Proton transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyl­diazenyl)aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzene­sulfonate salts, and the 1:2 adduct with 3,5-dinitro­benzoic acid

The structures of two 1:1 proton-transfer red–black dye compounds formed by reaction of aniline yellow [4-(phenyl­diazenyl)aniline] with 5-sulfosalicylic acid and benzene­sulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitro­benzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydra­zin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C₁₂H₁₂N₃⁺·C₇H₅O₆S⁻·CH₃OH, (I), 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 4-(phenyldiazenyl)anilinium bis(benzenesulfonate), 2C₁₂H₁₂N₃⁺·2C₆H₅O₃S⁻, (II), and 4-(phenyl­diazenyl)aniline–3,5-dinitro­benzoic acid (1/2), C₁₂H₁₁N₃·2C₇H₄N₂O₆, (III). In compound (I), the diazenyl rather than the aniline group of aniline yellow is protonated, and this group subsequently takes part in a primary hydrogen-bonding inter­action with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation–anion association also involving aromatic C—H...O hydrogen bonds, giving a conjoint R¹₂(6)R¹₂(7)R²₁(4) motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated, while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and these, together with other associations, give a one-dimensional chain structure. In compound (III), rather than proton transfer, there is preferential formation of a classic R²₂(8) cyclic head-to-head hydrogen-bonded car­box­ylic acid homodimer between the two 3,5-dinitro­benzoic acid mol­ecules, which, in association with the aniline yellow mol­ecule that is disordered across a crystallographic inversion centre, results in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzene­sulfonate compound.

S1. Comment

Aniline yellow [4-(phenylazo)aniline, p-aminoazobenzene, PAZAN] is a diazo-dye precursor (O'Neil, 2001) and in the structures of its proton-transfer compounds with organic acids [oxalic acid (Mahmoudkhani & Langer, 2001b), phenylphosphonic acid (two concomitant polymorphs) (Mahmoudkhani & Langer, 2002a), 1,4-butanebisphosphonic acid (Mahmoudkhani & Langer, 2002b) and the isomeric 3- and 4-nitrophthalic and 5-nitroisophthalic acids (Smith et al., 2008], as might intuitively be expected, the aniline functional group is protonated. However, in the purple–black hydrochloride (Yatsenko et al., 2000; Mahmoudkhani & Langer, 2001a) and the hydrochloride of the analogous 4-(phenylazo)-1,3-diaminobenzene (Moreiras et al., 1981) the azo group is protonated. Also, with phosphoric acid (Halasz et al., 2007), the orange monohydrogen phosphate is an anilinium salt while the purple dihydrogen phosphate salt is azo-group protonated. The dye methyl red [4-(N,N'-dimethylanilino)azobenzene-2-carboxylic acid] also gives azo-protonated salts and adducts with 2,5-dihydroxybenzoic acid (Benedict et al., 2006) and the MALDI host 2,6-dihydroxybenzoic acid (Cohen et al., 2007). It is of interest also that the azo dyes 4-[4-(N,N'-dimethylamino)phenylazo ] benzenesulfonic acid (Burke et al., 2004) and 4-[4-(N,N'-diethylamino)phenylazo ] benzenesulfonic (Burke et al., 2006) exist as sulfonate–azo-group zwitterions.

This study was therefore aimed at characterizing crystalline products from the reaction of aniline yellow with strong organic acids, to enable the identification of the nature of the interaction involved, i.e. proton transfer versus non-transfer, and its correlation with qualitative recognition through the observed colour of the crystals. Our general observation regarding the reaction of PAZAN with carboxylic acids has been that proton-transfer compounds are rarely formed (Smith et al., 2008). This is in evidence in the general paucity of reported structures of PAZAN–aminium salts in the literature. We now have obtained suitable crystalline salts of aniline yellow with the strong organic acids, 5-sulfosalicylic acid (5-SSA), benzenesulfonic acid (BSA) and 3,5-dinitrobenzoic acid (3,5-DNBA) which, unlike [those of] the aminium salts, are intense red–black or deep red in colour, crystallizing from solutions with a significantly different colour. The structures of the two red–black compounds, the methanol solvate 4-(phenylazonium)aniline–3-carboxy-4-hydroxybenzenesulfonate–methanol (1/1/1), C₁₂H₁₂N₃⁺. C₇H₅O₆S^-. CH₃OH, (I), and anhydrous 4-(phenylazonium)aniline 4-(phenylazo)anilinium bis(benzenesulfonate), 2(C₁₂H₁₂N₃⁺). 2(C₆H₅O₃S^-), (II), and the red crystal of the adduct compound 4-(phenylazo)aniline–3,5-dinitrobenzoic acid (1/2), C₁₂H₁₁N₃. 2(C₇H₄N₂O₆), (III), are reported here.

With both compounds (I) and (II), proton transfer has occurred while with (III) there is no transfer. However, the differences even between the structures of (I) and (II) are significant so the discussion considers each structure individually. In (I), the 1:1 methanol solvate compound of PAZAN with 5-SSA, the azo group rather than the amino group is protonated and gives a direct N11–H···O51A_sulfonate hydrogen bond while a sulfonate O acts as an acceptor in an interaction with the methanol hydroxyl group (O1B···O52A) (Fig. 1). Other lateral cation aromatic C–H···O_sulfonate hydrogen-bonding associations (Table 1) close conjoint cyclic ring systems [graph sets R¹₂(6), R¹₂(7) and R²₁(4) (Etter et al., 1990)], also shown in Fig. 1. The 5-sulfosalicylate anions form infinite head-to-tail homomolecular hydrogen-bonded chain structures through carboxylic acid proton donors and sulfonate-O acceptors, extending along the a cell direction (Fig. 4). The result is a three-dimensional framework structure.

In the dichroic proton-transfer compound (II) with BSA, the unusual feature is the presence of both azo- and amine-protonated PAZAN species (A and B, respectively) in the structure. The asymmetric unit in the triclinic unit cell comprises both of these cationic species as well as two benzenesulfonate anions (C and D), the D molecule having rotational disorder (80/20%) in the sulfonate group (Fig. 2). The azo-group proton on N11A interacts directly with a sulfonate O (O11C) while all three anilinium protons on N4B similarly form hydrogen bonds with both C- and D-anion sulfonate-O acceptors (Table 2). These and other N—H···O interactions result in one-dimensional chain structures (Fig. 5). Within these chain structures the A- and B-cation species are oriented approximately mutually perpendicularly in the unit cell, corresponding to the observed ca 90° red-to-black dichroism in the crystal. It should also be noted that there are solvent-accessible voids (41 ų) in the structure of (II) (PLATON; Spek, 2009), centred at (1/2, 0, 0) with the closest atom C5C [3.28 (1) Å].

The formation of the 1:2 adduct molecule (III) rather than a proton-transfer compound from the 1:1 reaction of aniline yellow with 3,5-dinitrobenzoic acid is unexpected, considering the relative strength of the acid (pK_a = 2.82). However, 3,5-DNBA has been recognized as a useful adduct-forming synthon for crystal engineering (Etter & Frankenbach, 1989), with a number of 1:1 non-transfer adducts being reported, including one with the azo dye methyl red (Aakeröy et al., 2004). However, most compounds involve proton transfer, with a number having an additional adduct molecule of 3,5-DNBA in the structure, although 1:2 adducts are not unknown, e.g. phenoxyacetic acid-(3,5-DNBA)-H₂O (1/2/1) (Lynch et al., 1991). However, in compound (III) the two molecules preferentially form an uncommon hydrogen-bonded homodimer adduct. The asymmetric unit of (III) (Fig. 3) comprises a 3,5-DNBA molecule and half of an inversion-related aniline yellow molecule. The single para-related amine substituent group as well as the para-related proton of the second ring are disordered over two 50%-occupancy sites. The two 3,5-DNBA molecules form classic cyclic hydrogen-bonded homodimers through cyclic carboxylic acid associations [graph set R²₂(8)] which lie across crystallographic inversion centres in the unit cell (Fig. 6). This dimer is similar to those found in the structures of polymorphs of the parent acid (Colapietro et al., 1983; Domenicano et al., 1990; Prince et al., 1991). The two amine protons of the PAZAN molecule give weak lateral hydrogen-bonding associations with two 3,5-DNBA nitro-O acceptors (O31, O32) (Fig. 3), completing a centrosymmetric cyclic R⁴₄(12) four-molecule unit which is then extended into a two-dimensional sheet structure lying in the [-2 1 - 2] plane in the cell. Within this layered structure the aromatic ring of 3,5-DNBA and one of the aniline yellow rings give partial overlap with weak π–π interactions [minimum ring centroid separation for ring C1–C6 to ring C1A–C6A, 3.7061 (19) Å].

With the cation species in (I) and (II), as well as the PAZAN molecule in (III), the two phenyl rings are essentially coplanar, as has been found in other compounds of aniline yellow (Mahmoudkhani & Langer, 2001a,b, 2002a,b; Smith et al., 2008). The torsion angles C2/6–C1–N1–N11 and C21–C11–N11–N1 are -177.08 (16) and 175.47 (16)°, respectively, for (I), 179.27 (14) and 165.81 (14)°, respectively, for (IIA), 179.45 (14) and -179.41 (15)°, respectively, for (IIB), and 167.00 (13)° for (III) [which of the two torsion angles does this value relate to?].

The anion in (I) has conformational features similar to those found in other proton-transfer compounds of 5-sulfosalicylic acid (Smith et al., 2005a,b,c, 2006). These include the presence of the intramolecular hydroxyl–carboxyl hydrogen bond [O···O, 2.634 (2) Å] which results in the essential coplanarity of the carboxylic acid group and the benzene ring [torsion angle C2A–C1A– C71A–O71A, -173.86 (16)°]. Also, the common C6–H···O_sulfonate interaction [C···O 2.888 (2) Å] is present. In (III) the 3,5-DNBA molecule is essentially planar [torsion angles C2–C1–C11–012 175.88 (13)°, C2–C3–N3–O32 -176.79 (14)°, C4–C5–N5–O52 178.35 (14)°].

