Hirshfeld surface analysis of two new phosphoro­thioic tri­amide structures

Hirshfeld surfaces and two-dimensional fingerprint plots are used to analyse the inter­molecular inter­actions in two new phospho­rothioic tri­amide structures, namely N,N′,N′′-tris­(3,4-di­methyl­phen­yl)phospho­rothioic tri­amide aceto­nitrile hemisolvate, P(S)[NHC₆H₃-3,4-(CH₃)₂]₃·0.5CH₃CN or C₂₄H₃₀N₃PS·0.5CH₃CN, (I), and N,N′,N′′-tris­(4-methyl­phen­yl)phospho­rothioic tri­amide–3-methyl­piperi­dinium chloride (1/1), P(S)[NHC₆H₄(4-CH₃)]₃·[3-CH₃-C₅H₉NH₂]⁺·Cl⁻ or C₂₁H₂₄N₃PS·C₆H₁₄N⁺·Cl⁻, (II). The asymmetric unit of (I) consists of two independent phospho­rothioic tri­amide mol­ecules and one aceto­nitrile solvent mol­ecule, whereas for (II), the asymmetric unit is composed of three components (mol­ecule, cation and anion). In the structure of (I), the different components are organized into a six-mol­ecule aggregate through N—H...S and N—H...N hydrogen bonds. The components of (II) are aggregated into a two-dimensional array through N—H...S and N—H...Cl hydrogen bonds. Moreover, inter­esting features of packing arise in this structure due to the presence of a double hydrogen-bond acceptor (the S atom of the phospho­rothioic tri­amide mol­ecule) and of a double hydrogen-bond donor (the N—H unit of the cation). For both (I) and (II), the full fingerprint plot of each component is asymmetric as a consequence of the presence of three fragments. These analyses reveal that H...H inter­actions [67.7 and 64.3% for the two symmetry-independent phos­pho­rothioic tri­amide mol­ecules of (I), 30.7% for the acetonitrile solvent of (I), 63.8% in the phospho­rothioic tri­amide mol­ecule of (II) and 62.9% in the 3-methyl­piperidinium cation of (II)] outnumber the other contacts for all the components in both structures, except for the chloride anion of (II), which only receives the Cl...H contact. The phospho­rothioic tri­amide mol­ecules of both structures include unsaturated C atoms, thus presenting C...H/H...C inter­actions: 17.6 and 21% for the two symmetry-independent phospho­rothioic tri­amide mol­ecules in (I), and 22.7% for the phospho­rothioic tri­amide mol­ecule of (II). Furthermore, the N—H...S hydrogen bonds in both (I) and (II), and the N—H...Cl hydrogen bonds in (II), are the most prominent inter­actions, appearing as large red spots on the Hirshfeld surface maps. The N...H/H...N contacts in structure (I) are considerable, whereas for (II), they give a negligible contribution to the total inter­actions in the system.

S1. Introduction

Three-dimensional Hirshfeld surfaces and the corresponding two-dimensional fingerprint maps are unique for each molecule/ion constituting the asymmetric unit of a crystal structure. They provide an easy means of comparing inter­molecular contacts relative to van der Waals radii through a simple red–white–blue colour scheme (McKinnon, Jayatilaka & Spackman, 2007).

So far, this type of analysis has been applied to the study of different families of compounds, such as polymorphic systems in CS₂ at low temperature (Dziubek & Katrusiak, 2004), piracetam (Fabbiani et al., 2005), R-glycylglycine (Moggach, Allan, Parsons & Sawyer, 2006), L-serine (Moggach, Marshall & Parsons, 2006), benzene (Budzianowski & Katrusiak, 2006), tetra­thia­fulvalene (McKinnon, Fabbiani & Spackman, 2007), naphthalene, phenanthrene and pyrene (Fabbiani et al., 2006) and a series of tri­aryl­carbonyl derivatives (Bacchi et al., 2006). In addition, symmetry-independent molecules within one structure (Tarahhomi et al. 2013; Gholivand et al., 2015), cation–anion compounds (Gholizadeh et al., 2014; Ling et al., 2010) and cocrystals (Clausen et al., 2010) have also been studied by Hirshfeld surface analysis.

Recently, we have used this analysis to study inter­molecular inter­actions in three different families of phospho­ramides (phospho­ric tri­amide, amido­phospho­ester and amido­pyrophosphate) (Tarahhomi et al., 2013) and also in organotin(IV)–phospho­ramide complexes (Pourayoubi, Shoghpour Bayraq et al., 2014). Such analysis has not been used to date for the study of phospho­rothioic tri­amide compounds.

In this work, we present crystal structure analyses complemented by an investigation of molecular inter­actions for two new phospho­rothioic tri­amide structures, i.e. P(S)[NHC₆H₃-3,4-(CH₃)₂]₃.CH₃CN, (I), and P(S)[NHC₆H₄(4-CH₃)]₃[3-CH₃—C₅H₉NH₂]⁺.Cl^-, (II) (see Schemes 1 and 2, respectively).

S2. Experimental

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of P(S)[NHC~6~H~3~-3,4-(CH~3~)~2~]~3~.CH~3~CN, (I)

A solution of 3,4-di­methyl­aniline (4.32 g, 35.76 mmol) in dry CH₃CN (10 ml) was added dropwise to a solution of thio­phospho­ryl chloride (1.01 g, 5.96 mmol) in the same solvent (10 ml) under stirring at 273 K. After 3 h, the stirring was stopped and the mixture was transferred to a beaker which was kept at room temperature to evaporate the solvent. After a few days, the solid formed was washed with distilled water. White single crystals were obtained from a solution of the product in CH₃CN/CHCl₃ (3:1 v/v) by slow evaporation at room temperature. Yield > 70%. IR (KBr disc, ν, cm^-1): 653, 810, 927, 980, 1017, 1059, 1119, 1181, 1229, 1280, 1381, 1457, 1513, 1616, 2937, 3182 (NH).

S2.1.2. Synthesis of P(S)[NHC~6~H~4~(4-CH~3~)]~3~[3-CH~3~—C~5~H~9ÑH~2~]^+^.Cl^-^, (II)

Compound (II) was obtained in an unsuccessful effort to prepare a mixed amido–phospho­rothioic tri­amide from a reaction of thio­phospho­ryl chloride (0.500 g, 2.95 mmol) and p-toluidine (1.264 g, 11.80 mmol) in dry CH₃CN (20 ml) at 273 K in the first step of the process. The solid formed was removed and then in the second step 3-methyl piperidine (0.585 g, 5.90 mmol) was added to the filtered solution under stirring at 273 K; the reaction time was 3 h per step. After stopping the second reaction, the mixture was transferred to a beaker to evaporate the solvent at room temperature. After a few days, the solid formed was washed with distilled water and dried. Crystals of (II) were obtained from a solution of the product in CH₃OH/n-C₇H₁₆ (5:1 v/v) by slow evaporation at room temperature. Yield [relative to to P(S)Cl₃] > 70%. IR (KBr disc, ν, cm^-1): 652, 685, 762, 803, 888, 922, 1023, 1091, 1157, 1196, 1211, 1297, 1421, 1452, 1487, 1591, 2851, 2927, 3307 (NH).

S2.2. Hirshfeld surface analysis and fingerprint plots

The three-dimensional Hirshfeld surfaces (HSs), mapped with d_norm (Spackman & McKinnon, 2002) and two-dimensional fingerprint plots of structures (I) and (II) were generated using the Crystal Explorer software (Wolff et al., 2013).

S2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For both structures, H atoms bonded to N atoms were found in difference Fourier maps and their coordinates were refined with a distance restraint N—H = 0.87 Å with a standatd uncertainty of 0.01 Å. All other H atoms in both structures were kept in their geometrically expected positions, with C—H = 0.96 Å. The isotropic atomic displacement parameters of the H atoms were evaluated as 1.2U_eq of the parent atom. In (II), two methyl groups bonded to aromatic rings were found to be disordered by rotation around the C—C axis. The disordered H-atom positions were clearly identified from difference Fourier maps. The occupancies for the two disordered positions were 0.51 (2) and 0.49 (2) for the methyl group at C7, and 0.40 (3) and 0.60 (3) for the methyl group at C14.

S3. Results and discussion

The asymmetric unit of (I) consists of two symmetry-independent phospho­rothioic tri­amide molecules [(IA) and (IB) hereafter] and one aceto­nitrile (CH₃CN) solvent molecule (Fig. 1), whereas, for (II), the asymmetric unit consists of one phospho­rothioic tri­amide molecule, one 3-methyl­piperidinium cation and one chloride anion (Fig. 2). Selected geometric parameters and hydrogen-bond geometries for (I) and (II) are given in Tables 2–5. In both structures, the P atoms are within a distorted tetra­hedral P[S][N]₃ environment with the bond angles ranging from 98.85 (9) (N1a—P1a—N3a) to 116.27 (7)° (S1a—P1a—N3a) for (IA), from 97.25 (10) (N1b—P1b—N2b) to 116.55 (8)° (S1b—P1b—N2b) for (IB), and from 97.91 (6) (N1—P1—N3) to 117.55 (4)° [S1—P1—N1] for (II).

The Pδb S and P—N bond lengths are within the ranges observed in analogous structures (Pourayoubi, Abrishami et al., 2014). The P—N—C angles, with values close to 120° show that the hybridization of the N atom is close to sp². All N atoms in the structures (I) and (II) have almost planar geometry, except for atom N3a of molecule (IA). In this case, a slightly nonplanar geometry is found, reflected in the bond-angle sum at N3a [353.3 (2)°].

Moreover, the positions of atoms directly bonded to N3a suggest an anti orientation of the lone electron pair with respect to the Pδb S bond. This is similar to the recently published analysis of the Cambridge Structural Database (CSD, Version 5.35, updated in February 2014; Groom & Allen, 2014) for structures with a P(S)[N]₃ fragment including nonplanar N atoms within a [P]N[X][Y] environment (X and Y are any atoms) (Raissi Shabari et al., 2015).

In the crystal structure of (I), two (IA) molecules and two (IB) molecules, together with two aceto­nitrile solvent molecules, form a six-molecule aggregate, as shown in Fig. 3. In this arrangement, the four phospho­rothioic tri­amide molecules are hydrogen bonded to each other via N—H···S hydrogen bonds, forming R₂²(8) and R₂¹(6) graph-set motifs (for the symbols defined for graph-set motifs, see Etter et al., 1990). The aceto­nitrile solvent molecules are linked at the two ends of this aggregate through N—H···N hydrogen bonds (Table 3), which accompany C—H···N inter­actions, forming R₂¹(6) and R₂¹(8) graph-set motifs.

