

Br1—C14	1.881 (2)	C5A—C6A	1.440 (3)
Br2—C16	1.881 (2)	C5A—H5A	0.93
N5—C17	1.332 (3)	C6A—C7A	1.391 (3)
N5—C13	1.343 (3)	C6A—C11A	1.437 (3)
N5—C18	1.491 (3)	C7A—C12A	1.429 (3)
C13—C14	1.378 (3)	C7A—C8A	1.429 (3)
C13—H13	0.93	C10A—C11A	1.355 (3)
C14—C15	1.374 (3)	C10A—H10A	0.93
C15—C16	1.384 (4)	C11A—H11A	0.93
C15—H15	0.93	N1B—C1B	1.150 (3)
C16—C17	1.377 (3)	N2B—C8B	1.153 (3)
C17—H17	0.93	N3B—C9B	1.149 (3)
C18—C19	1.510 (4)	N4B—C12B	1.153 (3)
C18—H18A	0.97	C1B—C2B	1.433 (3)
C18—H18B	0.97	C2B—C3B	1.390 (3)
C19—H19A	0.96	C2B—C9B	1.431 (3)
C19—H19B	0.96	C3B—C4B	1.438 (3)
C19—H19C	0.96	C3B—C10B	1.443 (3)
N1A—C1A	1.156 (4)	C4B—C5B	1.358 (3)
N2A—C8A	1.149 (3)	C4B—H4B	0.93
N3A—C9A	1.147 (3)	C5B—C6B	1.431 (3)
N4A—C12A	1.150 (3)	C5B—H5B	0.93
C1A—C2A	1.420 (4)	C6B—C7B	1.401 (3)
C2A—C3A	1.403 (3)	C6B—C11B	1.438 (3)
C2A—C9A	1.430 (3)	C7B—C12B	1.423 (3)
C3A—C10A	1.430 (3)	C7B—C8B	1.427 (3)
C3A—C4A	1.438 (3)	C10B—C11B	1.356 (3)
C4A—C5A	1.354 (3)	C10B—H10B	0.93
C4A—H4A	0.93	C11B—H11B	0.93
C17—N5—C13	122.3 (2)	C7A—C6A—C11A	120.8 (2)
C17—N5—C18	118.9 (2)	C7A—C6A—C5A	121.3 (2)
C13—N5—C18	118.8 (2)	C11A—C6A—C5A	117.9 (2)
N5—C13—C14	119.1 (2)	C6A—C7A—C12A	123.0 (2)
N5—C13—H13	120.5	C6A—C7A—C8A	122.2 (2)
C14—C13—H13	120.5	C12A—C7A—C8A	114.7 (2)
C15—C14—C13	120.9 (2)	N2A—C8A—C7A	177.9 (3)
C15—C14—Br1	120.73 (18)	N3A—C9A—C2A	178.2 (3)
C13—C14—Br1	118.25 (18)	C11A—C10A—C3A	121.0 (2)
C14—C15—C16	117.7 (2)	C11A—C10A—H10A	119.5
C14—C15—H15	121.2	C3A—C10A—H10A	119.5
C16—C15—H15	121.2	C10A—C11A—C6A	121.1 (2)
C17—C16—C15	120.8 (2)	C10A—C11A—H11A	119.4
C17—C16—Br2	118.98 (19)	C6A—C11A—H11A	119.4
C15—C16—Br2	120.27 (19)	N4A—C12A—C7A	177.6 (3)
N5—C17—C16	119.3 (2)	N1B—C1B—C2B	178.7 (2)
N5—C17—H17	120.4	C3B—C2B—C9B	123.4 (2)
C16—C17—H17	120.4	C3B—C2B—C1B	121.9 (2)
N5—C18—C19	110.5 (2)	C9B—C2B—C1B	114.64 (19)
N5—C18—H18A	109.6	C2B—C3B—C4B	120.6 (2)
C19—C18—H18A	109.6	C2B—C3B—C10B	121.58 (19)
N5—C18—H18B	109.6	C4B—C3B—C10B	117.84 (19)
C19—C18—H18B	109.6	C5B—C4B—C3B	120.9 (2)
H18A—C18—H18B	108.1	C5B—C4B—H4B	119.5
C18—C19—H19A	109.5	C3B—C4B—H4B	119.5
C18—C19—H19B	109.5	C4B—C5B—C6B	121.3 (2)
H19A—C19—H19B	109.5	C4B—C5B—H5B	119.4
C18—C19—H19C	109.5	C6B—C5B—H5B	119.4
H19A—C19—H19C	109.5	C7B—C6B—C5B	120.9 (2)
H19B—C19—H19C	109.5	C7B—C6B—C11B	121.1 (2)
N1A—C1A—C2A	179.8 (3)	C5B—C6B—C11B	118.0 (2)
C3A—C2A—C1A	121.2 (2)	C6B—C7B—C12B	122.4 (2)
C3A—C2A—C9A	122.5 (2)	C6B—C7B—C8B	121.4 (2)
C1A—C2A—C9A	116.3 (2)	C12B—C7B—C8B	116.2 (2)
C2A—C3A—C10A	121.7 (2)	N2B—C8B—C7B	179.6 (2)
C2A—C3A—C4A	120.2 (2)	N3B—C9B—C2B	177.2 (2)
C10A—C3A—C4A	118.1 (2)	C11B—C10B—C3B	120.88 (19)
C5A—C4A—C3A	121.1 (2)	C11B—C10B—H10B	119.6
C5A—C4A—H4A	119.4	C3B—C10B—H10B	119.6
C3A—C4A—H4A	119.4	C10B—C11B—C6B	121.1 (2)
C4A—C5A—C6A	120.8 (2)	C10B—C11B—H11B	119.4
C4A—C5A—H5A	119.6	C6B—C11B—H11B	119.4
C6A—C5A—H5A	119.6	N4B—C12B—C7B	179.2 (3)
C17—N5—C13—C14	0.1 (3)	C11A—C6A—C7A—C8A	179.0 (2)
C18—N5—C13—C14	179.1 (2)	C5A—C6A—C7A—C8A	−1.3 (3)
N5—C13—C14—C15	1.3 (3)	C2A—C3A—C10A—C11A	178.4 (2)
N5—C13—C14—Br1	−174.38 (15)	C4A—C3A—C10A—C11A	−0.1 (3)
C13—C14—C15—C16	−2.0 (3)	C3A—C10A—C11A—C6A	0.2 (3)
Br1—C14—C15—C16	173.55 (17)	C7A—C6A—C11A—C10A	179.5 (2)
C14—C15—C16—C17	1.4 (3)	C5A—C6A—C11A—C10A	−0.2 (3)
C14—C15—C16—Br2	−178.71 (17)	C9B—C2B—C3B—C4B	179.6 (2)
C13—N5—C17—C16	−0.7 (3)	C1B—C2B—C3B—C4B	−1.1 (3)
C18—N5—C17—C16	−179.7 (2)	C9B—C2B—C3B—C10B	−0.6 (3)
C15—C16—C17—N5	−0.1 (3)	C1B—C2B—C3B—C10B	178.63 (19)
Br2—C16—C17—N5	−179.96 (16)	C2B—C3B—C4B—C5B	−178.8 (2)
C17—N5—C18—C19	91.2 (3)	C10B—C3B—C4B—C5B	1.5 (3)
C13—N5—C18—C19	−87.8 (3)	C3B—C4B—C5B—C6B	−0.9 (3)
C1A—C2A—C3A—C10A	−179.5 (2)	C4B—C5B—C6B—C7B	−179.7 (2)
C9A—C2A—C3A—C10A	0.4 (3)	C4B—C5B—C6B—C11B	−0.3 (3)
C1A—C2A—C3A—C4A	−1.0 (3)	C5B—C6B—C7B—C12B	179.8 (2)
C9A—C2A—C3A—C4A	179.0 (2)	C11B—C6B—C7B—C12B	0.4 (3)
C2A—C3A—C4A—C5A	−178.4 (2)	C5B—C6B—C7B—C8B	−1.2 (3)
C10A—C3A—C4A—C5A	0.1 (3)	C11B—C6B—C7B—C8B	179.5 (2)
C3A—C4A—C5A—C6A	−0.2 (3)	C2B—C3B—C10B—C11B	179.4 (2)
C4A—C5A—C6A—C7A	−179.6 (2)	C4B—C3B—C10B—C11B	−0.8 (3)
C4A—C5A—C6A—C11A	0.2 (3)	C3B—C10B—C11B—C6B	−0.3 (3)
C11A—C6A—C7A—C12A	−0.4 (3)	C7B—C6B—C11B—C10B	−179.7 (2)
C5A—C6A—C7A—C12A	179.3 (2)	C5B—C6B—C11B—C10B	0.9 (3)

(tcnq_44bpy_et_rt)

Crystal data

C14H18N2·4(C12H4N4)	F(000) = 1064
Mr = 515.53	Dx = 1.319 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 6151 reflections
a = 13.0864 (2) Å	θ = 3.8–75.8°
b = 25.3377 (4) Å	µ = 0.67 mm^−1
c = 7.8403 (1) Å	T = 293 K
β = 92.651 (1)°	Prism, black
V = 2596.90 (7) Å^3	0.20 × 0.18 × 0.08 mm
Z = 4

Data collection

Xcalibur, Ruby, Nova diffractometer	5368 independent reflections
Radiation source: micro-focus sealed X-ray tube	4600 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.3°, θmin = 3.4°
ω scans	h = −15→16
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −25→31
Tmin = 0.635, Tmax = 1	l = −9→9
13505 measured reflections

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0841P)^2 + 0.5105P] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max = 0.001
5368 reflections	Δρmax = 0.26 e Å^−3
371 parameters	Δρmin = −0.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1A	0.17004 (13)	0.32241 (7)	0.7996 (2)	0.0816 (4)
N2A	0.71270 (11)	0.32343 (8)	0.2863 (2)	0.0911 (5)
N3A	−0.00114 (12)	0.29337 (8)	0.3208 (3)	0.0947 (5)
N4A	0.54210 (12)	0.30358 (6)	−0.19845 (18)	0.0707 (4)
C1A	0.17177 (12)	0.31822 (6)	0.6544 (2)	0.0603 (4)
C2A	0.17274 (11)	0.31209 (5)	0.47352 (19)	0.0538 (3)
C3A	0.26294 (10)	0.31466 (5)	0.38678 (17)	0.0472 (3)
C4A	0.35975 (10)	0.32239 (5)	0.47669 (17)	0.0498 (3)
H4A	0.361824	0.327183	0.594399	0.06*
C5A	0.44786 (10)	0.32285 (5)	0.39390 (16)	0.0483 (3)
H5A	0.509573	0.327914	0.455358	0.058*
C6A	0.44769 (10)	0.31562 (5)	0.21178 (16)	0.0446 (3)
C7A	0.53812 (10)	0.31530 (5)	0.12689 (17)	0.0478 (3)
C8A	0.63500 (11)	0.32005 (6)	0.2153 (2)	0.0588 (3)
C9A	0.07653 (12)	0.30195 (7)	0.3879 (2)	0.0647 (4)
C10A	0.26253 (10)	0.30830 (5)	0.20507 (17)	0.0486 (3)
H10A	0.200684	0.30378	0.143523	0.058*
C11A	0.35087 (10)	0.30877 (5)	0.12171 (16)	0.0470 (3)
H11A	0.348635	0.304568	0.003758	0.056*
C12A	0.54004 (11)	0.30845 (5)	−0.05365 (18)	0.0519 (3)
N1B	0.26856 (11)	0.45175 (7)	0.60833 (16)	0.0722 (4)
N2B	0.81007 (9)	0.45718 (6)	0.05523 (17)	0.0673 (4)
N3B	0.09296 (10)	0.42098 (7)	0.14257 (18)	0.0737 (4)
N4B	0.63247 (11)	0.42310 (6)	−0.40552 (16)	0.0688 (4)
C1B	0.27099 (10)	0.44587 (6)	0.46391 (16)	0.0500 (3)
C2B	0.27072 (10)	0.43757 (5)	0.28424 (15)	0.0444 (3)
C3B	0.36032 (9)	0.43864 (5)	0.19346 (14)	0.0405 (3)
C4B	0.45807 (9)	0.44726 (5)	0.27736 (14)	0.0424 (3)
H4B	0.462088	0.452851	0.394713	0.051*
C5B	0.54529 (9)	0.44751 (5)	0.19010 (14)	0.0415 (3)
H5B	0.607777	0.453471	0.248276	0.05*
C6B	0.54218 (9)	0.43868 (4)	0.00919 (14)	0.0392 (3)
C7B	0.63146 (9)	0.43968 (5)	−0.08257 (15)	0.0418 (3)
C8B	0.72971 (10)	0.44924 (5)	−0.00375 (16)	0.0470 (3)
C9B	0.17267 (10)	0.42870 (6)	0.20376 (16)	0.0505 (3)
C10B	0.35742 (9)	0.42978 (5)	0.01261 (14)	0.0420 (3)
H10B	0.294947	0.423786	−0.045563	0.05*
C11B	0.44439 (9)	0.43001 (5)	−0.07468 (14)	0.0414 (3)
H11B	0.440325	0.424398	−0.19202	0.05*
C12B	0.63050 (10)	0.43044 (5)	−0.26182 (16)	0.0468 (3)
N5	0.08431 (10)	0.61862 (5)	0.32417 (17)	0.0637 (3)
C13	0.11449 (13)	0.60521 (7)	0.4842 (2)	0.0672 (4)
H13	0.15781	0.627546	0.547883	0.081*
C14	0.08238 (12)	0.55912 (6)	0.55476 (19)	0.0609 (4)
H14	0.103677	0.550598	0.666177	0.073*
C15	0.01830 (9)	0.52486 (5)	0.46198 (15)	0.0457 (3)
C16	−0.00998 (12)	0.53947 (6)	0.29558 (18)	0.0576 (3)
H16	−0.052082	0.517486	0.22836	0.069*
C17	0.02392 (13)	0.58617 (7)	0.2300 (2)	0.0652 (4)
H17	0.004626	0.595427	0.11831	0.078*
C18	0.1149 (2)	0.67164 (10)	0.2581 (4)	0.1139 (9)
H18A	0.076735	0.67645	0.150145	0.137*
H18B	0.088577	0.697502	0.336058	0.137*
C19A	0.2016 (5)	0.6846 (4)	0.234 (3)	0.201 (7)	0.493 (11)
H19A	0.202236	0.720149	0.191631	0.301*	0.493 (11)
H19B	0.241801	0.682615	0.339306	0.301*	0.493 (11)
H19C	0.229849	0.661367	0.151654	0.301*	0.493 (11)
C19B	0.1391 (11)	0.6765 (2)	0.0906 (11)	0.151 (5)	0.507 (11)
H19D	0.156916	0.71243	0.067575	0.226*	0.507 (11)
H19E	0.196028	0.653945	0.068781	0.226*	0.507 (11)
H19F	0.08127	0.666368	0.017998	0.226*	0.507 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0798 (10)	0.1047 (12)	0.0615 (9)	0.0015 (9)	0.0163 (7)	0.0023 (8)
N2A	0.0527 (8)	0.1267 (15)	0.0931 (11)	−0.0024 (8)	−0.0065 (7)	−0.0264 (10)
N3A	0.0546 (8)	0.1094 (13)	0.1196 (14)	−0.0092 (8)	−0.0027 (9)	−0.0101 (11)
N4A	0.0873 (10)	0.0696 (8)	0.0560 (8)	−0.0032 (7)	0.0105 (7)	−0.0099 (6)
C1A	0.0557 (8)	0.0635 (8)	0.0627 (9)	−0.0004 (6)	0.0123 (6)	0.0048 (7)
C2A	0.0518 (7)	0.0510 (7)	0.0591 (8)	−0.0019 (6)	0.0073 (6)	0.0021 (6)
C3A	0.0488 (7)	0.0435 (6)	0.0492 (7)	−0.0017 (5)	0.0026 (5)	0.0023 (5)
C4A	0.0537 (7)	0.0531 (7)	0.0424 (6)	−0.0015 (6)	0.0012 (5)	0.0013 (5)
C5A	0.0476 (7)	0.0521 (7)	0.0448 (6)	−0.0014 (5)	−0.0030 (5)	0.0007 (5)
C6A	0.0479 (6)	0.0395 (6)	0.0462 (6)	−0.0010 (5)	0.0009 (5)	0.0007 (5)
C7A	0.0489 (7)	0.0447 (6)	0.0498 (7)	−0.0015 (5)	0.0026 (5)	−0.0020 (5)
C8A	0.0491 (8)	0.0674 (9)	0.0603 (8)	−0.0014 (6)	0.0058 (6)	−0.0090 (7)
C9A	0.0529 (8)	0.0659 (9)	0.0761 (10)	−0.0028 (7)	0.0112 (7)	−0.0028 (7)
C10A	0.0462 (6)	0.0490 (7)	0.0503 (7)	−0.0042 (5)	−0.0028 (5)	−0.0027 (5)
C11A	0.0518 (7)	0.0459 (6)	0.0431 (6)	−0.0026 (5)	−0.0012 (5)	−0.0031 (5)
C12A	0.0545 (7)	0.0469 (7)	0.0546 (8)	−0.0025 (5)	0.0070 (6)	−0.0059 (5)
N1B	0.0716 (8)	0.1024 (11)	0.0428 (7)	0.0061 (8)	0.0058 (6)	−0.0052 (6)
N2B	0.0467 (7)	0.0955 (10)	0.0588 (7)	0.0013 (6)	−0.0064 (5)	−0.0042 (7)
N3B	0.0474 (7)	0.1057 (12)	0.0672 (8)	−0.0003 (7)	−0.0042 (6)	−0.0065 (8)
N4B	0.0733 (8)	0.0914 (10)	0.0418 (6)	0.0058 (7)	0.0041 (5)	−0.0067 (6)
C1B	0.0465 (7)	0.0603 (8)	0.0433 (7)	0.0019 (6)	0.0038 (5)	−0.0003 (5)
C2B	0.0452 (6)	0.0493 (6)	0.0388 (6)	0.0008 (5)	0.0012 (5)	0.0004 (5)
C3B	0.0434 (6)	0.0420 (6)	0.0358 (6)	−0.0005 (5)	−0.0005 (4)	0.0012 (4)
C4B	0.0479 (6)	0.0477 (6)	0.0312 (5)	−0.0014 (5)	−0.0013 (4)	−0.0011 (4)
C5B	0.0425 (6)	0.0463 (6)	0.0351 (6)	−0.0019 (5)	−0.0042 (4)	−0.0003 (4)
C6B	0.0435 (6)	0.0393 (6)	0.0345 (5)	0.0009 (4)	−0.0005 (4)	0.0011 (4)
C7B	0.0439 (6)	0.0452 (6)	0.0360 (6)	0.0024 (5)	−0.0002 (4)	−0.0003 (4)
C8B	0.0451 (7)	0.0559 (7)	0.0400 (6)	0.0046 (5)	0.0024 (5)	−0.0008 (5)
C9B	0.0455 (7)	0.0618 (8)	0.0445 (6)	0.0031 (6)	0.0043 (5)	−0.0009 (6)
C10B	0.0417 (6)	0.0476 (6)	0.0363 (6)	−0.0023 (5)	−0.0041 (4)	−0.0006 (5)
C11B	0.0461 (6)	0.0461 (6)	0.0317 (5)	−0.0007 (5)	−0.0025 (4)	−0.0015 (4)
C12B	0.0451 (6)	0.0540 (7)	0.0414 (7)	0.0033 (5)	0.0020 (5)	−0.0008 (5)
N5	0.0621 (7)	0.0616 (7)	0.0676 (8)	−0.0053 (6)	0.0049 (6)	0.0064 (6)
C13	0.0662 (9)	0.0681 (9)	0.0664 (9)	−0.0170 (7)	−0.0074 (7)	−0.0031 (7)
C14	0.0624 (8)	0.0682 (9)	0.0507 (7)	−0.0116 (7)	−0.0119 (6)	−0.0004 (6)
C15	0.0392 (6)	0.0557 (7)	0.0418 (6)	0.0029 (5)	−0.0009 (4)	−0.0047 (5)
C16	0.0602 (8)	0.0648 (8)	0.0470 (7)	−0.0063 (6)	−0.0080 (6)	−0.0003 (6)
C17	0.0694 (9)	0.0721 (10)	0.0533 (8)	−0.0024 (8)	−0.0045 (7)	0.0099 (7)
C18	0.142 (2)	0.0834 (14)	0.1171 (19)	−0.0288 (15)	0.0149 (16)	0.0290 (13)
C19A	0.088 (4)	0.144 (6)	0.370 (19)	−0.028 (4)	0.006 (6)	0.137 (9)
C19B	0.262 (13)	0.067 (3)	0.134 (6)	0.001 (4)	0.126 (7)	0.013 (3)

Geometric parameters (Å, º)

N1A—C1A	1.145 (2)	C5B—C6B	1.4347 (15)
N2A—C8A	1.140 (2)	C5B—H5B	0.93
N3A—C9A	1.144 (2)	C6B—C7B	1.4003 (17)
N4A—C12A	1.1435 (19)	C6B—C11B	1.4285 (16)
C1A—C2A	1.427 (2)	C7B—C8B	1.4214 (17)
C2A—C3A	1.3908 (19)	C7B—C12B	1.4242 (16)
C2A—C9A	1.422 (2)	C10B—C11B	1.3550 (17)
C3A—C10A	1.4336 (18)	C10B—H10B	0.93
C3A—C4A	1.4345 (19)	C11B—H11B	0.93
C4A—C5A	1.3491 (19)	N5—C17	1.339 (2)
C4A—H4A	0.93	N5—C13	1.341 (2)
C5A—C6A	1.4395 (18)	N5—C18	1.501 (2)
C5A—H5A	0.93	C13—C14	1.367 (2)
C6A—C7A	1.3843 (18)	C13—H13	0.93
C6A—C11A	1.4323 (18)	C14—C15	1.3890 (19)
C7A—C8A	1.4215 (19)	C14—H14	0.93
C7A—C12A	1.4275 (19)	C15—C16	1.3897 (18)
C10A—C11A	1.3541 (19)	C15—C15^i	1.483 (3)
C10A—H10A	0.93	C16—C17	1.372 (2)
C11A—H11A	0.93	C16—H16	0.93
N1B—C1B	1.1440 (18)	C17—H17	0.93
N2B—C8B	1.1467 (18)	C18—C19A	1.205 (6)
N3B—C9B	1.1447 (19)	C18—C19B	1.371 (6)
N4B—C12B	1.1434 (18)	C18—H18A	0.97
C1B—C2B	1.4241 (17)	C18—H18B	0.97
C2B—C3B	1.3998 (17)	C19A—H19A	0.96
C2B—C9B	1.4214 (18)	C19A—H19B	0.96
C3B—C4B	1.4279 (16)	C19A—H19C	0.96
C3B—C10B	1.4343 (16)	C19B—H19D	0.96
C4B—C5B	1.3576 (17)	C19B—H19E	0.96
C4B—H4B	0.93	C19B—H19F	0.96
N1A—C1A—C2A	178.89 (19)	N2B—C8B—C7B	178.01 (14)
C3A—C2A—C9A	122.04 (14)	N3B—C9B—C2B	178.31 (16)
C3A—C2A—C1A	121.84 (13)	C11B—C10B—C3B	120.94 (11)
C9A—C2A—C1A	116.11 (13)	C11B—C10B—H10B	119.5
C2A—C3A—C10A	121.10 (12)	C3B—C10B—H10B	119.5
C2A—C3A—C4A	121.09 (12)	C10B—C11B—C6B	121.59 (10)
C10A—C3A—C4A	117.79 (12)	C10B—C11B—H11B	119.2
C5A—C4A—C3A	121.32 (12)	C6B—C11B—H11B	119.2
C5A—C4A—H4A	119.3	N4B—C12B—C7B	178.21 (14)
C3A—C4A—H4A	119.3	C17—N5—C13	120.07 (14)
C4A—C5A—C6A	120.93 (12)	C17—N5—C18	121.28 (17)
C4A—C5A—H5A	119.5	C13—N5—C18	118.56 (17)
C6A—C5A—H5A	119.5	N5—C13—C14	120.82 (14)
C7A—C6A—C11A	121.24 (12)	N5—C13—H13	119.6
C7A—C6A—C5A	121.03 (12)	C14—C13—H13	119.6
C11A—C6A—C5A	117.72 (11)	C13—C14—C15	120.76 (14)
C6A—C7A—C8A	121.88 (12)	C13—C14—H14	119.6
C6A—C7A—C12A	122.15 (12)	C15—C14—H14	119.6
C8A—C7A—C12A	115.94 (12)	C14—C15—C16	116.95 (13)
N2A—C8A—C7A	179.5 (2)	C14—C15—C15^i	121.25 (14)
N3A—C9A—C2A	179.1 (2)	C16—C15—C15^i	121.79 (14)
C11A—C10A—C3A	120.97 (12)	C17—C16—C15	120.33 (13)
C11A—C10A—H10A	119.5	C17—C16—H16	119.8
C3A—C10A—H10A	119.5	C15—C16—H16	119.8
C10A—C11A—C6A	121.24 (12)	N5—C17—C16	121.05 (14)
C10A—C11A—H11A	119.4	N5—C17—H17	119.5
C6A—C11A—H11A	119.4	C16—C17—H17	119.5
N4A—C12A—C7A	179.14 (16)	C19A—C18—N5	124.5 (4)
N1B—C1B—C2B	178.00 (16)	C19B—C18—N5	119.2 (3)
C3B—C2B—C9B	122.52 (11)	C19A—C18—H18A	106.2
C3B—C2B—C1B	122.43 (11)	N5—C18—H18A	106.2
C9B—C2B—C1B	115.05 (11)	C19A—C18—H18B	106.2
C2B—C3B—C4B	121.49 (10)	N5—C18—H18B	106.2
C2B—C3B—C10B	121.00 (11)	H18A—C18—H18B	106.4
C4B—C3B—C10B	117.49 (11)	C18—C19A—H19A	109.5
C5B—C4B—C3B	121.65 (10)	C18—C19A—H19B	109.5
C5B—C4B—H4B	119.2	H19A—C19A—H19B	109.5
C3B—C4B—H4B	119.2	C18—C19A—H19C	109.5
C4B—C5B—C6B	120.76 (11)	H19A—C19A—H19C	109.5
C4B—C5B—H5B	119.6	H19B—C19A—H19C	109.5
C6B—C5B—H5B	119.6	C18—C19B—H19D	109.5
C7B—C6B—C11B	121.15 (10)	C18—C19B—H19E	109.5
C7B—C6B—C5B	121.26 (11)	H19D—C19B—H19E	109.5
C11B—C6B—C5B	117.58 (10)	C18—C19B—H19F	109.5
C6B—C7B—C8B	122.63 (10)	H19D—C19B—H19F	109.5
C6B—C7B—C12B	122.31 (11)	H19E—C19B—H19F	109.5
C8B—C7B—C12B	115.06 (11)
C9A—C2A—C3A—C10A	1.4 (2)	C4B—C5B—C6B—C7B	178.97 (11)
C1A—C2A—C3A—C10A	179.86 (13)	C4B—C5B—C6B—C11B	0.36 (17)
C9A—C2A—C3A—C4A	−176.95 (14)	C11B—C6B—C7B—C8B	178.71 (11)
C1A—C2A—C3A—C4A	1.5 (2)	C5B—C6B—C7B—C8B	0.14 (19)
C2A—C3A—C4A—C5A	177.37 (13)	C11B—C6B—C7B—C12B	−2.16 (18)
C10A—C3A—C4A—C5A	−1.03 (19)	C5B—C6B—C7B—C12B	179.28 (11)
C3A—C4A—C5A—C6A	0.1 (2)	C2B—C3B—C10B—C11B	−178.97 (12)
C4A—C5A—C6A—C7A	−179.04 (12)	C4B—C3B—C10B—C11B	−0.47 (18)
C4A—C5A—C6A—C11A	0.95 (19)	C3B—C10B—C11B—C6B	0.43 (18)
C11A—C6A—C7A—C8A	−177.57 (13)	C7B—C6B—C11B—C10B	−178.98 (11)
C5A—C6A—C7A—C8A	2.4 (2)	C5B—C6B—C11B—C10B	−0.36 (17)
C11A—C6A—C7A—C12A	0.30 (19)	C17—N5—C13—C14	−1.6 (3)
C5A—C6A—C7A—C12A	−179.71 (12)	C18—N5—C13—C14	175.1 (2)
C2A—C3A—C10A—C11A	−177.41 (13)	N5—C13—C14—C15	0.5 (3)
C4A—C3A—C10A—C11A	1.00 (19)	C13—C14—C15—C16	0.7 (2)
C3A—C10A—C11A—C6A	0.01 (19)	C13—C14—C15—C15^i	−179.08 (16)
C7A—C6A—C11A—C10A	179.01 (12)	C14—C15—C16—C17	−0.8 (2)
C5A—C6A—C11A—C10A	−0.98 (18)	C15^i—C15—C16—C17	178.95 (16)
C9B—C2B—C3B—C4B	−179.55 (12)	C13—N5—C17—C16	1.4 (3)
C1B—C2B—C3B—C4B	1.1 (2)	C18—N5—C17—C16	−175.1 (2)
C9B—C2B—C3B—C10B	−1.11 (19)	C15—C16—C17—N5	−0.2 (3)
C1B—C2B—C3B—C10B	179.58 (12)	C17—N5—C18—C19A	−117.3 (13)
C2B—C3B—C4B—C5B	178.96 (12)	C13—N5—C18—C19A	66.1 (13)
C10B—C3B—C4B—C5B	0.47 (18)	C17—N5—C18—C19B	−40.1 (8)
C3B—C4B—C5B—C6B	−0.43 (19)	C13—N5—C18—C19B	143.2 (8)

Symmetry code: (i) −x, −y+1, −z+1.