It has been shown in the structures of compounds (I) and (II) that the protonated PAZAN cation species act as acid–base indicators, undergoing a colour change from red [the anilinium ('benzenoid') form] to red–black (the 'quinoid' form) in much the same manner as the analogous azo-dye indicator methyl red (yellow to red). Compound (II) has fortuitously captured the dichroic red to red–black equilibrium state with the presence of both hybrid colour forms, the ca 90° colour dichroism being consistent with the orientation of the two protonated forms in the crystal. These forms are readily identified crystallographically, not only with the proton location and the associated hydrogen bonding, but also convincingly in the comparative bond distances and angles in the aniline moiety and the azo-group extension (Table 4). In (I) and molecule A in (II), these are consistent with the presence of the localized single–double bond 'quinoid' system in the aniline molecular moiety, as is also found in the hydrochloride (Mahmoudkhani & Langer, 2001a). The red anilinium-protonated examples [molecule B in (II) and the three isomeric PAZAN hydrogen nitrophthalates (Smith et al., 2008)] are considered 'normal' for aminium-protonated compounds.

S2. Experimental

Compounds (I)–(III) were synthesized by heating together for 10 min under reflux 4-(phenylazo)aniline (1 mmol) and, respectively, 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid), benzenesulfonic acid or 3,5-dinitrobenzoic acid (1 mmol), in either methanol (50 ml) [for (I)] or 1:1 ethanol–water (50 ml) [for (II) and (III)]. Both (I) (m.p. 435–437 K) and (II) (m.p. >538 K ) were obtained as red–black needle prisms, with (II) exhibiting red to red–black dichroism, and (III) (m.p. 433 K) as red needles, after partial room-temperature evaporation of solvent.

S3. Refinement

H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included at calculated positions, with C—H = 0.93 Å, and treated as riding, with U_iso(H) = 1.2U_eq(C). The sulfonate group of the D benzenesulfonate anion in (II) is rotationally disordered, with refined occupancies of the major and minor component O atoms of 0.80 (1) for O11D/O12D/O13D and 0.20 (1) for O14D/O15D/O16D. The occupancies of these atoms were subsequently fixed at these values and the atoms of the minor component were refined isotropically.

Computing details

Data collection: SMART (Bruker, 2000) for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Cell refinement: SMART (Bruker, 2000) for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Data reduction: SAINT (Bruker, 1999) for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR92 (Altomare et al., 1994) for (II); SHELXS97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (III). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I); SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (II), (III). For all compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the 4-(phenylazo)anilinium cation, the 5-sulfosalicylate anion and the methanol solvent molecule of (I). Dashed lines indicate inter-species hydrogen bonds, including C—H···O associations which complete conjoint cyclic edge-on cation–anion interactions. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular configuration and atom-numbering scheme for the two 4-(phenylazo)aniline cation species A and B, and the two benzenesulfonate anions C and D, in the asymmetric unit of (II). Isotropic O atoms of the rotationally disordered sulfonate group with site-occupancy factors of 0.20 (1) are O14D, O15D and O16D. Inter-species hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular configuration and atom-numbering scheme for the 4-(phenylazo)aniline and 3,5-dinitrobenzoic acid molecules in (III). The phenylazoaniline molecule lies across a crystallographic inversion centre, with the single amine group having 50% occupancy. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate inter-species hydrogen bonds. [Symmetry code: (iii) -x + 1, -y + 4, -z + 1].
	Fig. 4. The formal hydrogen bonding in the unit cell of (II), in a perspective view approximately perpendicular to the head-to-tail anion chain structures and their peripheral cation and solvent extensions across b. Non-interactive H atoms have been omitted. [Symmetry code: (iv) x + 1, y, z; for other symmetry codes see Table 1.]
	Fig. 5. The hydrogen-bonded cation–anion extensions in (II), viewed perpendicular to the a axial direction. The minor-occupancy disordered sulfonate atoms of the D anion (O14D, O15D and O16D) have been omitted, as have the non-interactive H atoms. Hydrogen bonds are shown as dashed lines. For symmetry codes, see Table 2.
	Fig. 6. A perspective view of the hydrogen-bonded sheet structure of (III) relative to the unit cell, showing the centrosymmetric cyclic R^22(8) hydrogen-bonded 3,5-DNBA acid homodimers and peripheral R^44(12) extensions via the aniline yellow molecules. For symmetry codes, see Fig. 3 and Table 3.

(I) 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate

Crystal data

C12H12N3^+·C7H5O6S^−·CH4O	F(000) = 936
Mr = 447.46	Dx = 1.437 Mg m^−3
Monoclinic, P21/c	Melting point = 485–488 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.7174 (7) Å	Cell parameters from 3449 reflections
b = 20.1160 (16) Å	θ = 2.4–27.1°
c = 11.8827 (9) Å	µ = 0.21 mm^−1
β = 97.145 (2)°	T = 130 K
V = 2067.6 (3) Å^3	Prism, red-black
Z = 4	0.45 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3640 independent reflections
Radiation source: sealed tube	3102 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.91, Tmax = 0.96	k = −21→23
10840 measured reflections	l = −14→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0552P)^2 + 0.4842P] where P = (Fo^2 + 2Fc^2)/3
3640 reflections	(Δ/σ)max < 0.001
305 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.78242 (17)	0.46205 (8)	1.01332 (12)	0.0246 (5)
N4	1.1149 (2)	0.36212 (10)	0.69069 (15)	0.0304 (6)
N11	0.72559 (17)	0.52174 (8)	1.01081 (13)	0.0233 (5)
C1	0.8681 (2)	0.44231 (9)	0.93342 (15)	0.0238 (6)
C2	0.9185 (2)	0.37486 (9)	0.94103 (16)	0.0279 (6)
C3	0.9995 (2)	0.34780 (9)	0.86188 (16)	0.0283 (6)
C4	1.0383 (2)	0.38742 (9)	0.76953 (15)	0.0249 (6)
C5	0.9929 (2)	0.45582 (9)	0.76398 (15)	0.0252 (6)
C6	0.9100 (2)	0.48194 (9)	0.84200 (15)	0.0239 (6)
C11	0.6330 (2)	0.54270 (9)	1.09300 (15)	0.0233 (5)
C21	0.5890 (2)	0.49893 (10)	1.17349 (15)	0.0285 (6)
C31	0.4954 (2)	0.52202 (10)	1.25116 (16)	0.0322 (6)
C41	0.4486 (2)	0.58784 (10)	1.25095 (16)	0.0318 (6)
C51	0.4936 (2)	0.63108 (10)	1.17027 (16)	0.0301 (6)
C61	0.5847 (2)	0.60885 (9)	1.09048 (15)	0.0272 (6)
S5A	0.77589 (5)	0.66095 (2)	0.75604 (4)	0.0213 (1)
O2A	0.28226 (17)	0.73177 (8)	0.38947 (12)	0.0365 (5)
O51A	0.70411 (14)	0.62667 (6)	0.84291 (10)	0.0271 (4)
O52A	0.88066 (14)	0.61723 (6)	0.70188 (10)	0.0256 (4)
O53A	0.85243 (15)	0.72214 (7)	0.79400 (11)	0.0322 (4)
O71A	0.17089 (16)	0.64824 (7)	0.69100 (11)	0.0320 (5)
O72A	0.08191 (15)	0.69695 (7)	0.52619 (11)	0.0329 (4)
C1A	0.3538 (2)	0.68866 (9)	0.57885 (15)	0.0231 (5)
C2A	0.3909 (2)	0.71480 (9)	0.47587 (15)	0.0268 (6)
C3A	0.5464 (2)	0.72337 (10)	0.45986 (16)	0.0283 (6)
C4A	0.6626 (2)	0.70695 (9)	0.54426 (15)	0.0261 (6)
C5A	0.6252 (2)	0.68110 (9)	0.64739 (14)	0.0215 (5)
C6A	0.4731 (2)	0.67221 (9)	0.66416 (15)	0.0223 (5)
C7A	0.1901 (2)	0.67887 (9)	0.59552 (16)	0.0261 (6)
O1B	0.8397 (2)	0.55217 (8)	0.49274 (14)	0.0501 (6)
C1B	0.7595 (3)	0.49165 (13)	0.49324 (19)	0.0521 (9)
H41	0.38620	0.60320	1.30570	0.0380*
H2	0.89500	0.34830	1.00270	0.0340*
H3	1.03040	0.30250	0.86790	0.0340*
H5	1.02140	0.48320	0.70480	0.0300*
H6	0.87910	0.52720	0.83610	0.0290*
H11	0.738 (2)	0.5498 (10)	0.9590 (17)	0.026 (5)*
H21	0.62240	0.45390	1.17530	0.0340*
H31	0.46270	0.49220	1.30550	0.0390*
H43	1.135 (2)	0.3197 (12)	0.6923 (17)	0.037 (6)*
H42	1.135 (3)	0.3862 (12)	0.633 (2)	0.046 (7)*
H51	0.46180	0.67630	1.16980	0.0360*
H61	0.61400	0.63840	1.03450	0.0330*
H2A	0.192 (3)	0.7255 (13)	0.417 (2)	0.057 (8)*
H3A	0.57150	0.74070	0.39010	0.0340*
H4A	0.76770	0.71300	0.53300	0.0310*
H6A	0.44900	0.65480	0.73420	0.0270*
H71A	0.070 (3)	0.6443 (12)	0.698 (2)	0.050 (7)*
H1B	0.846 (3)	0.5699 (13)	0.553 (2)	0.054 (8)*
H11B	0.75490	0.47070	0.41840	0.0780*
H12B	0.81330	0.46210	0.55070	0.0780*
H13B	0.65430	0.49990	0.51090	0.0780*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0252 (8)	0.0244 (9)	0.0233 (8)	−0.0001 (7)	−0.0004 (6)	0.0011 (6)
N4	0.0387 (10)	0.0250 (10)	0.0277 (10)	0.0064 (8)	0.0046 (8)	−0.0015 (8)
N11	0.0255 (8)	0.0223 (9)	0.0220 (8)	0.0000 (7)	0.0031 (6)	0.0030 (7)
C1	0.0235 (9)	0.0238 (10)	0.0232 (10)	−0.0001 (8)	−0.0005 (7)	−0.0004 (7)
C2	0.0312 (10)	0.0254 (11)	0.0265 (10)	−0.0007 (8)	0.0011 (8)	0.0048 (8)
C3	0.0330 (11)	0.0193 (10)	0.0317 (10)	0.0028 (8)	0.0008 (8)	0.0007 (8)
C4	0.0249 (9)	0.0246 (10)	0.0235 (10)	−0.0006 (8)	−0.0033 (8)	−0.0025 (7)
C5	0.0272 (10)	0.0236 (10)	0.0241 (10)	−0.0014 (8)	0.0005 (8)	0.0025 (8)
C6	0.0248 (9)	0.0204 (10)	0.0257 (10)	0.0017 (8)	−0.0001 (7)	0.0011 (7)
C11	0.0206 (9)	0.0269 (10)	0.0216 (9)	−0.0016 (8)	−0.0006 (7)	−0.0024 (7)
C21	0.0318 (10)	0.0260 (11)	0.0274 (10)	−0.0020 (8)	0.0026 (8)	0.0007 (8)
C31	0.0357 (11)	0.0353 (12)	0.0264 (10)	−0.0046 (9)	0.0065 (8)	0.0033 (8)
C41	0.0294 (10)	0.0400 (12)	0.0264 (10)	−0.0014 (9)	0.0054 (8)	−0.0060 (9)
C51	0.0307 (11)	0.0284 (11)	0.0311 (11)	0.0021 (8)	0.0037 (8)	−0.0037 (8)
C61	0.0290 (10)	0.0264 (10)	0.0264 (10)	−0.0017 (8)	0.0044 (8)	0.0024 (8)
S5A	0.0215 (2)	0.0203 (3)	0.0226 (2)	−0.0005 (2)	0.0052 (2)	0.0011 (2)
O2A	0.0328 (8)	0.0484 (10)	0.0272 (8)	0.0024 (7)	−0.0002 (6)	0.0072 (6)
O51A	0.0273 (7)	0.0296 (8)	0.0257 (7)	0.0041 (6)	0.0080 (5)	0.0065 (5)
O52A	0.0226 (7)	0.0272 (7)	0.0279 (7)	0.0013 (5)	0.0065 (5)	0.0013 (5)
O53A	0.0352 (8)	0.0248 (7)	0.0352 (8)	−0.0054 (6)	−0.0012 (6)	−0.0008 (6)
O71A	0.0206 (7)	0.0443 (9)	0.0321 (8)	−0.0013 (6)	0.0069 (6)	0.0053 (6)
O72A	0.0253 (7)	0.0384 (8)	0.0340 (8)	0.0019 (6)	0.0001 (6)	−0.0001 (6)
C1A	0.0255 (10)	0.0198 (9)	0.0246 (9)	−0.0003 (8)	0.0055 (7)	−0.0023 (7)
C2A	0.0306 (10)	0.0243 (10)	0.0251 (10)	0.0013 (8)	0.0019 (8)	−0.0004 (8)
C3A	0.0345 (11)	0.0286 (11)	0.0229 (10)	−0.0009 (8)	0.0076 (8)	0.0039 (8)
C4A	0.0258 (10)	0.0245 (10)	0.0294 (10)	−0.0009 (8)	0.0094 (8)	0.0003 (8)
C5A	0.0244 (9)	0.0182 (9)	0.0227 (9)	0.0014 (7)	0.0057 (7)	−0.0001 (7)
C6A	0.0263 (10)	0.0195 (9)	0.0221 (9)	0.0002 (7)	0.0065 (7)	0.0005 (7)
C7A	0.0277 (10)	0.0220 (10)	0.0283 (10)	0.0006 (8)	0.0024 (8)	−0.0052 (8)
O1B	0.0865 (14)	0.0374 (9)	0.0287 (9)	0.0017 (9)	0.0158 (8)	−0.0042 (7)
C1B	0.0475 (14)	0.0724 (18)	0.0350 (13)	−0.0121 (13)	0.0000 (11)	0.0041 (12)