In the crystal structure of (II), a two-dimensional arrangement parallel to the (101) plane is built from N—H···S and N—H···Cl hydrogen bonds involving the neutral molecules, cations and anions, as shown in Fig. 4. Within this pattern, two phospho­rothioic tri­amide molecules and two cations form R₂²(4) graph-set motifs, through a Pδb S···[H—N]₂ inter­action with one N—H unit from each adjacent CH₃—C₅H₉NH₂⁺ cation. In this motif, we can distinguish two kinds of three-centred hydrogen bonding, i.e. S connected with two H-donor sites (double hydrogen-bond acceptor), and an N—H unit connected to two S atoms (bifurcated hydrogen bond). The other NH unit of the cation and all three NH units of the P(S)[NHC₆H₄(4-CH₃)]₃ molecule take part in N—H···Cl hydrogen bonds.

The three-dimensional HS generated for structures (I) and (II) are presented in Figs. 5 and 6, respectively. The contacts shown in red highlight the inter­molecular inter­actions with distances closer than the sum of the van der Waals (vdW) radii, while white is used for contacts near the vdW separation, and blue represents longer contacts (McKinnon, Jayatilaka & Spackman, 2007).

For structure (I), the Hirshfeld surfaces are plotted separately for the two symmetry-independent phospho­rothioic tri­amide molecules (Figs. 5a and 5b). In these maps, two different N—H···Sδb P hydrogen bonds, connecting molecules (IA) and (IB) to each other, appear as large red areas labelled 1 and 2. The other large red spots in Fig. 5a (labels 3 and 4) correspond to pairs of N—H···Sδb P hydrogen bonds between molecules (IA). On the other hand, molecule (IB) is also linked to the aceto­nitrile solvent molecule through N—H···N (labels 6 and 7) and C—H···N (label 8). These inter­actions are seen in Fig. 5(b) as large and small red areas, respectively, in accord with the strengths of the inter­actions.

Furthermore, it should be noted that the only remarkable H···C contact in structure (I) is related to the inter­action of one methyl H atom [on the 3,4-(CH₃)₂C₆H₃NH fragment] in molecule (IB) with the aromatic ring of an adjacent molecule (IB) (C15b—H2c15b···C2b; label 9 in Fig. 5b) that is seen as a pale-red spot. The HS for the aceto­nitrile solvent molecule does not provide any further information and was not included.

Concerning the structure of (II), the Hirshfeld surfaces were generated for the P(S)[NHC₆H₄-4-CH₃]₃ molecule, for the 3-CH₃—C₅H₉NH₂⁺ cation and for the Cl^- anion and are presented in Figs. 6(a), 6(b) and 6(c), respectively.

Three NH units of the phospho­rothioic tri­amide molecule take part in different N—H···Cl hydrogen bonds with two neighbouring Cl^- anions (labels 1–3 in Fig. 6a). These hydrogen bonds and the N—H···Cl hydrogen bond between the cation and the anion (which will be discussed later) are the most important inter­actions in structure (II) and are shown as large red spots on the HS.

The S atom of the phospho­rothioic tri­amide molecule is not only involved in the two N—H···S hydrogen bonds (labels 4 and 6) with the two neighbouring cations, but it also takes part in an S···S contact with a neighbouring phospho­rothioic tri­amide molecule (label 5). A search of the CSD shows that such an inter­action was found only in one structure with a P(S)[N]₃ segment, viz. [H₂N][CH₃NH]P(S)–N(CH₃)–P(S)[NH₂]₂ (CSD refcode MTHPAM; Herbst-Irmer et al., 1996).

The other light-red spots in Fig. 6(a) (labels 7–15) are related to C—H···C inter­actions between the C—H units of the cation and the phospho­rothioic tri­amide molecule, with the acceptor C atom belonging to the aromatic ring of the phospho­rothioic tri­amide molecule. Furthermore, one NH unit of the cation participates in an N—H···Cl inter­action that appears as a large red spot with label 16 in Fig. 6(b).

The Cl^- anion in the crystal inter­acts with the above mentioned three NH units and with another one from the cation, resulting in four deep red spots in Fig. 6(c).

Two-dimensional fingerprint plots (FPs) are derived from the Hirshfeld surface (HS) by plotting the fraction of points on the surface as a function of (d_e, d_i), where d_e and d_i represent the distances from a point on the HS to the nearest atoms outside and inside the surface, respectively. The points are coloured as a function of the fraction of surface points, ranging from blue (relatively few points) through green (moderate fraction) to red (highest fraction) (McKinnon et al., 2004).

The FPs of the chemically equivalent molecules (IA) and (IB) (Figs. 7 and 8, and Fig. S1 in the Supporting information; in the following discussion, all figure numbers with a prefix `S' refer to figures that can be found in the Supporting information) are not identical because Hirshfeld surfaces and the corresponding FPs depend on the molecular conformation, as well as on the molecular environment in the crystal (Fabbiani et al., 2007). Molecule (IA), through two different N—H···S hydrogen bonds, is linked to molecules (IA) and (IB). For its part, molecule (IB) connects to molecule (IA) through the above-mentioned inter­action and also connects to the aceto­nitrile solvent molecule via C—H···N and N—H···N inter­actions. As a result, the full FPs of molecules (IA) and (IB) are different (Figs. 7a and 8a).

Inter­actions of the types H···H, C···H/H···C, S···H/H···S and N···H/H···N exist for both molecules [Figs. 7b, 7c, S1a and S1b, respectively, for molecule (IA) , and Figs. 8b, 8c, S2a and S2b, respectively, for molecule (IB)]. Moreover, C···C inter­actions for both (IA) and (IB) and N···N and C···N inter­actions for (IB) have negligible contributions, which are not visible in FPs. The H···H contacts represent the largest relative contribution, amounting to 67.7% in (IA) and 64.3% in (IB), with one distinct spike for both molecules (Figs. 7b and 8b).

Furthermore, in the fingerprint plots of the two molecules, the C···H/H···C contacts [17.6% for (IA) (Fig. 7c) and 21% for (IB) (Fig. 8c)] appear as two short spikes, while the S···H/H···S inter­actions [10.3% in (IA) (Fig. S1a) and 7.6% for (IB) (Fig. S2a)] develop as two sharp spikes.

On the other hand, the contribution of N···H/H···N inter­actions in (IA) is very small (1.1%; Fig. S1b), whereas in (IB), it becomes more considerable (4.3%; Fig. S2b), with the differences between the spikes in the N···H diagram being very clear.

For structure (II), FPs are shown in Figs. 9(a), 9(b), 9(c), S3(a) and S3(b) for the phospho­rothioic tri­amide molecule, in Figs. 10(a), 10(b), 10(c), S4(a) and S4(b) for the 3-methyl­piperidinium cation, and in Fig. 11 for the chloride anion. The full FP for each component is not symmetric (Figs. 9a, 10a and 11), as the three components have quite different shapes and also each component has a different environment.

Figs. 9(b) and 9(c) depict the majority H···H (63.8%) and C···H/H···C (22.7%) contacts, while Fig. S3(a) shows the FP for the less important S···H/H···S (6.7%) contacts for the phospho­rothioic tri­amide molecule. As for the C···H/H···C contacts (Fig. 9c), the shortest d_e + d_i (shown as blue points on the divided fingerprint) in spikes is near 2.6 Å and for S···H/H···S (Fig. S3a), it is near 2.3 Å. In contrast to the structure of (I), the N···H/H···N inter­actions have negligible contributions to the total inter­actions in (II).

For the [3-CH₃—C₅H₉NH₂]⁺ cation of (II), the full fingerprint plot is shown in Fig. 10(a). The most important inter­actions are the H···H contacts (62.9%; Fig. 10b), followed by H···C (22.5%; Fig. 10c), H···S (7.4%) and H···Cl (6.1%) (Figs. S4a and S4b, respectively). All the inter­actions discussed for the cation appear as a single spike in the region d_e > d_i in divided FPs, as expected. In other words, no S···H, Cl···H and meaningful C···H inter­actions were found with the cation, hence the corresponding fingerprint plots are quite asymmetric. Additionally, an acceptor spike is revealed for the Cl···H contacts which mostly concentrates in the region of d_e < d_i, the `lower part' of the fingerprint plot (Fig. 11). As there is no other inter­action received by this anion, the inter­actions mentioned involve a 100% contribution to the Hirshfeld surface.

Computing details

For both compounds, data collection: (CrysAlis PRO; Agilent, 2014); cell refinement: (CrysAlis PRO; Agilent, 2014); data reduction: (CrysAlis PRO; Agilent, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. Displacement ellipsoid plot (50% probability) of the components of the asymmetric unit of structure (I), showing the atom-numbering scheme. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Displacement ellipsoid plot (50% probability) of the asymmetric unit of structure (II), showing the atom-numbering scheme. H atoms are drawn as spheres of arbitrary radii. Two methyl groups exhibit disorder.
	Fig. 3. Part of the crystal packing of structure (I), showing the hexamolecular aggregate mediated by N—H···S and N—H···N hydrogen bonds. C—H···N hydrogen bonds are also shown. The hydrogen bonds are shown as dotted lines and H atoms not involved in hydrogen bonds have been omitted for clarity. Molecules of the same colour are related by symmetry. At the two ends of the aggregate, only one motif is labelled and the black dotted lines pertain to the labelled motifs.
	Fig. 4. A view of the two-dimensional array of (II) built from N—H···S and N—H···Cl hydrogen bonds. The hydrogen bonds are shown as dotted lines and H atoms not involved in hydrogen bonds have been omitted for clarity. The phosphorothioic triamide molecules, cations and anions are represented as blue, red and green, respectively.
	Fig. 5. Front and back views of the Hirshfeld surface for (IA) and (IB). For guidance, the phosphorothioic triamide molecules are shown on the left in the corresponding orientation, and the solvent molecule is shown near the HS of molecule (IB). The hydrogen bonds according to the labels in the figures are as follows, with the labels in parentheses: (a) molecule (IA): N3b—H1n3b···S1aδb P1a (1), N2a—H1n2a···S1bδb P1b (2), N1a—H1n1a···S1aδb P1a (3), N3a—H1n3a···S1aδb P1a (4) and C16a—H2c16a···H1c5b—C5b (5); (b) molecule (IB): N3b—H1n3b···S1aδb P1a (1), N2a—H1n2a···S1bδb P1b (2), C16a—H2c16a···H1c5b—C5b (5), N2b—H1n2b···N4—C25 (6), N1b—H1n1b···N4—C25 (7), C18b—H1c18b···N4—C25 (8) and C15b—H2c15b···C2b (9).
	Fig. 6. Front and back views of the Hirshfeld surface for the components of structure (II). The hydrogen bonds corresponding to the labels in figures are as follows, with the labels in parentheses: (a) phosphorothioic triamide molecule: N1—H1n1···Cl1 (1), N3—H1n3···Cl1 (2), N2—H1n2···Cl1 (3), N4—H2n4···S1 (4), S1···S1 (5), N4—H2n4···S1 (6), C22—H2c22···C13 (7), C22—H2c22···C12 (8), C22—H2c22···C8 (9), C26—H1c26···C15 (10), C26—H1c26···C20 (11), C26—H1c26···C16 (12), C19—H1c19···C27 (13), C23—H2c23···C2 (14) and C7—H2c7a···C11 (15); (b) 3-methylpiperidinium cation: C22—H2c22···C13 (7), C22—H2c22···C12 (8), C22—H2c22···C8 (9), C26—H1c26···C15 (10), C26—H1c26···C20 (11), C26—H1c26···C16 (12) and N4—H1n4···Cl1 (16); (c) chloride anion: N1—H1n1···Cl1 (1), N3—H1n3···Cl1 (2), N2—H1n2···Cl1 (3) and N4—H1n4···C1l (16).
	Fig. 7. Two-dimensional fingerprint plots of the molecule (IA): (a) full; (b) H···H; (c) C···H/H···C.
	Fig. 8. Two-dimensional fingerprint plots of the molecule IB: (a) full; (b) H···H; (c) C···H/H···C.
	Fig. 9. Two-dimensional fingerprint plots of the phosphorothioic triamide molecule of (II): (a) full; (b) H···H; (c) C···H/H···C.
	Fig. 10. Two-dimensional fingerprint plots of the 3-methyl piperidinium cation of (II): (a) full; (b) H···H; (c) H···C.
	Fig. 11. Two-dimensional fingerprint plot for the chloride anion of structure (II): Cl···H contacts.