(tcnq_me2-44bpy_100k_2)

Crystal data

3(C12H4N4)·C12H14N2	Z = 1
Mr = 798.83	F(000) = 412
Triclinic, P1	Dx = 1.387 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.8212 (5) Å	Cell parameters from 3540 reflections
b = 9.7542 (7) Å	θ = 4.6–75.6°
c = 13.2653 (7) Å	µ = 0.71 mm^−1
α = 78.103 (5)°	T = 293 K
β = 75.829 (5)°	Prism, black
γ = 82.246 (5)°	0.31 × 0.12 × 0.10 mm
V = 956.32 (11) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	3944 independent reflections
Radiation source: micro-focus sealed X-ray tube	3294 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.048
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.5°, θmin = 3.5°
ω scans	h = −9→9
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −12→12
Tmin = 0.677, Tmax = 1	l = −16→13
8051 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.207	w = 1/[σ^2(Fo^2) + (0.1571P)^2 + 0.2595P] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
3944 reflections	Δρmax = 0.47 e Å^−3
280 parameters	Δρmin = −0.33 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1A	0.7366 (2)	1.23930 (18)	0.64925 (13)	0.0384 (4)
N2A	0.3383 (2)	1.6326 (2)	0.11831 (13)	0.0442 (4)
N3A	0.2103 (2)	1.12314 (19)	0.81394 (12)	0.0409 (4)
N4A	−0.1781 (2)	1.47915 (19)	0.26901 (13)	0.0386 (4)
C1A	0.5914 (2)	1.23974 (19)	0.64457 (13)	0.0320 (4)
C2A	0.4110 (2)	1.23734 (19)	0.64034 (14)	0.0311 (4)
C3A	0.3469 (2)	1.29494 (18)	0.55001 (13)	0.0292 (4)
C4A	0.4595 (2)	1.36275 (19)	0.45530 (13)	0.0302 (4)
H4A	0.578243	1.36698	0.453806	0.036*
C5A	0.3963 (2)	1.42066 (19)	0.36811 (13)	0.0304 (4)
H5A	0.472411	1.464001	0.308012	0.036*
C6A	0.2137 (2)	1.41637 (19)	0.36676 (13)	0.0299 (4)
C7A	0.1466 (2)	1.4837 (2)	0.27904 (13)	0.0314 (4)
C8A	0.2531 (2)	1.5651 (2)	0.19001 (14)	0.0345 (4)
C9A	0.2985 (2)	1.1743 (2)	0.73610 (14)	0.0332 (4)
C10A	0.1647 (2)	1.28815 (19)	0.54820 (13)	0.0303 (4)
H10A	0.088868	1.243985	0.608054	0.036*
C11A	0.1022 (2)	1.34515 (19)	0.46059 (14)	0.0310 (4)
H11A	−0.015391	1.338046	0.461163	0.037*
C12A	−0.0337 (2)	1.4803 (2)	0.27498 (13)	0.0319 (4)
N1B	0.0311 (2)	1.1036 (2)	0.31272 (12)	0.0382 (4)
N3B	0.5429 (2)	1.2284 (3)	0.14632 (14)	0.0574 (6)
C1B	0.1740 (2)	1.1076 (2)	0.31993 (13)	0.0307 (4)
C2B	0.3527 (2)	1.11687 (19)	0.32274 (13)	0.0293 (4)
C3B	0.4261 (2)	1.05750 (18)	0.41091 (13)	0.0281 (4)
C4B	0.3216 (2)	0.98628 (18)	0.50599 (13)	0.0283 (4)
H4B	0.202991	0.977914	0.509973	0.034*
C5B	0.3927 (2)	0.93014 (19)	0.59130 (13)	0.0285 (4)
H5B	0.322069	0.882911	0.652083	0.034*
C9B	0.4588 (2)	1.1796 (2)	0.22583 (14)	0.0364 (4)
N5	0.1722 (2)	1.14756 (17)	1.05222 (11)	0.0330 (4)
C13	−0.0036 (2)	1.1812 (2)	1.07861 (14)	0.0352 (4)
H13	−0.078652	1.110893	1.111413	0.042*
C14	−0.0735 (2)	1.3182 (2)	1.05766 (14)	0.0354 (4)
H14	−0.195392	1.339568	1.075156	0.042*
C15	0.0373 (2)	1.4254 (2)	1.01031 (13)	0.0311 (4)
C16	0.2189 (2)	1.3866 (2)	0.98299 (14)	0.0336 (4)
H16	0.296862	1.454942	0.950403	0.04*
C17	0.2827 (2)	1.2485 (2)	1.00392 (14)	0.0351 (4)
H17	0.403769	1.223815	0.984639	0.042*
C18	0.2445 (3)	0.9996 (2)	1.07412 (15)	0.0393 (4)
H18A	0.371138	0.993743	1.050639	0.059*	0.5
H18B	0.213082	0.964281	1.148715	0.059*	0.5
H18C	0.196526	0.944536	1.037261	0.059*	0.5
H18D	0.149359	0.941297	1.107105	0.059*	0.5
H18E	0.307415	0.97076	1.009029	0.059*	0.5
H18F	0.323971	0.990504	1.120483	0.059*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0326 (8)	0.0480 (9)	0.0383 (9)	−0.0079 (7)	−0.0129 (6)	−0.0075 (7)
N2A	0.0361 (9)	0.0650 (11)	0.0306 (8)	−0.0150 (8)	−0.0094 (7)	0.0023 (7)
N3A	0.0429 (9)	0.0534 (10)	0.0270 (8)	−0.0133 (8)	−0.0062 (7)	−0.0048 (7)
N4A	0.0301 (8)	0.0550 (10)	0.0321 (8)	−0.0055 (7)	−0.0097 (6)	−0.0066 (7)
C1A	0.0354 (10)	0.0375 (9)	0.0254 (8)	−0.0058 (7)	−0.0104 (7)	−0.0048 (6)
C2A	0.0302 (8)	0.0395 (9)	0.0261 (8)	−0.0059 (7)	−0.0079 (6)	−0.0080 (7)
C3A	0.0271 (8)	0.0358 (9)	0.0270 (8)	−0.0036 (7)	−0.0069 (6)	−0.0090 (7)
C4A	0.0247 (8)	0.0396 (9)	0.0288 (9)	−0.0055 (7)	−0.0081 (6)	−0.0077 (7)
C5A	0.0261 (8)	0.0395 (9)	0.0260 (8)	−0.0068 (7)	−0.0042 (6)	−0.0062 (7)
C6A	0.0275 (8)	0.0375 (9)	0.0263 (8)	−0.0040 (7)	−0.0076 (6)	−0.0073 (7)
C7A	0.0279 (8)	0.0413 (9)	0.0258 (8)	−0.0049 (7)	−0.0066 (6)	−0.0062 (7)
C8A	0.0288 (8)	0.0490 (10)	0.0278 (9)	−0.0045 (7)	−0.0113 (7)	−0.0052 (8)
C9A	0.0328 (9)	0.0432 (10)	0.0275 (9)	−0.0056 (7)	−0.0118 (7)	−0.0080 (7)
C10A	0.0257 (8)	0.0400 (9)	0.0253 (8)	−0.0061 (7)	−0.0033 (6)	−0.0068 (7)
C11A	0.0245 (8)	0.0407 (9)	0.0293 (8)	−0.0046 (7)	−0.0068 (6)	−0.0079 (7)
C12A	0.0304 (9)	0.0409 (9)	0.0250 (8)	−0.0033 (7)	−0.0074 (6)	−0.0056 (7)
N1B	0.0258 (8)	0.0612 (10)	0.0293 (8)	−0.0086 (7)	−0.0095 (6)	−0.0049 (7)
N3B	0.0340 (9)	0.1102 (18)	0.0277 (9)	−0.0281 (10)	−0.0098 (7)	0.0060 (9)
C1B	0.0285 (9)	0.0428 (9)	0.0210 (8)	−0.0050 (7)	−0.0059 (6)	−0.0043 (7)
C2B	0.0233 (8)	0.0416 (9)	0.0245 (8)	−0.0060 (6)	−0.0062 (6)	−0.0064 (7)
C3B	0.0247 (8)	0.0372 (9)	0.0245 (8)	−0.0026 (6)	−0.0074 (6)	−0.0083 (7)
C4B	0.0215 (7)	0.0384 (9)	0.0267 (8)	−0.0050 (6)	−0.0062 (6)	−0.0072 (7)
C5B	0.0241 (8)	0.0388 (9)	0.0236 (8)	−0.0071 (6)	−0.0047 (6)	−0.0060 (6)
C9B	0.0265 (8)	0.0585 (12)	0.0272 (9)	−0.0097 (8)	−0.0112 (7)	−0.0048 (8)
N5	0.0303 (7)	0.0460 (9)	0.0247 (7)	−0.0059 (6)	−0.0082 (5)	−0.0065 (6)
C13	0.0305 (9)	0.0488 (10)	0.0276 (8)	−0.0109 (7)	−0.0063 (7)	−0.0048 (7)
C14	0.0262 (8)	0.0498 (10)	0.0308 (9)	−0.0086 (7)	−0.0064 (7)	−0.0052 (7)
C15	0.0244 (8)	0.0489 (11)	0.0223 (8)	−0.0078 (7)	−0.0071 (6)	−0.0060 (7)
C16	0.0257 (8)	0.0489 (10)	0.0281 (8)	−0.0100 (7)	−0.0058 (6)	−0.0071 (7)
C17	0.0256 (8)	0.0531 (11)	0.0286 (8)	−0.0057 (7)	−0.0072 (6)	−0.0091 (7)
C18	0.0366 (10)	0.0469 (11)	0.0357 (10)	−0.0031 (8)	−0.0093 (8)	−0.0093 (8)

Geometric parameters (Å, º)

N1A—C1A	1.152 (3)	C2B—C9B	1.416 (3)
N2A—C8A	1.154 (3)	C3B—C4B	1.424 (2)
N3A—C9A	1.150 (2)	C3B—C5B^i	1.431 (2)
N4A—C12A	1.153 (3)	C4B—C5B	1.364 (2)
C1A—C2A	1.429 (2)	C4B—H4B	0.93
C2A—C3A	1.394 (2)	C5B—H5B	0.93
C2A—C9A	1.429 (2)	N5—C13	1.346 (2)
C3A—C4A	1.437 (2)	N5—C17	1.351 (3)
C3A—C10A	1.442 (2)	N5—C18	1.474 (3)
C4A—C5A	1.355 (2)	C13—C14	1.373 (3)
C4A—H4A	0.93	C13—H13	0.93
C5A—C6A	1.439 (2)	C14—C15	1.395 (3)
C5A—H5A	0.93	C14—H14	0.93
C6A—C7A	1.397 (3)	C15—C16	1.397 (2)
C6A—C11A	1.438 (2)	C15—C15^ii	1.488 (4)
C7A—C8A	1.424 (3)	C16—C17	1.368 (3)
C7A—C12A	1.430 (2)	C16—H16	0.93
C10A—C11A	1.355 (3)	C17—H17	0.93
C10A—H10A	0.93	C18—H18A	0.96
C11A—H11A	0.93	C18—H18B	0.96
N1B—C1B	1.152 (2)	C18—H18C	0.96
N3B—C9B	1.145 (3)	C18—H18D	0.96
C1B—C2B	1.422 (2)	C18—H18E	0.96
C2B—C3B	1.412 (2)	C18—H18F	0.96
N1A—C1A—C2A	178.7 (2)	C5B—C4B—C3B	121.08 (16)
C3A—C2A—C9A	121.79 (16)	C5B—C4B—H4B	119.5
C3A—C2A—C1A	122.70 (16)	C3B—C4B—H4B	119.5
C9A—C2A—C1A	115.50 (15)	C4B—C5B—C3B^i	121.27 (16)
C2A—C3A—C4A	121.41 (15)	C4B—C5B—H5B	119.4
C2A—C3A—C10A	121.07 (16)	C3B^i—C5B—H5B	119.4
C4A—C3A—C10A	117.52 (15)	N3B—C9B—C2B	178.4 (2)
C5A—C4A—C3A	121.34 (15)	C13—N5—C17	120.27 (17)
C5A—C4A—H4A	119.3	C13—N5—C18	119.96 (16)
C3A—C4A—H4A	119.3	C17—N5—C18	119.76 (16)
C4A—C5A—C6A	121.25 (16)	N5—C13—C14	120.76 (17)
C4A—C5A—H5A	119.4	N5—C13—H13	119.6
C6A—C5A—H5A	119.4	C14—C13—H13	119.6
C7A—C6A—C11A	121.56 (16)	C13—C14—C15	120.45 (17)
C7A—C6A—C5A	121.02 (16)	C13—C14—H14	119.8
C11A—C6A—C5A	117.37 (15)	C15—C14—H14	119.8
C6A—C7A—C8A	121.52 (16)	C14—C15—C16	117.26 (18)
C6A—C7A—C12A	122.33 (16)	C14—C15—C15^ii	120.74 (19)
C8A—C7A—C12A	116.09 (16)	C16—C15—C15^ii	122.0 (2)
N2A—C8A—C7A	179.1 (2)	C17—C16—C15	120.36 (18)
N3A—C9A—C2A	178.84 (18)	C17—C16—H16	119.8
C11A—C10A—C3A	120.98 (16)	C15—C16—H16	119.8
C11A—C10A—H10A	119.5	N5—C17—C16	120.87 (16)
C3A—C10A—H10A	119.5	N5—C17—H17	119.6
C10A—C11A—C6A	121.50 (16)	C16—C17—H17	119.6
C10A—C11A—H11A	119.2	N5—C18—H18A	109.5
C6A—C11A—H11A	119.2	N5—C18—H18B	109.5
N4A—C12A—C7A	178.25 (19)	H18A—C18—H18B	109.5
N1B—C1B—C2B	176.69 (19)	N5—C18—H18C	109.5
C3B—C2B—C9B	121.39 (15)	H18A—C18—H18C	109.5
C3B—C2B—C1B	123.68 (16)	H18B—C18—H18C	109.5
C9B—C2B—C1B	114.67 (15)	H18D—C18—H18E	109.5
C2B—C3B—C4B	121.28 (15)	H18D—C18—H18F	109.5
C2B—C3B—C5B^i	121.05 (16)	H18E—C18—H18F	109.5
C4B—C3B—C5B^i	117.65 (15)
C9A—C2A—C3A—C4A	177.65 (15)	C9B—C2B—C3B—C4B	−175.78 (16)
C1A—C2A—C3A—C4A	−1.0 (3)	C1B—C2B—C3B—C4B	−1.9 (3)
C9A—C2A—C3A—C10A	−2.6 (3)	C9B—C2B—C3B—C5B^i	5.8 (3)
C1A—C2A—C3A—C10A	178.84 (16)	C1B—C2B—C3B—C5B^i	179.69 (16)
C2A—C3A—C4A—C5A	−178.94 (16)	C2B—C3B—C4B—C5B	−179.43 (16)
C10A—C3A—C4A—C5A	1.3 (2)	C5B^i—C3B—C4B—C5B	−0.9 (3)
C3A—C4A—C5A—C6A	−0.1 (3)	C3B—C4B—C5B—C3B^i	1.0 (3)
C4A—C5A—C6A—C7A	176.03 (16)	C17—N5—C13—C14	−0.4 (3)
C4A—C5A—C6A—C11A	−1.5 (3)	C18—N5—C13—C14	−179.21 (15)
C11A—C6A—C7A—C8A	174.13 (16)	N5—C13—C14—C15	−1.2 (3)
C5A—C6A—C7A—C8A	−3.3 (3)	C13—C14—C15—C16	1.8 (3)
C11A—C6A—C7A—C12A	−3.1 (3)	C13—C14—C15—C15^ii	−178.54 (18)
C5A—C6A—C7A—C12A	179.48 (16)	C14—C15—C16—C17	−0.9 (3)
C2A—C3A—C10A—C11A	179.49 (16)	C15^ii—C15—C16—C17	179.49 (17)
C4A—C3A—C10A—C11A	−0.7 (3)	C13—N5—C17—C16	1.4 (3)
C3A—C10A—C11A—C6A	−1.0 (3)	C18—N5—C17—C16	−179.82 (15)
C7A—C6A—C11A—C10A	−175.46 (16)	C15—C16—C17—N5	−0.7 (3)
C5A—C6A—C11A—C10A	2.1 (3)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+3, −z+2.

(tcnq_3brme_100k)

Crystal data

2(C12H4N4)·2(C6H7BrN)·I	Z = 2
Mr = 881.35	F(000) = 862
Triclinic, P1	Dx = 1.681 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.5693 (3) Å	Cell parameters from 11346 reflections
b = 13.0300 (3) Å	θ = 3.6–76.3°
c = 18.5239 (5) Å	µ = 10.25 mm^−1
α = 105.159 (2)°	T = 100 K
β = 90.971 (3)°	Prism, black
γ = 98.382 (3)°	0.31 × 0.14 × 0.12 mm
V = 1741.67 (9) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	7163 independent reflections
Radiation source: micro-focus sealed X-ray tube	6810 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.050
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.4°, θmin = 3.6°
ω scans	h = −9→9
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −15→16
Tmin = 0.346, Tmax = 1	l = −23→21
15827 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0885P)^2 + 1.3487P] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max = 0.003
7163 reflections	Δρmax = 1.31 e Å^−3
442 parameters	Δρmin = −1.42 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.75691 (2)	0.71798 (2)	0.51287 (2)	0.02400 (9)
Br1A	0.39800 (5)	0.87441 (3)	0.56359 (2)	0.02991 (11)
N5A	−0.0558 (4)	0.9575 (3)	0.66353 (15)	0.0253 (6)
C13A	0.0815 (5)	0.9060 (3)	0.63888 (18)	0.0258 (7)
H13A	0.092003	0.841266	0.649646	0.031*
C14A	0.2071 (5)	0.9491 (3)	0.59758 (18)	0.0265 (7)
C15A	0.1911 (5)	1.0451 (3)	0.58057 (19)	0.0295 (7)
H15A	0.275315	1.075125	0.552943	0.035*
C16A	0.0447 (5)	1.0949 (3)	0.6063 (2)	0.0332 (8)
H16A	0.029721	1.158894	0.595314	0.04*
C17A	−0.0779 (5)	1.0499 (3)	0.64775 (19)	0.0302 (7)
H17A	−0.175568	1.083319	0.664754	0.036*
C18A	−0.1902 (5)	0.9089 (3)	0.70752 (19)	0.0289 (7)
H18A	−0.279789	0.954495	0.721212	0.043*
H18B	−0.245365	0.8393	0.677787	0.043*
H18C	−0.132083	0.901644	0.751993	0.043*
Br1B	1.12547 (5)	0.61390 (3)	0.41964 (2)	0.02826 (11)
N5B	1.5756 (4)	0.4799 (2)	0.35980 (15)	0.0252 (6)
C13B	1.4176 (5)	0.4995 (3)	0.38853 (18)	0.0242 (6)
H13B	1.361719	0.457953	0.417956	0.029*
C14B	1.3391 (4)	0.5823 (3)	0.37379 (18)	0.0255 (6)
C15B	1.4216 (5)	0.6433 (3)	0.3293 (2)	0.0298 (7)
H15B	1.368502	0.697824	0.318233	0.036*
C16B	1.5852 (5)	0.6215 (3)	0.30166 (19)	0.0301 (7)
H16B	1.643425	0.661949	0.272034	0.036*
C17B	1.6611 (5)	0.5400 (3)	0.31810 (18)	0.0258 (7)
H17B	1.771882	0.526289	0.300347	0.031*
C18B	1.6615 (5)	0.3943 (3)	0.3781 (2)	0.0326 (8)
H18D	1.772239	0.389809	0.35376	0.049*
H18E	1.684636	0.410739	0.431306	0.049*
H18F	1.583535	0.326626	0.361014	0.049*
N1A	1.0316 (4)	1.0961 (3)	1.10503 (17)	0.0315 (6)
N2A	0.5220 (4)	1.1256 (3)	0.71904 (17)	0.0309 (6)
N3A	0.5639 (5)	1.1455 (3)	1.23150 (18)	0.0355 (7)
N4A	0.0048 (4)	1.1389 (3)	0.82587 (17)	0.0298 (6)
C1A	0.8841 (5)	1.1083 (3)	1.10365 (17)	0.0244 (6)
C2A	0.7004 (4)	1.1218 (3)	1.10263 (17)	0.0209 (6)
C3A	0.6084 (4)	1.1225 (2)	1.03691 (17)	0.0204 (6)
C4A	0.6993 (4)	1.1112 (3)	0.96830 (17)	0.0215 (6)
H4A	0.819233	1.102918	0.968024	0.026*
C5A	0.6120 (4)	1.1124 (3)	0.90400 (17)	0.0225 (6)
H5A	0.673259	1.105558	0.86031	0.027*
C6A	0.4264 (4)	1.1242 (2)	0.90247 (17)	0.0207 (6)
C7A	0.3406 (4)	1.1272 (3)	0.83539 (18)	0.0222 (6)
C8A	0.4382 (5)	1.1260 (3)	0.77034 (18)	0.0240 (6)
C9A	0.6217 (5)	1.1357 (3)	1.17332 (18)	0.0250 (6)
C10A	0.4235 (4)	1.1333 (2)	1.03529 (17)	0.0204 (6)
H10A	0.362307	1.1403	1.078993	0.025*
C11A	0.3355 (4)	1.1333 (3)	0.97044 (17)	0.0215 (6)
H11A	0.214591	1.139357	0.97039	0.026*
C12A	0.1555 (4)	1.1344 (3)	0.83040 (17)	0.0224 (6)
N1B	0.5435 (4)	1.3688 (3)	1.16869 (17)	0.0299 (6)
N2B	0.0093 (4)	1.3736 (3)	0.76948 (17)	0.0338 (7)
N3B	0.0246 (5)	1.3360 (3)	1.27008 (18)	0.0369 (7)
N4B	−0.4931 (4)	1.3798 (2)	0.88192 (16)	0.0272 (6)
C1B	0.3914 (5)	1.3678 (3)	1.16406 (18)	0.0245 (6)
C2B	0.2033 (4)	1.3660 (3)	1.15800 (18)	0.0232 (6)
C3B	0.1165 (4)	1.3728 (2)	1.09241 (17)	0.0208 (6)
C4B	0.2118 (4)	1.3766 (2)	1.02693 (18)	0.0216 (6)
H4B	0.335177	1.378759	1.028752	0.026*
C5B	0.1251 (4)	1.3773 (3)	0.96163 (17)	0.0208 (6)
H5B	0.189782	1.378659	0.919567	0.025*
C6B	−0.0648 (4)	1.3758 (2)	0.95755 (17)	0.0201 (6)
C7B	−0.1537 (4)	1.3766 (3)	0.89109 (17)	0.0214 (6)
C8B	−0.0630 (5)	1.3746 (3)	0.82369 (18)	0.0251 (6)
C9B	0.1051 (5)	1.3510 (3)	1.22027 (18)	0.0260 (7)
C10B	−0.0726 (4)	1.3725 (3)	1.08860 (18)	0.0218 (6)
H10B	−0.137051	1.370965	1.1307	0.026*
C11B	−0.1596 (4)	1.3746 (3)	1.02390 (17)	0.0210 (6)
H11B	−0.28229	1.37523	1.022798	0.025*
C12B	−0.3414 (5)	1.3777 (3)	0.88617 (17)	0.0225 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02414 (13)	0.02709 (13)	0.02008 (12)	0.00156 (9)	0.00465 (8)	0.00621 (8)
Br1A	0.02532 (19)	0.0339 (2)	0.03088 (18)	0.00651 (14)	0.00592 (14)	0.00810 (15)
N5A	0.0256 (14)	0.0325 (15)	0.0175 (12)	−0.0008 (12)	0.0008 (10)	0.0089 (11)
C13A	0.0255 (16)	0.0276 (16)	0.0223 (14)	0.0023 (13)	−0.0003 (12)	0.0041 (12)
C14A	0.0226 (15)	0.0316 (17)	0.0232 (15)	0.0016 (13)	−0.0004 (12)	0.0050 (13)
C15A	0.0266 (17)	0.0371 (19)	0.0271 (15)	0.0046 (14)	0.0060 (13)	0.0126 (14)
C16A	0.0308 (18)	0.038 (2)	0.0380 (18)	0.0108 (15)	0.0090 (15)	0.0199 (16)
C17A	0.0327 (18)	0.0379 (19)	0.0247 (15)	0.0152 (15)	0.0052 (13)	0.0113 (14)
C18A	0.0284 (17)	0.0326 (18)	0.0247 (15)	0.0003 (14)	0.0056 (13)	0.0080 (13)
Br1B	0.02328 (18)	0.0353 (2)	0.02728 (18)	0.00585 (14)	0.00280 (13)	0.00945 (14)
N5B	0.0268 (14)	0.0293 (14)	0.0188 (12)	0.0022 (12)	0.0044 (10)	0.0063 (11)
C13B	0.0235 (15)	0.0304 (17)	0.0198 (13)	0.0043 (13)	0.0055 (11)	0.0085 (12)
C14B	0.0205 (15)	0.0311 (17)	0.0212 (14)	−0.0003 (13)	0.0004 (11)	0.0027 (12)
C15B	0.0306 (18)	0.0361 (19)	0.0259 (15)	0.0048 (14)	0.0001 (13)	0.0142 (14)
C16B	0.0309 (18)	0.0402 (19)	0.0208 (15)	−0.0027 (15)	0.0014 (13)	0.0155 (14)
C17B	0.0232 (16)	0.0324 (17)	0.0192 (14)	−0.0020 (13)	0.0021 (12)	0.0056 (12)
C18B	0.0305 (18)	0.0345 (19)	0.0380 (19)	0.0081 (15)	0.0115 (14)	0.0165 (15)
N1A	0.0246 (15)	0.0401 (17)	0.0314 (14)	0.0054 (13)	0.0003 (11)	0.0121 (13)
N2A	0.0337 (16)	0.0356 (16)	0.0262 (14)	0.0082 (13)	0.0033 (12)	0.0116 (12)
N3A	0.0391 (18)	0.0397 (18)	0.0261 (14)	−0.0004 (14)	0.0067 (13)	0.0093 (13)
N4A	0.0257 (15)	0.0355 (16)	0.0282 (14)	0.0052 (12)	0.0019 (11)	0.0080 (12)
C1A	0.0283 (17)	0.0255 (16)	0.0186 (13)	0.0003 (13)	0.0017 (12)	0.0063 (12)
C2A	0.0218 (15)	0.0202 (14)	0.0206 (14)	0.0013 (11)	0.0035 (11)	0.0065 (11)
C3A	0.0229 (15)	0.0162 (13)	0.0210 (14)	0.0014 (11)	0.0032 (11)	0.0038 (11)
C4A	0.0195 (14)	0.0229 (15)	0.0221 (14)	0.0028 (11)	0.0048 (11)	0.0061 (11)
C5A	0.0218 (15)	0.0257 (15)	0.0200 (13)	0.0022 (12)	0.0050 (11)	0.0068 (11)
C6A	0.0216 (14)	0.0195 (14)	0.0211 (14)	0.0019 (11)	0.0007 (11)	0.0063 (11)
C7A	0.0227 (15)	0.0230 (15)	0.0219 (14)	0.0042 (12)	0.0026 (12)	0.0073 (11)
C8A	0.0256 (16)	0.0261 (16)	0.0221 (15)	0.0035 (12)	−0.0015 (12)	0.0103 (12)
C9A	0.0258 (16)	0.0265 (16)	0.0230 (15)	0.0008 (13)	0.0026 (12)	0.0091 (12)
C10A	0.0226 (15)	0.0187 (14)	0.0191 (13)	0.0016 (11)	0.0041 (11)	0.0044 (11)
C11A	0.0213 (14)	0.0202 (14)	0.0233 (14)	0.0041 (11)	0.0030 (11)	0.0058 (11)
C12A	0.0262 (16)	0.0234 (15)	0.0183 (13)	0.0035 (12)	0.0007 (11)	0.0070 (11)
N1B	0.0231 (15)	0.0352 (16)	0.0298 (14)	0.0051 (12)	0.0002 (11)	0.0058 (12)
N2B	0.0317 (16)	0.0464 (19)	0.0254 (14)	0.0071 (14)	0.0065 (12)	0.0122 (13)
N3B	0.0320 (17)	0.053 (2)	0.0272 (15)	0.0071 (15)	0.0053 (13)	0.0130 (14)
N4B	0.0203 (14)	0.0316 (15)	0.0304 (14)	0.0008 (11)	0.0002 (11)	0.0113 (12)
C1B	0.0263 (17)	0.0245 (15)	0.0217 (14)	0.0041 (12)	0.0007 (12)	0.0040 (12)
C2B	0.0200 (15)	0.0231 (15)	0.0254 (15)	0.0028 (12)	0.0022 (12)	0.0047 (12)
C3B	0.0215 (15)	0.0199 (14)	0.0223 (14)	0.0039 (11)	0.0032 (11)	0.0075 (11)
C4B	0.0177 (14)	0.0210 (14)	0.0261 (15)	0.0031 (11)	0.0045 (11)	0.0060 (12)
C5B	0.0187 (14)	0.0235 (15)	0.0213 (13)	0.0041 (11)	0.0052 (11)	0.0072 (11)
C6B	0.0206 (14)	0.0178 (14)	0.0219 (14)	0.0030 (11)	0.0024 (11)	0.0054 (11)
C7B	0.0205 (15)	0.0202 (14)	0.0228 (14)	0.0019 (11)	0.0015 (12)	0.0050 (11)
C8B	0.0234 (15)	0.0286 (16)	0.0236 (15)	0.0028 (12)	−0.0002 (12)	0.0086 (12)
C9B	0.0269 (16)	0.0309 (17)	0.0213 (15)	0.0055 (13)	−0.0011 (13)	0.0083 (13)
C10B	0.0175 (14)	0.0251 (15)	0.0238 (14)	0.0019 (11)	0.0030 (11)	0.0088 (12)
C11B	0.0173 (14)	0.0236 (15)	0.0227 (14)	0.0023 (11)	0.0036 (11)	0.0076 (11)
C12B	0.0269 (17)	0.0213 (14)	0.0190 (13)	0.0004 (12)	0.0015 (11)	0.0068 (11)