Geometric parameters (Å, º)

S5A—C5A	1.7706 (18)	C21—C31	1.386 (3)
S5A—O53A	1.4453 (14)	C31—C41	1.385 (3)
S5A—O51A	1.4468 (13)	C41—C51	1.387 (3)
S5A—O52A	1.4724 (13)	C51—C61	1.385 (3)
O2A—C2A	1.351 (2)	C2—H2	0.9500
O71A—C7A	1.320 (2)	C3—H3	0.9500
O72A—C7A	1.228 (2)	C5—H5	0.9500
O2A—H2A	0.90 (3)	C6—H6	0.9500
O71A—H71A	0.90 (3)	C21—H21	0.9500
O1B—C1B	1.404 (3)	C31—H31	0.9500
O1B—H1B	0.80 (2)	C41—H41	0.9500
N1—C1	1.339 (2)	C51—H51	0.9500
N1—N11	1.298 (2)	C61—H61	0.9500
N4—C4	1.318 (3)	C1A—C2A	1.406 (3)
N11—C11	1.407 (2)	C1A—C7A	1.478 (2)
N4—H42	0.88 (2)	C1A—C6A	1.399 (3)
N4—H43	0.87 (2)	C2A—C3A	1.403 (2)
N11—H11	0.85 (2)	C3A—C4A	1.374 (3)
C1—C6	1.431 (3)	C4A—C5A	1.406 (2)
C1—C2	1.426 (3)	C5A—C6A	1.377 (2)
C2—C3	1.358 (3)	C3A—H3A	0.9500
C3—C4	1.430 (3)	C4A—H4A	0.9500
C4—C5	1.431 (3)	C6A—H6A	0.9500
C5—C6	1.351 (3)	C1B—H11B	0.9800
C11—C21	1.389 (3)	C1B—H12B	0.9800
C11—C61	1.395 (3)	C1B—H13B	0.9800
O52A—S5A—O53A	110.96 (8)	C5—C6—H6	120.00
O52A—S5A—C5A	105.21 (8)	C1—C6—H6	120.00
O53A—S5A—C5A	107.73 (8)	C31—C21—H21	121.00
O51A—S5A—O53A	114.02 (8)	C11—C21—H21	121.00
O51A—S5A—C5A	106.37 (8)	C41—C31—H31	119.00
O51A—S5A—O52A	111.96 (7)	C21—C31—H31	119.00
C2A—O2A—H2A	104.5 (16)	C31—C41—H41	120.00
C7A—O71A—H71A	110.6 (15)	C51—C41—H41	120.00
C1B—O1B—H1B	111.3 (18)	C41—C51—H51	120.00
N11—N1—C1	120.20 (15)	C61—C51—H51	120.00
N1—N11—C11	120.77 (15)	C51—C61—H61	120.00
H43—N4—H42	120 (2)	C11—C61—H61	120.00
C4—N4—H43	118.8 (13)	C2A—C1A—C7A	119.79 (16)
C4—N4—H42	120.8 (16)	C6A—C1A—C7A	120.97 (16)
C11—N11—H11	116.0 (13)	C2A—C1A—C6A	119.24 (16)
N1—N11—H11	123.2 (13)	O2A—C2A—C3A	117.63 (16)
C2—C1—C6	118.21 (16)	C1A—C2A—C3A	119.66 (16)
N1—C1—C6	126.20 (17)	O2A—C2A—C1A	122.71 (16)
N1—C1—C2	115.59 (16)	C2A—C3A—C4A	120.57 (17)
C1—C2—C3	121.35 (17)	C3A—C4A—C5A	119.68 (16)
C2—C3—C4	120.06 (17)	C4A—C5A—C6A	120.40 (16)
C3—C4—C5	118.73 (16)	S5A—C5A—C4A	119.25 (13)
N4—C4—C3	121.27 (17)	S5A—C5A—C6A	120.35 (13)
N4—C4—C5	120.00 (17)	C1A—C6A—C5A	120.47 (16)
C4—C5—C6	120.73 (16)	O71A—C7A—O72A	123.10 (16)
C1—C6—C5	120.88 (17)	O71A—C7A—C1A	113.91 (16)
N11—C11—C21	121.30 (16)	O72A—C7A—C1A	122.99 (17)
C21—C11—C61	120.74 (17)	C4A—C3A—H3A	120.00
N11—C11—C61	117.95 (16)	C2A—C3A—H3A	120.00
C11—C21—C31	118.82 (18)	C3A—C4A—H4A	120.00
C21—C31—C41	121.12 (18)	C5A—C4A—H4A	120.00
C31—C41—C51	119.48 (17)	C1A—C6A—H6A	120.00
C41—C51—C61	120.43 (18)	C5A—C6A—H6A	120.00
C11—C61—C51	119.39 (17)	O1B—C1B—H11B	109.00
C1—C2—H2	119.00	O1B—C1B—H12B	109.00
C3—C2—H2	119.00	O1B—C1B—H13B	109.00
C4—C3—H3	120.00	H11B—C1B—H12B	109.00
C2—C3—H3	120.00	H11B—C1B—H13B	109.00
C4—C5—H5	120.00	H12B—C1B—H13B	109.00
C6—C5—H5	120.00
O51A—S5A—C5A—C4A	−171.49 (14)	C61—C11—C21—C31	0.3 (3)
O52A—S5A—C5A—C4A	−52.56 (16)	N11—C11—C61—C51	−179.93 (17)
O53A—S5A—C5A—C4A	65.87 (16)	C11—C21—C31—C41	−1.4 (3)
O51A—S5A—C5A—C6A	9.19 (17)	C21—C31—C41—C51	1.3 (3)
O52A—S5A—C5A—C6A	128.12 (15)	C31—C41—C51—C61	−0.1 (3)
O53A—S5A—C5A—C6A	−113.45 (16)	C41—C51—C61—C11	−1.0 (3)
N11—N1—C1—C6	1.7 (3)	C2A—C1A—C7A—O71A	173.86 (16)
C1—N1—N11—C11	178.80 (16)	C2A—C1A—C7A—O72A	−5.4 (3)
N11—N1—C1—C2	−177.08 (16)	C6A—C1A—C7A—O71A	−6.1 (3)
N1—N11—C11—C21	−5.3 (3)	C6A—C1A—C7A—O72A	174.71 (18)
N1—N11—C11—C61	175.47 (16)	C7A—C1A—C2A—O2A	0.0 (3)
C6—C1—C2—C3	−2.3 (3)	C7A—C1A—C2A—C3A	−179.32 (17)
N1—C1—C2—C3	176.64 (17)	C2A—C1A—C6A—C5A	−0.4 (3)
N1—C1—C6—C5	−177.72 (17)	C7A—C1A—C6A—C5A	179.54 (17)
C2—C1—C6—C5	1.1 (3)	C6A—C1A—C2A—O2A	179.89 (17)
C1—C2—C3—C4	1.1 (3)	C6A—C1A—C2A—C3A	0.6 (3)
C2—C3—C4—C5	1.2 (3)	O2A—C2A—C3A—C4A	−179.86 (18)
C2—C3—C4—N4	−179.02 (18)	C1A—C2A—C3A—C4A	−0.5 (3)
N4—C4—C5—C6	177.82 (18)	C2A—C3A—C4A—C5A	0.2 (3)
C3—C4—C5—C6	−2.4 (3)	C3A—C4A—C5A—C6A	0.0 (3)
C4—C5—C6—C1	1.3 (3)	C3A—C4A—C5A—S5A	−179.34 (15)
N11—C11—C21—C31	−178.85 (16)	S5A—C5A—C6A—C1A	179.41 (14)
C21—C11—C61—C51	0.9 (3)	C4A—C5A—C6A—C1A	0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···O72A	0.90 (3)	1.80 (3)	2.624 (2)	151 (2)
O71A—H71A···O52A^i	0.90 (3)	1.74 (3)	2.6246 (19)	166 (2)
O1B—H1B···O52A	0.80 (2)	2.00 (2)	2.792 (2)	175 (2)
N11—H11···O51A	0.85 (2)	2.07 (2)	2.895 (2)	163.1 (17)
N4—H43···O53A^ii	0.87 (2)	1.97 (2)	2.834 (2)	170.5 (17)
N4—H42···O1B^iii	0.88 (2)	1.98 (2)	2.845 (2)	173 (2)
C6—H6···O51A	0.95	2.52	3.421 (2)	158
C6—H6···O52A	0.95	2.41	3.184 (2)	138
C6A—H6A···O51A	0.95	2.49	2.888 (2)	105
C61—H61···O51A	0.95	2.51	3.260 (2)	136