(I) N,N',N''-Tris(3,4-dimethylphenyl)phosphorothioic triamide acetonitrile hemisolvate

Crystal data

2C24H30N3PS·C2H3N	Z = 2
Mr = 888.2	F(000) = 948
Triclinic, P1	Dx = 1.218 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 11.8547 (5) Å	Cell parameters from 6051 reflections
b = 13.5312 (4) Å	θ = 3.3–67.0°
c = 15.3394 (6) Å	µ = 1.94 mm^−1
α = 91.849 (3)°	T = 120 K
β = 98.378 (3)°	Polygon shape, white
γ = 94.991 (3)°	0.19 × 0.17 × 0.11 mm
V = 2422.56 (16) Å^3

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	8394 independent reflections
Radiation source: X-ray tube	6369 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.042
Detector resolution: 5.1873 pixels mm^-1	θmax = 67.1°, θmin = 3.3°
ω scans	h = −13→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −16→13
Tmin = 0.658, Tmax = 1	l = −18→13
15711 measured reflections

Refinement

Refinement on F	234 constraints
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.053	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
S = 1.45	(Δ/σ)max = 0.012
8394 reflections	Δρmax = 0.36 e Å^−3
568 parameters	Δρmin = −0.26 e Å^−3
6 restraints

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Multi-scan absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