Geometric parameters (Å, º)

Br1A—C14A	1.885 (4)	C2A—C3A	1.395 (4)
N5A—C13A	1.341 (5)	C2A—C9A	1.427 (4)
N5A—C17A	1.343 (5)	C3A—C10A	1.427 (4)
N5A—C18A	1.486 (5)	C3A—C4A	1.439 (4)
C13A—C14A	1.378 (5)	C4A—C5A	1.357 (4)
C13A—H13A	0.93	C4A—H4A	0.93
C14A—C15A	1.387 (5)	C5A—C6A	1.436 (4)
C15A—C16A	1.393 (5)	C5A—H5A	0.93
C15A—H15A	0.93	C6A—C7A	1.404 (4)
C16A—C17A	1.378 (5)	C6A—C11A	1.431 (4)
C16A—H16A	0.93	C7A—C8A	1.422 (5)
C17A—H17A	0.93	C7A—C12A	1.421 (5)
C18A—H18A	0.96	C10A—C11A	1.364 (4)
C18A—H18B	0.96	C10A—H10A	0.93
C18A—H18C	0.96	C11A—H11A	0.93
Br1B—C14B	1.888 (3)	N1B—C1B	1.151 (5)
N5B—C13B	1.349 (4)	N2B—C8B	1.150 (5)
N5B—C17B	1.347 (5)	N3B—C9B	1.157 (5)
N5B—C18B	1.478 (5)	N4B—C12B	1.154 (5)
C13B—C14B	1.387 (5)	C1B—C2B	1.423 (5)
C13B—H13B	0.93	C2B—C3B	1.401 (4)
C14B—C15B	1.385 (5)	C2B—C9B	1.423 (5)
C15B—C16B	1.387 (5)	C3B—C4B	1.430 (4)
C15B—H15B	0.93	C3B—C10B	1.431 (4)
C16B—C17B	1.376 (5)	C4B—C5B	1.369 (4)
C16B—H16B	0.93	C4B—H4B	0.93
C17B—H17B	0.93	C5B—C6B	1.435 (4)
C18B—H18D	0.96	C5B—H5B	0.93
C18B—H18E	0.96	C6B—C7B	1.396 (4)
C18B—H18F	0.96	C6B—C11B	1.436 (4)
N1A—C1A	1.151 (5)	C7B—C12B	1.425 (5)
N2A—C8A	1.151 (5)	C7B—C8B	1.431 (5)
N3A—C9A	1.153 (5)	C10B—C11B	1.366 (4)
N4A—C12A	1.154 (5)	C10B—H10B	0.93
C1A—C2A	1.427 (5)	C11B—H11B	0.93
C13A—N5A—C17A	121.8 (3)	C2A—C3A—C10A	121.6 (3)
C13A—N5A—C18A	118.9 (3)	C2A—C3A—C4A	120.1 (3)
C17A—N5A—C18A	119.2 (3)	C10A—C3A—C4A	118.3 (3)
N5A—C13A—C14A	119.9 (3)	C5A—C4A—C3A	120.8 (3)
N5A—C13A—H13A	120	C5A—C4A—H4A	119.6
C14A—C13A—H13A	120	C3A—C4A—H4A	119.6
C13A—C14A—C15A	120.3 (3)	C4A—C5A—C6A	120.9 (3)
C13A—C14A—Br1A	118.8 (3)	C4A—C5A—H5A	119.5
C15A—C14A—Br1A	120.9 (3)	C6A—C5A—H5A	119.5
C14A—C15A—C16A	117.8 (3)	C7A—C6A—C11A	122.3 (3)
C14A—C15A—H15A	121.1	C7A—C6A—C5A	119.6 (3)
C16A—C15A—H15A	121.1	C11A—C6A—C5A	118.1 (3)
C17A—C16A—C15A	120.4 (3)	C6A—C7A—C8A	120.7 (3)
C17A—C16A—H16A	119.8	C6A—C7A—C12A	121.6 (3)
C15A—C16A—H16A	119.8	C8A—C7A—C12A	117.6 (3)
N5A—C17A—C16A	119.7 (3)	N2A—C8A—C7A	177.9 (3)
N5A—C17A—H17A	120.2	N3A—C9A—C2A	177.3 (4)
C16A—C17A—H17A	120.2	C11A—C10A—C3A	120.8 (3)
N5A—C18A—H18A	109.5	C11A—C10A—H10A	119.6
N5A—C18A—H18B	109.5	C3A—C10A—H10A	119.6
H18A—C18A—H18B	109.5	C10A—C11A—C6A	121.0 (3)
N5A—C18A—H18C	109.5	C10A—C11A—H11A	119.5
H18A—C18A—H18C	109.5	C6A—C11A—H11A	119.5
H18B—C18A—H18C	109.5	N4A—C12A—C7A	179.2 (4)
C13B—N5B—C17B	121.6 (3)	N1B—C1B—C2B	179.7 (4)
C13B—N5B—C18B	119.1 (3)	C3B—C2B—C9B	121.1 (3)
C17B—N5B—C18B	119.3 (3)	C3B—C2B—C1B	121.8 (3)
N5B—C13B—C14B	119.4 (3)	C9B—C2B—C1B	117.0 (3)
N5B—C13B—H13B	120.3	C2B—C3B—C4B	121.4 (3)
C14B—C13B—H13B	120.3	C2B—C3B—C10B	120.4 (3)
C13B—C14B—C15B	120.2 (3)	C4B—C3B—C10B	118.1 (3)
C13B—C14B—Br1B	118.6 (3)	C5B—C4B—C3B	121.3 (3)
C15B—C14B—Br1B	121.1 (3)	C5B—C4B—H4B	119.3
C16B—C15B—C14B	118.6 (3)	C3B—C4B—H4B	119.3
C16B—C15B—H15B	120.7	C4B—C5B—C6B	120.5 (3)
C14B—C15B—H15B	120.7	C4B—C5B—H5B	119.7
C17B—C16B—C15B	119.9 (3)	C6B—C5B—H5B	119.7
C17B—C16B—H16B	120	C7B—C6B—C5B	120.7 (3)
C15B—C16B—H16B	120	C7B—C6B—C11B	121.3 (3)
N5B—C17B—C16B	120.2 (3)	C5B—C6B—C11B	118.0 (3)
N5B—C17B—H17B	119.9	C6B—C7B—C12B	121.7 (3)
C16B—C17B—H17B	119.9	C6B—C7B—C8B	122.2 (3)
N5B—C18B—H18D	109.5	C12B—C7B—C8B	116.0 (3)
N5B—C18B—H18E	109.5	N2B—C8B—C7B	179.5 (4)
H18D—C18B—H18E	109.5	N3B—C9B—C2B	178.3 (4)
N5B—C18B—H18F	109.5	C11B—C10B—C3B	120.8 (3)
H18D—C18B—H18F	109.5	C11B—C10B—H10B	119.6
H18E—C18B—H18F	109.5	C3B—C10B—H10B	119.6
N1A—C1A—C2A	178.8 (4)	C10B—C11B—C6B	121.1 (3)
C3A—C2A—C1A	121.5 (3)	C10B—C11B—H11B	119.4
C3A—C2A—C9A	123.6 (3)	C6B—C11B—H11B	119.4
C1A—C2A—C9A	114.9 (3)	N4B—C12B—C7B	179.1 (4)
C17A—N5A—C13A—C14A	1.5 (5)	C4A—C5A—C6A—C11A	−0.7 (5)
C18A—N5A—C13A—C14A	179.6 (3)	C11A—C6A—C7A—C8A	175.3 (3)
N5A—C13A—C14A—C15A	−0.7 (5)	C5A—C6A—C7A—C8A	−4.3 (5)
N5A—C13A—C14A—Br1A	−179.8 (2)	C11A—C6A—C7A—C12A	−3.0 (5)
C13A—C14A—C15A—C16A	−0.3 (5)	C5A—C6A—C7A—C12A	177.4 (3)
Br1A—C14A—C15A—C16A	178.8 (3)	C2A—C3A—C10A—C11A	−179.7 (3)
C14A—C15A—C16A—C17A	0.6 (6)	C4A—C3A—C10A—C11A	−0.3 (5)
C13A—N5A—C17A—C16A	−1.2 (5)	C3A—C10A—C11A—C6A	−0.9 (5)
C18A—N5A—C17A—C16A	−179.2 (3)	C7A—C6A—C11A—C10A	−178.1 (3)
C15A—C16A—C17A—N5A	0.1 (6)	C5A—C6A—C11A—C10A	1.4 (5)
C17B—N5B—C13B—C14B	1.2 (5)	C9B—C2B—C3B—C4B	−173.4 (3)
C18B—N5B—C13B—C14B	177.8 (3)	C1B—C2B—C3B—C4B	3.1 (5)
N5B—C13B—C14B—C15B	0.7 (5)	C9B—C2B—C3B—C10B	4.5 (5)
N5B—C13B—C14B—Br1B	−176.1 (2)	C1B—C2B—C3B—C10B	−178.9 (3)
C13B—C14B—C15B—C16B	−1.5 (5)	C2B—C3B—C4B—C5B	176.3 (3)
Br1B—C14B—C15B—C16B	175.2 (3)	C10B—C3B—C4B—C5B	−1.7 (5)
C14B—C15B—C16B—C17B	0.6 (5)	C3B—C4B—C5B—C6B	1.0 (5)
C13B—N5B—C17B—C16B	−2.1 (5)	C4B—C5B—C6B—C7B	179.9 (3)
C18B—N5B—C17B—C16B	−178.7 (3)	C4B—C5B—C6B—C11B	0.5 (4)
C15B—C16B—C17B—N5B	1.2 (5)	C5B—C6B—C7B—C12B	−178.5 (3)
C1A—C2A—C3A—C10A	178.4 (3)	C11B—C6B—C7B—C12B	0.8 (5)
C9A—C2A—C3A—C10A	−2.6 (5)	C5B—C6B—C7B—C8B	2.6 (5)
C1A—C2A—C3A—C4A	−0.9 (5)	C11B—C6B—C7B—C8B	−178.1 (3)
C9A—C2A—C3A—C4A	178.1 (3)	C2B—C3B—C10B—C11B	−177.2 (3)
C2A—C3A—C4A—C5A	−179.6 (3)	C4B—C3B—C10B—C11B	0.8 (5)
C10A—C3A—C4A—C5A	1.1 (5)	C3B—C10B—C11B—C6B	0.7 (5)
C3A—C4A—C5A—C6A	−0.5 (5)	C7B—C6B—C11B—C10B	179.2 (3)
C4A—C5A—C6A—C7A	178.8 (3)	C5B—C6B—C11B—C10B	−1.4 (5)

(tcnq_35brme)

Crystal data

2(C12H4N4)·C6H6Br2N	Z = 2
Mr = 660.32	F(000) = 654
Triclinic, P1	Dx = 1.619 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 6.6911 (2) Å	Cell parameters from 6687 reflections
b = 7.8201 (3) Å	θ = 3.2–76.3°
c = 27.6491 (6) Å	µ = 4.12 mm^−1
α = 97.673 (2)°	T = 293 K
β = 90.168 (2)°	Plate, black
γ = 108.973 (3)°	0.33 × 0.19 × 0.04 mm
V = 1354.24 (8) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	5582 independent reflections
Radiation source: micro-focus sealed X-ray tube	5100 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.043
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.5°, θmin = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.563, Tmax = 1	l = −23→34
11901 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0711P)^2 + 0.6968P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5582 reflections	Δρmax = 0.87 e Å^−3
370 parameters	Δρmin = −0.68 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.96358 (4)	−0.03531 (4)	0.20508 (2)	0.02977 (11)
Br2	0.30401 (5)	0.05369 (4)	0.32482 (2)	0.03150 (11)
N5	0.4141 (3)	−0.3825 (3)	0.24558 (7)	0.0224 (4)
C13	0.6004 (4)	−0.3134 (3)	0.22598 (8)	0.0227 (5)
H13	0.658769	−0.39	0.206647	0.027*
C14	0.7055 (4)	−0.1280 (3)	0.23457 (8)	0.0224 (5)
C15	0.6219 (4)	−0.0116 (3)	0.26385 (7)	0.0232 (5)
H15	0.692374	0.113638	0.269877	0.028*
C16	0.4283 (4)	−0.0905 (4)	0.28375 (8)	0.0243 (5)
C17	0.3237 (4)	−0.2765 (4)	0.27380 (8)	0.0239 (5)
H17	0.192436	−0.327917	0.286425	0.029*
C18	0.3043 (4)	−0.5829 (4)	0.23776 (10)	0.0300 (5)
H18A	0.17343	−0.610465	0.25406	0.045*
H18B	0.275795	−0.624952	0.203401	0.045*
H18C	0.392526	−0.642841	0.250752	0.045*
N1A	0.7125 (4)	0.0081 (3)	0.54910 (8)	0.0297 (5)
N2A	0.7891 (4)	0.4755 (3)	0.29460 (8)	0.0300 (5)
N3A	0.7381 (4)	0.5184 (3)	0.63798 (8)	0.0299 (5)
N4A	0.7914 (5)	0.9919 (4)	0.37778 (9)	0.0361 (5)
C1A	0.7233 (4)	0.1587 (4)	0.55031 (8)	0.0228 (5)
C2A	0.7392 (4)	0.3459 (3)	0.55176 (8)	0.0204 (4)
C3A	0.7524 (3)	0.4260 (3)	0.50915 (8)	0.0206 (5)
C4A	0.7492 (4)	0.3210 (3)	0.46235 (8)	0.0205 (4)
H4A	0.737846	0.198586	0.460519	0.025*
C5A	0.7623 (4)	0.3973 (4)	0.42058 (8)	0.0217 (5)
H5A	0.760027	0.326424	0.390636	0.026*
C6A	0.7796 (3)	0.5847 (3)	0.42202 (8)	0.0203 (4)
C7A	0.7900 (4)	0.6627 (4)	0.37889 (8)	0.0225 (5)
C8A	0.7892 (4)	0.5593 (4)	0.33232 (9)	0.0242 (5)
C9A	0.7390 (4)	0.4441 (4)	0.59927 (9)	0.0229 (5)
C10A	0.7684 (4)	0.6139 (3)	0.51078 (8)	0.0212 (4)
H10A	0.769589	0.684363	0.540727	0.025*
C11A	0.7818 (4)	0.6905 (3)	0.46885 (8)	0.0210 (4)
H11A	0.792532	0.812736	0.470592	0.025*
C12A	0.7930 (4)	0.8456 (4)	0.37885 (8)	0.0264 (5)
N1B	0.4952 (4)	−0.4401 (4)	0.10323 (9)	0.0357 (5)
N3B	0.4306 (4)	0.0781 (4)	0.17008 (8)	0.0357 (5)
C1B	0.4856 (4)	−0.2986 (4)	0.09823 (9)	0.0280 (5)
C2B	0.4719 (4)	−0.1250 (4)	0.09221 (8)	0.0252 (5)
C3B	0.4859 (4)	−0.0624 (4)	0.04625 (8)	0.0242 (5)
C4B	0.5087 (4)	−0.1744 (4)	0.00295 (9)	0.0251 (5)
H4B	0.514623	−0.290406	0.004974	0.03*
C9B	0.4485 (4)	−0.0132 (4)	0.13551 (9)	0.0275 (5)
C10B	0.4779 (4)	0.1140 (4)	0.04160 (8)	0.0243 (5)
H10B	0.463231	0.18985	0.069302	0.029*
N1C	1.0064 (4)	0.0206 (3)	0.08490 (8)	0.0284 (5)
N3C	0.9561 (5)	0.5129 (4)	0.17100 (8)	0.0378 (6)
C1C	0.9974 (4)	0.1650 (4)	0.08525 (8)	0.0231 (5)
C2C	0.9838 (4)	0.3443 (4)	0.08579 (8)	0.0220 (5)
C3C	0.9907 (4)	0.4218 (4)	0.04347 (8)	0.0214 (5)
C4C	1.0152 (4)	0.3239 (4)	−0.00298 (8)	0.0225 (5)
H4C	1.024349	0.207208	−0.004311	0.027*
C9C	0.9657 (4)	0.4384 (4)	0.13287 (9)	0.0266 (5)
C10C	0.9750 (4)	0.6011 (4)	0.04459 (8)	0.0223 (5)
H10C	0.958021	0.666039	0.074125	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.03255 (17)	0.02551 (17)	0.02784 (16)	0.00424 (11)	0.00987 (11)	0.00530 (10)
Br2	0.04144 (18)	0.03258 (18)	0.02386 (15)	0.01756 (13)	0.00733 (11)	0.00183 (11)
N5	0.0276 (10)	0.0180 (10)	0.0200 (9)	0.0046 (8)	−0.0010 (7)	0.0045 (7)
C13	0.0315 (12)	0.0233 (12)	0.0151 (9)	0.0110 (10)	0.0006 (8)	0.0038 (8)
C14	0.0273 (11)	0.0225 (12)	0.0157 (9)	0.0048 (9)	0.0026 (8)	0.0053 (8)
C15	0.0320 (13)	0.0196 (12)	0.0176 (10)	0.0076 (10)	0.0008 (9)	0.0033 (8)
C16	0.0316 (12)	0.0251 (13)	0.0167 (9)	0.0096 (10)	0.0006 (8)	0.0042 (8)
C17	0.0279 (11)	0.0255 (13)	0.0197 (10)	0.0092 (10)	0.0025 (8)	0.0066 (8)
C18	0.0360 (13)	0.0182 (13)	0.0319 (12)	0.0030 (10)	−0.0007 (10)	0.0054 (9)
N1A	0.0368 (11)	0.0237 (12)	0.0266 (10)	0.0057 (9)	0.0038 (9)	0.0070 (8)
N2A	0.0374 (12)	0.0320 (13)	0.0202 (10)	0.0096 (10)	−0.0003 (8)	0.0063 (8)
N3A	0.0357 (11)	0.0335 (13)	0.0225 (10)	0.0138 (10)	0.0031 (8)	0.0047 (9)
N4A	0.0524 (15)	0.0350 (14)	0.0286 (11)	0.0223 (12)	0.0052 (10)	0.0101 (9)
C1A	0.0230 (11)	0.0264 (14)	0.0169 (10)	0.0038 (9)	0.0020 (8)	0.0065 (8)
C2A	0.0188 (10)	0.0223 (12)	0.0187 (10)	0.0040 (9)	0.0021 (8)	0.0054 (8)
C3A	0.0168 (10)	0.0242 (12)	0.0193 (10)	0.0038 (9)	0.0006 (8)	0.0060 (9)
C4A	0.0198 (10)	0.0195 (11)	0.0201 (10)	0.0031 (9)	−0.0005 (8)	0.0040 (8)
C5A	0.0206 (10)	0.0234 (12)	0.0183 (10)	0.0037 (9)	−0.0007 (8)	0.0020 (8)
C6A	0.0166 (9)	0.0242 (12)	0.0195 (10)	0.0042 (9)	−0.0003 (8)	0.0071 (9)
C7A	0.0218 (10)	0.0260 (13)	0.0189 (10)	0.0054 (9)	−0.0005 (8)	0.0061 (9)
C8A	0.0230 (11)	0.0276 (13)	0.0229 (11)	0.0063 (10)	0.0007 (8)	0.0111 (10)
C9A	0.0236 (11)	0.0248 (13)	0.0220 (11)	0.0085 (9)	0.0017 (8)	0.0083 (9)
C10A	0.0219 (10)	0.0233 (12)	0.0179 (9)	0.0066 (9)	0.0008 (8)	0.0034 (8)
C11A	0.0214 (10)	0.0204 (12)	0.0216 (10)	0.0064 (9)	0.0007 (8)	0.0055 (8)
C12A	0.0295 (12)	0.0335 (15)	0.0194 (10)	0.0126 (11)	0.0024 (9)	0.0093 (9)
N1B	0.0395 (13)	0.0359 (14)	0.0320 (11)	0.0114 (11)	−0.0013 (9)	0.0080 (10)
N3B	0.0448 (13)	0.0431 (15)	0.0231 (10)	0.0188 (12)	0.0025 (9)	0.0067 (10)
C1B	0.0262 (11)	0.0351 (15)	0.0207 (10)	0.0068 (10)	−0.0003 (9)	0.0051 (9)
C2B	0.0242 (11)	0.0289 (13)	0.0209 (10)	0.0062 (10)	0.0002 (8)	0.0047 (9)
C3B	0.0196 (10)	0.0313 (14)	0.0194 (10)	0.0047 (9)	0.0013 (8)	0.0048 (9)
C4B	0.0239 (11)	0.0260 (13)	0.0246 (11)	0.0067 (10)	0.0017 (9)	0.0047 (9)
C9B	0.0288 (12)	0.0339 (15)	0.0204 (11)	0.0099 (11)	−0.0001 (9)	0.0070 (10)
C10B	0.0227 (10)	0.0301 (13)	0.0184 (10)	0.0069 (9)	0.0016 (8)	0.0019 (9)
N1C	0.0358 (11)	0.0275 (13)	0.0233 (9)	0.0112 (9)	0.0029 (8)	0.0068 (8)
N3C	0.0588 (16)	0.0414 (15)	0.0215 (11)	0.0268 (13)	0.0058 (10)	0.0072 (9)
C1C	0.0253 (11)	0.0285 (14)	0.0153 (9)	0.0078 (10)	0.0013 (8)	0.0054 (8)
C2C	0.0244 (11)	0.0232 (12)	0.0181 (10)	0.0068 (9)	0.0010 (8)	0.0048 (9)
C3C	0.0195 (10)	0.0240 (12)	0.0196 (10)	0.0051 (9)	0.0006 (8)	0.0043 (9)
C4C	0.0251 (11)	0.0217 (12)	0.0201 (10)	0.0073 (9)	0.0008 (8)	0.0019 (9)
C9C	0.0343 (13)	0.0269 (13)	0.0225 (12)	0.0137 (11)	0.0032 (9)	0.0080 (10)
C10C	0.0255 (11)	0.0232 (12)	0.0174 (9)	0.0076 (9)	0.0017 (8)	0.0010 (8)

Geometric parameters (Å, º)