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

(II) 2-(4-aminophenyl)-1-phenylhydrazin-1-ium (4-phenyldiazenyl)anilinium bis(benzenesulfonate)

Crystal data

2C12H12N3^+·2C6H5O3S^−	Z = 2
Mr = 710.82	F(000) = 744
Triclinic, P1	Dx = 1.363 Mg m^−3
Hall symbol: -P 1	Melting point > 533 K
a = 5.7601 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.0794 (8) Å	Cell parameters from 9206 reflections
c = 23.6556 (15) Å	θ = 3.1–28.8°
α = 77.937 (5)°	µ = 0.21 mm^−1
β = 83.985 (5)°	T = 200 K
γ = 86.971 (5)°	Flat prism, red-black
V = 1732.4 (2) Å^3	0.40 × 0.20 × 0.12 mm

Data collection

Oxford Gemini-S CCD area-detector diffractometer	7187 independent reflections
Radiation source: Enhance (Mo) X-ray source	5717 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 26.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.870, Tmax = 0.980	k = −16→16
22657 measured reflections	l = −29→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 0.1286P] where P = (Fo^2 + 2Fc^2)/3
7187 reflections	(Δ/σ)max = 0.002
487 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1A	0.5326 (2)	0.15945 (10)	0.55716 (5)	0.0249 (4)
N4A	−0.2488 (2)	0.41954 (11)	0.52166 (7)	0.0302 (4)
N11A	0.6418 (2)	0.14091 (10)	0.60432 (6)	0.0252 (4)
C1A	0.3444 (3)	0.22648 (12)	0.55278 (6)	0.0234 (4)
C2A	0.2423 (3)	0.28433 (12)	0.59501 (7)	0.0276 (5)
C3A	0.0487 (3)	0.34701 (13)	0.58471 (7)	0.0288 (5)
C4A	−0.0586 (3)	0.35780 (11)	0.53126 (7)	0.0237 (4)
C5A	0.0447 (3)	0.30193 (13)	0.48861 (7)	0.0284 (5)
C6A	0.2387 (3)	0.23909 (13)	0.49927 (7)	0.0279 (5)
C11A	0.8343 (3)	0.06750 (12)	0.61005 (6)	0.0246 (4)
C21A	0.9775 (3)	0.06756 (12)	0.65455 (7)	0.0270 (5)
C31A	1.1706 (3)	−0.00158 (13)	0.66037 (7)	0.0315 (5)
C41A	1.2221 (3)	−0.06907 (13)	0.62224 (7)	0.0330 (5)
C51A	1.0777 (3)	−0.06926 (13)	0.57850 (8)	0.0351 (6)
C61A	0.8820 (3)	−0.00135 (13)	0.57228 (7)	0.0308 (5)
N1B	0.9485 (2)	0.62632 (11)	0.92492 (6)	0.0315 (4)
N4B	0.8937 (3)	0.38824 (12)	0.75157 (7)	0.0297 (5)
N11B	1.1276 (2)	0.61019 (11)	0.95245 (6)	0.0313 (4)
C1B	0.9441 (3)	0.56207 (12)	0.88232 (7)	0.0256 (5)
C2B	0.7475 (3)	0.57629 (13)	0.85084 (7)	0.0305 (5)
C3B	0.7279 (3)	0.51812 (13)	0.80848 (7)	0.0283 (5)
C4B	0.9062 (3)	0.44658 (12)	0.79819 (6)	0.0234 (4)
C5B	1.1024 (3)	0.43097 (13)	0.82944 (7)	0.0294 (5)
C6B	1.1205 (3)	0.48867 (13)	0.87155 (7)	0.0295 (5)
C11B	1.1364 (3)	0.67357 (13)	0.99493 (7)	0.0291 (5)
C21B	0.9626 (3)	0.74718 (15)	1.00706 (8)	0.0376 (6)
C31B	0.9901 (4)	0.80453 (17)	1.04875 (9)	0.0484 (7)
C41B	1.1895 (3)	0.78828 (16)	1.07946 (8)	0.0458 (7)
C51B	1.3604 (3)	0.71506 (16)	1.06759 (8)	0.0411 (6)
C61B	1.3348 (3)	0.65765 (15)	1.02560 (7)	0.0364 (6)
S1D	0.37349 (7)	0.53551 (3)	0.64795 (2)	0.0253 (1)
O11D	0.4719 (4)	0.5609 (2)	0.58754 (10)	0.0322 (7)	0.80 (1)
O12D	0.4817 (4)	0.44266 (13)	0.68188 (9)	0.0437 (7)	0.80 (1)
O13D	0.1139 (3)	0.53091 (17)	0.65288 (9)	0.0292 (6)	0.80 (1)
C1D	0.4297 (3)	0.64119 (12)	0.68114 (6)	0.0229 (4)
C2D	0.6437 (3)	0.69011 (13)	0.66785 (7)	0.0299 (5)
C3D	0.6903 (3)	0.76852 (14)	0.69672 (8)	0.0396 (6)
C4D	0.5269 (3)	0.79604 (14)	0.73903 (8)	0.0421 (6)
C5D	0.3164 (3)	0.74701 (14)	0.75231 (8)	0.0391 (6)
C6D	0.2653 (3)	0.66965 (12)	0.72327 (7)	0.0285 (5)
O16D	0.5670 (17)	0.4570 (8)	0.6626 (4)	0.056 (3)*	0.20 (1)
O14D	0.415 (2)	0.5810 (10)	0.5842 (6)	0.047 (4)*	0.20 (1)
O15D	0.1543 (19)	0.5028 (8)	0.6657 (5)	0.048 (3)*	0.20 (1)
S1C	0.42375 (7)	0.18835 (3)	0.76892 (2)	0.0247 (1)
O11C	0.5634 (2)	0.18672 (10)	0.71390 (5)	0.0423 (4)
O12C	0.50971 (19)	0.26263 (9)	0.79942 (5)	0.0312 (3)
O13C	0.1729 (2)	0.20097 (9)	0.76321 (6)	0.0413 (4)
C1C	0.4682 (3)	0.06238 (12)	0.81416 (7)	0.0278 (5)
C2C	0.6882 (3)	0.01280 (14)	0.81285 (8)	0.0372 (6)
C3C	0.7235 (4)	−0.08399 (15)	0.84969 (9)	0.0468 (7)
C4C	0.5430 (4)	−0.13037 (16)	0.88718 (9)	0.0539 (8)
C5C	0.3268 (4)	−0.08039 (19)	0.88912 (10)	0.0663 (9)
C6C	0.2877 (3)	0.01656 (17)	0.85245 (9)	0.0486 (7)
H43A	−0.313 (3)	0.4262 (14)	0.4872 (9)	0.041 (5)*
H2A	0.30910	0.27890	0.62970	0.0330*
H3A	−0.01570	0.38360	0.61270	0.0340*
H5A	−0.02020	0.30840	0.45360	0.0340*
H6A	0.30440	0.20340	0.47110	0.0340*
H11A	0.595 (3)	0.1643 (15)	0.6357 (8)	0.042 (5)*
H21A	0.94410	0.11320	0.67990	0.0320*
H31A	1.26550	−0.00250	0.69000	0.0380*
H41A	1.35260	−0.11410	0.62590	0.0400*
H42A	−0.298 (3)	0.4526 (16)	0.5477 (9)	0.047 (6)*
H51A	1.11180	−0.11490	0.55320	0.0420*
H61A	0.78500	−0.00210	0.54330	0.0370*
H44B	0.946 (4)	0.4341 (18)	0.7143 (10)	0.062 (7)*
H2B	0.63000	0.62460	0.85820	0.0370*
H3B	0.59780	0.52710	0.78750	0.0340*