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

	x	y	z	Uiso*/Ueq
S1a	0.45406 (5)	0.84796 (4)	0.40382 (4)	0.02819 (18)
P1a	0.53714 (5)	0.97192 (4)	0.37541 (4)	0.02405 (18)
S1b	0.42803 (5)	0.77086 (4)	0.13783 (4)	0.03331 (19)
P1b	0.44642 (5)	0.63722 (4)	0.17822 (4)	0.02589 (18)
N2a	0.57137 (17)	0.95709 (13)	0.27667 (13)	0.0275 (6)
N3b	0.49367 (17)	0.64552 (13)	0.28479 (13)	0.0287 (6)
N1b	0.32971 (17)	0.55794 (14)	0.16015 (13)	0.0306 (6)
C12a	0.7301 (2)	1.16239 (18)	0.11946 (16)	0.0331 (8)
C11a	0.6892 (2)	1.06682 (18)	0.08830 (18)	0.0395 (9)
C19a	0.8508 (2)	0.81035 (17)	0.46913 (17)	0.0332 (8)
C5b	0.0520 (2)	0.4793 (2)	0.22765 (19)	0.0426 (9)
N1a	0.46811 (17)	1.07283 (13)	0.37898 (13)	0.0282 (6)
C7b	0.0875 (2)	0.73721 (19)	0.33593 (19)	0.0447 (10)
C10b	0.6953 (2)	0.52333 (19)	0.06945 (17)	0.0356 (8)
N2b	0.52934 (17)	0.57056 (14)	0.12711 (14)	0.0326 (7)
C7a	0.1551 (3)	0.9734 (2)	0.1337 (2)	0.0524 (11)
C4b	0.0283 (2)	0.56120 (19)	0.27607 (18)	0.0389 (9)
C9a	0.6256 (2)	1.02799 (16)	0.22549 (15)	0.0274 (7)
C20b	0.6401 (2)	0.42819 (17)	0.44595 (17)	0.0335 (8)
C3b	0.1072 (2)	0.64451 (18)	0.28598 (16)	0.0333 (8)
N3a	0.65448 (16)	1.01093 (13)	0.44398 (13)	0.0261 (6)
C24b	0.6973 (3)	0.35174 (19)	0.5011 (2)	0.0453 (10)
C10a	0.6383 (2)	1.00005 (18)	0.14031 (17)	0.0379 (9)
C21b	0.6625 (2)	0.52997 (17)	0.47083 (16)	0.0297 (8)
C18b	0.5133 (2)	0.46978 (16)	0.31617 (17)	0.0339 (8)
C19b	0.5650 (2)	0.40171 (17)	0.36961 (17)	0.0367 (9)
C24a	1.0261 (2)	0.7873 (2)	0.5773 (2)	0.0465 (10)
C20a	0.9300 (2)	0.84639 (17)	0.54029 (17)	0.0337 (8)
C6b	0.1508 (2)	0.47772 (18)	0.18969 (17)	0.0364 (8)
N4	0.4354 (3)	0.35711 (18)	0.10487 (19)	0.0730 (13)
C16a	0.7595 (2)	1.29352 (18)	0.24193 (18)	0.0434 (10)
C3a	0.2147 (2)	1.04925 (19)	0.20156 (17)	0.0383 (9)
C11b	0.8041 (2)	0.5449 (2)	0.05012 (17)	0.0399 (9)
C17b	0.53862 (19)	0.57039 (16)	0.33906 (15)	0.0268 (7)
C15a	0.7838 (2)	1.23445 (19)	0.06074 (18)	0.0413 (9)
C4a	0.1772 (2)	1.14392 (18)	0.21103 (17)	0.0369 (9)
C5a	0.2335 (2)	1.21025 (19)	0.27517 (18)	0.0413 (9)
C14b	0.7017 (2)	0.68695 (18)	0.13451 (17)	0.0346 (8)
C23b	0.7417 (2)	0.56380 (19)	0.55388 (18)	0.0426 (9)
C18a	0.7593 (2)	0.86216 (16)	0.43452 (16)	0.0297 (8)
C22b	0.6113 (2)	0.59902 (16)	0.41631 (15)	0.0281 (7)
C14a	0.6661 (2)	1.12338 (16)	0.25769 (16)	0.0300 (8)
C9b	0.6421 (2)	0.59541 (17)	0.11145 (16)	0.0298 (8)
C1b	0.2301 (2)	0.56106 (16)	0.19988 (15)	0.0277 (7)
C13b	0.8117 (2)	0.70960 (19)	0.11377 (18)	0.0391 (9)
C15b	0.9830 (2)	0.6584 (2)	0.0468 (2)	0.0530 (11)
C22a	0.82669 (19)	0.99142 (16)	0.54501 (15)	0.0278 (7)
C13a	0.7179 (2)	1.19063 (16)	0.20548 (16)	0.0305 (8)
C16b	0.8718 (3)	0.8107 (2)	0.1375 (2)	0.0542 (11)
C17a	0.74582 (19)	0.95328 (15)	0.47407 (15)	0.0255 (7)
C21a	0.9184 (2)	0.94052 (17)	0.57864 (16)	0.0307 (8)
C8b	−0.0809 (3)	0.5601 (2)	0.3163 (2)	0.0558 (12)
C2a	0.3116 (2)	1.02488 (18)	0.25837 (17)	0.0350 (8)
C2b	0.2073 (2)	0.64355 (17)	0.24787 (16)	0.0307 (8)
C12b	0.8637 (2)	0.6375 (2)	0.07018 (17)	0.0387 (9)
C25	0.4266 (2)	0.2741 (2)	0.09140 (18)	0.0421 (10)
C6a	0.3295 (2)	1.18666 (17)	0.33053 (18)	0.0365 (9)
C23a	1.0045 (2)	0.98559 (19)	0.65409 (18)	0.0401 (9)
C1a	0.3692 (2)	1.09322 (17)	0.32166 (16)	0.0306 (8)
C8a	0.0732 (3)	1.1710 (2)	0.1498 (2)	0.0602 (12)
C26	0.4114 (3)	0.16901 (19)	0.0710 (2)	0.0502 (11)
H1c11a	0.696461	1.046443	0.028998	0.0474*
H1c19a	0.859067	0.746832	0.442278	0.0398*
H1c5b	−0.002172	0.421498	0.220186	0.0511*
H1c7b	0.147081	0.788376	0.330482	0.0536*
H2c7b	0.01468	0.758793	0.3122	0.0536*
H3c7b	0.088043	0.723696	0.397044	0.0536*
H1c10b	0.655834	0.458729	0.054084	0.0427*
H1c7a	0.189528	0.911984	0.141471	0.0629*
H2c7a	0.075679	0.963185	0.140157	0.0629*
H3c7a	0.161939	0.996159	0.07594	0.0629*
H1c24b	0.67448	0.353885	0.558594	0.0544*
H2c24b	0.675181	0.286959	0.473361	0.0544*
H3c24b	0.778947	0.365521	0.506566	0.0544*
H1c10a	0.611688	0.934019	0.11718	0.0455*
H1c18b	0.460639	0.448161	0.264061	0.0406*
H1c19b	0.548096	0.332419	0.352921	0.0441*
H1c24a	1.022043	0.776514	0.638399	0.0558*
H2c24a	1.019426	0.724425	0.545251	0.0558*
H3c24a	1.098083	0.823115	0.572002	0.0558*
H1c6b	0.164635	0.419707	0.156605	0.0436*
H1c16a	0.754468	1.297776	0.303817	0.052*
H2c16a	0.837632	1.30844	0.233335	0.052*
H3c16a	0.712922	1.340294	0.211977	0.052*
H1c11b	0.839984	0.494345	0.021883	0.0479*
H1c15a	0.78957	1.201001	0.005625	0.0496*
H2c15a	0.737185	1.288621	0.050167	0.0496*
H3c15a	0.858914	1.259507	0.089127	0.0496*
H1c5a	0.205978	1.274306	0.281973	0.0496*
H1c14b	0.666917	0.736078	0.165432	0.0415*
H1c23b	0.816166	0.542239	0.550849	0.0512*
H2c23b	0.74749	0.634952	0.560232	0.0512*
H3c23b	0.712259	0.535848	0.603653	0.0512*
H1c18a	0.706421	0.835353	0.384194	0.0356*
H1c22b	0.626963	0.66843	0.432855	0.0338*
H1c14a	0.65836	1.143399	0.316972	0.0359*
H1c15b	0.994436	0.726595	0.031976	0.0636*
H2c15b	1.03851	0.64592	0.09633	0.0636*
H3c15b	0.991537	0.616022	−0.002738	0.0636*
H1c22a	0.818431	1.055175	0.571423	0.0333*
H1c16b	0.833729	0.843968	0.17947	0.0651*
H2c16b	0.949725	0.804684	0.16296	0.0651*
H3c16b	0.870607	0.848329	0.085487	0.0651*
H1c8b	−0.062509	0.575497	0.378561	0.067*
H2c8b	−0.12751	0.608765	0.289461	0.067*
H3c8b	−0.122096	0.495519	0.306387	0.067*
H1c2a	0.337785	0.960111	0.253035	0.042*
H1c2b	0.261379	0.70133	0.255125	0.0369*
H1c6a	0.368589	1.234374	0.374855	0.0438*
H1c23a	1.012817	0.939591	0.700448	0.0481*
H2c23a	1.077014	1.00028	0.634175	0.0481*
H3c23a	0.978839	1.045712	0.675874	0.0481*
H1c8a	0.022086	1.112395	0.132753	0.0722*
H2c8a	0.034629	1.218306	0.179601	0.0722*
H3c8a	0.097169	1.199469	0.098157	0.0722*
H1c26	0.424592	0.134141	0.124548	0.0602*
H2c26	0.33465	0.150877	0.042029	0.0602*
H3c26	0.464723	0.151755	0.032871	0.0602*
H1n3b	0.493 (2)	0.7023 (11)	0.3123 (15)	0.0345*
H1n1b	0.328 (2)	0.5095 (14)	0.1221 (14)	0.0367*
H1n3a	0.648 (2)	1.0565 (14)	0.4833 (13)	0.0313*
H1n2a	0.544 (2)	0.9012 (11)	0.2494 (15)	0.033*
H1n2b	0.506 (2)	0.5086 (9)	0.1151 (18)	0.0391*
H1n1a	0.481 (2)	1.1070 (16)	0.4289 (10)	0.0339*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1a	0.0323 (3)	0.0238 (3)	0.0294 (3)	−0.0003 (2)	0.0100 (2)	−0.0012 (2)
P1a	0.0248 (3)	0.0229 (3)	0.0253 (3)	0.0017 (2)	0.0070 (2)	0.0007 (2)
S1b	0.0380 (3)	0.0305 (3)	0.0302 (3)	0.0039 (2)	0.0006 (3)	0.0008 (2)
P1b	0.0239 (3)	0.0278 (3)	0.0258 (3)	0.0021 (2)	0.0040 (2)	−0.0025 (2)
N2a	0.0334 (11)	0.0233 (9)	0.0261 (11)	−0.0021 (8)	0.0090 (8)	−0.0021 (8)
N3b	0.0319 (11)	0.0247 (9)	0.0286 (11)	0.0039 (8)	0.0016 (9)	−0.0032 (8)
N1b	0.0274 (11)	0.0317 (10)	0.0312 (11)	−0.0011 (8)	0.0050 (9)	−0.0115 (8)
C12a	0.0291 (13)	0.0393 (13)	0.0332 (14)	0.0059 (10)	0.0090 (11)	0.0092 (11)
C11a	0.0497 (17)	0.0386 (14)	0.0341 (15)	0.0028 (12)	0.0199 (12)	0.0016 (11)
C19a	0.0343 (14)	0.0304 (12)	0.0386 (15)	0.0068 (10)	0.0159 (11)	0.0001 (11)
C5b	0.0377 (15)	0.0441 (15)	0.0456 (17)	−0.0088 (12)	0.0132 (13)	−0.0033 (12)
N1a	0.0300 (11)	0.0270 (10)	0.0291 (11)	0.0061 (8)	0.0074 (9)	−0.0007 (8)
C7b	0.0417 (16)	0.0490 (15)	0.0463 (17)	0.0149 (13)	0.0113 (13)	−0.0032 (13)
C10b	0.0344 (14)	0.0397 (13)	0.0341 (14)	0.0084 (11)	0.0074 (11)	0.0008 (11)
N2b	0.0315 (11)	0.0299 (10)	0.0372 (12)	0.0000 (9)	0.0116 (9)	−0.0069 (9)
C7a	0.0486 (18)	0.0539 (17)	0.0524 (19)	0.0025 (14)	0.0028 (14)	−0.0071 (15)
C4b	0.0329 (14)	0.0475 (15)	0.0371 (15)	0.0019 (12)	0.0089 (12)	0.0013 (12)
C9a	0.0262 (12)	0.0293 (11)	0.0285 (13)	0.0041 (9)	0.0089 (10)	0.0047 (10)
C20b	0.0348 (14)	0.0318 (12)	0.0363 (14)	0.0042 (10)	0.0116 (11)	0.0067 (11)
C3b	0.0309 (13)	0.0408 (13)	0.0282 (13)	0.0070 (11)	0.0025 (10)	−0.0016 (11)
N3a	0.0278 (10)	0.0235 (9)	0.0272 (11)	0.0027 (8)	0.0059 (8)	−0.0031 (8)
C24b	0.0536 (18)	0.0359 (14)	0.0474 (17)	0.0057 (12)	0.0075 (14)	0.0125 (12)
C10a	0.0480 (16)	0.0300 (12)	0.0385 (15)	0.0009 (11)	0.0173 (12)	−0.0003 (11)
C21b	0.0284 (13)	0.0342 (12)	0.0282 (13)	0.0039 (10)	0.0085 (10)	0.0033 (10)
C18b	0.0383 (14)	0.0284 (12)	0.0327 (14)	−0.0010 (10)	0.0012 (11)	−0.0016 (10)
C19b	0.0421 (15)	0.0258 (12)	0.0420 (15)	0.0001 (10)	0.0077 (12)	−0.0002 (11)
C24a	0.0405 (16)	0.0543 (16)	0.0476 (17)	0.0178 (13)	0.0075 (13)	0.0056 (14)
C20a	0.0296 (13)	0.0377 (13)	0.0370 (14)	0.0064 (10)	0.0126 (11)	0.0066 (11)
C6b	0.0360 (14)	0.0357 (13)	0.0362 (15)	−0.0034 (11)	0.0072 (11)	−0.0064 (11)
N4	0.131 (3)	0.0330 (14)	0.0522 (17)	−0.0003 (15)	0.0126 (17)	−0.0056 (12)
C16a	0.0485 (17)	0.0375 (14)	0.0435 (17)	−0.0047 (12)	0.0101 (14)	0.0023 (12)
C3a	0.0382 (15)	0.0439 (14)	0.0330 (14)	−0.0038 (11)	0.0109 (12)	0.0008 (11)
C11b	0.0351 (15)	0.0523 (16)	0.0356 (15)	0.0160 (12)	0.0088 (12)	0.0055 (12)
C17b	0.0267 (12)	0.0270 (11)	0.0272 (12)	0.0016 (9)	0.0059 (10)	0.0016 (9)
C15a	0.0399 (16)	0.0451 (15)	0.0407 (16)	−0.0001 (12)	0.0121 (12)	0.0106 (12)
C4a	0.0368 (15)	0.0378 (13)	0.0383 (15)	0.0044 (11)	0.0106 (12)	0.0090 (11)
C5a	0.0418 (16)	0.0370 (14)	0.0463 (17)	0.0071 (12)	0.0075 (13)	0.0049 (12)
C14b	0.0289 (13)	0.0382 (13)	0.0364 (14)	0.0046 (10)	0.0041 (11)	−0.0003 (11)
C23b	0.0495 (17)	0.0418 (14)	0.0348 (15)	0.0065 (12)	−0.0017 (13)	0.0039 (12)
C18a	0.0294 (13)	0.0287 (12)	0.0316 (13)	0.0010 (10)	0.0091 (10)	−0.0036 (10)
C22b	0.0301 (13)	0.0261 (11)	0.0283 (13)	0.0024 (9)	0.0053 (10)	−0.0011 (10)
C14a	0.0295 (13)	0.0319 (12)	0.0288 (13)	−0.0004 (10)	0.0076 (10)	0.0018 (10)
C9b	0.0273 (13)	0.0371 (13)	0.0264 (13)	0.0063 (10)	0.0066 (10)	0.0042 (10)
C1b	0.0253 (12)	0.0333 (12)	0.0239 (12)	0.0030 (9)	0.0015 (10)	0.0001 (10)
C13b	0.0299 (14)	0.0463 (14)	0.0401 (15)	0.0014 (11)	0.0009 (11)	0.0107 (12)
C15b	0.0322 (15)	0.078 (2)	0.0536 (19)	0.0126 (14)	0.0118 (13)	0.0228 (17)
C22a	0.0283 (12)	0.0280 (11)	0.0281 (13)	−0.0003 (9)	0.0099 (10)	−0.0010 (10)
C13a	0.0248 (12)	0.0304 (12)	0.0358 (14)	0.0021 (9)	0.0018 (10)	0.0051 (10)
C16b	0.0366 (17)	0.0560 (17)	0.068 (2)	−0.0067 (14)	0.0050 (15)	0.0063 (15)
C17a	0.0244 (12)	0.0251 (11)	0.0286 (12)	0.0007 (9)	0.0099 (10)	0.0039 (9)
C21a	0.0270 (13)	0.0378 (13)	0.0286 (13)	−0.0010 (10)	0.0106 (10)	0.0036 (10)
C8b	0.0449 (18)	0.0626 (19)	0.064 (2)	−0.0009 (14)	0.0263 (16)	−0.0024 (16)
C2a	0.0330 (14)	0.0388 (13)	0.0357 (14)	0.0039 (11)	0.0121 (11)	0.0077 (11)
C2b	0.0277 (13)	0.0326 (12)	0.0306 (13)	0.0025 (10)	0.0015 (10)	−0.0034 (10)
C12b	0.0271 (13)	0.0587 (16)	0.0323 (14)	0.0089 (12)	0.0055 (11)	0.0156 (12)
C25	0.0541 (18)	0.0388 (15)	0.0326 (15)	−0.0001 (12)	0.0081 (13)	−0.0038 (12)
C6a	0.0374 (15)	0.0315 (12)	0.0415 (15)	0.0043 (11)	0.0075 (12)	0.0058 (11)
C23a	0.0318 (14)	0.0502 (15)	0.0373 (15)	0.0016 (12)	0.0033 (12)	0.0046 (12)
C1a	0.0279 (13)	0.0370 (13)	0.0288 (13)	0.0020 (10)	0.0097 (10)	0.0073 (10)
C8a	0.055 (2)	0.066 (2)	0.059 (2)	0.0148 (16)	−0.0014 (16)	0.0086 (16)
C26	0.059 (2)	0.0400 (15)	0.0527 (19)	0.0002 (13)	0.0159 (15)	−0.0003 (13)