Br1—C14	1.877 (2)	C6A—C7A	1.402 (3)
Br2—C16	1.878 (3)	C6A—C11A	1.438 (3)
N5—C13	1.336 (3)	C7A—C12A	1.424 (4)
N5—C17	1.348 (3)	C7A—C8A	1.425 (3)
N5—C18	1.484 (3)	C10A—C11A	1.364 (3)
C13—C14	1.377 (4)	C10A—H10A	0.93
C13—H13	0.93	C11A—H11A	0.93
C14—C15	1.391 (3)	N1B—C1B	1.155 (4)
C15—C16	1.392 (3)	N3B—C9B	1.145 (4)
C15—H15	0.93	C1B—C2B	1.422 (4)
C16—C17	1.382 (4)	C2B—C3B	1.414 (3)
C17—H17	0.93	C2B—C9B	1.426 (4)
C18—H18A	0.96	C3B—C10B	1.420 (4)
C18—H18B	0.96	C3B—C4B	1.425 (3)
C18—H18C	0.96	C4B—C10B^i	1.370 (3)
N1A—C1A	1.152 (4)	C4B—H4B	0.93
N2A—C8A	1.155 (4)	C10B—H10B	0.93
N3A—C9A	1.149 (4)	N1C—C1C	1.149 (4)
N4A—C12A	1.152 (4)	N3C—C9C	1.147 (4)
C1A—C2A	1.428 (4)	C1C—C2C	1.432 (4)
C2A—C3A	1.397 (3)	C2C—C3C	1.382 (3)
C2A—C9A	1.431 (3)	C2C—C9C	1.433 (3)
C3A—C10A	1.432 (4)	C3C—C10C	1.436 (4)
C3A—C4A	1.433 (3)	C3C—C4C	1.443 (3)
C4A—C5A	1.360 (3)	C4C—C10C^ii	1.352 (3)
C4A—H4A	0.93	C4C—H4C	0.93
C5A—C6A	1.427 (4)	C10C—H10C	0.93
C5A—H5A	0.93
C13—N5—C17	122.2 (2)	C6A—C7A—C12A	122.3 (2)
C13—N5—C18	119.6 (2)	C6A—C7A—C8A	121.3 (2)
C17—N5—C18	118.2 (2)	C12A—C7A—C8A	116.4 (2)
N5—C13—C14	119.6 (2)	N2A—C8A—C7A	179.8 (3)
N5—C13—H13	120.2	N3A—C9A—C2A	178.0 (3)
C14—C13—H13	120.2	C11A—C10A—C3A	120.7 (2)
C13—C14—C15	121.0 (2)	C11A—C10A—H10A	119.7
C13—C14—Br1	118.34 (18)	C3A—C10A—H10A	119.7
C15—C14—Br1	120.61 (19)	C10A—C11A—C6A	120.9 (2)
C14—C15—C16	117.2 (2)	C10A—C11A—H11A	119.6
C14—C15—H15	121.4	C6A—C11A—H11A	119.6
C16—C15—H15	121.4	N4A—C12A—C7A	178.2 (3)
C17—C16—C15	120.7 (2)	N1B—C1B—C2B	179.5 (3)
C17—C16—Br2	118.64 (19)	C3B—C2B—C1B	122.6 (2)
C15—C16—Br2	120.62 (19)	C3B—C2B—C9B	121.1 (2)
N5—C17—C16	119.3 (2)	C1B—C2B—C9B	116.3 (2)
N5—C17—H17	120.4	C2B—C3B—C10B	121.3 (2)
C16—C17—H17	120.4	C2B—C3B—C4B	121.1 (2)
N5—C18—H18A	109.5	C10B—C3B—C4B	117.7 (2)
N5—C18—H18B	109.5	C10B^i—C4B—C3B	121.1 (3)
H18A—C18—H18B	109.5	C10B^i—C4B—H4B	119.4
N5—C18—H18C	109.5	C3B—C4B—H4B	119.4
H18A—C18—H18C	109.5	N3B—C9B—C2B	179.3 (3)
H18B—C18—H18C	109.5	C4B^i—C10B—C3B	121.2 (2)
N1A—C1A—C2A	179.3 (3)	C4B^i—C10B—H10B	119.4
C3A—C2A—C1A	121.6 (2)	C3B—C10B—H10B	119.4
C3A—C2A—C9A	122.6 (2)	N1C—C1C—C2C	179.4 (3)
C1A—C2A—C9A	115.8 (2)	C3C—C2C—C1C	121.8 (2)
C2A—C3A—C10A	121.4 (2)	C3C—C2C—C9C	122.4 (2)
C2A—C3A—C4A	120.5 (2)	C1C—C2C—C9C	115.8 (2)
C10A—C3A—C4A	118.2 (2)	C2C—C3C—C10C	121.1 (2)
C5A—C4A—C3A	121.1 (2)	C2C—C3C—C4C	120.5 (2)
C5A—C4A—H4A	119.4	C10C—C3C—C4C	118.5 (2)
C3A—C4A—H4A	119.4	C10C^ii—C4C—C3C	121.1 (2)
C4A—C5A—C6A	120.9 (2)	C10C^ii—C4C—H4C	119.4
C4A—C5A—H5A	119.5	C3C—C4C—H4C	119.4
C6A—C5A—H5A	119.5	N3C—C9C—C2C	178.1 (3)
C7A—C6A—C5A	120.9 (2)	C4C^ii—C10C—C3C	120.4 (2)
C7A—C6A—C11A	120.9 (2)	C4C^ii—C10C—H10C	119.8
C5A—C6A—C11A	118.2 (2)	C3C—C10C—H10C	119.8
C17—N5—C13—C14	0.0 (3)	C5A—C6A—C7A—C8A	−1.7 (4)
C18—N5—C13—C14	−177.9 (2)	C11A—C6A—C7A—C8A	179.6 (2)
N5—C13—C14—C15	0.8 (3)	C2A—C3A—C10A—C11A	179.8 (2)
N5—C13—C14—Br1	−178.45 (16)	C4A—C3A—C10A—C11A	−0.5 (3)
C13—C14—C15—C16	−0.2 (3)	C3A—C10A—C11A—C6A	0.2 (3)
Br1—C14—C15—C16	178.99 (16)	C7A—C6A—C11A—C10A	179.0 (2)
C14—C15—C16—C17	−1.1 (3)	C5A—C6A—C11A—C10A	0.2 (3)
C14—C15—C16—Br2	178.77 (16)	C1B—C2B—C3B—C10B	−178.2 (2)
C13—N5—C17—C16	−1.3 (3)	C9B—C2B—C3B—C10B	0.2 (4)
C18—N5—C17—C16	176.6 (2)	C1B—C2B—C3B—C4B	1.8 (4)
C15—C16—C17—N5	1.9 (3)	C9B—C2B—C3B—C4B	−179.8 (2)
Br2—C16—C17—N5	−177.99 (17)	C2B—C3B—C4B—C10B^i	179.9 (2)
C1A—C2A—C3A—C10A	180.0 (2)	C10B—C3B—C4B—C10B^i	−0.1 (4)
C9A—C2A—C3A—C10A	0.5 (3)	C2B—C3B—C10B—C4B^i	−179.9 (2)
C1A—C2A—C3A—C4A	0.3 (3)	C4B—C3B—C10B—C4B^i	0.1 (4)
C9A—C2A—C3A—C4A	−179.2 (2)	C1C—C2C—C3C—C10C	179.5 (2)
C2A—C3A—C4A—C5A	−179.8 (2)	C9C—C2C—C3C—C10C	−1.4 (4)
C10A—C3A—C4A—C5A	0.5 (3)	C1C—C2C—C3C—C4C	−0.9 (4)
C3A—C4A—C5A—C6A	−0.1 (4)	C9C—C2C—C3C—C4C	178.2 (2)
C4A—C5A—C6A—C7A	−179.0 (2)	C2C—C3C—C4C—C10C^ii	−179.1 (2)
C4A—C5A—C6A—C11A	−0.3 (3)	C10C—C3C—C4C—C10C^ii	0.5 (4)
C5A—C6A—C7A—C12A	175.7 (2)	C2C—C3C—C10C—C4C^ii	179.1 (2)
C11A—C6A—C7A—C12A	−3.0 (4)	C4C—C3C—C10C—C4C^ii	−0.5 (4)

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z.

(tcnq_nmepy_100k_2)

Crystal data

2(C12H4N4)·C6H8N	Z = 2
Mr = 502.52	F(000) = 518
Triclinic, P1	Dx = 1.328 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.7274 (4) Å	Cell parameters from 5442 reflections
b = 13.1422 (6) Å	θ = 3.5–75.2°
c = 13.3145 (6) Å	µ = 0.68 mm^−1
α = 99.902 (4)°	T = 100 K
β = 106.251 (5)°	Prism, black
γ = 97.225 (4)°	0.35 × 0.32 × 0.20 mm
V = 1257.00 (11) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	4926 independent reflections
Radiation source: micro-focus sealed X-ray tube	4067 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.071
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.7°, θmin = 3.5°
ω scans	h = −8→9
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −15→16
Tmin = 0.354, Tmax = 1	l = −16→15
8993 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.082	H-atom parameters constrained
wR(F^2) = 0.238	w = 1/[σ^2(Fo^2) + (0.080P)^2 + 0.0841P] where P = (Fo^2 + 2Fc^2)/3
S = 1.70	(Δ/σ)max < 0.001
4926 reflections	Δρmax = 0.43 e Å^−3
352 parameters	Δρmin = −0.35 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1A	0.6623 (3)	1.02060 (18)	1.32911 (17)	0.0444 (5)
N2A	0.8690 (3)	0.74490 (16)	0.75826 (16)	0.0392 (5)
N3A	0.0818 (3)	0.96471 (17)	1.14969 (17)	0.0418 (5)
N4A	0.2723 (3)	0.66432 (17)	0.60476 (16)	0.0422 (5)
C1A	0.5512 (3)	0.98820 (17)	1.24761 (18)	0.0343 (5)
C2A	0.4111 (3)	0.94931 (16)	1.14681 (17)	0.0306 (4)
C3A	0.4462 (3)	0.90448 (15)	1.05491 (17)	0.0292 (4)
C4A	0.6289 (3)	0.89609 (15)	1.05256 (16)	0.0296 (4)
H4A	0.726948	0.922366	1.11484	0.036*
C5A	0.6617 (3)	0.85107 (15)	0.96237 (17)	0.0300 (4)
H5A	0.781898	0.848035	0.963624	0.036*
C6A	0.5146 (3)	0.80758 (15)	0.86410 (16)	0.0301 (4)
C7A	0.5451 (3)	0.75718 (16)	0.77219 (17)	0.0315 (5)
C8A	0.7247 (3)	0.75019 (16)	0.76483 (17)	0.0328 (5)
C9A	0.2285 (3)	0.95776 (16)	1.14907 (17)	0.0321 (5)
C10A	0.2992 (3)	0.86325 (15)	0.95568 (16)	0.0300 (4)
H10A	0.179619	0.868839	0.953735	0.036*
C11A	0.3315 (3)	0.81683 (15)	0.86578 (17)	0.0307 (4)
H11A	0.233423	0.790242	0.803565	0.037*
C12A	0.3950 (3)	0.70588 (17)	0.67839 (18)	0.0346 (5)
N1B	0.2272 (3)	0.54299 (17)	0.33710 (17)	0.0444 (5)
N2B	0.4564 (3)	0.27919 (16)	−0.21957 (16)	0.0408 (5)
N3B	−0.3610 (3)	0.45662 (15)	0.17094 (16)	0.0373 (4)
N4B	−0.1294 (3)	0.16750 (17)	−0.37628 (17)	0.0441 (5)
C1B	0.1112 (3)	0.50494 (17)	0.25938 (18)	0.0341 (5)
C2B	−0.0316 (3)	0.45641 (15)	0.16156 (17)	0.0296 (4)
C3B	0.0059 (3)	0.41171 (15)	0.07002 (16)	0.0285 (4)
C4B	0.1927 (3)	0.41746 (15)	0.06784 (16)	0.0290 (4)
H4B	0.288472	0.452138	0.128707	0.035*
C5B	0.2304 (3)	0.37354 (15)	−0.02067 (16)	0.0292 (4)
H5B	0.352114	0.37907	−0.019672	0.035*
C6B	0.0879 (3)	0.31817 (15)	−0.11698 (17)	0.0296 (4)
C7B	0.1273 (3)	0.27125 (16)	−0.20694 (17)	0.0307 (4)
C8B	0.3096 (3)	0.27592 (16)	−0.21307 (17)	0.0334 (5)
C9B	−0.2153 (3)	0.45531 (15)	0.16628 (16)	0.0310 (5)
C10B	−0.1369 (3)	0.35747 (15)	−0.02605 (16)	0.0286 (4)
H10B	−0.258591	0.352949	−0.027357	0.034*
C11B	−0.0984 (3)	0.31286 (15)	−0.11458 (17)	0.0297 (4)
H11B	−0.194198	0.277934	−0.175354	0.036*
C12B	−0.0148 (3)	0.21314 (17)	−0.30093 (18)	0.0338 (5)
N5	0.7639 (3)	0.71377 (17)	0.49261 (15)	0.0415 (5)
C13	0.5917 (3)	0.7310 (2)	0.47847 (18)	0.0423 (6)
H13	0.493222	0.675425	0.447088	0.051*
C14	0.5605 (3)	0.8299 (2)	0.50994 (19)	0.0437 (6)
H14	0.441355	0.841483	0.5009	0.052*
C15	0.7069 (4)	0.9122 (2)	0.5552 (2)	0.0455 (6)
H15	0.687126	0.979842	0.576357	0.055*
C16	0.8822 (4)	0.8937 (2)	0.5687 (2)	0.0474 (6)
H16	0.981694	0.948958	0.598479	0.057*
C17	0.9098 (3)	0.7942 (2)	0.5384 (2)	0.0445 (6)
H17	1.028396	0.781118	0.549002	0.053*
C18	0.7967 (6)	0.6064 (2)	0.4596 (2)	0.0634 (8)
H18A	0.926137	0.607839	0.475135	0.095*
H18B	0.747949	0.560814	0.498082	0.095*
H18C	0.737331	0.580975	0.384017	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0399 (11)	0.0541 (12)	0.0348 (10)	0.0108 (9)	0.0052 (8)	0.0071 (8)
N2A	0.0393 (10)	0.0442 (10)	0.0366 (10)	0.0157 (8)	0.0108 (8)	0.0116 (8)
N3A	0.0349 (10)	0.0466 (11)	0.0421 (11)	0.0095 (8)	0.0114 (8)	0.0042 (8)
N4A	0.0423 (11)	0.0432 (10)	0.0351 (11)	0.0078 (9)	0.0066 (9)	0.0010 (8)
C1A	0.0331 (10)	0.0351 (10)	0.0339 (11)	0.0098 (8)	0.0077 (9)	0.0074 (8)
C2A	0.0325 (10)	0.0279 (9)	0.0295 (10)	0.0069 (8)	0.0054 (8)	0.0074 (7)
C3A	0.0303 (10)	0.0260 (9)	0.0297 (10)	0.0071 (8)	0.0041 (8)	0.0086 (7)
C4A	0.0294 (10)	0.0291 (9)	0.0283 (10)	0.0093 (8)	0.0032 (8)	0.0077 (7)
C5A	0.0314 (10)	0.0285 (9)	0.0301 (10)	0.0094 (8)	0.0067 (8)	0.0076 (7)
C6A	0.0324 (10)	0.0260 (9)	0.0306 (10)	0.0079 (8)	0.0054 (8)	0.0076 (7)
C7A	0.0354 (11)	0.0285 (9)	0.0305 (10)	0.0093 (8)	0.0078 (8)	0.0073 (7)
C8A	0.0385 (12)	0.0314 (10)	0.0281 (10)	0.0126 (8)	0.0070 (8)	0.0066 (7)
C9A	0.0366 (11)	0.0284 (9)	0.0282 (10)	0.0062 (8)	0.0058 (8)	0.0045 (7)
C10A	0.0286 (10)	0.0283 (9)	0.0303 (10)	0.0053 (8)	0.0050 (8)	0.0054 (7)
C11A	0.0293 (10)	0.0288 (9)	0.0300 (10)	0.0052 (8)	0.0034 (8)	0.0052 (7)
C12A	0.0371 (11)	0.0329 (10)	0.0350 (11)	0.0113 (9)	0.0121 (9)	0.0056 (8)
N1B	0.0422 (11)	0.0487 (11)	0.0333 (10)	0.0029 (9)	0.0038 (9)	0.0022 (8)
N2B	0.0380 (11)	0.0472 (11)	0.0377 (10)	0.0133 (9)	0.0110 (8)	0.0080 (8)
N3B	0.0359 (10)	0.0377 (9)	0.0383 (10)	0.0068 (8)	0.0124 (8)	0.0066 (7)
N4B	0.0414 (11)	0.0488 (11)	0.0348 (11)	0.0071 (9)	0.0065 (9)	0.0001 (8)
C1B	0.0359 (11)	0.0334 (10)	0.0327 (11)	0.0084 (9)	0.0101 (9)	0.0059 (8)
C2B	0.0315 (10)	0.0276 (9)	0.0290 (10)	0.0089 (8)	0.0058 (8)	0.0072 (7)
C3B	0.0297 (10)	0.0249 (9)	0.0283 (10)	0.0065 (7)	0.0040 (8)	0.0059 (7)
C4B	0.0292 (10)	0.0283 (9)	0.0260 (9)	0.0087 (8)	0.0020 (7)	0.0053 (7)
C5B	0.0295 (10)	0.0290 (9)	0.0271 (10)	0.0082 (8)	0.0045 (8)	0.0054 (7)
C6B	0.0302 (10)	0.0274 (9)	0.0304 (10)	0.0097 (8)	0.0050 (8)	0.0081 (7)
C7B	0.0324 (10)	0.0305 (9)	0.0274 (10)	0.0091 (8)	0.0054 (8)	0.0058 (7)
C8B	0.0366 (11)	0.0334 (10)	0.0275 (10)	0.0107 (8)	0.0051 (8)	0.0044 (8)
C9B	0.0372 (11)	0.0272 (9)	0.0264 (10)	0.0057 (8)	0.0070 (8)	0.0050 (7)
C10B	0.0297 (10)	0.0251 (9)	0.0294 (10)	0.0063 (7)	0.0060 (8)	0.0060 (7)
C11B	0.0292 (10)	0.0274 (9)	0.0298 (10)	0.0062 (8)	0.0041 (8)	0.0065 (7)
C12B	0.0333 (11)	0.0339 (10)	0.0335 (11)	0.0107 (9)	0.0086 (9)	0.0049 (8)
N5	0.0511 (12)	0.0477 (11)	0.0279 (9)	0.0175 (9)	0.0103 (8)	0.0106 (7)
C13	0.0390 (12)	0.0484 (13)	0.0310 (11)	−0.0013 (10)	0.0018 (9)	0.0078 (9)
C14	0.0366 (11)	0.0557 (14)	0.0374 (12)	0.0108 (10)	0.0063 (9)	0.0134 (10)
C15	0.0499 (14)	0.0424 (12)	0.0423 (13)	0.0115 (11)	0.0076 (11)	0.0130 (10)
C16	0.0416 (13)	0.0493 (14)	0.0436 (13)	−0.0012 (11)	0.0024 (10)	0.0151 (10)
C17	0.0333 (11)	0.0679 (16)	0.0356 (12)	0.0131 (11)	0.0085 (9)	0.0210 (11)
C18	0.098 (2)	0.0543 (16)	0.0436 (16)	0.0317 (16)	0.0223 (16)	0.0112 (12)

Geometric parameters (Å, º)

N1A—C1A	1.151 (3)	C3B—C4B	1.444 (3)
N2A—C8A	1.153 (3)	C4B—C5B	1.345 (3)
N3A—C9A	1.151 (3)	C4B—H4B	0.93
N4A—C12A	1.151 (3)	C5B—C6B	1.440 (3)
C1A—C2A	1.430 (3)	C5B—H5B	0.93
C2A—C3A	1.377 (3)	C6B—C7B	1.380 (3)
C2A—C9A	1.437 (3)	C6B—C11B	1.442 (3)
C3A—C4A	1.438 (3)	C7B—C8B	1.428 (3)
C3A—C10A	1.445 (3)	C7B—C12B	1.431 (3)
C4A—C5A	1.349 (3)	C10B—C11B	1.350 (3)
C4A—H4A	0.93	C10B—H10B	0.93
C5A—C6A	1.442 (3)	C11B—H11B	0.93
C5A—H5A	0.93	N5—C13	1.345 (3)
C6A—C7A	1.383 (3)	N5—C17	1.361 (4)
C6A—C11A	1.442 (3)	N5—C18	1.479 (3)
C7A—C8A	1.431 (3)	C13—C14	1.367 (4)
C7A—C12A	1.436 (3)	C13—H13	0.93
C10A—C11A	1.349 (3)	C14—C15	1.378 (4)
C10A—H10A	0.93	C14—H14	0.93
C11A—H11A	0.93	C15—C16	1.374 (4)
N1B—C1B	1.147 (3)	C15—H15	0.93
N2B—C8B	1.158 (3)	C16—C17	1.363 (4)
N3B—C9B	1.147 (3)	C16—H16	0.93
N4B—C12B	1.145 (3)	C17—H17	0.93
C1B—C2B	1.433 (3)	C18—H18A	0.96
C2B—C3B	1.382 (3)	C18—H18B	0.96
C2B—C9B	1.437 (3)	C18—H18C	0.96
C3B—C10B	1.435 (3)
N1A—C1A—C2A	178.9 (3)	C6B—C5B—H5B	119.1
C3A—C2A—C1A	123.1 (2)	C7B—C6B—C5B	121.7 (2)
C3A—C2A—C9A	122.13 (19)	C7B—C6B—C11B	121.46 (19)
C1A—C2A—C9A	114.79 (19)	C5B—C6B—C11B	116.79 (19)
C2A—C3A—C4A	122.16 (19)	C6B—C7B—C8B	123.18 (19)
C2A—C3A—C10A	121.0 (2)	C6B—C7B—C12B	121.4 (2)
C4A—C3A—C10A	116.83 (19)	C8B—C7B—C12B	115.43 (19)
C5A—C4A—C3A	121.71 (19)	N2B—C8B—C7B	179.0 (2)
C5A—C4A—H4A	119.1	N3B—C9B—C2B	178.6 (2)
C3A—C4A—H4A	119.1	C11B—C10B—C3B	121.47 (19)
C4A—C5A—C6A	121.4 (2)	C11B—C10B—H10B	119.3
C4A—C5A—H5A	119.3	C3B—C10B—H10B	119.3
C6A—C5A—H5A	119.3	C10B—C11B—C6B	121.47 (19)
C7A—C6A—C5A	122.2 (2)	C10B—C11B—H11B	119.3
C7A—C6A—C11A	120.80 (19)	C6B—C11B—H11B	119.3
C5A—C6A—C11A	117.03 (19)	N4B—C12B—C7B	179.3 (3)
C6A—C7A—C8A	123.0 (2)	C13—N5—C17	120.7 (2)
C6A—C7A—C12A	121.1 (2)	C13—N5—C18	120.1 (2)
C8A—C7A—C12A	115.93 (19)	C17—N5—C18	119.2 (3)
N2A—C8A—C7A	179.5 (2)	N5—C13—C14	120.4 (2)
N3A—C9A—C2A	179.2 (2)	N5—C13—H13	119.8
C11A—C10A—C3A	121.6 (2)	C14—C13—H13	119.8
C11A—C10A—H10A	119.2	C13—C14—C15	119.5 (2)
C3A—C10A—H10A	119.2	C13—C14—H14	120.2
C10A—C11A—C6A	121.42 (19)	C15—C14—H14	120.2
C10A—C11A—H11A	119.3	C16—C15—C14	119.6 (3)
C6A—C11A—H11A	119.3	C16—C15—H15	120.2
N4A—C12A—C7A	178.4 (2)	C14—C15—H15	120.2
N1B—C1B—C2B	179.0 (3)	C17—C16—C15	119.7 (2)
C3B—C2B—C1B	122.0 (2)	C17—C16—H16	120.1
C3B—C2B—C9B	122.60 (18)	C15—C16—H16	120.1
C1B—C2B—C9B	115.41 (19)	N5—C17—C16	120.1 (2)
C2B—C3B—C10B	122.01 (19)	N5—C17—H17	120
C2B—C3B—C4B	120.76 (18)	C16—C17—H17	120
C10B—C3B—C4B	117.23 (19)	N5—C18—H18A	109.5
C5B—C4B—C3B	121.15 (18)	N5—C18—H18B	109.5
C5B—C4B—H4B	119.4	H18A—C18—H18B	109.5
C3B—C4B—H4B	119.4	N5—C18—H18C	109.5
C4B—C5B—C6B	121.9 (2)	H18A—C18—H18C	109.5
C4B—C5B—H5B	119.1	H18B—C18—H18C	109.5
C1A—C2A—C3A—C4A	−1.9 (3)	C2B—C3B—C4B—C5B	179.53 (18)
C9A—C2A—C3A—C4A	179.94 (18)	C10B—C3B—C4B—C5B	−0.1 (3)
C1A—C2A—C3A—C10A	177.99 (18)	C3B—C4B—C5B—C6B	−0.5 (3)
C9A—C2A—C3A—C10A	−0.2 (3)	C4B—C5B—C6B—C7B	−178.59 (18)
C2A—C3A—C4A—C5A	179.32 (18)	C4B—C5B—C6B—C11B	0.6 (3)
C10A—C3A—C4A—C5A	−0.6 (3)	C5B—C6B—C7B—C8B	−1.7 (3)
C3A—C4A—C5A—C6A	−1.0 (3)	C11B—C6B—C7B—C8B	179.11 (18)
C4A—C5A—C6A—C7A	−177.18 (19)	C5B—C6B—C7B—C12B	177.69 (18)
C4A—C5A—C6A—C11A	1.6 (3)	C11B—C6B—C7B—C12B	−1.5 (3)
C5A—C6A—C7A—C8A	−4.3 (3)	C2B—C3B—C10B—C11B	−179.09 (18)
C11A—C6A—C7A—C8A	176.99 (18)	C4B—C3B—C10B—C11B	0.5 (3)
C5A—C6A—C7A—C12A	174.06 (18)	C3B—C10B—C11B—C6B	−0.4 (3)
C11A—C6A—C7A—C12A	−4.7 (3)	C7B—C6B—C11B—C10B	179.03 (18)
C2A—C3A—C10A—C11A	−178.34 (19)	C5B—C6B—C11B—C10B	−0.2 (3)
C4A—C3A—C10A—C11A	1.5 (3)	C17—N5—C13—C14	0.0 (3)
C3A—C10A—C11A—C6A	−0.9 (3)	C18—N5—C13—C14	179.3 (2)
C7A—C6A—C11A—C10A	178.17 (18)	N5—C13—C14—C15	0.8 (4)
C5A—C6A—C11A—C10A	−0.6 (3)	C13—C14—C15—C16	−0.5 (4)
C1B—C2B—C3B—C10B	176.13 (17)	C14—C15—C16—C17	−0.7 (4)
C9B—C2B—C3B—C10B	−2.3 (3)	C13—N5—C17—C16	−1.2 (3)
C1B—C2B—C3B—C4B	−3.5 (3)	C18—N5—C17—C16	179.6 (2)
C9B—C2B—C3B—C4B	178.07 (17)	C15—C16—C17—N5	1.5 (4)

(tcnq_nmepy_2)

Crystal data

2(C12H4N4)·C5N	Z = 1
Mr = 482.44	F(000) = 245
Triclinic, P1	Dx = 1.230 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.2867 (5) Å	Cell parameters from 1771 reflections
b = 7.7545 (4) Å	θ = 6.3–76.1°
c = 13.1305 (7) Å	µ = 0.64 mm^−1
α = 92.616 (5)°	T = 293 K
β = 103.414 (5)°	Prism, black
γ = 113.979 (6)°	0.20 × 0.17 × 0.07 mm
V = 651.18 (7) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	2624 independent reflections
Radiation source: micro-focus sealed X-ray tube	1975 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.2°, θmin = 3.5°
ω scans	h = −8→9
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→7
Tmin = 0.745, Tmax = 1	l = −16→14
4998 measured reflections

Refinement

Refinement on F^2	90 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.120	H-atom parameters constrained
wR(F^2) = 0.393	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.56	(Δ/σ)max < 0.001
2624 reflections	Δρmax = 0.85 e Å^−3
190 parameters	Δρmin = −0.78 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.2913 (8)	0.1578 (8)	0.1180 (3)	0.1212 (15)
N2	0.2562 (6)	0.6469 (5)	0.2725 (3)	0.1022 (11)
N3	0.2350 (6)	−0.3528 (5)	0.6584 (3)	0.0925 (10)
N4	0.2602 (8)	0.1464 (6)	0.8285 (3)	0.1117 (13)
C1	0.2520 (4)	0.2344 (4)	0.3749 (2)	0.0608 (7)
C2	0.2493 (4)	0.3294 (4)	0.4704 (2)	0.0638 (7)
H2	0.249581	0.449516	0.471271	0.077*
C3	0.2463 (4)	0.2479 (4)	0.5591 (2)	0.0633 (7)
H3	0.244883	0.313102	0.619906	0.076*
C4	0.2452 (4)	0.0626 (4)	0.5612 (2)	0.0590 (7)
C5	0.2442 (4)	−0.0335 (4)	0.4652 (2)	0.0621 (7)
H5	0.241086	−0.154724	0.463765	0.074*
C6	0.2478 (4)	0.0493 (4)	0.3763 (2)	0.0637 (7)
H6	0.247507	−0.016138	0.315038	0.076*
C7	0.2609 (4)	0.3210 (5)	0.2839 (2)	0.0701 (8)
C8	0.2774 (6)	0.2308 (6)	0.1919 (3)	0.0827 (9)
C9	0.2592 (5)	0.5018 (5)	0.2779 (3)	0.0783 (9)
C10	0.2445 (4)	−0.0209 (4)	0.6526 (2)	0.0639 (7)
C11	0.2396 (4)	−0.2053 (4)	0.6554 (2)	0.0691 (8)
C12	0.2539 (5)	0.0735 (5)	0.7501 (2)	0.0754 (9)
N5	0.0802 (9)	0.5508 (11)	−0.0118 (5)	0.1458 (18)	0.5
C13	−0.0224 (13)	0.6312 (9)	0.0310 (5)	0.0817 (16)	0.5
C14	0.149 (2)	0.7467 (19)	0.0000 (8)	0.139 (3)	0.5
C15	0.2573 (15)	0.685 (2)	−0.0427 (8)	0.130 (3)	0.5
C16	0.191 (2)	0.496 (2)	−0.0575 (10)	0.166 (5)	0.5
C17	0.0802 (9)	0.5508 (11)	−0.0118 (5)	0.1458 (18)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.155 (4)	0.160 (4)	0.073 (2)	0.081 (3)	0.049 (2)	0.033 (2)
N2	0.117 (2)	0.0789 (18)	0.102 (2)	0.0395 (17)	0.0153 (19)	0.0336 (16)
N3	0.112 (2)	0.0927 (19)	0.099 (2)	0.0625 (18)	0.0393 (17)	0.0378 (16)
N4	0.147 (3)	0.119 (3)	0.0659 (18)	0.055 (2)	0.0293 (18)	0.0056 (17)
C1	0.0536 (13)	0.0666 (14)	0.0591 (15)	0.0224 (11)	0.0152 (10)	0.0150 (11)
C2	0.0619 (13)	0.0582 (13)	0.0648 (15)	0.0208 (10)	0.0150 (11)	0.0104 (10)
C3	0.0625 (14)	0.0614 (14)	0.0583 (14)	0.0210 (11)	0.0133 (10)	0.0059 (10)
C4	0.0520 (12)	0.0657 (14)	0.0571 (14)	0.0227 (10)	0.0154 (10)	0.0109 (10)
C5	0.0659 (14)	0.0677 (13)	0.0639 (15)	0.0362 (11)	0.0234 (11)	0.0157 (11)
C6	0.0659 (14)	0.0731 (16)	0.0611 (14)	0.0351 (12)	0.0231 (11)	0.0142 (11)
C7	0.0649 (14)	0.0798 (16)	0.0637 (16)	0.0284 (12)	0.0173 (11)	0.0223 (12)
C8	0.090 (2)	0.104 (2)	0.0655 (18)	0.0454 (18)	0.0305 (15)	0.0292 (16)
C9	0.0750 (17)	0.0787 (18)	0.0693 (18)	0.0236 (14)	0.0131 (13)	0.0250 (14)
C10	0.0617 (13)	0.0731 (15)	0.0570 (14)	0.0285 (11)	0.0166 (10)	0.0154 (11)
C11	0.0697 (15)	0.0814 (17)	0.0641 (16)	0.0378 (13)	0.0211 (12)	0.0215 (12)
C12	0.0862 (19)	0.0806 (17)	0.0567 (16)	0.0340 (15)	0.0178 (13)	0.0133 (13)
N5	0.124 (4)	0.187 (5)	0.107 (3)	0.046 (3)	0.032 (3)	0.041 (3)
C13	0.114 (4)	0.064 (3)	0.055 (3)	0.049 (3)	−0.016 (3)	−0.008 (2)
C14	0.168 (8)	0.135 (6)	0.082 (6)	0.059 (6)	−0.008 (5)	−0.006 (5)
C15	0.095 (5)	0.170 (8)	0.087 (6)	0.024 (5)	0.012 (4)	0.042 (5)
C16	0.203 (11)	0.213 (10)	0.099 (7)	0.153 (9)	−0.035 (7)	−0.036 (8)
C17	0.124 (4)	0.187 (5)	0.107 (3)	0.046 (3)	0.032 (3)	0.041 (3)