H5B	1.21950	0.38240	0.82200	0.0350*
H6B	1.24990	0.47870	0.89270	0.0350*
H21B	0.82950	0.75740	0.98720	0.0450*
H31B	0.87610	0.85410	1.05650	0.0580*
H41B	1.20660	0.82660	1.10770	0.0550*
H42B	0.759 (5)	0.3715 (19)	0.7518 (10)	0.068 (8)*
H43B	0.998 (4)	0.3254 (18)	0.7557 (9)	0.055 (6)*
H51B	1.49260	0.70440	1.08780	0.0490*
H61B	1.44980	0.60850	1.01780	0.0440*
H3D	0.83130	0.80250	0.68760	0.0480*
H6D	0.12240	0.63720	0.73190	0.0340*
H4D	0.55990	0.84770	0.75840	0.0500*
H5D	0.20800	0.76550	0.78070	0.0470*
H2D	0.75400	0.67070	0.64010	0.0360*
H2C	0.81110	0.04400	0.78760	0.0450*
H3C	0.87030	−0.11720	0.84880	0.0560*
H4C	0.56670	−0.19530	0.91120	0.0650*
H5C	0.20540	−0.11130	0.91500	0.0800*
H6C	0.14100	0.04980	0.85390	0.0580*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0252 (6)	0.0261 (7)	0.0231 (7)	−0.0006 (5)	−0.0037 (5)	−0.0040 (5)
N4A	0.0290 (7)	0.0313 (8)	0.0323 (8)	0.0053 (6)	−0.0065 (6)	−0.0111 (7)
N11A	0.0253 (7)	0.0289 (7)	0.0222 (7)	0.0021 (5)	−0.0032 (5)	−0.0075 (6)
C1A	0.0237 (7)	0.0225 (8)	0.0241 (8)	−0.0021 (6)	−0.0023 (6)	−0.0047 (6)
C2A	0.0326 (8)	0.0290 (8)	0.0242 (8)	0.0006 (7)	−0.0094 (6)	−0.0093 (7)
C3A	0.0332 (9)	0.0285 (8)	0.0282 (9)	0.0022 (7)	−0.0037 (7)	−0.0145 (7)
C4A	0.0243 (8)	0.0198 (7)	0.0270 (8)	−0.0034 (6)	−0.0022 (6)	−0.0040 (6)
C5A	0.0300 (8)	0.0345 (9)	0.0222 (8)	0.0027 (7)	−0.0072 (6)	−0.0081 (7)
C6A	0.0320 (8)	0.0313 (9)	0.0226 (8)	0.0019 (7)	−0.0027 (6)	−0.0110 (7)
C11A	0.0236 (7)	0.0247 (8)	0.0240 (8)	−0.0006 (6)	−0.0008 (6)	−0.0021 (6)
C21A	0.0286 (8)	0.0272 (8)	0.0258 (8)	−0.0012 (6)	−0.0028 (6)	−0.0065 (6)
C31A	0.0288 (8)	0.0334 (9)	0.0312 (9)	−0.0018 (7)	−0.0076 (7)	−0.0016 (7)
C41A	0.0296 (8)	0.0283 (9)	0.0379 (10)	0.0057 (7)	−0.0029 (7)	−0.0016 (7)
C51A	0.0417 (10)	0.0304 (9)	0.0341 (10)	0.0068 (8)	−0.0031 (7)	−0.0107 (7)
C61A	0.0362 (9)	0.0316 (9)	0.0260 (8)	0.0024 (7)	−0.0077 (7)	−0.0075 (7)
N1B	0.0330 (7)	0.0345 (8)	0.0290 (7)	0.0029 (6)	−0.0074 (6)	−0.0099 (6)
N4B	0.0278 (8)	0.0295 (8)	0.0350 (9)	0.0001 (6)	−0.0065 (6)	−0.0125 (6)
N11B	0.0312 (7)	0.0365 (8)	0.0274 (7)	−0.0009 (6)	−0.0063 (6)	−0.0079 (6)
C1B	0.0276 (8)	0.0255 (8)	0.0243 (8)	0.0000 (6)	−0.0035 (6)	−0.0059 (6)
C2B	0.0280 (8)	0.0317 (9)	0.0328 (9)	0.0095 (7)	−0.0070 (7)	−0.0093 (7)
C3B	0.0252 (8)	0.0326 (9)	0.0280 (8)	0.0039 (7)	−0.0090 (6)	−0.0065 (7)
C4B	0.0252 (8)	0.0218 (7)	0.0232 (8)	−0.0034 (6)	−0.0021 (6)	−0.0039 (6)
C5B	0.0241 (8)	0.0291 (9)	0.0357 (9)	0.0052 (7)	−0.0050 (7)	−0.0089 (7)
C6B	0.0242 (8)	0.0339 (9)	0.0325 (9)	0.0035 (7)	−0.0096 (7)	−0.0091 (7)
C11B	0.0324 (8)	0.0319 (9)	0.0227 (8)	−0.0046 (7)	−0.0027 (6)	−0.0041 (7)
C21B	0.0374 (10)	0.0461 (11)	0.0325 (10)	0.0035 (8)	−0.0108 (7)	−0.0130 (8)
C31B	0.0515 (12)	0.0532 (12)	0.0472 (12)	0.0124 (10)	−0.0117 (9)	−0.0254 (10)
C41B	0.0544 (12)	0.0530 (12)	0.0365 (11)	−0.0029 (10)	−0.0105 (9)	−0.0210 (9)
C51B	0.0385 (10)	0.0562 (12)	0.0318 (10)	−0.0040 (9)	−0.0114 (8)	−0.0117 (9)
C61B	0.0328 (9)	0.0431 (10)	0.0349 (10)	0.0010 (8)	−0.0069 (7)	−0.0105 (8)
S1D	0.0300 (2)	0.0225 (2)	0.0249 (2)	0.0015 (2)	−0.0078 (2)	−0.0064 (2)
O11D	0.0311 (12)	0.0422 (13)	0.0263 (10)	0.0013 (11)	−0.0014 (9)	−0.0154 (8)
O12D	0.0653 (14)	0.0198 (8)	0.0498 (13)	0.0073 (9)	−0.0322 (11)	−0.0047 (8)
O13D	0.0259 (9)	0.0322 (10)	0.0324 (10)	−0.0068 (8)	−0.0049 (8)	−0.0108 (9)
C1D	0.0258 (8)	0.0209 (7)	0.0226 (8)	0.0013 (6)	−0.0079 (6)	−0.0035 (6)
C2D	0.0248 (8)	0.0298 (9)	0.0335 (9)	0.0012 (7)	−0.0058 (7)	−0.0016 (7)
C3D	0.0340 (9)	0.0309 (9)	0.0546 (12)	−0.0089 (8)	−0.0225 (8)	0.0007 (8)
C4D	0.0598 (12)	0.0262 (9)	0.0470 (11)	0.0017 (8)	−0.0279 (10)	−0.0126 (8)
C5D	0.0521 (11)	0.0341 (10)	0.0332 (10)	0.0084 (8)	−0.0072 (8)	−0.0123 (8)
C6D	0.0295 (8)	0.0267 (8)	0.0290 (9)	0.0017 (7)	−0.0035 (7)	−0.0056 (7)
S1C	0.0268 (2)	0.0245 (2)	0.0253 (2)	0.0042 (2)	−0.0072 (2)	−0.0099 (2)
O11C	0.0589 (8)	0.0420 (7)	0.0242 (6)	0.0176 (6)	−0.0033 (6)	−0.0077 (5)
O12C	0.0342 (6)	0.0294 (6)	0.0340 (6)	−0.0025 (5)	−0.0068 (5)	−0.0134 (5)
O13C	0.0299 (6)	0.0324 (7)	0.0663 (9)	0.0056 (5)	−0.0199 (6)	−0.0148 (6)
C1C	0.0335 (9)	0.0269 (8)	0.0265 (8)	−0.0008 (7)	−0.0098 (7)	−0.0099 (7)
C2C	0.0380 (10)	0.0350 (10)	0.0385 (10)	0.0059 (8)	−0.0091 (8)	−0.0063 (8)
C3C	0.0536 (12)	0.0386 (11)	0.0504 (12)	0.0100 (9)	−0.0228 (10)	−0.0083 (9)
C4C	0.0698 (15)	0.0381 (11)	0.0524 (13)	−0.0080 (10)	−0.0304 (11)	0.0077 (9)
C5C	0.0620 (15)	0.0632 (15)	0.0608 (15)	−0.0211 (12)	−0.0038 (11)	0.0203 (12)
C6C	0.0381 (10)	0.0516 (12)	0.0507 (12)	−0.0024 (9)	−0.0025 (9)	0.0012 (10)