Geometric parameters (Å, º)

S1a—P1a	1.9643 (8)	C20a—C21a	1.412 (3)
P1a—N2a	1.635 (2)	C6b—C1b	1.393 (3)
P1a—N1a	1.655 (2)	C6b—H1c6b	0.96
P1a—N3a	1.6523 (18)	N4—C25	1.128 (4)
S1b—P1b	1.9501 (8)	C16a—C13a	1.498 (3)
P1b—N3b	1.646 (2)	C16a—H1c16a	0.96
P1b—N1b	1.6591 (19)	C16a—H2c16a	0.96
P1b—N2b	1.652 (2)	C16a—H3c16a	0.96
N2a—C9a	1.427 (3)	C3a—C4a	1.402 (4)
N2a—H1n2a	0.866 (17)	C3a—C2a	1.407 (4)
N3b—C17b	1.425 (3)	C11b—C12b	1.386 (4)
N3b—H1n3b	0.865 (17)	C11b—H1c11b	0.96
N1b—C1b	1.409 (3)	C17b—C22b	1.383 (3)
N1b—H1n1b	0.86 (2)	C15a—H1c15a	0.96
C12a—C11a	1.385 (3)	C15a—H2c15a	0.96
C12a—C15a	1.511 (4)	C15a—H3c15a	0.96
C12a—C13a	1.393 (4)	C4a—C5a	1.366 (3)
C11a—C10a	1.382 (4)	C4a—C8a	1.517 (4)
C11a—H1c11a	0.96	C5a—C6a	1.385 (4)
C19a—C20a	1.378 (3)	C5a—H1c5a	0.96
C19a—C18a	1.393 (3)	C14b—C9b	1.380 (3)
C19a—H1c19a	0.96	C14b—C13b	1.398 (4)
C5b—C4b	1.386 (4)	C14b—H1c14b	0.96
C5b—C6b	1.384 (4)	C23b—H1c23b	0.96
C5b—H1c5b	0.96	C23b—H2c23b	0.96
N1a—C1a	1.412 (3)	C23b—H3c23b	0.96
N1a—H1n1a	0.869 (17)	C18a—C17a	1.388 (3)
C7b—C3b	1.502 (4)	C18a—H1c18a	0.96
C7b—H1c7b	0.96	C22b—H1c22b	0.96
C7b—H2c7b	0.96	C14a—C13a	1.393 (3)
C7b—H3c7b	0.96	C14a—H1c14a	0.96
C10b—C11b	1.375 (4)	C1b—C2b	1.385 (3)
C10b—C9b	1.396 (4)	C13b—C16b	1.495 (4)
C10b—H1c10b	0.96	C13b—C12b	1.400 (4)
N2b—C9b	1.406 (3)	C15b—C12b	1.514 (4)
N2b—H1n2b	0.864 (13)	C15b—H1c15b	0.96
C7a—C3a	1.492 (4)	C15b—H2c15b	0.96
C7a—H1c7a	0.96	C15b—H3c15b	0.96
C7a—H2c7a	0.96	C22a—C17a	1.394 (3)
C7a—H3c7a	0.96	C22a—C21a	1.383 (3)
C4b—C3b	1.390 (3)	C22a—H1c22a	0.96
C4b—C8b	1.513 (4)	C16b—H1c16b	0.96
C9a—C10a	1.381 (4)	C16b—H2c16b	0.96
C9a—C14a	1.387 (3)	C16b—H3c16b	0.96
C20b—C24b	1.503 (4)	C21a—C23a	1.502 (3)
C20b—C21b	1.409 (3)	C8b—H1c8b	0.96
C20b—C19b	1.380 (3)	C8b—H2c8b	0.96
C3b—C2b	1.398 (4)	C8b—H3c8b	0.96
N3a—C17a	1.421 (3)	C2a—C1a	1.380 (3)
N3a—H1n3a	0.86 (2)	C2a—H1c2a	0.96
C24b—H1c24b	0.96	C2b—H1c2b	0.96
C24b—H2c24b	0.96	C25—C26	1.436 (4)
C24b—H3c24b	0.96	C6a—C1a	1.397 (3)
C10a—H1c10a	0.96	C6a—H1c6a	0.96
C21b—C23b	1.501 (3)	C23a—H1c23a	0.96
C21b—C22b	1.393 (3)	C23a—H2c23a	0.96
C18b—C19b	1.378 (3)	C23a—H3c23a	0.96
C18b—C17b	1.391 (3)	C8a—H1c8a	0.96
C18b—H1c18b	0.96	C8a—H2c8a	0.96
C19b—H1c19b	0.96	C8a—H3c8a	0.96
C24a—C20a	1.503 (4)	C26—H1c26	0.96
C24a—H1c24a	0.96	C26—H2c26	0.96
C24a—H2c24a	0.96	C26—H3c26	0.96
C24a—H3c24a	0.96
S1a—P1a—N2a	108.21 (7)	C10b—C11b—H1c11b	119.02
S1a—P1a—N1a	115.88 (8)	C12b—C11b—H1c11b	119.02
S1a—P1a—N3a	116.27 (7)	N3b—C17b—C18b	122.24 (19)
N2a—P1a—N1a	108.72 (10)	N3b—C17b—C22b	118.57 (19)
N2a—P1a—N3a	108.38 (10)	C18b—C17b—C22b	119.2 (2)
N1a—P1a—N3a	98.85 (9)	C12a—C15a—H1c15a	109.47
S1b—P1b—N3b	108.31 (7)	C12a—C15a—H2c15a	109.47
S1b—P1b—N1b	115.80 (8)	C12a—C15a—H3c15a	109.47
S1b—P1b—N2b	116.55 (8)	H1c15a—C15a—H2c15a	109.47
N3b—P1b—N1b	108.65 (10)	H1c15a—C15a—H3c15a	109.47
N3b—P1b—N2b	109.73 (10)	H2c15a—C15a—H3c15a	109.47
N1b—P1b—N2b	97.25 (10)	C3a—C4a—C5a	120.1 (2)
P1a—N2a—C9a	128.87 (15)	C3a—C4a—C8a	119.1 (2)
P1a—N2a—H1n2a	114.5 (16)	C5a—C4a—C8a	120.7 (2)
C9a—N2a—H1n2a	116.0 (16)	C4a—C5a—C6a	121.1 (2)
P1b—N3b—C17b	128.04 (15)	C4a—C5a—H1c5a	119.44
P1b—N3b—H1n3b	117.7 (15)	C6a—C5a—H1c5a	119.44
C17b—N3b—H1n3b	114.3 (15)	C9b—C14b—C13b	121.4 (2)
P1b—N1b—C1b	127.14 (16)	C9b—C14b—H1c14b	119.32
P1b—N1b—H1n1b	117.6 (17)	C13b—C14b—H1c14b	119.32
C1b—N1b—H1n1b	115.3 (17)	C21b—C23b—H1c23b	109.47
C11a—C12a—C15a	120.7 (2)	C21b—C23b—H2c23b	109.47
C11a—C12a—C13a	118.2 (2)	C21b—C23b—H3c23b	109.47
C15a—C12a—C13a	121.1 (2)	H1c23b—C23b—H2c23b	109.47
C12a—C11a—C10a	121.7 (2)	H1c23b—C23b—H3c23b	109.47
C12a—C11a—H1c11a	119.13	H2c23b—C23b—H3c23b	109.47
C10a—C11a—H1c11a	119.13	C19a—C18a—C17a	118.8 (2)
C20a—C19a—C18a	122.8 (2)	C19a—C18a—H1c18a	120.58
C20a—C19a—H1c19a	118.61	C17a—C18a—H1c18a	120.58
C18a—C19a—H1c19a	118.61	C21b—C22b—C17b	121.9 (2)
C4b—C5b—C6b	122.4 (2)	C21b—C22b—H1c22b	119.07
C4b—C5b—H1c5b	118.82	C17b—C22b—H1c22b	119.07
C6b—C5b—H1c5b	118.82	C9a—C14a—C13a	121.1 (2)
P1a—N1a—C1a	126.46 (15)	C9a—C14a—H1c14a	119.44
P1a—N1a—H1n1a	115.7 (15)	C13a—C14a—H1c14a	119.44
C1a—N1a—H1n1a	115.0 (17)	C10b—C9b—N2b	117.7 (2)
C3b—C7b—H1c7b	109.47	C10b—C9b—C14b	118.8 (2)
C3b—C7b—H2c7b	109.47	N2b—C9b—C14b	123.6 (2)
C3b—C7b—H3c7b	109.47	N1b—C1b—C6b	118.4 (2)
H1c7b—C7b—H2c7b	109.47	N1b—C1b—C2b	122.9 (2)
H1c7b—C7b—H3c7b	109.47	C6b—C1b—C2b	118.7 (2)
H2c7b—C7b—H3c7b	109.47	C14b—C13b—C16b	119.6 (2)
C11b—C10b—C9b	119.9 (2)	C14b—C13b—C12b	119.5 (2)
C11b—C10b—H1c10b	120.03	C16b—C13b—C12b	120.9 (2)
C9b—C10b—H1c10b	120.03	C12b—C15b—H1c15b	109.47
P1b—N2b—C9b	129.06 (16)	C12b—C15b—H2c15b	109.47
P1b—N2b—H1n2b	117.0 (19)	C12b—C15b—H3c15b	109.47
C9b—N2b—H1n2b	113.2 (19)	H1c15b—C15b—H2c15b	109.47
C3a—C7a—H1c7a	109.47	H1c15b—C15b—H3c15b	109.47
C3a—C7a—H2c7a	109.47	H2c15b—C15b—H3c15b	109.47
C3a—C7a—H3c7a	109.47	C17a—C22a—C21a	122.2 (2)
H1c7a—C7a—H2c7a	109.47	C17a—C22a—H1c22a	118.89
H1c7a—C7a—H3c7a	109.47	C21a—C22a—H1c22a	118.89
H2c7a—C7a—H3c7a	109.47	C12a—C13a—C16a	120.2 (2)
C5b—C4b—C3b	118.2 (3)	C12a—C13a—C14a	120.0 (2)
C5b—C4b—C8b	120.8 (2)	C16a—C13a—C14a	119.8 (2)
C3b—C4b—C8b	121.0 (2)	C13b—C16b—H1c16b	109.47
N2a—C9a—C10a	118.44 (19)	C13b—C16b—H2c16b	109.47
N2a—C9a—C14a	122.8 (2)	C13b—C16b—H3c16b	109.47
C10a—C9a—C14a	118.7 (2)	H1c16b—C16b—H2c16b	109.47
C24b—C20b—C21b	120.5 (2)	H1c16b—C16b—H3c16b	109.47
C24b—C20b—C19b	121.6 (2)	H2c16b—C16b—H3c16b	109.47
C21b—C20b—C19b	117.9 (2)	N3a—C17a—C18a	122.83 (19)
C7b—C3b—C4b	121.8 (2)	N3a—C17a—C22a	118.26 (19)
C7b—C3b—C2b	118.4 (2)	C18a—C17a—C22a	118.9 (2)
C4b—C3b—C2b	119.8 (2)	C20a—C21a—C22a	118.9 (2)
P1a—N3a—C17a	126.12 (14)	C20a—C21a—C23a	120.9 (2)
P1a—N3a—H1n3a	116.6 (16)	C22a—C21a—C23a	120.2 (2)
C17a—N3a—H1n3a	110.6 (15)	C4b—C8b—H1c8b	109.47
C20b—C24b—H1c24b	109.47	C4b—C8b—H2c8b	109.47
C20b—C24b—H2c24b	109.47	C4b—C8b—H3c8b	109.47
C20b—C24b—H3c24b	109.47	H1c8b—C8b—H2c8b	109.47
H1c24b—C24b—H2c24b	109.47	H1c8b—C8b—H3c8b	109.47
H1c24b—C24b—H3c24b	109.47	H2c8b—C8b—H3c8b	109.47
H2c24b—C24b—H3c24b	109.47	C3a—C2a—C1a	120.6 (2)
C11a—C10a—C9a	120.2 (2)	C3a—C2a—H1c2a	119.7
C11a—C10a—H1c10a	119.89	C1a—C2a—H1c2a	119.7
C9a—C10a—H1c10a	119.89	C3b—C2b—C1b	121.5 (2)
C20b—C21b—C23b	120.7 (2)	C3b—C2b—H1c2b	119.28
C20b—C21b—C22b	118.9 (2)	C1b—C2b—H1c2b	119.27
C23b—C21b—C22b	120.4 (2)	C11b—C12b—C13b	118.4 (2)
C19b—C18b—C17b	118.8 (2)	C11b—C12b—C15b	120.2 (3)
C19b—C18b—H1c18b	120.59	C13b—C12b—C15b	121.4 (2)
C17b—C18b—H1c18b	120.59	N4—C25—C26	177.4 (3)
C20b—C19b—C18b	123.2 (2)	C5a—C6a—C1a	119.8 (2)
C20b—C19b—H1c19b	118.38	C5a—C6a—H1c6a	120.12
C18b—C19b—H1c19b	118.38	C1a—C6a—H1c6a	120.12
C20a—C24a—H1c24a	109.47	C21a—C23a—H1c23a	109.47
C20a—C24a—H2c24a	109.47	C21a—C23a—H2c23a	109.47
C20a—C24a—H3c24a	109.47	C21a—C23a—H3c23a	109.47
H1c24a—C24a—H2c24a	109.47	H1c23a—C23a—H2c23a	109.47
H1c24a—C24a—H3c24a	109.47	H1c23a—C23a—H3c23a	109.47
H2c24a—C24a—H3c24a	109.47	H2c23a—C23a—H3c23a	109.47
C19a—C20a—C24a	121.3 (2)	N1a—C1a—C2a	122.6 (2)
C19a—C20a—C21a	118.3 (2)	N1a—C1a—C6a	117.8 (2)
C24a—C20a—C21a	120.3 (2)	C2a—C1a—C6a	119.6 (2)
C5b—C6b—C1b	119.4 (2)	C4a—C8a—H1c8a	109.47
C5b—C6b—H1c6b	120.28	C4a—C8a—H2c8a	109.47
C1b—C6b—H1c6b	120.28	C4a—C8a—H3c8a	109.47
C13a—C16a—H1c16a	109.47	H1c8a—C8a—H2c8a	109.47
C13a—C16a—H2c16a	109.47	H1c8a—C8a—H3c8a	109.47
C13a—C16a—H3c16a	109.47	H2c8a—C8a—H3c8a	109.47
H1c16a—C16a—H2c16a	109.47	C25—C26—H1c26	109.47
H1c16a—C16a—H3c16a	109.47	C25—C26—H2c26	109.47
H2c16a—C16a—H3c16a	109.47	C25—C26—H3c26	109.47
C7a—C3a—C4a	122.3 (2)	H1c26—C26—H2c26	109.47
C7a—C3a—C2a	118.9 (2)	H1c26—C26—H3c26	109.47
C4a—C3a—C2a	118.8 (2)	H2c26—C26—H3c26	109.47
C10b—C11b—C12b	122.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3b—H1n3b···S1a	0.866 (17)	2.497 (19)	3.3479 (19)	168 (2)
N1b—H1n1b···N4	0.86 (2)	2.54 (2)	3.229 (3)	137.5 (19)
N3a—H1n3a···S1a^i	0.87 (2)	2.62 (2)	3.430 (2)	156 (2)
N2a—H1n2a···S1b	0.866 (17)	2.57 (2)	3.410 (2)	163 (2)
N2b—H1n2b···N4	0.865 (14)	2.138 (14)	2.994 (3)	171 (2)
N1a—H1n1a···S1a^i	0.869 (17)	2.606 (16)	3.435 (2)	160.2 (18)
C18b—H1c18b···N4	0.96	2.66	3.500 (4)	146