Geometric parameters (Å, º)

N1—C8	1.146 (6)	C5—H5	0.93
N2—C9	1.139 (5)	C6—H6	0.93
N3—C11	1.133 (4)	C7—C9	1.413 (5)
N4—C12	1.134 (5)	C7—C8	1.422 (5)
C1—C7	1.399 (4)	C10—C11	1.418 (4)
C1—C6	1.424 (4)	C10—C12	1.419 (4)
C1—C2	1.433 (4)	C13—C17	1.343 (10)
C2—C3	1.350 (4)	C13—C16^i	1.362 (15)
C2—H2	0.93	C13—C14	1.373 (14)
C3—C4	1.436 (4)	C14—C15	1.285 (14)
C3—H3	0.93	C14—C17	1.380 (15)
C4—C10	1.390 (4)	C15—C16	1.334 (14)
C4—C5	1.431 (4)	C15—C17	1.452 (11)
C5—C6	1.359 (4)	C16—C17	1.296 (14)
C7—C1—C6	121.1 (3)	N5^i—C13—C16^i	58.4 (6)
C7—C1—C2	121.3 (3)	C17—C13—C16^i	114.1 (7)
C6—C1—C2	117.7 (2)	N5^i—C13—C14	116.8 (9)
C3—C2—C1	121.3 (2)	C17—C13—C14	61.1 (7)
C3—C2—H2	119.4	C16^i—C13—C14	175.2 (9)
C1—C2—H2	119.4	C15—C14—C13	124.3 (12)
C2—C3—C4	121.2 (3)	C15—C14—C17	65.9 (8)
C2—C3—H3	119.4	C13—C14—C17	58.4 (7)
C4—C3—H3	119.4	C14—C15—C16	115.4 (11)
C10—C4—C5	121.2 (3)	C14—C15—C17	60.2 (8)
C10—C4—C3	121.4 (3)	C16—C15—C17	55.2 (8)
C5—C4—C3	117.4 (2)	C17—C16—C15	67.0 (8)
C6—C5—C4	121.1 (2)	C17—C16—C13^i	58.1 (8)
C6—C5—H5	119.4	C15—C16—C13^i	125.1 (11)
C4—C5—H5	119.4	N5^i—C17—C13^i	64.2 (8)
C5—C6—C1	121.3 (3)	N5^i—C17—C16	127.6 (13)
C5—C6—H6	119.4	C13^i—C17—C16	63.5 (8)
C1—C6—H6	119.4	N5^i—C17—C13	60.0 (7)
C1—C7—C9	123.1 (3)	C13^i—C17—C13	124.2 (5)
C1—C7—C8	120.8 (3)	C16—C17—C13	171.9 (9)
C9—C7—C8	116.2 (3)	N5^i—C17—C14	120.4 (12)
N1—C8—C7	179.7 (4)	C13^i—C17—C14	174.4 (8)
N2—C9—C7	179.5 (4)	C16—C17—C14	111.6 (9)
C4—C10—C11	122.1 (3)	C13—C17—C14	60.5 (7)
C4—C10—C12	122.6 (3)	N5^i—C17—C15	173.3 (12)
C11—C10—C12	115.2 (3)	C13^i—C17—C15	121.3 (9)
N3—C11—C10	179.4 (3)	C16—C17—C15	57.8 (7)
N4—C12—C10	179.0 (4)	C13—C17—C15	114.4 (9)
N5^i—C13—C17	55.8 (5)	C14—C17—C15	53.9 (6)
C7—C1—C2—C3	−178.2 (2)	C13^i—C16—C17—N5^i	−3.4 (10)
C6—C1—C2—C3	1.1 (4)	C15—C16—C17—C13^i	178.4 (8)
C1—C2—C3—C4	−0.1 (4)	C15—C16—C17—C14	1.6 (10)
C2—C3—C4—C10	179.3 (2)	C13^i—C16—C17—C14	−176.9 (8)
C2—C3—C4—C5	−0.9 (4)	C13^i—C16—C17—C15	−178.4 (8)
C10—C4—C5—C6	−179.1 (2)	C16^i—C13—C17—N5^i	2.8 (9)
C3—C4—C5—C6	1.1 (4)	C14—C13—C17—N5^i	−176.4 (8)
C4—C5—C6—C1	−0.2 (4)	N5^i—C13—C17—C13^i	0.0010 (10)
C7—C1—C6—C5	178.4 (2)	C16^i—C13—C17—C13^i	2.8 (9)
C2—C1—C6—C5	−0.9 (4)	C14—C13—C17—C13^i	−176.4 (8)
C6—C1—C7—C9	178.1 (2)	N5^i—C13—C17—C14	176.4 (8)
C2—C1—C7—C9	−2.7 (5)	C16^i—C13—C17—C14	179.1 (9)
C6—C1—C7—C8	−3.4 (4)	N5^i—C13—C17—C15	175.8 (9)
C2—C1—C7—C8	175.9 (3)	C16^i—C13—C17—C15	178.5 (8)
C5—C4—C10—C11	−0.9 (4)	C14—C13—C17—C15	−0.6 (8)
C3—C4—C10—C11	178.8 (2)	C15—C14—C17—N5^i	−175.7 (10)
C5—C4—C10—C12	177.4 (2)	C13—C14—C17—N5^i	3.6 (8)
C3—C4—C10—C12	−2.9 (5)	C15—C14—C17—C16	−1.6 (10)
N5^i—C13—C14—C15	−2.6 (14)	C13—C14—C17—C16	177.7 (8)
C17—C13—C14—C15	0.8 (10)	C15—C14—C17—C13	−179.3 (9)
N5^i—C13—C14—C17	−3.4 (8)	C13—C14—C17—C15	179.3 (9)
C13—C14—C15—C16	0.9 (17)	C14—C15—C17—C13^i	176.6 (9)
C17—C14—C15—C16	1.6 (10)	C16—C15—C17—C13^i	−1.6 (9)
C13—C14—C15—C17	−0.7 (9)	C14—C15—C17—C16	178.2 (11)
C14—C15—C16—C17	−1.7 (11)	C14—C15—C17—C13	0.7 (8)
C14—C15—C16—C13^i	−0.1 (18)	C16—C15—C17—C13	−177.5 (9)
C17—C15—C16—C13^i	1.6 (9)	C16—C15—C17—C14	−178.2 (11)
C15—C16—C17—N5^i	175.1 (11)

Symmetry code: (i) −x, −y+1, −z.

(tcnq_phen_100k)

Crystal data

C12H8N2·2(C12H4N4)	Z = 1
Mr = 588.59	F(000) = 302
Triclinic, P1	Dx = 1.345 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.1249 (13) Å	Cell parameters from 2008 reflections
b = 7.6572 (13) Å	θ = 6.2–75.6°
c = 14.4249 (10) Å	µ = 0.69 mm^−1
α = 89.017 (10)°	T = 100 K
β = 83.589 (12)°	Prism, black
γ = 68.340 (17)°	0.21 × 0.09 × 0.08 mm
V = 726.6 (2) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	2996 independent reflections
Radiation source: micro-focus sealed X-ray tube	2391 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.057
Detector resolution: 10.4323 pixels mm^-1	θmax = 79.1°, θmin = 3.1°
ω scans	h = −8→6
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.633, Tmax = 1	l = −18→18
5931 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.128	H-atom parameters constrained
wR(F^2) = 0.382	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.48	(Δ/σ)max < 0.001
2996 reflections	Δρmax = 1.25 e Å^−3
217 parameters	Δρmin = −0.4 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.0486 (5)	1.2187 (5)	0.6994 (2)	0.0497 (8)
N2	0.4997 (5)	0.5429 (5)	0.2099 (2)	0.0506 (9)
N3	−0.0714 (5)	0.7492 (5)	0.8379 (2)	0.0507 (9)
N4	0.3905 (5)	0.0828 (5)	0.3580 (2)	0.0473 (8)
C1	0.0614 (5)	1.0673 (5)	0.6956 (2)	0.0410 (8)
C2	0.0732 (5)	0.8770 (5)	0.6907 (2)	0.0417 (8)
C3	0.1539 (5)	0.7630 (5)	0.6106 (2)	0.0381 (8)
C4	0.2285 (5)	0.8330 (5)	0.5266 (2)	0.0393 (8)
H4	0.228534	0.954426	0.526488	0.047*
C5	0.2983 (5)	0.7241 (5)	0.4483 (2)	0.0406 (8)
H5	0.343752	0.772694	0.394693	0.049*
C6	0.3039 (4)	0.5352 (5)	0.4460 (2)	0.0378 (8)
C7	0.3780 (5)	0.4227 (5)	0.3647 (2)	0.0395 (8)
C8	0.4430 (5)	0.4919 (5)	0.2793 (2)	0.0423 (8)
C9	−0.0053 (5)	0.8069 (5)	0.7727 (2)	0.0426 (8)
C10	0.1598 (5)	0.5746 (5)	0.6089 (2)	0.0397 (8)
H10	0.112896	0.526495	0.662313	0.048*
C11	0.2333 (5)	0.4645 (5)	0.5300 (2)	0.0373 (8)
H11	0.237742	0.34157	0.530659	0.045*
C12	0.3830 (5)	0.2351 (5)	0.3608 (2)	0.0402 (8)
N5	0.0661 (5)	1.1910 (5)	0.9383 (2)	0.0441 (8)	0.5
C16	0.2728 (5)	0.8660 (5)	0.9585 (2)	0.0492 (9)	0.5
N6	0.2728 (5)	0.8660 (5)	0.9585 (2)	0.0492 (9)	0.5
C18	0.0661 (5)	1.1910 (5)	0.9383 (2)	0.0441 (8)	0.5
C13	0.2303 (6)	1.2150 (6)	0.8876 (2)	0.0488 (9)
H13	0.21615	1.332124	0.863538	0.059*
C14	0.4143 (6)	1.0688 (7)	0.8721 (3)	0.0522 (10)
H14	0.524664	1.0853	0.837614	0.063*
C15	0.4320 (6)	0.8944 (7)	0.9094 (3)	0.0540 (10)
H15	0.55678	0.794969	0.900199	0.065*
C17	0.0868 (6)	1.0152 (6)	0.9733 (2)	0.0463 (9)
C19	0.2825 (11)	0.6963 (12)	0.9966 (6)	0.0505 (17)	0.5
H19	0.40864	0.598796	0.986881	0.061*	0.5
C20	−0.1224 (7)	1.3502 (8)	0.9504 (4)	0.0263 (11)	0.5
H20	−0.139736	1.468509	0.927079	0.032*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0612 (19)	0.0489 (18)	0.0399 (17)	−0.0239 (14)	0.0046 (14)	−0.0088 (13)
N2	0.0584 (18)	0.066 (2)	0.0289 (14)	−0.0293 (15)	0.0106 (13)	−0.0078 (13)
N3	0.0552 (17)	0.062 (2)	0.0333 (15)	−0.0253 (14)	0.0151 (13)	−0.0131 (13)
N4	0.0540 (17)	0.0567 (19)	0.0352 (15)	−0.0285 (14)	0.0092 (13)	−0.0123 (13)
C1	0.0384 (16)	0.058 (2)	0.0276 (15)	−0.0199 (13)	0.0042 (12)	−0.0092 (13)
C2	0.0345 (14)	0.054 (2)	0.0341 (17)	−0.0152 (12)	0.0053 (12)	−0.0118 (14)
C3	0.0398 (16)	0.0470 (18)	0.0274 (16)	−0.0177 (12)	0.0036 (12)	−0.0079 (13)
C4	0.0392 (15)	0.0501 (18)	0.0284 (15)	−0.0188 (13)	0.0069 (12)	−0.0099 (13)
C5	0.0386 (16)	0.055 (2)	0.0291 (16)	−0.0202 (13)	0.0044 (12)	−0.0082 (13)
C6	0.0352 (15)	0.0461 (18)	0.0306 (16)	−0.0149 (12)	0.0038 (12)	−0.0067 (12)
C7	0.0420 (16)	0.0436 (17)	0.0321 (16)	−0.0181 (12)	0.0088 (12)	−0.0090 (12)
C8	0.0459 (17)	0.0541 (19)	0.0280 (16)	−0.0222 (14)	0.0059 (13)	−0.0111 (13)
C9	0.0416 (16)	0.0515 (19)	0.0337 (17)	−0.0180 (13)	0.0056 (13)	−0.0170 (14)
C10	0.0395 (15)	0.055 (2)	0.0255 (15)	−0.0211 (13)	0.0050 (11)	−0.0038 (13)
C11	0.0384 (15)	0.0483 (17)	0.0252 (15)	−0.0177 (12)	0.0040 (11)	−0.0061 (12)
C12	0.0398 (16)	0.056 (2)	0.0244 (15)	−0.0198 (13)	0.0073 (12)	−0.0106 (13)
N5	0.0466 (17)	0.0571 (19)	0.0294 (15)	−0.0222 (14)	0.0047 (12)	−0.0095 (12)
C16	0.0514 (18)	0.060 (2)	0.0363 (16)	−0.0244 (15)	0.0093 (14)	−0.0163 (14)
N6	0.0514 (18)	0.060 (2)	0.0363 (16)	−0.0244 (15)	0.0093 (14)	−0.0163 (14)
C18	0.0466 (17)	0.0571 (19)	0.0294 (15)	−0.0222 (14)	0.0047 (12)	−0.0095 (12)
C13	0.060 (2)	0.065 (2)	0.0275 (15)	−0.0322 (17)	0.0038 (14)	−0.0042 (14)
C14	0.052 (2)	0.076 (3)	0.0344 (18)	−0.0341 (18)	0.0118 (15)	−0.0161 (17)
C15	0.0466 (19)	0.070 (3)	0.042 (2)	−0.0226 (17)	0.0141 (15)	−0.0175 (17)
C17	0.056 (2)	0.060 (2)	0.0279 (16)	−0.0303 (17)	0.0068 (15)	−0.0123 (14)
C19	0.045 (3)	0.059 (4)	0.044 (4)	−0.016 (3)	0.003 (3)	−0.014 (3)
C20	0.0151 (19)	0.040 (3)	0.019 (2)	−0.0057 (18)	0.0050 (16)	−0.0077 (18)

Geometric parameters (Å, º)

N1—C1	1.131 (5)	N5—C17	1.392 (6)
N2—C8	1.154 (5)	N5—C20	1.438 (6)
N3—C9	1.159 (5)	C16—C15	1.354 (5)
N4—C12	1.149 (5)	C16—C19	1.383 (10)
C1—C2	1.431 (5)	C16—C17	1.391 (5)
C2—C3	1.394 (5)	N6—C15	1.354 (5)
C2—C9	1.432 (5)	N6—C19	1.383 (10)
C3—C10	1.429 (5)	N6—C17	1.391 (5)
C3—C4	1.443 (5)	C18—C13	1.379 (5)
C4—C5	1.349 (5)	C18—C17	1.392 (6)
C4—H4	0.93	C18—C20	1.438 (6)
C5—C6	1.433 (5)	C13—C14	1.372 (6)
C5—H5	0.93	C13—H13	0.93
C6—C7	1.398 (5)	C14—C15	1.398 (7)
C6—C11	1.435 (5)	C14—H14	0.93
C7—C12	1.426 (5)	C15—H15	0.93
C7—C8	1.430 (5)	C17—C17^i	1.473 (7)
C10—C11	1.361 (5)	C19—C20^i	1.452 (10)
C10—H10	0.93	C19—H19	0.93
C11—H11	0.93	C20—H20	0.93
N5—C13	1.379 (5)
N1—C1—C2	178.8 (4)	C15—C16—C19	124.1 (5)
C3—C2—C1	122.8 (3)	C15—C16—C17	119.1 (4)
C3—C2—C9	120.5 (3)	C19—C16—C17	116.8 (4)
C1—C2—C9	116.8 (3)	C15—N6—C19	124.1 (5)
C2—C3—C10	120.6 (3)	C15—N6—C17	119.1 (4)
C2—C3—C4	121.2 (3)	C19—N6—C17	116.8 (4)
C10—C3—C4	118.2 (3)	C13—C18—C17	119.5 (3)
C5—C4—C3	120.7 (3)	C13—C18—C20	117.7 (4)
C5—C4—H4	119.6	C17—C18—C20	122.8 (4)
C3—C4—H4	119.6	C14—C13—N5	121.0 (4)
C4—C5—C6	121.4 (3)	C14—C13—C18	121.0 (4)
C4—C5—H5	119.3	C14—C13—H13	119.5
C6—C5—H5	119.3	N5—C13—H13	119.5
C7—C6—C5	121.1 (3)	C13—C14—C15	118.4 (4)
C7—C6—C11	121.1 (3)	C13—C14—H14	120.8
C5—C6—C11	117.8 (3)	C15—C14—H14	120.8
C6—C7—C12	121.9 (3)	N6—C15—C14	121.9 (4)
C6—C7—C8	122.1 (3)	C16—C15—C14	121.9 (4)
C12—C7—C8	115.9 (3)	C16—C15—H15	119
N2—C8—C7	178.1 (4)	C14—C15—H15	119
N3—C9—C2	178.5 (4)	N6—C17—C18	120.1 (3)
C11—C10—C3	120.8 (3)	C16—C17—N5	120.1 (3)
C11—C10—H10	119.6	C16—C17—C17^i	119.2 (5)
C3—C10—H10	119.6	N5—C17—C17^i	120.6 (5)
C10—C11—C6	121.0 (3)	N6—C19—C20^i	128.8 (6)
C10—C11—H11	119.5	C16—C19—C20^i	128.8 (6)
C6—C11—H11	119.5	C16—C19—H19	115.6
N4—C12—C7	178.8 (4)	C20^i—C19—H19	115.6
C13—N5—C17	119.5 (3)	N5—C20—C19^i	111.7 (5)
C13—N5—C20	117.7 (4)	N5—C20—H20	124.1
C17—N5—C20	122.8 (4)	C19^i—C20—H20	124.1
C1—C2—C3—C10	−179.2 (3)	C17—C16—C15—C14	−0.7 (6)
C9—C2—C3—C10	0.0 (5)	C13—C14—C15—N6	1.1 (6)
C1—C2—C3—C4	−0.9 (5)	C13—C14—C15—C16	1.1 (6)
C9—C2—C3—C4	178.3 (3)	C15—N6—C17—C18	−0.4 (5)
C2—C3—C4—C5	−177.1 (3)	C19—N6—C17—C18	179.1 (5)
C10—C3—C4—C5	1.2 (5)	C15—N6—C17—C17^i	180.0 (4)
C3—C4—C5—C6	−1.0 (5)	C19—N6—C17—C17^i	−0.5 (7)
C4—C5—C6—C7	−179.4 (3)	C15—C16—C17—N5	−0.4 (5)
C4—C5—C6—C11	−0.2 (5)	C19—C16—C17—N5	179.1 (5)
C5—C6—C7—C12	−179.4 (3)	C15—C16—C17—C17^i	180.0 (4)
C11—C6—C7—C12	1.4 (5)	C19—C16—C17—C17^i	−0.5 (7)
C5—C6—C7—C8	−2.9 (5)	C13—C18—C17—N6	1.1 (5)
C11—C6—C7—C8	177.9 (3)	C20—C18—C17—N6	179.4 (3)
C2—C3—C10—C11	178.1 (3)	C13—C18—C17—C17^i	−179.3 (3)
C4—C3—C10—C11	−0.2 (5)	C20—C18—C17—C17^i	−1.0 (6)
C3—C10—C11—C6	−1.0 (5)	C13—N5—C17—C16	1.1 (5)
C7—C6—C11—C10	−179.6 (3)	C20—N5—C17—C16	179.4 (3)
C5—C6—C11—C10	1.2 (5)	C13—N5—C17—C17^i	−179.3 (3)
C17—N5—C13—C14	−0.8 (5)	C20—N5—C17—C17^i	−1.0 (6)
C20—N5—C13—C14	−179.1 (4)	C15—N6—C19—C20^i	−179.6 (6)
C17—C18—C13—C14	−0.8 (5)	C17—N6—C19—C20^i	1.0 (10)
C20—C18—C13—C14	−179.1 (4)	C15—C16—C19—C20^i	−179.6 (6)
N5—C13—C14—C15	−0.3 (6)	C17—C16—C19—C20^i	1.0 (10)
C18—C13—C14—C15	−0.3 (6)	C13—C18—C20—C19^i	178.9 (4)
C19—N6—C15—C14	179.8 (5)	C17—C18—C20—C19^i	0.6 (7)
C17—N6—C15—C14	−0.7 (6)	C13—N5—C20—C19^i	178.9 (4)
C19—C16—C15—C14	179.8 (5)	C17—N5—C20—C19^i	0.6 (7)

Symmetry code: (i) −x, −y+2, −z+2.

(tcnq_phen_1)

Crystal data

C12H8N2·2(C12H4N4)	Z = 1
Mr = 588.59	F(000) = 302
Triclinic, P1	Dx = 1.306 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.2179 (10) Å	Cell parameters from 2275 reflections
b = 7.6887 (14) Å	θ = 6.2–74.7°
c = 14.5445 (13) Å	µ = 0.67 mm^−1
α = 89.176 (10)°	T = 293 K
β = 82.570 (9)°	Prism, black
γ = 69.284 (14)°	0.32 × 0.11 × 0.09 mm
V = 748.2 (2) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	3038 independent reflections
Radiation source: micro-focus sealed X-ray tube	2470 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.037
Detector resolution: 10.4323 pixels mm^-1	θmax = 77.1°, θmin = 3.1°
ω scans	h = −9→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.676, Tmax = 1	l = −17→18
6183 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.108	H-atom parameters constrained
wR(F^2) = 0.348	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.4	(Δ/σ)max = 0.001
3038 reflections	Δρmax = 0.92 e Å^−3
217 parameters	Δρmin = −0.24 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.0448 (6)	1.2117 (4)	0.6984 (2)	0.0861 (9)
N2	0.5031 (6)	0.5333 (5)	0.21299 (19)	0.0890 (9)
N3	−0.0731 (5)	0.7475 (5)	0.8374 (2)	0.0873 (9)
N4	0.3940 (5)	0.0799 (4)	0.3600 (2)	0.0845 (9)
C1	0.0568 (4)	1.0608 (4)	0.69478 (18)	0.0642 (7)
C2	0.0700 (4)	0.8717 (4)	0.69094 (18)	0.0599 (7)
C3	0.1522 (4)	0.7577 (4)	0.61071 (17)	0.0563 (6)
C4	0.2259 (4)	0.8278 (4)	0.52693 (18)	0.0575 (6)
H4	0.22311	0.949685	0.52641	0.069*
C5	0.2991 (4)	0.7184 (4)	0.44893 (17)	0.0578 (6)
H5	0.34653	0.76632	0.395716	0.069*
C6	0.3050 (4)	0.5298 (4)	0.44657 (16)	0.0552 (6)
C7	0.3791 (4)	0.4183 (4)	0.36604 (17)	0.0585 (6)
C8	0.4458 (4)	0.4855 (4)	0.28093 (18)	0.0654 (7)
C9	−0.0081 (4)	0.8035 (4)	0.77229 (19)	0.0659 (7)
C10	0.1592 (4)	0.5699 (4)	0.60904 (18)	0.0588 (7)
H10	0.112176	0.522043	0.662412	0.071*
C11	0.2335 (4)	0.4595 (4)	0.53063 (17)	0.0582 (6)
H11	0.23802	0.337095	0.531467	0.07*
C12	0.3867 (4)	0.2308 (4)	0.36301 (18)	0.0623 (7)
N5	0.0618 (5)	1.1912 (4)	0.93702 (17)	0.0721 (8)	0.5
C16	0.2710 (5)	0.8730 (5)	0.9597 (2)	0.0812 (9)	0.5
N6	0.2710 (5)	0.8730 (5)	0.9597 (2)	0.0812 (9)	0.5
C18	0.0618 (5)	1.1912 (4)	0.93702 (17)	0.0721 (8)	0.5
C13	0.2226 (6)	1.2184 (6)	0.8868 (2)	0.0847 (10)
H13	0.208335	1.334303	0.86249	0.102*
C14	0.4035 (7)	1.0775 (7)	0.8720 (3)	0.0957 (12)
H14	0.511757	1.096447	0.837128	0.115*
C15	0.4246 (6)	0.9053 (7)	0.9095 (3)	0.0915 (11)
H15	0.548552	0.809886	0.89963	0.11*
C17	0.0846 (5)	1.0164 (5)	0.97332 (18)	0.0717 (8)
C19	0.2743 (12)	0.7075 (10)	1.0002 (6)	0.0859 (18)	0.5
H19	0.399337	0.613306	0.992173	0.103*	0.5
C20	−0.1261 (8)	1.3433 (8)	0.9497 (4)	0.0623 (11)	0.5
H20	−0.145822	1.461315	0.927058	0.075*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.114 (2)	0.0633 (15)	0.0807 (18)	−0.0300 (14)	−0.0136 (16)	−0.0009 (12)
N2	0.114 (2)	0.100 (2)	0.0551 (14)	−0.0462 (18)	0.0037 (14)	0.0084 (13)
N3	0.107 (2)	0.096 (2)	0.0571 (14)	−0.0412 (17)	0.0099 (13)	−0.0011 (13)
N4	0.108 (2)	0.0741 (17)	0.0780 (17)	−0.0448 (15)	0.0010 (15)	−0.0051 (13)
C1	0.0733 (15)	0.0641 (15)	0.0528 (13)	−0.0212 (11)	−0.0091 (11)	0.0002 (10)
C2	0.0612 (13)	0.0643 (14)	0.0520 (13)	−0.0199 (10)	−0.0063 (10)	0.0006 (10)
C3	0.0576 (12)	0.0598 (14)	0.0503 (12)	−0.0198 (10)	−0.0061 (9)	0.0010 (10)
C4	0.0645 (13)	0.0539 (12)	0.0530 (13)	−0.0208 (10)	−0.0052 (9)	0.0029 (9)
C5	0.0663 (14)	0.0599 (14)	0.0473 (12)	−0.0229 (10)	−0.0064 (9)	0.0053 (9)
C6	0.0592 (13)	0.0597 (13)	0.0480 (12)	−0.0230 (10)	−0.0068 (9)	0.0047 (9)
C7	0.0648 (13)	0.0628 (14)	0.0481 (12)	−0.0241 (10)	−0.0039 (9)	0.0005 (10)
C8	0.0756 (16)	0.0718 (16)	0.0496 (13)	−0.0291 (12)	−0.0027 (11)	0.0008 (11)
C9	0.0744 (15)	0.0686 (16)	0.0530 (14)	−0.0258 (12)	−0.0003 (11)	−0.0048 (11)
C10	0.0631 (13)	0.0645 (14)	0.0495 (12)	−0.0261 (11)	−0.0001 (9)	0.0042 (10)
C11	0.0668 (14)	0.0583 (13)	0.0513 (13)	−0.0266 (10)	−0.0010 (10)	0.0007 (10)
C12	0.0725 (15)	0.0675 (16)	0.0494 (12)	−0.0298 (12)	−0.0021 (10)	−0.0011 (10)
N5	0.0917 (18)	0.0787 (17)	0.0515 (13)	−0.0375 (14)	−0.0086 (11)	0.0050 (11)
C16	0.089 (2)	0.088 (2)	0.0658 (16)	−0.0344 (16)	0.0029 (14)	−0.0102 (14)
N6	0.089 (2)	0.088 (2)	0.0658 (16)	−0.0344 (16)	0.0029 (14)	−0.0102 (14)
C18	0.0917 (18)	0.0787 (17)	0.0515 (13)	−0.0375 (14)	−0.0086 (11)	0.0050 (11)
C13	0.107 (2)	0.102 (2)	0.0598 (16)	−0.057 (2)	−0.0077 (15)	0.0098 (15)
C14	0.102 (3)	0.128 (3)	0.0688 (19)	−0.062 (3)	0.0091 (17)	−0.0061 (19)
C15	0.082 (2)	0.113 (3)	0.076 (2)	−0.0368 (19)	0.0109 (16)	−0.0130 (19)
C17	0.095 (2)	0.0823 (19)	0.0465 (12)	−0.0427 (16)	−0.0063 (12)	−0.0038 (12)
C19	0.085 (4)	0.074 (4)	0.085 (4)	−0.012 (3)	−0.005 (3)	−0.002 (3)
C20	0.065 (3)	0.064 (3)	0.053 (2)	−0.019 (2)	−0.0092 (19)	0.014 (2)