Geometric parameters (Å, º)

S1D—O16D	1.493 (10)	C61A—H61A	0.9300
S1D—O15D	1.351 (11)	C1B—C2B	1.403 (2)
S1D—O13D	1.4910 (18)	C1B—C6B	1.401 (2)
S1D—O11D	1.458 (2)	C2B—C3B	1.395 (2)
S1D—O12D	1.458 (2)	C3B—C4B	1.390 (2)
S1D—C1D	1.7849 (16)	C4B—C5B	1.398 (2)
S1D—O14D	1.500 (14)	C5B—C6B	1.385 (2)
S1C—C1C	1.7892 (17)	C11B—C61B	1.400 (2)
S1C—O13C	1.4628 (12)	C11B—C21B	1.402 (3)
S1C—O11C	1.4601 (12)	C21B—C31B	1.384 (3)
S1C—O12C	1.4589 (12)	C31B—C41B	1.406 (3)
N1A—N11A	1.3103 (18)	C41B—C51B	1.386 (3)
N1A—C1A	1.356 (2)	C51B—C61B	1.388 (3)
N4A—C4A	1.336 (2)	C2B—H2B	0.9300
N11A—C11A	1.426 (2)	C3B—H3B	0.9300
N4A—H43A	0.92 (2)	C5B—H5B	0.9300
N4A—H42A	0.84 (2)	C6B—H6B	0.9300
N11A—H11A	0.873 (19)	C21B—H21B	0.9300
N1B—C1B	1.444 (2)	C31B—H31B	0.9300
N1B—N11B	1.2623 (17)	C41B—H41B	0.9300
N4B—C4B	1.476 (2)	C51B—H51B	0.9300
N11B—C11B	1.436 (2)	C61B—H61B	0.9300
N4B—H44B	0.99 (2)	C1D—C6D	1.396 (2)
N4B—H43B	0.99 (2)	C1D—C2D	1.395 (2)
N4B—H42B	0.82 (3)	C2D—C3D	1.397 (3)
C1A—C2A	1.436 (2)	C3D—C4D	1.391 (3)
C1A—C6A	1.437 (2)	C4D—C5D	1.378 (3)
C2A—C3A	1.361 (2)	C5D—C6D	1.395 (2)
C3A—C4A	1.442 (2)	C2D—H2D	0.9300
C4A—C5A	1.429 (2)	C3D—H3D	0.9300
C5A—C6A	1.365 (2)	C4D—H4D	0.9300
C11A—C21A	1.404 (2)	C5D—H5D	0.9300
C11A—C61A	1.394 (2)	C6D—H6D	0.9300
C21A—C31A	1.396 (2)	C1C—C2C	1.393 (2)
C31A—C41A	1.389 (2)	C1C—C6C	1.379 (3)
C41A—C51A	1.394 (2)	C2C—C3C	1.397 (3)
C51A—C61A	1.398 (2)	C3C—C4C	1.373 (3)
C2A—H2A	0.9300	C4C—C5C	1.377 (3)
C3A—H3A	0.9300	C5C—C6C	1.401 (3)
C5A—H5A	0.9300	C2C—H2C	0.9300
C6A—H6A	0.9300	C3C—H3C	0.9300
C21A—H21A	0.9300	C4C—H4C	0.9300
C31A—H31A	0.9300	C5C—H5C	0.9300
C41A—H41A	0.9300	C6C—H6C	0.9300
C51A—H51A	0.9300
O15D—S1D—C1D	109.6 (5)	N1B—C1B—C6B	124.10 (15)
O16D—S1D—C1D	105.0 (4)	C1B—C2B—C3B	120.18 (16)
O14D—S1D—O15D	114.4 (7)	C2B—C3B—C4B	118.79 (15)
O14D—S1D—O16D	106.8 (6)	N4B—C4B—C3B	119.45 (15)
O15D—S1D—O16D	116.4 (6)	N4B—C4B—C5B	118.77 (15)
O12D—S1D—O13D	112.43 (12)	C3B—C4B—C5B	121.73 (15)
O12D—S1D—C1D	105.85 (10)	C4B—C5B—C6B	119.21 (16)
O13D—S1D—C1D	104.83 (10)	C1B—C6B—C5B	120.13 (16)
O14D—S1D—C1D	103.5 (5)	C21B—C11B—C61B	119.80 (16)
O11D—S1D—O12D	113.57 (13)	N11B—C11B—C61B	115.63 (15)
O11D—S1D—O13D	111.75 (12)	N11B—C11B—C21B	124.57 (15)
O11D—S1D—C1D	107.73 (12)	C11B—C21B—C31B	119.65 (17)
O11C—S1C—C1C	106.08 (8)	C21B—C31B—C41B	120.4 (2)
O12C—S1C—O13C	113.22 (7)	C31B—C41B—C51B	119.84 (18)
O12C—S1C—C1C	105.28 (7)	C41B—C51B—C61B	120.15 (17)
O11C—S1C—O12C	111.91 (7)	C11B—C61B—C51B	120.19 (17)
O13C—S1C—C1C	106.44 (8)	C3B—C2B—H2B	120.00
O11C—S1C—O13C	113.16 (8)	C1B—C2B—H2B	120.00
N11A—N1A—C1A	120.09 (12)	C2B—C3B—H3B	121.00
N1A—N11A—C11A	120.31 (13)	C4B—C3B—H3B	121.00
C4A—N4A—H43A	119.4 (12)	C6B—C5B—H5B	120.00
H42A—N4A—H43A	124.0 (17)	C4B—C5B—H5B	120.00
C4A—N4A—H42A	116.5 (13)	C5B—C6B—H6B	120.00
N1A—N11A—H11A	124.6 (12)	C1B—C6B—H6B	120.00
C11A—N11A—H11A	114.6 (12)	C31B—C21B—H21B	120.00
N11B—N1B—C1B	113.66 (13)	C11B—C21B—H21B	120.00
N1B—N11B—C11B	114.68 (14)	C41B—C31B—H31B	120.00
H42B—N4B—H43B	110 (2)	C21B—C31B—H31B	120.00
C4B—N4B—H44B	108.1 (14)	C51B—C41B—H41B	120.00
H42B—N4B—H44B	111 (2)	C31B—C41B—H41B	120.00
H43B—N4B—H44B	106.8 (18)	C41B—C51B—H51B	120.00
C4B—N4B—H43B	112.6 (13)	C61B—C51B—H51B	120.00
C4B—N4B—H42B	108.8 (17)	C11B—C61B—H61B	120.00
N1A—C1A—C2A	127.53 (14)	C51B—C61B—H61B	120.00
N1A—C1A—C6A	114.66 (13)	C2D—C1D—C6D	120.27 (15)
C2A—C1A—C6A	117.81 (15)	S1D—C1D—C2D	119.94 (12)
C1A—C2A—C3A	120.56 (15)	S1D—C1D—C6D	119.65 (13)
C2A—C3A—C4A	121.23 (15)	C1D—C2D—C3D	119.24 (15)
N4A—C4A—C3A	120.68 (15)	C2D—C3D—C4D	120.33 (16)
C3A—C4A—C5A	118.48 (15)	C3D—C4D—C5D	120.24 (17)
N4A—C4A—C5A	120.84 (15)	C4D—C5D—C6D	120.24 (17)
C4A—C5A—C6A	119.97 (15)	C1D—C6D—C5D	119.68 (16)
C1A—C6A—C5A	121.93 (15)	C1D—C2D—H2D	120.00
N11A—C11A—C61A	121.38 (14)	C3D—C2D—H2D	120.00
C21A—C11A—C61A	120.70 (15)	C2D—C3D—H3D	120.00