Symmetry code: (i) −x+1, −y+2, −z+1.

(II) N,N',N''-Tris(4-methylphenyl)phosphorothioic triamide–3-methylpiperidinium chloride (1/1)

Crystal data

C21H24N3PS·C6H14N^+·Cl^−	F(000) = 1104
Mr = 517.1	Dx = 1.203 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yabc	Cell parameters from 25037 reflections
a = 14.2245 (2) Å	θ = 3.7–67.1°
b = 14.2802 (3) Å	µ = 2.56 mm^−1
c = 14.8887 (3) Å	T = 120 K
β = 109.2930 (16)°	Polygon crystal, white
V = 2854.48 (10) Å^3	0.25 × 0.21 × 0.17 mm
Z = 4

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	5073 independent reflections
Radiation source: X-ray tube	4567 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.032
Detector resolution: 10.3745 pixels mm^-1	θmax = 67.1°, θmin = 3.7°
ω scans	h = −16→16
Absorption correction: analytical (CrysAlis PRO; Agilent, 2014)	k = −17→16
Tmin = 0.950, Tmax = 0.970	l = −17→17
48608 measured reflections

Refinement

Refinement on F^2	171 constraints
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.094	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0016I^2)
S = 1.76	(Δ/σ)max = 0.018
5073 reflections	Δρmax = 0.22 e Å^−3
324 parameters	Δρmin = −0.21 e Å^−3
11 restraints