Geometric parameters (Å, º)

N1—C1	1.134 (4)	N5—C17	1.399 (4)
N2—C8	1.129 (4)	N5—C20	1.436 (6)
N3—C9	1.148 (4)	C16—C15	1.343 (5)
N4—C12	1.144 (4)	C16—C19	1.388 (9)
C1—C2	1.424 (4)	C16—C17	1.398 (5)
C2—C3	1.402 (4)	N6—C15	1.343 (5)
C2—C9	1.418 (4)	N6—C19	1.388 (9)
C3—C10	1.428 (4)	N6—C17	1.398 (5)
C3—C4	1.440 (3)	C18—C13	1.368 (4)
C4—C5	1.354 (4)	C18—C17	1.399 (4)
C4—H4	0.93	C18—C20	1.436 (6)
C5—C6	1.436 (4)	C13—C14	1.363 (7)
C5—H5	0.93	C13—H13	0.93
C6—C7	1.391 (4)	C14—C15	1.390 (7)
C6—C11	1.438 (3)	C14—H14	0.93
C7—C12	1.424 (4)	C15—H15	0.93
C7—C8	1.426 (4)	C17—C17^i	1.458 (6)
C10—C11	1.362 (4)	C19—C20^i	1.383 (10)
C10—H10	0.93	C19—H19	0.93
C11—H11	0.93	C20—H20	0.93
N5—C13	1.368 (4)
N1—C1—C2	179.3 (3)	C15—C16—C17	118.7 (3)
C3—C2—C9	120.9 (3)	C19—C16—C17	114.4 (4)
C3—C2—C1	122.3 (2)	C15—N6—C19	126.9 (4)
C9—C2—C1	116.8 (2)	C15—N6—C17	118.7 (3)
C2—C3—C10	120.6 (2)	C19—N6—C17	114.4 (4)
C2—C3—C4	121.2 (2)	C13—C18—C17	119.3 (3)
C10—C3—C4	118.1 (2)	C13—C18—C20	118.6 (3)
C5—C4—C3	120.8 (2)	C17—C18—C20	122.1 (3)
C5—C4—H4	119.6	C14—C13—N5	120.7 (4)
C3—C4—H4	119.6	C14—C13—C18	120.7 (4)
C4—C5—C6	121.4 (2)	C14—C13—H13	119.6
C4—C5—H5	119.3	N5—C13—H13	119.6
C6—C5—H5	119.3	C13—C14—C15	119.4 (3)
C7—C6—C5	121.2 (2)	C13—C14—H14	120.3
C7—C6—C11	121.1 (2)	C15—C14—H14	120.3
C5—C6—C11	117.7 (2)	N6—C15—C14	121.8 (4)
C6—C7—C12	121.7 (2)	C16—C15—C14	121.8 (4)
C6—C7—C8	122.4 (2)	C16—C15—H15	119.1
C12—C7—C8	115.8 (2)	C14—C15—H15	119.1
N2—C8—C7	177.8 (3)	N6—C17—C18	120.0 (3)
N3—C9—C2	179.0 (3)	C16—C17—N5	120.0 (3)
C11—C10—C3	121.1 (2)	C16—C17—C17^i	119.6 (4)
C11—C10—H10	119.4	N5—C17—C17^i	120.4 (4)
C3—C10—H10	119.4	C20^i—C19—C16	131.9 (6)
C10—C11—C6	120.9 (2)	C20^i—C19—N6	131.9 (6)
C10—C11—H11	119.6	C20^i—C19—H19	114.1
C6—C11—H11	119.6	C16—C19—H19	114.1
N4—C12—C7	179.4 (3)	C19^i—C20—N5	111.6 (5)
C13—N5—C17	119.3 (3)	C19^i—C20—C18	111.6 (5)
C13—N5—C20	118.6 (3)	C19^i—C20—H20	124.2
C17—N5—C20	122.1 (3)	N5—C20—H20	124.2
C15—C16—C19	126.9 (4)
C9—C2—C3—C10	0.0 (4)	C17—C16—C15—C14	0.8 (6)
C1—C2—C3—C10	−178.8 (2)	C13—C14—C15—N6	0.5 (6)
C9—C2—C3—C4	178.0 (2)	C13—C14—C15—C16	0.5 (6)
C1—C2—C3—C4	−0.8 (4)	C15—N6—C17—C18	−1.6 (5)
C2—C3—C4—C5	−177.8 (2)	C19—N6—C17—C18	179.2 (4)
C10—C3—C4—C5	0.1 (4)	C15—N6—C17—C17^i	179.3 (3)
C3—C4—C5—C6	0.4 (4)	C19—N6—C17—C17^i	0.1 (6)
C4—C5—C6—C7	179.5 (2)	C15—C16—C17—N5	−1.6 (5)
C4—C5—C6—C11	−1.0 (4)	C19—C16—C17—N5	179.2 (4)
C5—C6—C7—C12	179.7 (2)	C15—C16—C17—C17^i	179.3 (3)
C11—C6—C7—C12	0.3 (4)	C19—C16—C17—C17^i	0.1 (6)
C5—C6—C7—C8	−2.5 (4)	C13—C18—C17—N6	1.3 (4)
C11—C6—C7—C8	178.2 (2)	C20—C18—C17—N6	−179.5 (3)
C2—C3—C10—C11	178.1 (2)	C13—C18—C17—C17^i	−179.7 (3)
C4—C3—C10—C11	0.1 (4)	C20—C18—C17—C17^i	−0.5 (5)
C3—C10—C11—C6	−0.8 (4)	C13—N5—C17—C16	1.3 (4)
C7—C6—C11—C10	−179.3 (2)	C20—N5—C17—C16	−179.5 (3)
C5—C6—C11—C10	1.3 (4)	C13—N5—C17—C17^i	−179.7 (3)
C17—N5—C13—C14	0.0 (5)	C20—N5—C17—C17^i	−0.5 (5)
C20—N5—C13—C14	−179.2 (4)	C15—C16—C19—C20^i	−177.7 (7)
C17—C18—C13—C14	0.0 (5)	C17—C16—C19—C20^i	1.4 (11)
C20—C18—C13—C14	−179.2 (4)	C15—N6—C19—C20^i	−177.7 (7)
N5—C13—C14—C15	−0.8 (6)	C17—N6—C19—C20^i	1.4 (11)
C18—C13—C14—C15	−0.8 (6)	C13—N5—C20—C19^i	178.5 (5)
C19—N6—C15—C14	179.9 (5)	C17—N5—C20—C19^i	−0.7 (7)
C17—N6—C15—C14	0.8 (6)	C13—C18—C20—C19^i	178.5 (5)
C19—C16—C15—C14	179.9 (5)	C17—C18—C20—C19^i	−0.7 (7)

Symmetry code: (i) −x, −y+2, −z+2.

(tcnq_4pic_100k)

Crystal data

C12H4N4·0.5(C6H10N2)	Z = 2
Mr = 259.27	F(000) = 268
Triclinic, P1	Dx = 1.317 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.0634 (4) Å	Cell parameters from 3009 reflections
b = 7.8154 (5) Å	θ = 3.4–75.9°
c = 13.4680 (8) Å	µ = 0.68 mm^−1
α = 73.628 (5)°	T = 100 K
β = 89.550 (5)°	Plate, black
γ = 67.258 (6)°	0.38 × 0.32 × 0.05 mm
V = 653.56 (7) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	2657 independent reflections
Radiation source: micro-focus sealed X-ray tube	2343 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.2°, θmin = 3.4°
ω scans	h = −7→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −6→9
Tmin = 0.658, Tmax = 1	l = −14→16
4851 measured reflections

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.181	w = 1/[σ^2(Fo^2) + (0.1254P)^2 + 0.1608P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.01
2657 reflections	Δρmax = 0.33 e Å^−3
190 parameters	Δρmin = −0.31 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.5875 (3)	0.5127 (2)	0.37441 (11)	0.0395 (4)
N2	0.1206 (2)	1.4828 (2)	−0.14850 (11)	0.0331 (4)
N3	0.4212 (2)	0.1646 (2)	0.21465 (11)	0.0349 (4)
N4	0.0032 (3)	1.1402 (3)	−0.32539 (11)	0.0425 (4)
C1	0.5139 (3)	0.5043 (2)	0.30076 (12)	0.0292 (4)
C2	0.4234 (2)	0.4965 (2)	0.20843 (12)	0.0262 (3)
C3	0.3462 (2)	0.6587 (2)	0.12084 (11)	0.0246 (3)
C4	0.3452 (2)	0.8424 (2)	0.12179 (12)	0.0252 (3)
H4	0.393733	0.853543	0.182661	0.03*
C5	0.2748 (2)	0.9997 (2)	0.03582 (11)	0.0245 (3)
H5	0.275637	1.116913	0.038767	0.029*
C6	0.1987 (2)	0.9887 (2)	−0.06039 (11)	0.0242 (3)
C7	0.1296 (2)	1.1502 (2)	−0.14854 (11)	0.0257 (3)
C8	0.1256 (2)	1.3341 (2)	−0.14850 (11)	0.0265 (4)
C9	0.4225 (2)	0.3132 (2)	0.21160 (11)	0.0278 (4)
C10	0.2671 (2)	0.6486 (2)	0.02525 (11)	0.0252 (3)
H10	0.262962	0.532379	0.022762	0.03*
C11	0.1987 (2)	0.8055 (2)	−0.06095 (12)	0.0252 (3)
H11	0.15058	0.794224	−0.121878	0.03*
C12	0.0600 (3)	1.1431 (2)	−0.24636 (12)	0.0297 (4)
N5	0.7039 (2)	−0.1076 (2)	0.54078 (10)	0.0317 (4)	0.5
N6	0.9238 (3)	−0.2242 (3)	0.58524 (14)	0.0481 (5)	0.5
C13	0.4006 (3)	0.1840 (2)	0.50635 (12)	0.0337 (4)
H13	0.333425	0.309354	0.511202	0.04*
C14	0.6038 (3)	0.0773 (3)	0.54656 (12)	0.0339 (4)
H14	0.673824	0.131092	0.577962	0.041*
C15	0.7039 (2)	−0.1076 (2)	0.54078 (10)	0.0317 (4)	0.5
C16	0.9238 (3)	−0.2242 (3)	0.58524 (14)	0.0481 (5)	0.5
H16A	0.940 (5)	−0.365 (3)	0.615 (2)	0.072*
H16C	1.012 (4)	−0.247 (4)	0.5306 (18)	0.072*
H16B	0.967 (5)	−0.207 (4)	0.6485 (17)	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0516 (10)	0.0382 (8)	0.0261 (7)	−0.0163 (7)	−0.0046 (6)	−0.0082 (6)
N2	0.0386 (8)	0.0329 (7)	0.0284 (7)	−0.0162 (6)	−0.0004 (5)	−0.0074 (5)
N3	0.0441 (9)	0.0318 (7)	0.0303 (7)	−0.0156 (6)	0.0047 (6)	−0.0110 (6)
N4	0.0499 (10)	0.0552 (10)	0.0248 (7)	−0.0225 (8)	−0.0014 (6)	−0.0131 (7)
C1	0.0343 (9)	0.0277 (7)	0.0227 (7)	−0.0106 (6)	0.0007 (6)	−0.0061 (6)
C2	0.0262 (8)	0.0287 (7)	0.0231 (7)	−0.0096 (6)	0.0024 (5)	−0.0091 (6)
C3	0.0226 (7)	0.0292 (7)	0.0227 (7)	−0.0101 (6)	0.0028 (5)	−0.0093 (6)
C4	0.0267 (7)	0.0283 (7)	0.0210 (7)	−0.0102 (6)	0.0003 (5)	−0.0095 (6)
C5	0.0248 (8)	0.0280 (7)	0.0215 (7)	−0.0102 (6)	0.0004 (5)	−0.0091 (5)
C6	0.0221 (7)	0.0291 (7)	0.0215 (7)	−0.0095 (6)	0.0020 (5)	−0.0091 (6)
C7	0.0261 (7)	0.0308 (7)	0.0208 (7)	−0.0110 (6)	0.0011 (5)	−0.0091 (6)
C8	0.0248 (8)	0.0328 (8)	0.0206 (7)	−0.0116 (6)	0.0002 (5)	−0.0058 (6)
C9	0.0291 (8)	0.0304 (8)	0.0217 (7)	−0.0094 (6)	0.0019 (6)	−0.0081 (6)
C10	0.0264 (7)	0.0279 (7)	0.0228 (7)	−0.0101 (6)	0.0026 (5)	−0.0109 (6)
C11	0.0248 (7)	0.0300 (7)	0.0222 (7)	−0.0099 (6)	0.0019 (5)	−0.0113 (6)
C12	0.0327 (8)	0.0344 (8)	0.0217 (8)	−0.0135 (6)	0.0008 (6)	−0.0078 (6)
N5	0.0352 (8)	0.0390 (8)	0.0186 (6)	−0.0142 (6)	0.0005 (5)	−0.0060 (6)
N6	0.0423 (10)	0.0585 (11)	0.0325 (9)	−0.0115 (8)	−0.0036 (7)	−0.0096 (8)
C13	0.0429 (10)	0.0335 (8)	0.0245 (7)	−0.0143 (7)	0.0013 (6)	−0.0098 (6)
C14	0.0401 (9)	0.0405 (9)	0.0259 (8)	−0.0195 (7)	0.0014 (6)	−0.0126 (6)
C15	0.0352 (8)	0.0390 (8)	0.0186 (6)	−0.0142 (6)	0.0005 (5)	−0.0060 (6)
C16	0.0423 (10)	0.0585 (11)	0.0325 (9)	−0.0115 (8)	−0.0036 (7)	−0.0096 (8)

Geometric parameters (Å, º)

N1—C1	1.153 (2)	C6—C11	1.434 (2)
N2—C8	1.148 (2)	C7—C8	1.427 (2)
N3—C9	1.154 (2)	C7—C12	1.433 (2)
N4—C12	1.150 (2)	C10—C11	1.354 (2)
C1—C2	1.430 (2)	C10—H10	0.93
C2—C3	1.389 (2)	C11—H11	0.93
C2—C9	1.424 (2)	C13—C14	1.372 (3)
C3—C4	1.437 (2)	C13—H13	0.93
C3—C10	1.442 (2)	C14—C15	1.366 (2)
C4—C5	1.354 (2)	C14—H14	0.93
C4—H4	0.93	C16—H16A	1.023 (16)
C5—C6	1.4441 (19)	C16—H16C	0.972 (17)
C5—H5	0.93	C16—H16B	0.968 (16)
C6—C7	1.389 (2)
N1—C1—C2	179.07 (17)	N2—C8—C7	179.38 (17)
C3—C2—C9	122.85 (13)	N3—C9—C2	179.62 (17)
C3—C2—C1	121.08 (13)	C11—C10—C3	121.11 (13)
C9—C2—C1	116.05 (13)	C11—C10—H10	119.4
C2—C3—C4	121.08 (13)	C3—C10—H10	119.4
C2—C3—C10	121.40 (14)	C10—C11—C6	121.47 (13)
C4—C3—C10	117.52 (13)	C10—C11—H11	119.3
C5—C4—C3	121.30 (13)	C6—C11—H11	119.3
C5—C4—H4	119.4	N4—C12—C7	179.01 (17)
C3—C4—H4	119.4	N5^i—C13—C14	120.48 (16)
C4—C5—C6	121.16 (13)	N5^i—C13—H13	119.8
C4—C5—H5	119.4	C14—C13—H13	119.8
C6—C5—H5	119.4	C15—C14—C13	120.41 (15)
C7—C6—C11	121.86 (13)	C15—C14—H14	119.8
C7—C6—C5	120.70 (13)	C13—C14—H14	119.8
C11—C6—C5	117.43 (13)	C13^i—C15—C14	119.11 (16)
C6—C7—C8	122.39 (13)	H16A—C16—H16C	95 (2)
C6—C7—C12	122.33 (14)	H16A—C16—H16B	98.4 (18)
C8—C7—C12	115.27 (13)	H16C—C16—H16B	123 (2)
C9—C2—C3—C4	178.36 (13)	C5—C6—C7—C8	−1.4 (2)
C1—C2—C3—C4	−3.2 (2)	C11—C6—C7—C12	−2.0 (2)
C9—C2—C3—C10	−2.6 (2)	C5—C6—C7—C12	177.65 (14)
C1—C2—C3—C10	175.89 (13)	C2—C3—C10—C11	−177.67 (14)
C2—C3—C4—C5	178.31 (14)	C4—C3—C10—C11	1.4 (2)
C10—C3—C4—C5	−0.8 (2)	C3—C10—C11—C6	−1.1 (2)
C3—C4—C5—C6	−0.2 (2)	C7—C6—C11—C10	179.73 (14)
C4—C5—C6—C7	−179.10 (14)	C5—C6—C11—C10	0.1 (2)
C4—C5—C6—C11	0.6 (2)	N5^i—C13—C14—C15	−0.5 (3)
C11—C6—C7—C8	178.95 (13)	C13—C14—C15—C13^i	0.5 (3)

Symmetry code: (i) −x+1, −y, −z+1.

(tcnq_4pic_1)

Crystal data

C12H4N4·0.5(C6H10N2)	Z = 2
Mr = 259.27	F(000) = 268
Triclinic, P1	Dx = 1.274 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.1924 (3) Å	Cell parameters from 2613 reflections
b = 7.8489 (5) Å	θ = 6.3–75.9°
c = 13.6170 (9) Å	µ = 0.66 mm^−1
α = 106.174 (6)°	T = 293 K
β = 90.739 (4)°	Plate, black
γ = 112.525 (5)°	0.30 × 0.28 × 0.05 mm
V = 675.74 (7) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	2719 independent reflections
Radiation source: micro-focus sealed X-ray tube	2333 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.028
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.1°, θmin = 3.4°
ω scans	h = −8→5
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.477, Tmax = 1	l = −16→16
5385 measured reflections

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.193	w = 1/[σ^2(Fo^2) + (0.1372P)^2 + 0.0307P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
2719 reflections	Δρmax = 0.23 e Å^−3
190 parameters	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.5900 (3)	0.4903 (3)	0.87114 (13)	0.0892 (5)
N2	0.1195 (3)	−0.4775 (2)	0.35130 (13)	0.0741 (4)
N3	0.4239 (3)	0.8328 (2)	0.71277 (13)	0.0789 (5)
N4	−0.0006 (3)	−0.1364 (3)	0.17785 (13)	0.0962 (6)
C1	0.5169 (3)	0.4972 (2)	0.79853 (12)	0.0632 (4)
C2	0.4262 (2)	0.5039 (2)	0.70676 (11)	0.0539 (4)
C3	0.34700 (19)	0.34177 (19)	0.61936 (11)	0.0495 (3)
C4	0.3468 (2)	0.15895 (19)	0.62008 (11)	0.0505 (3)
H4	0.39736	0.148148	0.680238	0.061*
C5	0.27444 (19)	0.00218 (19)	0.53470 (11)	0.0500 (3)
H5	0.274536	−0.11476	0.537625	0.06*
C6	0.19768 (18)	0.01275 (19)	0.43997 (11)	0.0485 (3)
C7	0.1268 (2)	−0.1476 (2)	0.35213 (11)	0.0524 (3)
C8	0.1242 (2)	−0.3304 (2)	0.35195 (11)	0.0558 (4)
C9	0.4247 (2)	0.6860 (2)	0.70923 (12)	0.0596 (4)
C10	0.2671 (2)	0.35155 (19)	0.52524 (11)	0.0513 (3)
H10	0.264127	0.467787	0.522922	0.062*
C11	0.1958 (2)	0.1954 (2)	0.43947 (11)	0.0517 (3)
H11	0.144919	0.206299	0.379422	0.062*
C12	0.0566 (3)	−0.1406 (2)	0.25563 (12)	0.0642 (4)
N5	0.3009 (3)	0.8891 (3)	0.96056 (12)	0.0767 (5)	0.5
N6	0.0829 (5)	0.7700 (5)	0.9162 (2)	0.1262 (10)	0.5
C13	0.4088 (4)	0.8204 (3)	1.00807 (15)	0.0813 (5)
H13	0.346653	0.696371	1.013937	0.098*
C14	0.3951 (4)	1.0716 (3)	0.95292 (15)	0.0833 (6)
H14	0.322951	1.1216	0.920452	0.1*
C15	0.3009 (3)	0.8891 (3)	0.96056 (12)	0.0767 (5)	0.5
C16	0.0829 (5)	0.7700 (5)	0.9162 (2)	0.1262 (10)	0.5
H16C	0.113 (7)	0.652 (5)	0.923 (3)	0.189*
H16A	−0.039 (4)	0.704 (6)	0.947 (3)	0.189*
H16B	0.034 (6)	0.731 (6)	0.8434 (15)	0.189*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.1176 (14)	0.0852 (11)	0.0654 (9)	0.0411 (10)	−0.0074 (9)	0.0246 (8)
N2	0.0882 (10)	0.0652 (8)	0.0785 (9)	0.0423 (7)	0.0074 (8)	0.0206 (7)
N3	0.1077 (12)	0.0597 (8)	0.0794 (10)	0.0404 (7)	0.0173 (9)	0.0266 (7)
N4	0.1166 (14)	0.1246 (15)	0.0604 (9)	0.0576 (12)	0.0000 (9)	0.0355 (9)
C1	0.0770 (9)	0.0562 (8)	0.0568 (8)	0.0277 (7)	0.0065 (7)	0.0169 (6)
C2	0.0583 (7)	0.0529 (7)	0.0553 (7)	0.0240 (5)	0.0117 (6)	0.0211 (6)
C3	0.0491 (6)	0.0512 (7)	0.0550 (7)	0.0230 (5)	0.0118 (5)	0.0224 (6)
C4	0.0534 (7)	0.0546 (7)	0.0523 (7)	0.0266 (5)	0.0058 (5)	0.0224 (6)
C5	0.0527 (7)	0.0528 (7)	0.0549 (7)	0.0276 (5)	0.0082 (5)	0.0227 (6)
C6	0.0478 (6)	0.0545 (7)	0.0526 (7)	0.0250 (5)	0.0115 (5)	0.0241 (6)
C7	0.0539 (7)	0.0599 (7)	0.0508 (7)	0.0278 (5)	0.0089 (5)	0.0210 (6)
C8	0.0581 (7)	0.0604 (8)	0.0528 (7)	0.0297 (6)	0.0064 (6)	0.0146 (6)
C9	0.0697 (8)	0.0547 (8)	0.0573 (8)	0.0260 (6)	0.0134 (6)	0.0200 (6)
C10	0.0559 (7)	0.0513 (7)	0.0574 (8)	0.0253 (5)	0.0125 (6)	0.0269 (6)
C11	0.0560 (7)	0.0571 (7)	0.0523 (7)	0.0263 (5)	0.0102 (5)	0.0269 (6)
C12	0.0727 (9)	0.0733 (9)	0.0538 (8)	0.0360 (7)	0.0076 (7)	0.0208 (7)
N5	0.0850 (10)	0.0905 (11)	0.0519 (7)	0.0368 (8)	0.0078 (7)	0.0158 (7)
N6	0.0988 (16)	0.159 (3)	0.0898 (15)	0.0298 (16)	−0.0024 (13)	0.0239 (16)
C13	0.1102 (15)	0.0693 (10)	0.0720 (10)	0.0391 (9)	0.0155 (10)	0.0287 (8)
C14	0.1057 (14)	0.1006 (14)	0.0707 (10)	0.0616 (12)	0.0097 (10)	0.0385 (10)
C15	0.0850 (10)	0.0905 (11)	0.0519 (7)	0.0368 (8)	0.0078 (7)	0.0158 (7)
C16	0.0988 (16)	0.159 (3)	0.0898 (15)	0.0298 (16)	−0.0024 (13)	0.0239 (16)

Geometric parameters (Å, º)

N1—C1	1.138 (2)	C6—C11	1.4410 (18)
N2—C8	1.140 (2)	C7—C12	1.424 (2)
N3—C9	1.143 (2)	C7—C8	1.4274 (19)
N4—C12	1.145 (2)	C10—C11	1.354 (2)
C1—C2	1.426 (2)	C10—H10	0.93
C2—C3	1.394 (2)	C11—H11	0.93
C2—C9	1.424 (2)	N5—C13	1.347 (3)
C3—C10	1.4311 (19)	N5—N6	1.495 (3)
C3—C4	1.4373 (17)	N6—H16C	1.062 (18)
C4—C5	1.354 (2)	N6—H16A	0.998 (17)
C4—H4	0.93	N6—H16B	0.968 (18)
C5—C6	1.4325 (18)	C13—C14^i	1.343 (3)
C5—H5	0.93	C13—H13	0.93
C6—C7	1.389 (2)	C14—H14	0.93
N1—C1—C2	179.22 (19)	N3—C9—C2	178.99 (17)
C3—C2—C9	122.28 (13)	C11—C10—C3	121.52 (12)
C3—C2—C1	121.56 (13)	C11—C10—H10	119.2
C9—C2—C1	116.15 (13)	C3—C10—H10	119.2
C2—C3—C10	121.56 (12)	C10—C11—C6	120.92 (12)
C2—C3—C4	120.91 (13)	C10—C11—H11	119.5
C10—C3—C4	117.52 (12)	C6—C11—H11	119.5
C5—C4—C3	121.15 (12)	N4—C12—C7	179.5 (2)
C5—C4—H4	119.4	C13—N5—N6	121.5 (2)
C3—C4—H4	119.4	N5—N6—H16C	85 (3)
C4—C5—C6	121.35 (12)	N5—N6—H16A	132 (2)
C4—C5—H5	119.3	H16C—N6—H16A	80 (2)
C6—C5—H5	119.3	N5—N6—H16B	123 (3)
C7—C6—C5	121.14 (12)	H16C—N6—H16B	103 (3)
C7—C6—C11	121.33 (12)	H16A—N6—H16B	105 (2)
C5—C6—C11	117.53 (12)	C14^i—C13—N5	120.98 (19)
C6—C7—C12	122.72 (13)	C14^i—C13—H13	119.5
C6—C7—C8	121.97 (13)	N5—C13—H13	119.5
C12—C7—C8	115.30 (13)	C13^i—C14—H14	119.8
N2—C8—C7	179.12 (17)
C9—C2—C3—C10	2.7 (2)	C11—C6—C7—C12	2.8 (2)
C1—C2—C3—C10	−176.14 (13)	C5—C6—C7—C8	0.8 (2)
C9—C2—C3—C4	−178.65 (12)	C11—C6—C7—C8	−178.82 (11)
C1—C2—C3—C4	2.5 (2)	C2—C3—C10—C11	178.00 (12)
C2—C3—C4—C5	−178.46 (12)	C4—C3—C10—C11	−0.7 (2)
C10—C3—C4—C5	0.2 (2)	C3—C10—C11—C6	0.1 (2)
C3—C4—C5—C6	0.8 (2)	C7—C6—C11—C10	−179.34 (12)
C4—C5—C6—C7	178.89 (12)	C5—C6—C11—C10	1.0 (2)
C4—C5—C6—C11	−1.4 (2)	N6—N5—C13—C14^i	179.6 (2)
C5—C6—C7—C12	−177.56 (12)

Symmetry code: (i) −x+1, −y+2, −z+2.