N11A—C11A—C21A	117.92 (14)	C4D—C3D—H3D	120.00
C11A—C21A—C31A	119.27 (15)	C5D—C4D—H4D	120.00
C21A—C31A—C41A	120.44 (15)	C3D—C4D—H4D	120.00
C31A—C41A—C51A	119.89 (16)	C4D—C5D—H5D	120.00
C41A—C51A—C61A	120.58 (16)	C6D—C5D—H5D	120.00
C11A—C61A—C51A	119.11 (16)	C5D—C6D—H6D	120.00
C3A—C2A—H2A	120.00	C1D—C6D—H6D	120.00
C1A—C2A—H2A	120.00	S1C—C1C—C2C	120.03 (13)
C2A—C3A—H3A	119.00	S1C—C1C—C6C	120.02 (14)
C4A—C3A—H3A	119.00	C2C—C1C—C6C	119.86 (16)
C6A—C5A—H5A	120.00	C1C—C2C—C3C	119.72 (17)
C4A—C5A—H5A	120.00	C2C—C3C—C4C	120.4 (2)
C5A—C6A—H6A	119.00	C3C—C4C—C5C	119.8 (2)
C1A—C6A—H6A	119.00	C4C—C5C—C6C	120.7 (2)
C31A—C21A—H21A	120.00	C1C—C6C—C5C	119.53 (18)
C11A—C21A—H21A	120.00	C1C—C2C—H2C	120.00
C41A—C31A—H31A	120.00	C3C—C2C—H2C	120.00
C21A—C31A—H31A	120.00	C2C—C3C—H3C	120.00
C51A—C41A—H41A	120.00	C4C—C3C—H3C	120.00
C31A—C41A—H41A	120.00	C3C—C4C—H4C	120.00
C61A—C51A—H51A	120.00	C5C—C4C—H4C	120.00
C41A—C51A—H51A	120.00	C4C—C5C—H5C	120.00
C11A—C61A—H61A	120.00	C6C—C5C—H5C	120.00
C51A—C61A—H61A	120.00	C1C—C6C—H6C	120.00
C2B—C1B—C6B	119.95 (15)	C5C—C6C—H6C	120.00
N1B—C1B—C2B	115.95 (14)
O11D—S1D—C1D—C2D	−39.56 (17)	C21A—C31A—C41A—C51A	−1.2 (3)
O12D—S1D—C1D—C2D	82.26 (16)	C31A—C41A—C51A—C61A	0.6 (3)
O13D—S1D—C1D—C2D	−158.70 (15)	C41A—C51A—C61A—C11A	0.7 (3)
O11D—S1D—C1D—C6D	144.84 (15)	C6B—C1B—C2B—C3B	−0.5 (2)
O12D—S1D—C1D—C6D	−93.35 (16)	N1B—C1B—C2B—C3B	179.68 (15)
O13D—S1D—C1D—C6D	25.69 (16)	N1B—C1B—C6B—C5B	−179.48 (15)
O12C—S1C—C1C—C6C	96.33 (16)	C2B—C1B—C6B—C5B	0.7 (2)
O11C—S1C—C1C—C2C	38.32 (16)	C1B—C2B—C3B—C4B	−0.1 (2)
O11C—S1C—C1C—C6C	−144.90 (15)	C2B—C3B—C4B—C5B	0.6 (2)
O13C—S1C—C1C—C6C	−24.11 (17)	C2B—C3B—C4B—N4B	−176.99 (15)
O13C—S1C—C1C—C2C	159.10 (14)	C3B—C4B—C5B—C6B	−0.4 (2)
O12C—S1C—C1C—C2C	−80.46 (15)	N4B—C4B—C5B—C6B	177.22 (15)
N11A—N1A—C1A—C2A	0.5 (2)	C4B—C5B—C6B—C1B	−0.3 (2)
C1A—N1A—N11A—C11A	177.61 (14)	C61B—C11B—C21B—C31B	0.9 (3)
N11A—N1A—C1A—C6A	−179.27 (14)	N11B—C11B—C21B—C31B	−179.59 (17)
N1A—N11A—C11A—C21A	165.81 (14)	C21B—C11B—C61B—C51B	−0.5 (3)
N1A—N11A—C11A—C61A	−13.2 (2)	N11B—C11B—C61B—C51B	179.93 (16)
N11B—N1B—C1B—C2B	179.45 (14)	C11B—C21B—C31B—C41B	−0.9 (3)
C1B—N1B—N11B—C11B	179.74 (13)	C21B—C31B—C41B—C51B	0.5 (3)
N11B—N1B—C1B—C6B	−0.4 (2)	C31B—C41B—C51B—C61B	−0.2 (3)
N1B—N11B—C11B—C21B	1.0 (2)	C41B—C51B—C61B—C11B	0.1 (3)
N1B—N11B—C11B—C61B	−179.41 (15)	S1D—C1D—C2D—C3D	−176.26 (13)
C6A—C1A—C2A—C3A	1.4 (2)	C2D—C1D—C6D—C5D	−0.3 (2)
N1A—C1A—C6A—C5A	178.49 (15)	C6D—C1D—C2D—C3D	−0.7 (2)
C2A—C1A—C6A—C5A	−1.3 (2)	S1D—C1D—C6D—C5D	175.27 (13)
N1A—C1A—C2A—C3A	−178.40 (16)	C1D—C2D—C3D—C4D	1.2 (3)
C1A—C2A—C3A—C4A	−0.4 (3)	C2D—C3D—C4D—C5D	−0.8 (3)
C2A—C3A—C4A—C5A	−0.8 (2)	C3D—C4D—C5D—C6D	−0.2 (3)
C2A—C3A—C4A—N4A	179.95 (18)	C4D—C5D—C6D—C1D	0.8 (3)
N4A—C4A—C5A—C6A	−179.87 (16)	S1C—C1C—C2C—C3C	177.88 (15)
C3A—C4A—C5A—C6A	0.8 (2)	C6C—C1C—C2C—C3C	1.1 (3)
C4A—C5A—C6A—C1A	0.2 (3)	S1C—C1C—C6C—C5C	−177.74 (16)
N11A—C11A—C61A—C51A	177.76 (15)	C2C—C1C—C6C—C5C	−1.0 (3)
C21A—C11A—C61A—C51A	−1.3 (2)	C1C—C2C—C3C—C4C	−0.1 (3)
C61A—C11A—C21A—C31A	0.6 (2)	C2C—C3C—C4C—C5C	−1.0 (3)
N11A—C11A—C21A—C31A	−178.43 (14)	C3C—C4C—C5C—C6C	1.2 (3)
C11A—C21A—C31A—C41A	0.6 (2)	C4C—C5C—C6C—C1C	−0.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11A—H11A···O11C	0.873 (19)	1.921 (19)	2.7672 (18)	162.9 (17)
N4A—H42A···O11D^i	0.84 (2)	2.18 (2)	2.967 (3)	155.7 (18)
N4A—H43A···O11D^ii	0.92 (2)	2.05 (2)	2.962 (3)	177.2 (18)
N4B—H42B···O12C	0.82 (3)	2.14 (3)	2.820 (2)	141 (2)
N4B—H42B···O12D	0.82 (3)	2.43 (3)	3.001 (3)	128 (2)
N4B—H43B···O13C^iii	0.99 (2)	1.85 (2)	2.838 (2)	175 (2)
N4B—H44B···O13D^iii	0.99 (2)	1.93 (2)	2.890 (3)	165 (2)
C3A—H3A···O13D	0.93	2.50	3.220 (3)	135
C5B—H5B···O12C^iii	0.93	2.33	3.258 (2)	178
C6C—H6C···O13C	0.93	2.59	2.951 (3)	103
C6D—H6D···O13D	0.93	2.56	2.926 (3)	104
C21A—H21A···O11C	0.93	2.47	3.148 (2)	130