Special details

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.65319 (3)	0.28741 (2)	0.11661 (2)	0.02555 (12)
P1	0.69591 (3)	0.00599 (2)	0.22624 (2)	0.01968 (12)
S1	0.60274 (3)	0.00560 (2)	0.09614 (2)	0.02613 (13)
N1	0.66923 (9)	−0.06110 (8)	0.30497 (8)	0.0233 (4)
N3	0.80789 (9)	−0.03656 (8)	0.23984 (8)	0.0229 (4)
N2	0.70379 (9)	0.11425 (8)	0.26446 (8)	0.0224 (4)
N4	0.44950 (9)	0.82533 (9)	0.07546 (8)	0.0254 (4)
C10	0.77323 (11)	0.28112 (11)	0.46434 (11)	0.0282 (5)
C1	0.58281 (10)	−0.05689 (10)	0.33122 (9)	0.0234 (4)
C16	0.86072 (11)	0.07470 (10)	0.13859 (10)	0.0259 (5)
C15	0.87657 (11)	−0.00449 (9)	0.19685 (10)	0.0221 (5)
C6	0.56747 (12)	−0.12803 (11)	0.38877 (11)	0.0306 (5)
C20	0.96611 (11)	−0.05264 (11)	0.21695 (10)	0.0271 (5)
C13	0.82515 (10)	0.10139 (10)	0.42776 (10)	0.0242 (5)
C8	0.75209 (10)	0.15001 (10)	0.35708 (9)	0.0212 (4)
C11	0.84679 (11)	0.23370 (11)	0.53513 (10)	0.0279 (5)
C17	0.93459 (12)	0.10374 (11)	0.10310 (10)	0.0294 (5)
C5	0.48415 (12)	−0.12713 (12)	0.41693 (11)	0.0357 (6)
C22	0.51320 (11)	0.75315 (11)	0.13982 (10)	0.0282 (5)
C4	0.41320 (12)	−0.05676 (12)	0.38943 (11)	0.0329 (5)
C12	0.87094 (11)	0.14382 (11)	0.51526 (10)	0.0276 (5)
C18	1.02519 (12)	0.05733 (11)	0.12350 (11)	0.0309 (5)
C24	0.29991 (11)	0.77174 (12)	0.11077 (11)	0.0303 (5)
C9	0.72596 (11)	0.23976 (10)	0.37666 (10)	0.0255 (5)
C2	0.51295 (11)	0.01440 (11)	0.30268 (11)	0.0281 (5)
C23	0.36435 (11)	0.85513 (11)	0.10584 (10)	0.0294 (5)
C25	0.36353 (12)	0.69582 (12)	0.17469 (11)	0.0335 (6)
C19	1.03898 (12)	−0.02141 (12)	0.18114 (11)	0.0319 (5)
C3	0.42938 (12)	0.01366 (12)	0.33169 (11)	0.0321 (6)
C27	0.21634 (14)	0.80332 (17)	0.14638 (14)	0.0523 (8)
C26	0.45110 (12)	0.66829 (11)	0.14295 (11)	0.0312 (5)
C14	0.89760 (13)	0.28004 (13)	0.63041 (12)	0.0381 (6)
C21	1.10526 (13)	0.09118 (14)	0.08533 (13)	0.0437 (7)
C7	0.32302 (13)	−0.05646 (15)	0.42111 (13)	0.0442 (7)
H1c10	0.754898	0.343398	0.476344	0.0338*
H1c16	0.799206	0.10871	0.123267	0.0311*
H1c6	0.615009	−0.177954	0.408987	0.0367*
H1c20	0.977564	−0.107853	0.255871	0.0325*
H1c13	0.843608	0.039092	0.415985	0.029*
H1c17	0.922729	0.158033	0.062858	0.0352*
H1c5	0.47509	−0.17678	0.456767	0.0428*
H1c22	0.541289	0.778627	0.202714	0.0338*
H2c22	0.566009	0.735276	0.116541	0.0338*
H1c12	0.920965	0.109776	0.563559	0.0331*
H1c24	0.270549	0.745643	0.048306	0.0364*
H1c9	0.674755	0.273353	0.329073	0.0306*
H1c4	0.522212	0.064125	0.263026	0.0337*
H1c23	0.324816	0.90022	0.061481	0.0352*
H2c23	0.389194	0.884392	0.16723	0.0352*
H1c25	0.387887	0.717954	0.239166	0.0401*
H2c25	0.323149	0.641696	0.173637	0.0401*
H1c19	1.100662	−0.05516	0.196631	0.0382*
H1c3	0.381489	0.063263	0.311217	0.0385*
H1c27	0.173088	0.751358	0.145086	0.0627*
H2c27	0.244155	0.826123	0.210386	0.0627*
H3c27	0.17904	0.852397	0.106143	0.0627*
H1c26	0.491602	0.623146	0.186539	0.0375*
H2c26	0.426691	0.640336	0.080888	0.0375*
H2c14a	0.966777	0.263037	0.652927	0.0457*	0.60 (3)
H3c14a	0.891593	0.34681	0.623334	0.0457*	0.60 (3)
H1c14a	0.86663	0.259632	0.675359	0.0457*	0.60 (3)
H2c21	1.133871	0.147992	0.117237	0.0525*
H1c21	1.15616	0.044272	0.096234	0.0525*
H3c21	1.076653	0.102802	0.018269	0.0525*
H3c7a	0.267304	−0.030598	0.371623	0.0531*	0.51 (2)
H2c7a	0.307886	−0.11943	0.434315	0.0531*	0.51 (2)
H1c7a	0.336394	−0.019154	0.477602	0.0531*	0.51 (2)
H1n1	0.7079 (11)	−0.1075 (9)	0.3293 (11)	0.0279*
H1n3	0.8260 (12)	−0.0839 (9)	0.2769 (10)	0.0275*
H1n2	0.6780 (11)	0.1536 (10)	0.2199 (9)	0.0268*
H1n4	0.4265 (12)	0.8015 (11)	0.0179 (8)	0.0304*
H2n4	0.4885 (11)	0.8727 (9)	0.0739 (12)	0.0304*
H1c7b	0.301209	0.006831	0.423483	0.0531*	0.49 (2)
H2c7b	0.270544	−0.091851	0.376878	0.0531*	0.49 (2)
H3c7b	0.339832	−0.084163	0.483179	0.0531*	0.49 (2)
H1c14b	0.90171	0.236416	0.680631	0.0457*	0.40 (3)
H2c14b	0.963458	0.299248	0.634133	0.0457*	0.40 (3)
H3c25b	0.859832	0.333815	0.636857	0.0457*	0.40 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0337 (2)	0.02031 (19)	0.01919 (18)	−0.00368 (12)	0.00410 (14)	−0.00158 (11)
P1	0.02053 (19)	0.0173 (2)	0.01818 (19)	−0.00150 (12)	0.00233 (14)	0.00186 (12)
S1	0.0269 (2)	0.0236 (2)	0.0215 (2)	−0.00514 (13)	−0.00064 (15)	0.00217 (12)
N1	0.0221 (6)	0.0211 (6)	0.0241 (6)	0.0011 (5)	0.0042 (5)	0.0062 (5)
N3	0.0247 (6)	0.0187 (6)	0.0238 (6)	0.0013 (5)	0.0059 (5)	0.0048 (5)
N2	0.0254 (6)	0.0183 (6)	0.0190 (6)	0.0010 (4)	0.0015 (5)	0.0033 (4)
N4	0.0297 (6)	0.0238 (7)	0.0215 (6)	−0.0050 (5)	0.0069 (5)	−0.0019 (5)
C10	0.0336 (8)	0.0252 (8)	0.0284 (8)	−0.0024 (6)	0.0137 (6)	−0.0044 (6)
C1	0.0247 (7)	0.0240 (7)	0.0191 (6)	−0.0051 (5)	0.0037 (5)	−0.0023 (5)
C16	0.0262 (7)	0.0240 (8)	0.0249 (7)	−0.0009 (6)	0.0051 (6)	0.0000 (6)
C15	0.0237 (7)	0.0213 (7)	0.0192 (7)	−0.0029 (5)	0.0041 (6)	−0.0036 (5)
C6	0.0348 (8)	0.0257 (8)	0.0306 (8)	−0.0020 (6)	0.0099 (6)	0.0048 (6)
C20	0.0302 (7)	0.0225 (8)	0.0270 (7)	0.0006 (6)	0.0072 (6)	−0.0031 (6)
C13	0.0240 (7)	0.0230 (8)	0.0239 (7)	0.0008 (5)	0.0059 (6)	0.0013 (5)
C8	0.0213 (6)	0.0217 (7)	0.0203 (6)	−0.0038 (5)	0.0063 (5)	−0.0001 (5)
C11	0.0268 (7)	0.0348 (8)	0.0235 (7)	−0.0053 (6)	0.0103 (6)	−0.0052 (6)
C17	0.0370 (8)	0.0252 (8)	0.0254 (7)	−0.0069 (6)	0.0096 (6)	−0.0015 (6)
C5	0.0415 (9)	0.0345 (9)	0.0335 (8)	−0.0081 (7)	0.0156 (7)	0.0038 (7)
C22	0.0240 (7)	0.0347 (9)	0.0234 (7)	0.0037 (6)	0.0046 (6)	−0.0006 (6)
C4	0.0335 (8)	0.0381 (9)	0.0294 (8)	−0.0081 (7)	0.0134 (6)	−0.0058 (6)
C12	0.0249 (7)	0.0334 (9)	0.0222 (7)	0.0000 (6)	0.0046 (6)	0.0014 (6)
C18	0.0351 (8)	0.0300 (8)	0.0306 (8)	−0.0083 (6)	0.0150 (6)	−0.0117 (6)
C24	0.0243 (7)	0.0415 (9)	0.0243 (7)	0.0014 (6)	0.0069 (6)	−0.0004 (6)
C9	0.0271 (7)	0.0245 (8)	0.0240 (7)	0.0012 (6)	0.0073 (6)	0.0023 (6)
C2	0.0294 (8)	0.0267 (8)	0.0282 (8)	−0.0007 (6)	0.0095 (6)	0.0041 (6)
C23	0.0347 (8)	0.0259 (8)	0.0255 (7)	0.0063 (6)	0.0074 (6)	−0.0017 (6)
C25	0.0364 (8)	0.0347 (9)	0.0297 (8)	−0.0034 (7)	0.0116 (7)	0.0069 (6)
C19	0.0287 (8)	0.0315 (8)	0.0361 (9)	0.0012 (6)	0.0116 (7)	−0.0091 (7)
C3	0.0289 (8)	0.0343 (9)	0.0328 (8)	0.0020 (6)	0.0097 (7)	−0.0013 (6)
C27	0.0367 (10)	0.0848 (16)	0.0382 (10)	0.0120 (9)	0.0162 (8)	0.0008 (9)
C26	0.0371 (8)	0.0269 (8)	0.0267 (7)	0.0059 (6)	0.0067 (6)	0.0054 (6)
C14	0.0379 (9)	0.0453 (10)	0.0288 (8)	−0.0019 (7)	0.0079 (7)	−0.0119 (7)
C21	0.0468 (10)	0.0444 (11)	0.0496 (10)	−0.0114 (8)	0.0288 (9)	−0.0134 (8)
C7	0.0404 (10)	0.0545 (12)	0.0450 (10)	−0.0077 (8)	0.0238 (8)	−0.0040 (8)

Geometric parameters (Å, º)