(tcnq_4bz_1)

Crystal data

2(C12H4N4)·C13H12NO	Z = 2
Mr = 606.62	F(000) = 626
Triclinic, P1	Dx = 1.289 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 9.1474 (2) Å	Cell parameters from 7021 reflections
b = 11.3666 (5) Å	θ = 4.1–76.0°
c = 15.9321 (6) Å	µ = 0.67 mm^−1
α = 106.234 (4)°	T = 293 K
β = 91.277 (3)°	Prism, black
γ = 99.804 (3)°	0.40 × 0.15 × 0.12 mm
V = 1562.98 (10) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	6405 independent reflections
Radiation source: micro-focus sealed X-ray tube	5339 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.023
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.3°, θmin = 2.9°
ω scans	h = −7→11
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −13→14
Tmin = 0.638, Tmax = 1	l = −18→20
13967 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.180	w = 1/[σ^2(Fo^2) + (0.1878P)^2 + 0.1076P] where P = (Fo^2 + 2Fc^2)/3
S = 0.71	(Δ/σ)max = 0.001
6405 reflections	Δρmax = 0.16 e Å^−3
424 parameters	Δρmin = −0.15 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1A	0.02559 (16)	0.40848 (16)	0.12251 (8)	0.0895 (4)
N2A	−0.1091 (2)	0.8997 (2)	0.59249 (12)	0.1138 (6)
N3A	0.3557 (2)	0.26997 (18)	0.25430 (13)	0.1107 (5)
N4A	0.18381 (18)	0.74219 (15)	0.73309 (8)	0.0897 (4)
C1A	0.09062 (15)	0.41307 (14)	0.18576 (9)	0.0704 (3)
C2A	0.17014 (14)	0.41861 (12)	0.26561 (9)	0.0650 (3)
C3A	0.14686 (13)	0.50020 (12)	0.34502 (8)	0.0613 (3)
C4A	0.04971 (15)	0.58740 (14)	0.34900 (8)	0.0669 (3)
H4A	0.00163	0.589177	0.297435	0.08*
C5A	0.02602 (14)	0.66707 (14)	0.42552 (8)	0.0667 (3)
H5A	−0.036267	0.723864	0.425858	0.08*
C6A	0.09630 (13)	0.66511 (12)	0.50688 (8)	0.0606 (3)
C7A	0.06875 (14)	0.74566 (13)	0.58563 (8)	0.0643 (3)
C8A	−0.02883 (17)	0.83162 (17)	0.59010 (9)	0.0796 (4)
C9A	0.27228 (19)	0.33571 (14)	0.25916 (10)	0.0779 (4)
C10A	0.21777 (14)	0.49975 (12)	0.42636 (9)	0.0635 (3)
H10A	0.282151	0.444461	0.425779	0.076*
C11A	0.19300 (14)	0.57767 (12)	0.50342 (8)	0.0629 (3)
H11A	0.239451	0.574534	0.555067	0.076*
C12A	0.13380 (15)	0.74427 (14)	0.66767 (8)	0.0698 (3)
N1B	0.34988 (19)	0.69244 (13)	0.22564 (8)	0.0887 (4)
N2B	0.16783 (18)	1.20297 (13)	0.69160 (8)	0.0846 (4)
N3B	0.6273 (2)	0.55090 (16)	0.37608 (11)	0.1014 (5)
N4B	0.46527 (17)	1.05779 (13)	0.84079 (8)	0.0837 (4)
C1B	0.39907 (15)	0.70348 (11)	0.29448 (7)	0.0613 (3)
C2B	0.46069 (14)	0.71117 (11)	0.37857 (7)	0.0572 (3)
C3B	0.43004 (12)	0.79576 (10)	0.45583 (7)	0.0516 (2)
C4B	0.33533 (12)	0.88302 (10)	0.45520 (7)	0.0520 (2)
H4B	0.293008	0.884934	0.402093	0.062*
C5B	0.30595 (12)	0.96329 (10)	0.53083 (7)	0.0526 (2)
H5B	0.243633	1.019214	0.528684	0.063*
C6B	0.36898 (12)	0.96347 (10)	0.61366 (7)	0.0524 (2)
C7B	0.34016 (14)	1.04759 (11)	0.69205 (7)	0.0577 (3)
C8B	0.24409 (16)	1.13321 (12)	0.69243 (7)	0.0641 (3)
C9B	0.55401 (17)	0.62362 (13)	0.37834 (9)	0.0704 (3)
C10B	0.49218 (13)	0.79598 (11)	0.53901 (7)	0.0573 (3)
H10B	0.553793	0.739592	0.541297	0.069*
C11B	0.46346 (13)	0.87626 (11)	0.61446 (7)	0.0568 (3)
H11B	0.505962	0.874492	0.667567	0.068*
C12B	0.40831 (15)	1.05255 (12)	0.77468 (8)	0.0648 (3)
O1	0.33177 (13)	1.30944 (13)	1.02498 (9)	0.0945 (4)
N5	0.34961 (12)	1.68056 (10)	0.92871 (7)	0.0631 (3)
C13	0.33628 (16)	1.66746 (14)	1.00962 (8)	0.0726 (3)
H13	0.352143	1.737988	1.057833	0.087*
C14	0.30010 (17)	1.55319 (14)	1.02211 (8)	0.0731 (4)
H14	0.292063	1.545942	1.078609	0.088*
C15	0.27517 (13)	1.44762 (12)	0.95132 (7)	0.0606 (3)
C16	0.28891 (15)	1.46255 (12)	0.86809 (7)	0.0658 (3)
H16	0.271886	1.393257	0.818993	0.079*
C17	0.32773 (16)	1.58000 (13)	0.85856 (8)	0.0671 (3)
H17	0.338919	1.58979	0.802892	0.081*
C18	0.3928 (2)	1.80613 (14)	0.91776 (11)	0.0841 (4)
H18A	0.403883	1.86724	0.974094	0.126*
H18B	0.485415	1.811648	0.890658	0.126*
H18C	0.317199	1.821269	0.881409	0.126*
C19	0.24779 (14)	1.32232 (14)	0.96953 (9)	0.0667 (3)
C20	0.12536 (14)	1.22230 (12)	0.92189 (8)	0.0652 (3)
C21	0.00605 (16)	1.24568 (14)	0.87776 (10)	0.0738 (3)
H21	0.003056	1.326267	0.875838	0.089*
C22	−0.1085 (2)	1.1487 (2)	0.83660 (13)	0.0957 (5)
H22	−0.188938	1.164654	0.807644	0.115*
C23	−0.1045 (3)	1.0299 (2)	0.83808 (16)	0.1102 (6)
H23	−0.181702	0.965305	0.809777	0.132*
C24	0.0136 (3)	1.00523 (19)	0.88138 (19)	0.1162 (7)
H24	0.01595	0.924102	0.882239	0.139*
C25	0.1284 (2)	1.10094 (16)	0.92353 (14)	0.0910 (5)
H25	0.207744	1.084269	0.953005	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0856 (8)	0.1219 (11)	0.0573 (7)	0.0236 (7)	0.0037 (6)	0.0173 (6)
N2A	0.1079 (11)	0.1516 (16)	0.0861 (10)	0.0579 (12)	0.0068 (8)	0.0208 (10)
N3A	0.1324 (14)	0.0982 (11)	0.1035 (11)	0.0486 (10)	−0.0058 (10)	0.0172 (9)
N4A	0.1027 (9)	0.1044 (10)	0.0579 (7)	−0.0044 (8)	−0.0065 (6)	0.0313 (6)
C1A	0.0689 (7)	0.0807 (8)	0.0566 (7)	0.0081 (6)	0.0080 (5)	0.0145 (6)
C2A	0.0657 (6)	0.0646 (7)	0.0610 (6)	0.0007 (5)	0.0017 (5)	0.0190 (5)
C3A	0.0609 (6)	0.0637 (7)	0.0571 (6)	−0.0013 (5)	0.0006 (5)	0.0218 (5)
C4A	0.0672 (6)	0.0823 (8)	0.0516 (6)	0.0108 (6)	−0.0020 (5)	0.0221 (6)
C5A	0.0637 (6)	0.0827 (8)	0.0544 (6)	0.0113 (6)	−0.0007 (5)	0.0223 (6)
C6A	0.0574 (6)	0.0708 (7)	0.0520 (6)	−0.0030 (5)	0.0011 (4)	0.0242 (5)
C7A	0.0613 (6)	0.0767 (8)	0.0518 (6)	−0.0021 (5)	0.0023 (5)	0.0223 (5)
C8A	0.0738 (8)	0.1039 (11)	0.0580 (7)	0.0156 (8)	0.0062 (6)	0.0189 (7)
C9A	0.0878 (9)	0.0686 (8)	0.0723 (8)	0.0101 (7)	−0.0012 (7)	0.0153 (6)
C10A	0.0663 (6)	0.0617 (6)	0.0635 (7)	0.0023 (5)	−0.0036 (5)	0.0256 (5)
C11A	0.0661 (6)	0.0656 (7)	0.0576 (6)	−0.0021 (5)	−0.0051 (5)	0.0277 (5)
C12A	0.0722 (7)	0.0784 (8)	0.0535 (6)	−0.0063 (6)	0.0024 (5)	0.0225 (5)
N1B	0.1273 (11)	0.0845 (8)	0.0463 (6)	0.0103 (7)	0.0010 (6)	0.0119 (5)
N2B	0.1138 (10)	0.0807 (8)	0.0649 (7)	0.0414 (7)	0.0180 (6)	0.0155 (6)
N3B	0.1190 (12)	0.0937 (10)	0.0984 (10)	0.0539 (9)	0.0101 (9)	0.0178 (8)
N4B	0.1038 (9)	0.0896 (8)	0.0492 (6)	0.0114 (7)	−0.0017 (6)	0.0106 (5)
C1B	0.0794 (7)	0.0531 (6)	0.0461 (6)	0.0068 (5)	0.0113 (5)	0.0086 (4)
C2B	0.0685 (6)	0.0509 (5)	0.0490 (5)	0.0102 (4)	0.0065 (4)	0.0093 (4)
C3B	0.0590 (5)	0.0483 (5)	0.0447 (5)	0.0060 (4)	0.0056 (4)	0.0110 (4)
C4B	0.0606 (5)	0.0522 (5)	0.0427 (5)	0.0082 (4)	0.0028 (4)	0.0144 (4)
C5B	0.0610 (5)	0.0508 (5)	0.0464 (5)	0.0105 (4)	0.0053 (4)	0.0140 (4)
C6B	0.0605 (5)	0.0491 (5)	0.0444 (5)	0.0049 (4)	0.0054 (4)	0.0113 (4)
C7B	0.0685 (6)	0.0553 (6)	0.0447 (5)	0.0061 (5)	0.0078 (4)	0.0097 (4)
C8B	0.0822 (7)	0.0600 (6)	0.0464 (5)	0.0135 (6)	0.0144 (5)	0.0085 (4)
C9B	0.0833 (8)	0.0640 (7)	0.0615 (7)	0.0227 (6)	0.0099 (6)	0.0087 (5)
C10B	0.0653 (6)	0.0560 (6)	0.0504 (5)	0.0152 (5)	0.0003 (4)	0.0128 (4)
C11B	0.0665 (6)	0.0582 (6)	0.0443 (5)	0.0105 (5)	−0.0009 (4)	0.0132 (4)
C12B	0.0782 (7)	0.0623 (6)	0.0459 (6)	0.0058 (5)	0.0075 (5)	0.0069 (5)
O1	0.0821 (6)	0.1143 (9)	0.0989 (8)	0.0200 (6)	−0.0144 (6)	0.0500 (7)
N5	0.0668 (5)	0.0651 (6)	0.0544 (5)	0.0173 (4)	−0.0041 (4)	0.0099 (4)
C13	0.0818 (8)	0.0756 (8)	0.0476 (6)	0.0094 (6)	0.0025 (5)	0.0003 (5)
C14	0.0837 (8)	0.0835 (9)	0.0441 (5)	0.0062 (6)	0.0067 (5)	0.0105 (5)
C15	0.0574 (5)	0.0728 (7)	0.0504 (6)	0.0166 (5)	0.0032 (4)	0.0128 (5)
C16	0.0832 (8)	0.0665 (7)	0.0448 (5)	0.0227 (6)	0.0032 (5)	0.0060 (5)
C17	0.0840 (8)	0.0719 (7)	0.0457 (5)	0.0236 (6)	0.0006 (5)	0.0121 (5)
C18	0.1023 (11)	0.0677 (8)	0.0789 (9)	0.0156 (7)	−0.0152 (8)	0.0173 (7)
C19	0.0642 (6)	0.0804 (8)	0.0606 (6)	0.0228 (6)	0.0073 (5)	0.0230 (6)
C20	0.0676 (6)	0.0692 (7)	0.0616 (6)	0.0221 (5)	0.0144 (5)	0.0167 (5)
C21	0.0718 (7)	0.0774 (8)	0.0704 (7)	0.0200 (6)	0.0042 (6)	0.0148 (6)
C22	0.0826 (10)	0.1020 (12)	0.0906 (11)	0.0119 (8)	−0.0065 (8)	0.0124 (9)
C23	0.1063 (13)	0.0848 (12)	0.1158 (15)	−0.0025 (10)	0.0041 (11)	0.0027 (10)
C24	0.1247 (16)	0.0698 (10)	0.148 (2)	0.0126 (10)	0.0211 (15)	0.0241 (11)
C25	0.0941 (10)	0.0784 (9)	0.1095 (13)	0.0275 (8)	0.0144 (9)	0.0340 (9)

Geometric parameters (Å, º)

N1A—C1A	1.1425 (19)	C6B—C11B	1.4240 (16)
N2A—C8A	1.148 (2)	C7B—C8B	1.4169 (18)
N3A—C9A	1.145 (2)	C7B—C12B	1.4265 (17)
N4A—C12A	1.1367 (19)	C10B—C11B	1.3525 (17)
C1A—C2A	1.4317 (19)	C10B—H10B	0.93
C2A—C3A	1.3890 (19)	C11B—H11B	0.93
C2A—C9A	1.422 (2)	O1—C19	1.2134 (17)
C3A—C4A	1.4295 (19)	N5—C17	1.3393 (16)
C3A—C10A	1.4380 (17)	N5—C13	1.3441 (18)
C4A—C5A	1.347 (2)	N5—C18	1.4744 (18)
C4A—H4A	0.93	C13—C14	1.355 (2)
C5A—C6A	1.4415 (16)	C13—H13	0.93
C5A—H5A	0.93	C14—C15	1.3794 (18)
C6A—C7A	1.388 (2)	C14—H14	0.93
C6A—C11A	1.4298 (19)	C15—C16	1.3888 (17)
C7A—C8A	1.420 (2)	C15—C19	1.5126 (19)
C7A—C12A	1.4293 (17)	C16—C17	1.3731 (19)
C10A—C11A	1.347 (2)	C16—H16	0.93
C10A—H10A	0.93	C17—H17	0.93
C11A—H11A	0.93	C18—H18A	0.96
N1B—C1B	1.1415 (18)	C18—H18B	0.96
N2B—C8B	1.1443 (19)	C18—H18C	0.96
N3B—C9B	1.144 (2)	C19—C20	1.473 (2)
N4B—C12B	1.1463 (18)	C20—C21	1.388 (2)
C1B—C2B	1.4157 (17)	C20—C25	1.392 (2)
C2B—C3B	1.4012 (15)	C21—C22	1.384 (2)
C2B—C9B	1.4165 (18)	C21—H21	0.93
C3B—C4B	1.4256 (15)	C22—C23	1.364 (3)
C3B—C10B	1.4295 (15)	C22—H22	0.93
C4B—C5B	1.3564 (16)	C23—C24	1.378 (3)
C4B—H4B	0.93	C23—H23	0.93
C5B—C6B	1.4277 (15)	C24—C25	1.381 (3)
C5B—H5B	0.93	C24—H24	0.93
C6B—C7B	1.4058 (15)	C25—H25	0.93
N1A—C1A—C2A	179.17 (15)	C3B—C10B—H10B	119.2
C3A—C2A—C9A	122.17 (13)	C10B—C11B—C6B	120.87 (10)
C3A—C2A—C1A	121.32 (13)	C10B—C11B—H11B	119.6
C9A—C2A—C1A	116.50 (13)	C6B—C11B—H11B	119.6
C2A—C3A—C4A	121.02 (12)	N4B—C12B—C7B	178.80 (15)
C2A—C3A—C10A	121.64 (13)	C17—N5—C13	120.24 (12)
C4A—C3A—C10A	117.33 (12)	C17—N5—C18	120.12 (12)
C5A—C4A—C3A	121.69 (12)	C13—N5—C18	119.61 (11)
C5A—C4A—H4A	119.2	N5—C13—C14	121.11 (11)
C3A—C4A—H4A	119.2	N5—C13—H13	119.4
C4A—C5A—C6A	120.62 (13)	C14—C13—H13	119.4
C4A—C5A—H5A	119.7	C13—C14—C15	120.24 (12)
C6A—C5A—H5A	119.7	C13—C14—H14	119.9
C7A—C6A—C11A	121.77 (11)	C15—C14—H14	119.9
C7A—C6A—C5A	120.26 (13)	C14—C15—C16	118.04 (13)
C11A—C6A—C5A	117.96 (12)	C14—C15—C19	117.89 (11)
C6A—C7A—C8A	122.33 (12)	C16—C15—C19	123.85 (11)
C6A—C7A—C12A	121.75 (13)	C17—C16—C15	119.77 (11)
C8A—C7A—C12A	115.90 (13)	C17—C16—H16	120.1
N2A—C8A—C7A	178.84 (19)	C15—C16—H16	120.1
N3A—C9A—C2A	179.3 (2)	N5—C17—C16	120.60 (11)
C11A—C10A—C3A	121.46 (12)	N5—C17—H17	119.7
C11A—C10A—H10A	119.3	C16—C17—H17	119.7
C3A—C10A—H10A	119.3	N5—C18—H18A	109.5
C10A—C11A—C6A	120.92 (11)	N5—C18—H18B	109.5
C10A—C11A—H11A	119.5	H18A—C18—H18B	109.5
C6A—C11A—H11A	119.5	N5—C18—H18C	109.5
N4A—C12A—C7A	179.07 (15)	H18A—C18—H18C	109.5
N1B—C1B—C2B	177.30 (13)	H18B—C18—H18C	109.5
C3B—C2B—C1B	123.32 (11)	O1—C19—C20	122.45 (14)
C3B—C2B—C9B	122.55 (11)	O1—C19—C15	116.40 (13)
C1B—C2B—C9B	114.12 (11)	C20—C19—C15	121.15 (11)
C2B—C3B—C4B	122.00 (10)	C21—C20—C25	119.28 (15)
C2B—C3B—C10B	120.51 (10)	C21—C20—C19	122.24 (13)
C4B—C3B—C10B	117.48 (10)	C25—C20—C19	118.46 (13)
C5B—C4B—C3B	121.06 (10)	C22—C21—C20	119.77 (16)
C5B—C4B—H4B	119.5	C22—C21—H21	120.1
C3B—C4B—H4B	119.5	C20—C21—H21	120.1
C4B—C5B—C6B	121.18 (10)	C23—C22—C21	120.66 (18)
C4B—C5B—H5B	119.4	C23—C22—H22	119.7
C6B—C5B—H5B	119.4	C21—C22—H22	119.7
C7B—C6B—C11B	120.84 (10)	C22—C23—C24	120.19 (19)
C7B—C6B—C5B	121.30 (11)	C22—C23—H23	119.9
C11B—C6B—C5B	117.87 (10)	C24—C23—H23	119.9
C6B—C7B—C8B	121.46 (11)	C23—C24—C25	120.05 (19)
C6B—C7B—C12B	121.69 (11)	C23—C24—H24	120
C8B—C7B—C12B	116.84 (10)	C25—C24—H24	120
N2B—C8B—C7B	178.81 (14)	C24—C25—C20	120.04 (18)
N3B—C9B—C2B	178.15 (16)	C24—C25—H25	120
C11B—C10B—C3B	121.54 (10)	C20—C25—H25	120
C11B—C10B—H10B	119.2
C9A—C2A—C3A—C4A	176.49 (12)	C2B—C3B—C10B—C11B	−179.61 (11)
C1A—C2A—C3A—C4A	−4.14 (19)	C4B—C3B—C10B—C11B	−0.44 (18)
C9A—C2A—C3A—C10A	−4.2 (2)	C3B—C10B—C11B—C6B	0.36 (19)
C1A—C2A—C3A—C10A	175.21 (11)	C7B—C6B—C11B—C10B	−179.47 (11)
C2A—C3A—C4A—C5A	179.98 (12)	C5B—C6B—C11B—C10B	−0.03 (17)
C10A—C3A—C4A—C5A	0.61 (19)	C17—N5—C13—C14	−0.3 (2)
C3A—C4A—C5A—C6A	−1.3 (2)	C18—N5—C13—C14	−178.47 (13)
C4A—C5A—C6A—C7A	−178.59 (12)	N5—C13—C14—C15	−0.4 (2)
C4A—C5A—C6A—C11A	0.92 (19)	C13—C14—C15—C16	0.3 (2)
C11A—C6A—C7A—C8A	−179.01 (12)	C13—C14—C15—C19	175.02 (12)
C5A—C6A—C7A—C8A	0.49 (19)	C14—C15—C16—C17	0.61 (19)
C11A—C6A—C7A—C12A	−0.97 (18)	C19—C15—C16—C17	−173.81 (11)
C5A—C6A—C7A—C12A	178.53 (11)	C13—N5—C17—C16	1.2 (2)
C2A—C3A—C10A—C11A	−178.90 (11)	C18—N5—C17—C16	179.36 (13)
C4A—C3A—C10A—C11A	0.47 (18)	C15—C16—C17—N5	−1.3 (2)
C3A—C10A—C11A—C6A	−0.82 (19)	C14—C15—C19—O1	−46.12 (18)
C7A—C6A—C11A—C10A	179.65 (11)	C16—C15—C19—O1	128.32 (15)
C5A—C6A—C11A—C10A	0.14 (18)	C14—C15—C19—C20	133.94 (13)
C1B—C2B—C3B—C4B	−1.17 (18)	C16—C15—C19—C20	−51.63 (17)
C9B—C2B—C3B—C4B	−179.69 (11)	O1—C19—C20—C21	161.48 (15)
C1B—C2B—C3B—C10B	177.96 (10)	C15—C19—C20—C21	−18.58 (19)
C9B—C2B—C3B—C10B	−0.56 (19)	O1—C19—C20—C25	−16.8 (2)
C2B—C3B—C4B—C5B	179.35 (10)	C15—C19—C20—C25	163.18 (13)
C10B—C3B—C4B—C5B	0.19 (16)	C25—C20—C21—C22	0.4 (2)
C3B—C4B—C5B—C6B	0.13 (17)	C19—C20—C21—C22	−177.78 (14)
C4B—C5B—C6B—C7B	179.22 (10)	C20—C21—C22—C23	−0.8 (3)
C4B—C5B—C6B—C11B	−0.22 (17)	C21—C22—C23—C24	0.5 (4)
C11B—C6B—C7B—C8B	−178.74 (11)	C22—C23—C24—C25	0.0 (4)
C5B—C6B—C7B—C8B	1.84 (18)	C23—C24—C25—C20	−0.4 (4)
C11B—C6B—C7B—C12B	2.50 (18)	C21—C20—C25—C24	0.1 (3)
C5B—C6B—C7B—C12B	−176.91 (10)	C19—C20—C25—C24	178.41 (18)

(tcnq_4damp_2)

Crystal data

C12H4N4·0.5(C8H8N2)	Z = 2
Mr = 270.27	F(000) = 376
Triclinic, P1	Dx = 1.267 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.5381 (5) Å	Cell parameters from 1911 reflections
b = 8.0130 (7) Å	θ = 3.4–75.6°
c = 13.3368 (12) Å	µ = 0.65 mm^−1
α = 103.618 (8)°	T = 293 K
β = 90.811 (6)°	Plate, black
γ = 115.727 (8)°	0.22 × 0.20 × 0.03 mm
V = 699.07 (11) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	2612 independent reflections
Radiation source: micro-focus sealed X-ray tube	2083 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.032
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.3°, θmin = 3.4°
ω scans	h = −9→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.552, Tmax = 1	l = −16→15
4489 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.073	H-atom parameters constrained
wR(F^2) = 0.237	w = 1/[σ^2(Fo^2) + (0.1677P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2612 reflections	Δρmax = 0.36 e Å^−3
217 parameters	Δρmin = −0.23 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.7652 (3)	1.0845 (3)	1.17210 (17)	0.0866 (6)
N2	0.9609 (3)	0.3834 (4)	0.6613 (2)	0.1014 (8)
N3	0.1338 (3)	0.7682 (3)	1.07620 (16)	0.0797 (6)
N4	0.3218 (4)	0.0383 (4)	0.56784 (18)	0.0943 (7)
C1	0.6381 (3)	0.9567 (3)	1.11328 (15)	0.0605 (5)
C2	0.4798 (2)	0.8016 (3)	1.04068 (14)	0.0542 (5)
C3	0.5109 (2)	0.6820 (2)	0.95687 (13)	0.0509 (4)
C4	0.7081 (2)	0.7081 (3)	0.93879 (14)	0.0559 (5)
H4	0.816888	0.806551	0.984595	0.067*
C5	0.7380 (2)	0.5922 (3)	0.85650 (15)	0.0566 (5)
H5	0.867029	0.612627	0.846847	0.068*
C6	0.5757 (2)	0.4388 (3)	0.78392 (14)	0.0528 (4)
C7	0.6075 (3)	0.3215 (3)	0.69862 (15)	0.0597 (5)
C8	0.8038 (3)	0.3547 (4)	0.67725 (17)	0.0712 (6)
C9	0.2866 (2)	0.7805 (3)	1.05959 (14)	0.0591 (5)
C10	0.3482 (2)	0.5278 (3)	0.88327 (14)	0.0538 (4)
H10	0.218977	0.507946	0.892103	0.065*
C11	0.3788 (2)	0.4119 (3)	0.80202 (14)	0.0559 (5)
H11	0.270291	0.31228	0.756605	0.067*
C12	0.4488 (3)	0.1648 (3)	0.62631 (15)	0.0672 (5)
N5	0.3076 (3)	0.2556 (3)	0.38919 (15)	0.0790 (6)
C13	0.2338 (6)	0.3414 (7)	0.4667 (4)	0.0711 (10)	0.5
H13	0.098044	0.287212	0.470543	0.085*	0.5
C14	0.6383 (3)	0.4908 (4)	0.46057 (17)	0.0690 (5)
C15	0.4363 (5)	0.4183 (5)	0.4586 (3)	0.0580 (8)	0.5
C16	0.5006 (8)	0.3209 (8)	0.3897 (3)	0.0749 (11)	0.5
H16	0.547771	0.251565	0.340995	0.09*	0.5
C17	0.1563 (11)	0.0739 (9)	0.3156 (6)	0.114 (2)	0.5
H17A	0.041989	−0.037757	0.275429	0.171*	0.5
H17B	0.226135	0.152248	0.271055	0.171*	0.5
H17C	0.242493	0.03467	0.346456	0.171*	0.5
C18	0.0967 (7)	0.1773 (10)	0.3923 (6)	0.111 (2)	0.5
C19	0.3847 (14)	0.1559 (9)	0.3061 (5)	0.109 (2)	0.5
H19A	0.275255	0.049013	0.259472	0.163*	0.5
H19B	0.463831	0.243995	0.268091	0.163*	0.5
H19C	0.464743	0.110345	0.336884	0.163*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0767 (11)	0.0788 (12)	0.0779 (12)	0.0173 (9)	−0.0078 (9)	0.0107 (10)
N2	0.0766 (12)	0.138 (2)	0.0960 (15)	0.0579 (13)	0.0329 (11)	0.0226 (14)
N3	0.0603 (9)	0.0960 (14)	0.0841 (12)	0.0397 (9)	0.0167 (8)	0.0171 (10)
N4	0.1039 (15)	0.0896 (15)	0.0735 (12)	0.0382 (12)	0.0018 (11)	0.0048 (11)
C1	0.0578 (8)	0.0645 (11)	0.0582 (10)	0.0253 (8)	0.0071 (7)	0.0190 (8)
C2	0.0492 (8)	0.0600 (10)	0.0563 (9)	0.0246 (7)	0.0078 (6)	0.0203 (8)
C3	0.0448 (7)	0.0565 (9)	0.0535 (9)	0.0220 (6)	0.0082 (6)	0.0200 (7)
C4	0.0422 (7)	0.0617 (10)	0.0610 (9)	0.0198 (6)	0.0074 (6)	0.0188 (8)
C5	0.0420 (7)	0.0687 (10)	0.0621 (9)	0.0234 (7)	0.0122 (6)	0.0255 (8)
C6	0.0502 (8)	0.0614 (10)	0.0533 (9)	0.0269 (7)	0.0118 (6)	0.0228 (7)
C7	0.0633 (9)	0.0722 (12)	0.0545 (9)	0.0362 (8)	0.0153 (7)	0.0246 (8)
C8	0.0736 (11)	0.0895 (15)	0.0647 (11)	0.0469 (10)	0.0248 (9)	0.0250 (10)
C9	0.0577 (9)	0.0648 (11)	0.0578 (9)	0.0303 (7)	0.0107 (7)	0.0161 (8)
C10	0.0400 (7)	0.0636 (10)	0.0571 (9)	0.0214 (6)	0.0076 (6)	0.0189 (8)
C11	0.0463 (8)	0.0647 (10)	0.0540 (9)	0.0229 (6)	0.0062 (6)	0.0154 (7)
C12	0.0758 (11)	0.0745 (12)	0.0573 (11)	0.0398 (10)	0.0131 (9)	0.0164 (9)
N5	0.0861 (12)	0.0706 (11)	0.0704 (11)	0.0259 (9)	−0.0034 (8)	0.0207 (9)
C13	0.0564 (17)	0.076 (3)	0.082 (3)	0.0267 (16)	0.0125 (16)	0.031 (2)
C14	0.0635 (10)	0.0857 (14)	0.0713 (12)	0.0396 (9)	0.0233 (8)	0.0325 (10)
C15	0.0574 (18)	0.065 (2)	0.0569 (18)	0.0262 (15)	0.0135 (13)	0.0272 (17)
C16	0.104 (3)	0.085 (3)	0.057 (2)	0.060 (2)	0.023 (2)	0.022 (2)
C17	0.127 (5)	0.076 (3)	0.102 (4)	0.020 (3)	−0.028 (4)	0.014 (3)
C18	0.063 (2)	0.098 (4)	0.138 (5)	0.004 (2)	−0.022 (3)	0.040 (4)
C19	0.185 (7)	0.078 (3)	0.069 (3)	0.067 (4)	0.008 (3)	0.016 (2)