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

(III) 4-(phenyldiazenyl)aniline–3,5-dinitrobenzoic acid (1/2)

Crystal data

C12H11N3·2C7H4N2O6	Z = 1
Mr = 621.48	F(000) = 320
Triclinic, P1	Dx = 1.489 Mg m^−3
Hall symbol: -P 1	Melting point: 453 K
a = 8.2048 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8859 (7) Å	Cell parameters from 4012 reflections
c = 11.5802 (9) Å	θ = 2.9–28.8°
α = 112.292 (8)°	µ = 0.12 mm^−1
β = 92.560 (7)°	T = 200 K
γ = 114.072 (8)°	Prism, red
V = 693.09 (13) Å^3	0.30 × 0.30 × 0.15 mm

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2440 independent reflections
Radiation source: Enhance (Mo) X-ray source	1989 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.930, Tmax = 0.980	k = −10→10
8021 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0446P)^2 + 0.0825P] where P = (Fo^2 + 2Fc^2)/3
2440 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1A	0.55044 (15)	2.00276 (15)	0.46048 (10)	0.0365 (3)
N4A	0.5346 (4)	1.3392 (4)	0.1456 (3)	0.0522 (10)	0.500
C1A	0.54603 (17)	1.83104 (18)	0.38400 (13)	0.0344 (4)
C2A	0.46975 (18)	1.67703 (18)	0.40837 (13)	0.0381 (5)
C3A	0.46505 (19)	1.51471 (19)	0.32679 (14)	0.0424 (5)
C4A	0.53747 (19)	1.5009 (2)	0.21861 (15)	0.0438 (5)
C5A	0.6170 (2)	1.6555 (2)	0.19546 (14)	0.0454 (5)
C6A	0.62273 (18)	1.81963 (19)	0.27822 (14)	0.0408 (5)
O11	−0.06079 (15)	0.12182 (14)	0.14147 (10)	0.0468 (4)
O12	0.08141 (14)	0.20224 (12)	−0.00162 (9)	0.0411 (3)
O31	0.32547 (15)	0.84705 (14)	0.07643 (10)	0.0491 (4)
O32	0.29333 (17)	1.04248 (14)	0.24268 (11)	0.0621 (4)
O51	−0.04017 (17)	0.84183 (14)	0.53163 (11)	0.0621 (4)
O52	−0.16179 (15)	0.55597 (15)	0.49171 (10)	0.0521 (4)
N3	0.26847 (16)	0.88755 (15)	0.17407 (11)	0.0389 (4)
N5	−0.07430 (16)	0.68298 (16)	0.46627 (11)	0.0379 (4)
C1	0.04311 (17)	0.42637 (16)	0.17231 (11)	0.0302 (4)
C2	0.14076 (17)	0.56494 (17)	0.13703 (12)	0.0303 (4)
C3	0.16234 (17)	0.73976 (16)	0.21019 (12)	0.0302 (4)
C4	0.09292 (17)	0.78354 (17)	0.31756 (12)	0.0314 (4)
C5	−0.00239 (17)	0.64194 (17)	0.34949 (12)	0.0309 (4)
C6	−0.03051 (17)	0.46434 (17)	0.27937 (12)	0.0311 (4)
C11	0.02321 (18)	0.23897 (18)	0.09566 (13)	0.0333 (4)
H2A	0.42170	1.68440	0.48040	0.0460*
H3A	0.41310	1.41310	0.34390	0.0510*
H4A	0.53290	1.39060	0.16290	0.0530*	0.500
H5A	0.66650	1.64850	0.12400	0.0540*
H6A	0.67820	1.92250	0.26290	0.0490*
H41A	0.572 (5)	1.324 (5)	0.078 (4)	0.074 (13)*	0.500
H42A	0.481 (5)	1.264 (5)	0.163 (4)	0.067 (14)*	0.500
H2	0.19080	0.54090	0.06570	0.0360*
H4	0.10930	0.90170	0.36580	0.0380*
H6	−0.09720	0.37240	0.30340	0.0370*
H11	−0.074 (3)	0.010 (3)	0.0908 (18)	0.078 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0334 (6)	0.0353 (6)	0.0360 (6)	0.0127 (5)	0.0070 (5)	0.0143 (5)
N4A	0.0599 (19)	0.0429 (16)	0.0554 (19)	0.0276 (15)	0.0310 (15)	0.0168 (14)
C1A	0.0275 (7)	0.0333 (7)	0.0361 (7)	0.0108 (6)	0.0041 (6)	0.0129 (6)
C2A	0.0361 (8)	0.0383 (8)	0.0378 (8)	0.0148 (6)	0.0072 (6)	0.0172 (6)
C3A	0.0391 (8)	0.0365 (8)	0.0511 (9)	0.0164 (6)	0.0083 (7)	0.0199 (7)
C4A	0.0354 (8)	0.0400 (8)	0.0497 (9)	0.0198 (7)	0.0064 (7)	0.0111 (7)
C5A	0.0385 (8)	0.0523 (9)	0.0445 (9)	0.0221 (7)	0.0173 (7)	0.0182 (7)
C6A	0.0340 (8)	0.0404 (8)	0.0475 (8)	0.0145 (6)	0.0128 (6)	0.0212 (7)
O11	0.0738 (8)	0.0320 (6)	0.0451 (6)	0.0293 (5)	0.0295 (5)	0.0200 (5)
O12	0.0556 (6)	0.0322 (5)	0.0386 (6)	0.0231 (5)	0.0214 (5)	0.0143 (4)
O31	0.0592 (7)	0.0489 (6)	0.0487 (6)	0.0256 (5)	0.0272 (5)	0.0282 (5)
O32	0.0910 (9)	0.0269 (6)	0.0610 (7)	0.0211 (6)	0.0299 (7)	0.0171 (5)
O51	0.0869 (9)	0.0423 (6)	0.0535 (7)	0.0327 (6)	0.0378 (6)	0.0119 (5)
O52	0.0644 (7)	0.0532 (7)	0.0528 (7)	0.0296 (6)	0.0337 (6)	0.0318 (6)
N3	0.0436 (7)	0.0331 (7)	0.0395 (7)	0.0154 (5)	0.0120 (6)	0.0174 (5)
N5	0.0406 (7)	0.0419 (7)	0.0344 (6)	0.0226 (6)	0.0138 (5)	0.0153 (6)
C1	0.0325 (7)	0.0293 (7)	0.0276 (7)	0.0151 (6)	0.0044 (5)	0.0106 (5)
C2	0.0329 (7)	0.0331 (7)	0.0249 (6)	0.0168 (6)	0.0072 (5)	0.0108 (5)
C3	0.0299 (7)	0.0283 (7)	0.0300 (7)	0.0120 (6)	0.0045 (5)	0.0121 (5)
C4	0.0321 (7)	0.0274 (6)	0.0304 (7)	0.0145 (6)	0.0038 (5)	0.0078 (5)
C5	0.0308 (7)	0.0334 (7)	0.0272 (7)	0.0163 (6)	0.0067 (5)	0.0104 (5)
C6	0.0317 (7)	0.0314 (7)	0.0313 (7)	0.0144 (6)	0.0070 (5)	0.0148 (6)
C11	0.0385 (8)	0.0305 (7)	0.0317 (7)	0.0172 (6)	0.0080 (6)	0.0130 (6)

Geometric parameters (Å, º)

O11—C11	1.306 (2)	C4A—C5A	1.396 (3)
O12—C11	1.2247 (18)	C5A—C6A	1.388 (2)
O31—N3	1.2258 (17)	C2A—H2A	0.9300
O32—N3	1.2226 (18)	C3A—H3A	0.9300
O51—N5	1.2214 (18)	C4A—H4A	0.9300
O52—N5	1.2190 (19)	C5A—H5A	0.9300
O11—H11	0.90 (2)	C6A—H6A	0.9300
N1A—C1A	1.429 (2)	C1—C6	1.3898 (19)
N1A—N1A^i	1.2625 (17)	C1—C11	1.494 (2)
N4A—C4A	1.352 (4)	C1—C2	1.390 (2)
N4A—H41A	0.84 (4)	C2—C3	1.388 (2)
N4A—H42A	0.74 (5)	C3—C4	1.3780 (19)
N3—C3	1.475 (2)	C4—C5	1.381 (2)
N5—C5	1.4774 (18)	C5—C6	1.385 (2)
C1A—C2A	1.398 (2)	C2—H2	0.9300
C1A—C6A	1.391 (2)	C4—H4	0.9300
C2A—C3A	1.376 (2)	C6—H6	0.9300
C3A—C4A	1.395 (2)
C11—O11—H11	111.2 (15)	C3A—C4A—H4A	121.00
N1A^i—N1A—C1A	114.21 (13)	C5A—C4A—H4A	121.00
H41A—N4A—H42A	124 (5)	C4A—C5A—H5A	120.00
C4A—N4A—H41A	120 (3)	C6A—C5A—H5A	120.00
H4A—N4A—H42A	120.00	C1A—C6A—H6A	120.00
C4A—N4A—H42A	114 (3)	C5A—C6A—H6A	120.00
H4A—N4A—H41A	113.00	C2—C1—C11	119.02 (12)
O32—N3—C3	118.15 (12)	C6—C1—C11	121.01 (13)
O31—N3—C3	117.83 (12)	C2—C1—C6	119.95 (13)
O31—N3—O32	124.02 (14)	C1—C2—C3	118.83 (12)
O51—N5—O52	124.44 (13)	N3—C3—C2	118.87 (12)
O52—N5—C5	117.62 (13)	C2—C3—C4	123.08 (13)
O51—N5—C5	117.94 (13)	N3—C3—C4	118.03 (12)
C2A—C1A—C6A	119.01 (14)	C3—C4—C5	116.16 (13)
N1A—C1A—C6A	116.52 (14)	N5—C5—C6	118.26 (13)
N1A—C1A—C2A	124.48 (13)	C4—C5—C6	123.42 (13)
C1A—C2A—C3A	120.63 (14)	N5—C5—C4	118.30 (13)
C2A—C3A—C4A	120.66 (16)	C1—C6—C5	118.56 (13)
N4A—C4A—C3A	117.4 (2)	O11—C11—C1	114.17 (12)
N4A—C4A—C5A	123.7 (2)	O12—C11—C1	121.55 (14)
C3A—C4A—C5A	118.81 (15)	O11—C11—O12	124.28 (14)
C4A—C5A—C6A	120.53 (15)	C1—C2—H2	121.00
C1A—C6A—C5A	120.32 (15)	C3—C2—H2	121.00
C3A—C2A—H2A	120.00	C3—C4—H4	122.00
C1A—C2A—H2A	120.00	C5—C4—H4	122.00
C4A—C3A—H3A	120.00	C1—C6—H6	121.00
C2A—C3A—H3A	120.00	C5—C6—H6	121.00
N1A^i—N1A—C1A—C2A	−12.6 (2)	N4A—C4A—C5A—C6A	−176.8 (2)
N1A^i—N1A—C1A—C6A	167.00 (13)	C4A—C5A—C6A—C1A	−1.2 (2)
C1A—N1A—N1A^i—C1A^i	−180.00 (12)	C6—C1—C2—C3	−0.1 (2)
O31—N3—C3—C2	3.6 (2)	C11—C1—C2—C3	−178.60 (13)
O31—N3—C3—C4	−177.94 (14)	C2—C1—C6—C5	−0.7 (2)
O32—N3—C3—C2	−176.79 (14)	C11—C1—C6—C5	177.76 (13)
O32—N3—C3—C4	1.6 (2)	C2—C1—C11—O11	175.89 (13)
O52—N5—C5—C4	178.35 (14)	C2—C1—C11—O12	−4.4 (2)
O52—N5—C5—C6	−3.1 (2)	C6—C1—C11—O11	−2.6 (2)
O51—N5—C5—C6	175.97 (14)	C6—C1—C11—O12	177.18 (14)
O51—N5—C5—C4	−2.6 (2)	C1—C2—C3—N3	179.03 (13)
N1A—C1A—C2A—C3A	177.48 (14)	C1—C2—C3—C4	0.7 (2)
C6A—C1A—C2A—C3A	−2.1 (2)	N3—C3—C4—C5	−178.73 (13)
C2A—C1A—C6A—C5A	2.5 (2)	C2—C3—C4—C5	−0.4 (2)
N1A—C1A—C6A—C5A	−177.13 (14)	C3—C4—C5—N5	177.99 (13)
C1A—C2A—C3A—C4A	0.5 (2)	C3—C4—C5—C6	−0.5 (2)
C2A—C3A—C4A—N4A	177.5 (2)	N5—C5—C6—C1	−177.47 (13)
C2A—C3A—C4A—C5A	0.8 (2)	C4—C5—C6—C1	1.0 (2)
C3A—C4A—C5A—C6A	−0.4 (2)

Symmetry code: (i) −x+1, −y+4, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O12^ii	0.90 (2)	1.75 (2)	2.6426 (16)	175 (2)
N4A—H41A···O31^iii	0.84 (4)	2.31 (4)	3.042 (4)	147 (4)
N4A—H42A···O32	0.74 (5)	2.48 (4)	3.213 (4)	173 (4)
C2A—H2A···O52^iv	0.93	2.47	3.134 (2)	129
C4—H4···O51^iv	0.93	2.45	3.339 (2)	161

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