Cl1—N1^i	3.2365 (12)	C12—H1c12	0.96
Cl1—N3^i	3.2266 (12)	C18—C19	1.389 (2)
Cl1—N2	3.2296 (12)	C18—C21	1.511 (3)
Cl1—N4^ii	3.1848 (12)	C24—C23	1.519 (2)
P1—S1	1.9524 (4)	C24—C25	1.527 (2)
P1—N1	1.6523 (14)	C24—C27	1.521 (3)
P1—N3	1.6536 (13)	C24—H1c24	0.96
P1—N2	1.6383 (12)	C9—H1c9	0.96
N1—C1	1.409 (2)	C2—C3	1.392 (3)
N1—H1n1	0.861 (13)	C2—H1c4	0.96
N3—C15	1.410 (2)	C23—H1c23	0.96
N3—H1n3	0.857 (13)	C23—H2c23	0.96
N2—C8	1.4171 (16)	C25—C26	1.523 (3)
N2—H1n2	0.854 (13)	C25—H1c25	0.96
N4—C22	1.4926 (18)	C25—H2c25	0.96
N4—C23	1.488 (2)	C19—H1c19	0.96
N4—H1n4	0.878 (12)	C3—H1c3	0.96
N4—H2n4	0.879 (15)	C27—H1c27	0.96
C10—C11	1.3912 (19)	C27—H2c27	0.96
C10—C9	1.387 (2)	C27—H3c27	0.96
C10—H1c10	0.96	C26—H1c26	0.96
C1—C6	1.392 (2)	C26—H2c26	0.96
C1—C2	1.388 (2)	C14—H2c14a	0.96
C16—C15	1.398 (2)	C14—H3c14a	0.96
C16—C17	1.386 (2)	C14—H1c14a	0.96
C16—H1c16	0.96	C14—H1c14b	0.96
C15—C20	1.390 (2)	C14—H2c14b	0.96
C6—C5	1.382 (3)	C14—H3c25b	0.96
C6—H1c6	0.96	C21—H2c21	0.96
C20—C19	1.387 (3)	C21—H1c21	0.96
C20—H1c20	0.96	C21—H3c21	0.96
C13—C8	1.3952 (17)	C7—H3c7a	0.96
C13—C12	1.3884 (19)	C7—H2c7a	0.96
C13—H1c13	0.96	C7—H1c7a	0.96
C8—C9	1.392 (2)	C7—H1c7b	0.96
C11—C12	1.386 (2)	C7—H2c7b	0.96
C11—C14	1.515 (2)	C7—H3c7b	0.96
C17—C18	1.391 (2)	H2c14a—H2c14b	0.5824
C17—H1c17	0.96	H3c14a—H3c25b	0.5824
C5—C4	1.387 (2)	H1c14a—H1c14b	0.5824
C5—H1c5	0.96	H3c7a—H1c7b	0.9319
C22—C26	1.509 (2)	H3c7a—H2c7b	0.8781
C22—H1c22	0.96	H2c7a—H2c7b	0.9319
C22—H2c22	0.96	H2c7a—H3c7b	0.878
C4—C3	1.391 (2)	H1c7a—H1c7b	0.878
C4—C7	1.506 (3)	H1c7a—H3c7b	0.9319
N1^i—Cl1—N3^i	45.38 (3)	N4—C23—H1c23	109.47
N1^i—Cl1—N2	107.11 (3)	N4—C23—H2c23	109.47
N1^i—Cl1—N4^ii	137.18 (4)	C24—C23—H1c23	109.47
N3^i—Cl1—N2	101.20 (3)	C24—C23—H2c23	109.47
N3^i—Cl1—N4^ii	156.34 (3)	H1c23—C23—H2c23	108.1
N2—Cl1—N4^ii	99.08 (3)	C24—C25—C26	111.54 (14)
S1—P1—N1	117.55 (4)	C24—C25—H1c25	109.47
S1—P1—N3	115.54 (5)	C24—C25—H2c25	109.47
S1—P1—N2	107.06 (4)	C26—C25—H1c25	109.47
N1—P1—N3	97.91 (6)	C26—C25—H2c25	109.47
N1—P1—N2	107.83 (7)	H1c25—C25—H2c25	107.32
N3—P1—N2	110.58 (6)	C20—C19—C18	121.82 (15)
Cl1^iii—N1—P1	107.98 (6)	C20—C19—H1c19	119.09
Cl1^iii—N1—C1	125.24 (8)	C18—C19—H1c19	119.09
Cl1^iii—N1—H1n1	11.4 (11)	C4—C3—C2	122.00 (15)
P1—N1—C1	126.73 (9)	C4—C3—H1c3	119
P1—N1—H1n1	118.7 (12)	C2—C3—H1c3	119
C1—N1—H1n1	114.2 (12)	C24—C27—H1c27	109.47
Cl1^iii—N3—P1	108.36 (6)	C24—C27—H2c27	109.47
Cl1^iii—N3—C15	124.12 (8)	C24—C27—H3c27	109.47
Cl1^iii—N3—H1n3	7.8 (12)	H1c27—C27—H2c27	109.47
P1—N3—C15	127.52 (9)	H1c27—C27—H3c27	109.47
P1—N3—H1n3	116.1 (12)	H2c27—C27—H3c27	109.47
C15—N3—H1n3	116.3 (12)	C22—C26—C25	110.45 (13)
Cl1—N2—P1	120.76 (5)	C22—C26—H1c26	109.47
Cl1—N2—C8	108.34 (8)	C22—C26—H2c26	109.47
Cl1—N2—H1n2	12.9 (10)	C25—C26—H1c26	109.47
P1—N2—C8	129.31 (9)	C25—C26—H2c26	109.47
P1—N2—H1n2	112.8 (9)	H1c26—C26—H2c26	108.48
C8—N2—H1n2	117.7 (9)	C11—C14—H2c14a	109.47
Cl1^ii—N4—C22	103.21 (8)	C11—C14—H3c14a	109.47
Cl1^ii—N4—C23	103.86 (7)	C11—C14—H1c14a	109.47
Cl1^ii—N4—H1n4	10.2 (11)	C11—C14—H1c14b	109.47
Cl1^ii—N4—H2n4	118.1 (12)	C11—C14—H2c14b	109.47
C22—N4—C23	112.63 (12)	C11—C14—H3c25b	109.47
C22—N4—H1n4	108.0 (10)	H2c14a—C14—H3c14a	109.47
C22—N4—H2n4	107.1 (9)	H2c14a—C14—H1c14a	109.47
C23—N4—H1n4	109.2 (12)	H2c14a—C14—H1c14b	76.84
C23—N4—H2n4	111.8 (11)	H2c14a—C14—H2c14b	35.32
H1n4—N4—H2n4	107.9 (16)	H2c14a—C14—H3c25b	135.26
C11—C10—C9	121.00 (14)	H3c14a—C14—H1c14a	109.47
C11—C10—H1c10	119.5	H3c14a—C14—H1c14b	135.26
C9—C10—H1c10	119.5	H3c14a—C14—H2c14b	76.84
N1—C1—C6	117.92 (13)	H3c14a—C14—H3c25b	35.32
N1—C1—C2	123.27 (14)	H1c14a—C14—H1c14b	35.32
C6—C1—C2	118.81 (15)	H1c14a—C14—H2c14b	135.26
C15—C16—C17	119.44 (14)	H1c14a—C14—H3c25b	76.84
C15—C16—H1c16	120.28	H1c14b—C14—H2c14b	109.47
C17—C16—H1c16	120.28	H1c14b—C14—H3c25b	109.47
N3—C15—C16	123.43 (13)	H2c14b—C14—H3c25b	109.47
N3—C15—C20	117.69 (13)	C18—C21—H2c21	109.47
C16—C15—C20	118.84 (15)	C18—C21—H1c21	109.47
C1—C6—C5	120.31 (14)	C18—C21—H3c21	109.47
C1—C6—H1c6	119.85	H2c21—C21—H1c21	109.47
C5—C6—H1c6	119.85	H2c21—C21—H3c21	109.47
C15—C20—C19	120.41 (14)	H1c21—C21—H3c21	109.47
C15—C20—H1c20	119.79	C4—C7—H3c7a	109.47
C19—C20—H1c20	119.79	C4—C7—H2c7a	109.47
C8—C13—C12	119.49 (14)	C4—C7—H1c7a	109.47
C8—C13—H1c13	120.26	C4—C7—H1c7b	109.47
C12—C13—H1c13	120.26	C4—C7—H2c7b	109.47
N2—C8—C13	123.75 (13)	C4—C7—H3c7b	109.47
N2—C8—C9	117.29 (11)	H3c7a—C7—H2c7a	109.47
C13—C8—C9	118.95 (12)	H3c7a—C7—H1c7a	109.47
C10—C11—C12	117.81 (13)	H3c7a—C7—H1c7b	58.07
C10—C11—C14	120.23 (14)	H3c7a—C7—H2c7b	54.43
C12—C11—C14	121.95 (13)	H3c7a—C7—H3c7b	141.01
C16—C17—C18	122.59 (14)	H2c7a—C7—H1c7a	109.47
C16—C17—H1c17	118.71	H2c7a—C7—H1c7b	141.01
C18—C17—H1c17	118.71	H2c7a—C7—H2c7b	58.07
C6—C5—C4	122.05 (16)	H2c7a—C7—H3c7b	54.43
C6—C5—H1c5	118.97	H1c7a—C7—H1c7b	54.43
C4—C5—H1c5	118.97	H1c7a—C7—H2c7b	141.01
N4—C22—C26	109.68 (11)	H1c7a—C7—H3c7b	58.07
N4—C22—H1c22	109.47	H1c7b—C7—H2c7b	109.47
N4—C22—H2c22	109.47	H1c7b—C7—H3c7b	109.47
C26—C22—H1c22	109.47	H2c7b—C7—H3c7b	109.47
C26—C22—H2c22	109.47	C14—H2c14a—H2c14b	72.34
H1c22—C22—H2c22	109.26	C14—H3c14a—H3c25b	72.34
C5—C4—C3	116.97 (17)	C14—H1c14a—H1c14b	72.34
C5—C4—C7	121.45 (16)	C7—H3c7a—H1c7b	60.96
C3—C4—C7	121.58 (15)	C7—H3c7a—H2c7b	62.79
C13—C12—C11	122.13 (12)	H1c7b—H3c7a—H2c7b	120
C13—C12—H1c12	118.93	C7—H2c7a—H2c7b	60.96
C11—C12—H1c12	118.93	C7—H2c7a—H3c7b	62.79
C17—C18—C19	116.90 (16)	H2c7b—H2c7a—H3c7b	120
C17—C18—C21	121.66 (14)	C7—H1c7a—H1c7b	62.79
C19—C18—C21	121.44 (15)	C7—H1c7a—H3c7b	60.96
C23—C24—C25	110.11 (12)	H1c7b—H1c7a—H3c7b	120
C23—C24—C27	109.76 (15)	C7—H1c7b—H3c7a	60.96
C23—C24—H1c24	109.5	C7—H1c7b—H1c7a	62.79
C25—C24—C27	111.33 (15)	H3c7a—H1c7b—H1c7a	120
C25—C24—H1c24	107.86	C7—H2c7b—H3c7a	62.79
C27—C24—H1c24	108.23	C7—H2c7b—H2c7a	60.97
C10—C9—C8	120.61 (12)	H3c7a—H2c7b—H2c7a	120
C10—C9—H1c9	119.7	C7—H3c7b—H2c7a	62.79
C8—C9—H1c9	119.7	C7—H3c7b—H1c7a	60.96
C1—C2—C3	119.86 (15)	H2c7a—H3c7b—H1c7a	120
C1—C2—H1c4	120.07	C14—H1c14b—H1c14a	72.34
C3—C2—H1c4	120.07	C14—H2c14b—H2c14a	72.34
N4—C23—C24	110.81 (13)	C14—H3c25b—H3c14a	72.34

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n1···Cl1^iii	0.861 (14)	2.399 (15)	3.2365 (13)	164.5 (14)
N3—H1n3···Cl1^iii	0.857 (13)	2.381 (13)	3.2267 (12)	169.4 (16)
N2—H1n2···Cl1	0.854 (14)	2.405 (14)	3.2298 (12)	162.6 (14)
N4—H1n4···Cl1^ii	0.879 (12)	2.325 (13)	3.1848 (12)	165.9 (15)
N4—H2n4···S1^iv	0.880 (15)	2.449 (14)	3.3211 (14)	171.2 (15)

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