Geometric parameters (Å, º)

N1—C1	1.153 (3)	N5—C16	1.314 (5)
N2—C8	1.137 (3)	N5—C15	1.344 (4)
N3—C9	1.142 (3)	N5—C13	1.366 (5)
N4—C12	1.148 (3)	N5—C18	1.439 (6)
C1—C2	1.421 (2)	N5—C19	1.486 (7)
C2—C3	1.386 (3)	N5—C17	1.496 (6)
C2—C9	1.425 (2)	C13—C14^i	1.383 (5)
C3—C10	1.440 (2)	C13—H13	0.93
C3—C4	1.441 (2)	C14—C15	1.371 (4)
C4—C5	1.352 (3)	C14—C16	1.401 (5)
C4—H4	0.93	C14—C15^i	1.418 (4)
C5—C6	1.430 (2)	C15—C15^i	1.433 (7)
C5—H5	0.93	C16—H16	0.93
C6—C7	1.391 (3)	C17—C18	1.368 (11)
C6—C11	1.437 (2)	C17—H17A	0.96
C7—C12	1.425 (3)	C17—H17B	0.96
C7—C8	1.431 (3)	C17—H17C	0.96
C10—C11	1.345 (3)	C19—H19A	0.96
C10—H10	0.93	C19—H19B	0.96
C11—H11	0.93	C19—H19C	0.96
N1—C1—C2	178.9 (2)	C15—N5—C17	177.0 (4)
C3—C2—C1	122.65 (15)	C13—N5—C17	115.2 (4)
C3—C2—C9	122.52 (16)	C18—N5—C17	55.5 (5)
C1—C2—C9	114.83 (16)	C19—N5—C17	63.7 (4)
C2—C3—C10	121.61 (14)	N5—C13—C14^i	119.8 (3)
C2—C3—C4	121.38 (15)	N5—C13—H13	120.1
C10—C3—C4	117.00 (15)	C14^i—C13—H13	120.1
C5—C4—C3	121.21 (15)	C15—C14—C13^i	121.1 (3)
C5—C4—H4	119.4	C15—C14—C16	56.0 (3)
C3—C4—H4	119.4	C13^i—C14—C16	177.0 (3)
C4—C5—C6	121.53 (14)	C15—C14—C15^i	61.8 (3)
C4—C5—H5	119.2	C13^i—C14—C15^i	59.6 (2)
C6—C5—H5	119.2	C16—C14—C15^i	117.4 (3)
C7—C6—C5	121.26 (15)	N5—C15—C14	122.7 (3)
C7—C6—C11	121.36 (16)	N5—C15—C14^i	118.8 (3)
C5—C6—C11	117.38 (16)	C14—C15—C14^i	118.2 (3)
C6—C7—C12	122.57 (16)	N5—C15—C15^i	173.7 (4)
C6—C7—C8	121.43 (19)	C14—C15—C15^i	60.7 (2)
C12—C7—C8	115.99 (18)	C14^i—C15—C15^i	57.5 (3)
N2—C8—C7	179.1 (3)	N5—C16—C14	122.7 (3)
N3—C9—C2	178.3 (2)	N5—C16—H16	118.7
C11—C10—C3	121.47 (14)	C14—C16—H16	118.7
C11—C10—H10	119.3	C18—C17—N5	60.2 (3)
C3—C10—H10	119.3	C18—C17—H17A	109.5
C10—C11—C6	121.40 (16)	N5—C17—H17A	169.6
C10—C11—H11	119.3	C18—C17—H17B	109.5
C6—C11—H11	119.3	N5—C17—H17B	75.9
N4—C12—C7	179.6 (3)	H17A—C17—H17B	109.5
C16—N5—C15	58.6 (3)	C18—C17—H17C	109.5
C16—N5—C13	120.1 (3)	N5—C17—H17C	75.9
C15—N5—C13	61.9 (2)	H17A—C17—H17C	109.5
C16—N5—C18	176.7 (4)	H17B—C17—H17C	109.5
C15—N5—C18	121.6 (4)	C17—C18—N5	64.4 (4)
C13—N5—C18	59.8 (4)	N5—C19—H19A	109.5
C16—N5—C19	60.8 (4)	N5—C19—H19B	109.5
C15—N5—C19	119.2 (4)	H19A—C19—H19B	109.5
C13—N5—C19	178.0 (3)	N5—C19—H19C	109.5
C18—N5—C19	119.2 (5)	H19A—C19—H19C	109.5
C16—N5—C17	124.2 (4)	H19B—C19—H19C	109.5
C1—C2—C3—C10	−178.87 (15)	C19—N5—C15—C14	−4.4 (5)
C9—C2—C3—C10	0.0 (3)	C16—N5—C15—C14^i	−173.3 (4)
C1—C2—C3—C4	0.3 (3)	C13—N5—C15—C14^i	−0.1 (3)
C9—C2—C3—C4	179.17 (16)	C18—N5—C15—C14^i	2.9 (5)
C2—C3—C4—C5	−179.46 (16)	C19—N5—C15—C14^i	−178.2 (3)
C10—C3—C4—C5	−0.2 (3)	C13^i—C14—C15—N5	−179.9 (3)
C3—C4—C5—C6	0.0 (3)	C16—C14—C15—N5	−0.5 (3)
C4—C5—C6—C7	179.16 (16)	C15^i—C14—C15—N5	−173.9 (5)
C4—C5—C6—C11	−0.2 (3)	C13^i—C14—C15—C14^i	−6.1 (4)
C5—C6—C7—C12	178.52 (16)	C16—C14—C15—C14^i	173.4 (4)
C11—C6—C7—C12	−2.1 (3)	C15^i—C14—C15—C14^i	−0.0020 (10)
C5—C6—C7—C8	−2.9 (3)	C13^i—C14—C15—C15^i	−6.1 (4)
C11—C6—C7—C8	176.46 (17)	C16—C14—C15—C15^i	173.4 (4)
C2—C3—C10—C11	−179.96 (17)	C15—N5—C16—C14	−0.5 (3)
C4—C3—C10—C11	0.8 (3)	C13—N5—C16—C14	−7.5 (5)
C3—C10—C11—C6	−1.1 (3)	C19—N5—C16—C14	174.6 (5)
C7—C6—C11—C10	−178.57 (17)	C17—N5—C16—C14	−179.3 (4)
C5—C6—C11—C10	0.8 (3)	C15—C14—C16—N5	0.5 (3)
C16—N5—C13—C14^i	6.9 (5)	C15^i—C14—C16—N5	7.1 (5)
C15—N5—C13—C14^i	0.1 (3)	C16—N5—C17—C18	176.1 (4)
C18—N5—C13—C14^i	−176.9 (5)	C13—N5—C17—C18	3.9 (5)
C17—N5—C13—C14^i	179.4 (4)	C19—N5—C17—C18	−178.0 (5)
C16—N5—C15—C14	0.5 (3)	C15—N5—C18—C17	−179.0 (4)
C13—N5—C15—C14	173.7 (4)	C13—N5—C18—C17	−175.9 (5)
C18—N5—C15—C14	176.7 (4)	C19—N5—C18—C17	2.1 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···N1^ii	0.96	3.09	3.535 (7)	110

Symmetry code: (ii) x−1, y−1, z−1.

(tcnq_pi_3)

Crystal data

2(C12H4N4)·C6H7IN	Z = 1
Mr = 628.41	F(000) = 311
Triclinic, P1	Dx = 1.534 Mg m^−3
Hall symbol: P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.0735 (5) Å	Cell parameters from 3990 reflections
b = 7.8171 (4) Å	θ = 6.3–75.7°
c = 13.8419 (4) Å	µ = 9.55 mm^−1
α = 74.353 (4)°	T = 298 K
β = 88.928 (4)°	Prism, black
γ = 67.934 (6)°	0.15 × 0.09 × 0.05 mm
V = 680.10 (7) Å^3

Data collection

Xcalibur, Ruby, Nova diffractometer	3377 independent reflections
Radiation source: micro-focus sealed X-ray tube	3335 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.032
Detector resolution: 10.4323 pixels mm^-1	θmax = 76.1°, θmin = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.440, Tmax = 1	l = −11→17
5812 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.063	w = 1/[σ^2(Fo^2) + (0.1185P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.146	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 2.77 e Å^−3
3377 reflections	Δρmin = −0.80 e Å^−3
362 parameters	Absolute structure: Refined as an inversion twin.
5 restraints	Absolute structure parameter: 0.997 (10)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.74601 (8)	−0.29384 (8)	1.24096 (6)	0.0708 (2)
N5	0.0347 (11)	0.1311 (11)	1.1171 (5)	0.0585 (14)
C13	0.1611 (13)	0.1797 (12)	1.1694 (6)	0.0564 (16)
H13	0.107148	0.299792	1.181156	0.068*
C14	0.3630 (13)	0.0630 (12)	1.2058 (6)	0.0564 (15)
H14	0.439702	0.103884	1.241422	0.068*
C15	0.4477 (10)	−0.1150 (10)	1.1882 (5)	0.0463 (12)
C16	0.3268 (15)	−0.1723 (13)	1.1359 (7)	0.0601 (17)
H16	0.380807	−0.292457	1.124204	0.072*
C17	0.1319 (17)	−0.0533 (14)	1.1023 (8)	0.058 (2)
H17	0.055757	−0.095164	1.066983	0.07*
C18	−0.1994 (7)	0.2726 (7)	1.0701 (3)	0.0291 (8)
H18A	−0.256404	0.207069	1.037103	0.044*
H18B	−0.280817	0.307105	1.123263	0.044*
H18C	−0.198485	0.386819	1.022164	0.044*
N1A	0.7487 (19)	−0.097 (2)	0.9689 (7)	0.086 (3)
N2A	0.3643 (14)	0.8250 (10)	0.4474 (6)	0.0627 (16)
N3A	0.6336 (12)	−0.4676 (11)	0.8093 (7)	0.0638 (17)
N4A	0.2236 (17)	0.4630 (13)	0.2914 (6)	0.070 (2)
C1A	0.6965 (12)	−0.1168 (12)	0.8947 (6)	0.0539 (15)
C2A	0.6309 (9)	−0.1354 (9)	0.8035 (5)	0.0415 (11)
C3A	0.5692 (8)	0.0185 (8)	0.7162 (4)	0.0365 (10)
C4A	0.5728 (9)	0.2017 (9)	0.7155 (5)	0.0396 (10)
H4A	0.618507	0.217075	0.773941	0.047*
C5A	0.5105 (9)	0.3525 (9)	0.6306 (5)	0.0406 (11)
H5A	0.513417	0.469668	0.632236	0.049*
C6A	0.4403 (7)	0.3350 (8)	0.5388 (4)	0.0364 (10)
C7A	0.3714 (9)	0.4913 (9)	0.4527 (5)	0.0411 (11)
C8A	0.3711 (10)	0.6752 (10)	0.4503 (5)	0.0464 (13)
C9A	0.6321 (10)	−0.3193 (10)	0.8067 (5)	0.0470 (13)
C10A	0.5019 (8)	−0.0004 (8)	0.6243 (5)	0.0377 (10)
H10A	0.500882	−0.118041	0.622315	0.045*
C11A	0.4392 (8)	0.1513 (8)	0.5396 (4)	0.0362 (10)
H11A	0.394725	0.135702	0.48097	0.043*
C12A	0.2924 (13)	0.4752 (11)	0.3635 (7)	0.0484 (15)
N1B	0.3208 (19)	−0.4883 (14)	1.0214 (7)	0.080 (2)
N2B	−0.0831 (12)	0.4548 (10)	0.5118 (6)	0.0589 (15)
N3B	0.1638 (14)	−0.8345 (11)	0.8665 (7)	0.0666 (17)
N4B	−0.2004 (19)	0.1155 (17)	0.3378 (7)	0.082 (2)
C1B	0.2558 (13)	−0.4951 (9)	0.9483 (5)	0.0512 (14)
C2B	0.1729 (9)	−0.5057 (9)	0.8588 (5)	0.0404 (11)
C3B	0.1058 (8)	−0.3488 (8)	0.7730 (4)	0.0364 (10)
C4B	0.1092 (8)	−0.1658 (9)	0.7734 (4)	0.0382 (10)
H4B	0.154732	−0.151731	0.832322	0.046*
C5B	0.0476 (8)	−0.0149 (8)	0.6900 (4)	0.0368 (10)
H5B	0.050627	0.101772	0.692576	0.044*
C6B	−0.0224 (8)	−0.0300 (8)	0.5973 (4)	0.0355 (10)
C7B	−0.0843 (9)	0.1276 (9)	0.5113 (5)	0.0409 (11)
C8B	−0.0832 (9)	0.3084 (10)	0.5112 (5)	0.0443 (12)
C9B	0.1680 (11)	−0.6862 (9)	0.8606 (5)	0.0465 (13)
C10B	0.0337 (8)	−0.3639 (8)	0.6803 (5)	0.0386 (10)
H10B	0.029539	−0.480119	0.67776	0.046*
C11B	−0.0284 (9)	−0.2112 (9)	0.5966 (4)	0.0395 (11)
H11B	−0.075548	−0.224122	0.537746	0.047*
C12B	−0.1500 (14)	0.1159 (10)	0.4167 (5)	0.0527 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0725 (3)	0.0693 (3)	0.0572 (3)	−0.01619 (19)	−0.00554 (17)	−0.01218 (18)
N5	0.073 (4)	0.066 (4)	0.039 (3)	−0.033 (3)	0.002 (3)	−0.010 (3)
C13	0.070 (4)	0.054 (4)	0.049 (4)	−0.027 (3)	−0.002 (3)	−0.016 (3)
C14	0.068 (4)	0.059 (4)	0.050 (4)	−0.028 (3)	0.001 (3)	−0.023 (3)
C15	0.051 (3)	0.047 (3)	0.038 (3)	−0.019 (2)	−0.002 (2)	−0.008 (2)
C16	0.079 (5)	0.058 (4)	0.053 (4)	−0.031 (4)	0.003 (4)	−0.023 (3)
C17	0.074 (5)	0.063 (5)	0.055 (5)	−0.038 (4)	0.005 (4)	−0.026 (4)
C18	0.038 (2)	0.032 (2)	0.0159 (18)	−0.0129 (17)	−0.0004 (16)	−0.0056 (15)
N1A	0.110 (7)	0.118 (8)	0.043 (4)	−0.059 (6)	−0.004 (4)	−0.022 (4)
N2A	0.092 (5)	0.049 (3)	0.056 (4)	−0.034 (3)	0.013 (3)	−0.020 (3)
N3A	0.071 (4)	0.057 (4)	0.069 (4)	−0.035 (3)	0.006 (3)	−0.010 (3)
N4A	0.105 (6)	0.067 (4)	0.043 (3)	−0.038 (4)	−0.007 (4)	−0.014 (3)
C1A	0.061 (4)	0.065 (4)	0.039 (3)	−0.030 (3)	0.002 (3)	−0.011 (3)
C2A	0.043 (2)	0.050 (3)	0.037 (3)	−0.024 (2)	0.005 (2)	−0.012 (2)
C3A	0.035 (2)	0.042 (3)	0.036 (3)	−0.0164 (19)	0.0039 (19)	−0.014 (2)
C4A	0.044 (2)	0.044 (3)	0.035 (3)	−0.019 (2)	0.002 (2)	−0.016 (2)
C5A	0.045 (2)	0.040 (2)	0.041 (3)	−0.018 (2)	0.003 (2)	−0.015 (2)
C6A	0.034 (2)	0.040 (2)	0.039 (3)	−0.0169 (19)	0.0044 (19)	−0.013 (2)
C7A	0.043 (2)	0.043 (3)	0.040 (3)	−0.018 (2)	0.002 (2)	−0.012 (2)
C8A	0.050 (3)	0.044 (3)	0.045 (3)	−0.019 (2)	0.010 (2)	−0.013 (2)
C9A	0.047 (3)	0.048 (3)	0.045 (3)	−0.024 (2)	0.003 (2)	−0.004 (2)
C10A	0.038 (2)	0.040 (2)	0.039 (3)	−0.019 (2)	0.001 (2)	−0.012 (2)
C11A	0.040 (2)	0.039 (2)	0.035 (2)	−0.020 (2)	0.0012 (19)	−0.011 (2)
C12A	0.052 (4)	0.043 (3)	0.045 (4)	−0.016 (3)	−0.002 (3)	−0.009 (3)
N1B	0.117 (7)	0.070 (4)	0.051 (4)	−0.035 (5)	−0.015 (4)	−0.013 (4)
N2B	0.078 (4)	0.051 (3)	0.055 (4)	−0.036 (3)	−0.002 (3)	−0.010 (3)
N3B	0.089 (5)	0.047 (3)	0.066 (4)	−0.029 (3)	0.003 (4)	−0.016 (3)
N4B	0.111 (7)	0.091 (6)	0.051 (4)	−0.042 (5)	−0.008 (4)	−0.026 (4)
C1B	0.074 (4)	0.040 (3)	0.037 (3)	−0.022 (3)	−0.003 (3)	−0.007 (2)
C2B	0.044 (2)	0.041 (3)	0.037 (3)	−0.016 (2)	0.002 (2)	−0.012 (2)
C3B	0.038 (2)	0.038 (2)	0.035 (3)	−0.0164 (19)	0.0028 (19)	−0.012 (2)
C4B	0.041 (2)	0.042 (3)	0.036 (3)	−0.019 (2)	0.0007 (19)	−0.014 (2)
C5B	0.038 (2)	0.037 (2)	0.040 (3)	−0.0181 (19)	0.0029 (19)	−0.012 (2)
C6B	0.034 (2)	0.040 (2)	0.035 (3)	−0.0178 (18)	0.0027 (18)	−0.010 (2)
C7B	0.043 (2)	0.047 (3)	0.036 (3)	−0.021 (2)	0.002 (2)	−0.012 (2)
C8B	0.043 (2)	0.049 (3)	0.041 (3)	−0.023 (2)	0.000 (2)	−0.005 (2)
C9B	0.059 (3)	0.039 (3)	0.039 (3)	−0.019 (2)	0.006 (3)	−0.008 (2)
C10B	0.042 (2)	0.040 (2)	0.038 (3)	−0.019 (2)	0.004 (2)	−0.015 (2)
C11B	0.042 (2)	0.045 (3)	0.035 (3)	−0.017 (2)	0.003 (2)	−0.017 (2)
C12B	0.075 (4)	0.046 (3)	0.034 (3)	−0.021 (3)	0.005 (3)	−0.010 (2)

Geometric parameters (Å, º)

I1—C15	2.057 (7)	C6A—C7A	1.394 (9)
N5—C13	1.377 (11)	C6A—C11A	1.436 (7)
N5—C17	1.415 (12)	C7A—C12A	1.420 (11)
N5—C18	1.632 (7)	C7A—C8A	1.428 (9)
C13—C14	1.388 (13)	C10A—C11A	1.360 (8)
C13—H13	0.93	C10A—H10A	0.93
C14—C15	1.380 (11)	C11A—H11A	0.93
C14—H14	0.93	N1B—C1B	1.141 (12)
C15—C16	1.393 (11)	N2B—C8B	1.147 (11)
C16—C17	1.345 (15)	N3B—C9B	1.151 (11)
C16—H16	0.93	N4B—C12B	1.156 (12)
C17—H17	0.93	C1B—C2B	1.416 (9)
C18—H18A	0.96	C2B—C3B	1.392 (8)
C18—H18B	0.96	C2B—C9B	1.418 (9)
C18—H18C	0.96	C3B—C4B	1.442 (7)
N1A—C1A	1.166 (13)	C3B—C10B	1.439 (8)
N2A—C8A	1.144 (11)	C4B—C5B	1.346 (8)
N3A—C9A	1.146 (12)	C4B—H4B	0.93
N4A—C12A	1.160 (13)	C5B—C6B	1.434 (8)
C1A—C2A	1.416 (10)	C5B—H5B	0.93
C2A—C3A	1.392 (9)	C6B—C7B	1.396 (8)
C2A—C9A	1.423 (9)	C6B—C11B	1.436 (8)
C3A—C10A	1.430 (8)	C7B—C8B	1.416 (9)
C3A—C4A	1.439 (8)	C7B—C12B	1.434 (10)
C4A—C5A	1.359 (9)	C10B—C11B	1.356 (9)
C4A—H4A	0.93	C10B—H10B	0.93
C5A—C6A	1.431 (8)	C11B—H11B	0.93
C5A—H5A	0.93
C13—N5—C17	113.1 (7)	C6A—C7A—C12A	120.9 (6)
C13—N5—C18	124.7 (7)	C6A—C7A—C8A	122.2 (6)
C17—N5—C18	122.1 (7)	C12A—C7A—C8A	116.9 (6)
N5—C13—C14	125.0 (8)	N2A—C8A—C7A	177.8 (8)
N5—C13—H13	117.5	N3A—C9A—C2A	179.8 (9)
C14—C13—H13	117.5	C11A—C10A—C3A	120.9 (5)
C15—C14—C13	118.7 (7)	C11A—C10A—H10A	119.5
C15—C14—H14	120.6	C3A—C10A—H10A	119.5
C13—C14—H14	120.6	C10A—C11A—C6A	121.4 (5)
C14—C15—C16	118.9 (7)	C10A—C11A—H11A	119.3
C14—C15—I1	120.3 (6)	C6A—C11A—H11A	119.3
C16—C15—I1	120.8 (6)	N4A—C12A—C7A	178.5 (10)
C17—C16—C15	119.9 (8)	N1B—C1B—C2B	178.8 (9)
C17—C16—H16	120.1	C3B—C2B—C1B	121.6 (5)
C15—C16—H16	120.1	C3B—C2B—C9B	122.0 (6)
C16—C17—N5	124.5 (8)	C1B—C2B—C9B	116.3 (6)
C16—C17—H17	117.7	C2B—C3B—C4B	121.0 (5)
N5—C17—H17	117.7	C2B—C3B—C10B	121.4 (5)
N5—C18—H18A	109.5	C4B—C3B—C10B	117.6 (5)
N5—C18—H18B	109.5	C5B—C4B—C3B	121.1 (5)
H18A—C18—H18B	109.5	C5B—C4B—H4B	119.4
N5—C18—H18C	109.5	C3B—C4B—H4B	119.4
H18A—C18—H18C	109.5	C4B—C5B—C6B	121.5 (5)
H18B—C18—H18C	109.5	C4B—C5B—H5B	119.3
N1A—C1A—C2A	178.3 (10)	C6B—C5B—H5B	119.3
C3A—C2A—C1A	121.3 (6)	C7B—C6B—C5B	120.7 (5)
C3A—C2A—C9A	122.6 (6)	C7B—C6B—C11B	121.6 (5)
C1A—C2A—C9A	116.1 (6)	C5B—C6B—C11B	117.7 (5)
C2A—C3A—C10A	121.2 (5)	C6B—C7B—C8B	122.3 (6)
C2A—C3A—C4A	121.0 (5)	C6B—C7B—C12B	122.1 (6)
C10A—C3A—C4A	117.8 (5)	C8B—C7B—C12B	115.6 (6)
C5A—C4A—C3A	121.0 (5)	N2B—C8B—C7B	179.4 (8)
C5A—C4A—H4A	119.5	N3B—C9B—C2B	177.0 (8)
C3A—C4A—H4A	119.5	C11B—C10B—C3B	121.0 (5)
C4A—C5A—C6A	121.4 (5)	C11B—C10B—H10B	119.5
C4A—C5A—H5A	119.3	C3B—C10B—H10B	119.5
C6A—C5A—H5A	119.3	C10B—C11B—C6B	121.1 (5)
C7A—C6A—C5A	121.3 (5)	C10B—C11B—H11B	119.4
C7A—C6A—C11A	121.3 (5)	C6B—C11B—H11B	119.4
C5A—C6A—C11A	117.4 (5)	N4B—C12B—C7B	176.1 (9)
C17—N5—C13—C14	−0.6 (12)	C2A—C3A—C10A—C11A	179.1 (5)
C18—N5—C13—C14	−177.1 (7)	C4A—C3A—C10A—C11A	−1.4 (8)
N5—C13—C14—C15	0.9 (13)	C3A—C10A—C11A—C6A	0.7 (8)
C13—C14—C15—C16	−1.0 (11)	C7A—C6A—C11A—C10A	−178.4 (5)
C13—C14—C15—I1	−179.8 (6)	C5A—C6A—C11A—C10A	0.1 (8)
C14—C15—C16—C17	0.9 (12)	C1B—C2B—C3B—C4B	−3.0 (9)
I1—C15—C16—C17	179.8 (7)	C9B—C2B—C3B—C4B	179.0 (5)
C15—C16—C17—N5	−0.8 (14)	C1B—C2B—C3B—C10B	176.0 (6)
C13—N5—C17—C16	0.5 (13)	C9B—C2B—C3B—C10B	−2.0 (9)
C18—N5—C17—C16	177.2 (7)	C2B—C3B—C4B—C5B	178.9 (5)
C1A—C2A—C3A—C10A	−179.6 (6)	C10B—C3B—C4B—C5B	−0.2 (8)
C9A—C2A—C3A—C10A	0.3 (8)	C3B—C4B—C5B—C6B	−0.4 (8)
C1A—C2A—C3A—C4A	0.9 (8)	C4B—C5B—C6B—C7B	−179.5 (5)
C9A—C2A—C3A—C4A	−179.1 (5)	C4B—C5B—C6B—C11B	1.1 (8)
C2A—C3A—C4A—C5A	−179.3 (5)	C5B—C6B—C7B—C8B	−0.6 (8)
C10A—C3A—C4A—C5A	1.2 (8)	C11B—C6B—C7B—C8B	178.7 (5)
C3A—C4A—C5A—C6A	−0.4 (9)	C5B—C6B—C7B—C12B	178.3 (6)
C4A—C5A—C6A—C7A	178.3 (5)	C11B—C6B—C7B—C12B	−2.3 (9)
C4A—C5A—C6A—C11A	−0.3 (8)	C2B—C3B—C10B—C11B	−178.9 (5)
C5A—C6A—C7A—C12A	−176.8 (6)	C4B—C3B—C10B—C11B	0.1 (8)
C11A—C6A—C7A—C12A	1.8 (9)	C3B—C10B—C11B—C6B	0.6 (8)
C5A—C6A—C7A—C8A	1.4 (8)	C7B—C6B—C11B—C10B	179.4 (5)
C11A—C6A—C7A—C8A	180.0 (5)	C5B—C6B—C11B—C10B	−1.2 (8)