The 1:1 proton-transfer compounds of 4-(phenyl­diazen­yl)aniline (aniline yellow) with 3-nitro­phthalic, 4-nitro­phthalic and 5-nitro­isophthalic acids

The structures of the anhydrous 1:1 proton-transfer compounds of the dye precursor aniline yellow [4-(phenyl­diazenyl)­aniline], namely isomeric 4-(phenyl­diazenyl)­anilin­ium 2-carb­oxy-6-nitro­benzoate, C₁₂H₁₂N₃⁺·C₈H₄NO₆⁻, (I), and 4-(phenyl­diazenyl)­anilinium 2-carb­oxy-4-nitro­benzoate, C₁₂H₁₂N₃⁺·C₈H₄NO₆⁻, (II), and 4-(phenyl­diazenyl)­anilinium 3-carb­oxy-5-nitro­benzoate monohydrate, C₁₂H₁₂N₃⁺·C₈H₄­NO₆⁻·H₂O, (III), have been determined at 130 K. In (I) the cation has longitudinal rotational disorder. All three compounds have substructures comprising backbones formed through strong head-to-tail carboxyl–carboxyl­ate hydrogen-bond inter­actions [graph set C(7) in (I) and (II), and C(8) in (III)]. Two-dimensional sheet structures are formed in all three compounds by the incorporation of the 4-(phenyl­diazenyl)­anilinium cations into the substructures, including, in the cases of (I) and (II), infinite H—N—H to carboxyl­ate O—C—O group inter­actions [graph set C(6)], and in the case of (III), bridging through the water mol­ecule of solvation. The peripheral alternating aromatic ring residues of both cations and anions give only weakly π-inter­active step features which lie between the sheets.

S1. Comment

Aniline yellow [4-(phenyldiazenyl)aniline or p-aminodiazenylbenzene] is used as an intermediate in the manufacture of acid yellow and diazo dyes and its salts are used in dyeing (O'Neil, 2001). The structures of proton-transfer compounds of aniline yellow are not common in the literature, being limited to 1:1 salts with oxalic acid (Mahmoudkhani & Langer, 2001b), phenylphosphonic acid (Mahmoudkhani & Langer, 2002a) and 1,4-butanebisphosphonic acid (Mahmoudkhani & Langer, 2002b), and the hydrochloride (Mahmoudkhani & Langer, 2001a). The structure of the hydrochloride had previously been determined from powder diffraction data (Yatsenko et al., 2000), demonstrating an application of this method for structural elucidation in compounds such as dyes which generally have poor crystallinity. In this compound, the diazenyl group is protonated, whereas in the oxalate, the phenylphosphonate and the 1,4-butanebisphosphonate, the aniline group is protonated. We have also confirmed the presence of the azonium group rather than the anilinium group in the intense red–black crystalline salts of aniline yellow with the strong organic acids 5-sulfosalicylic acid and picric acid (Smith, Wermuth & White, 2007). With the hydrochloride, the absorption maximum is shifted bathochromically by 850 cm^-1 from that of the ethanolic solution of the salt (Yatsenko et al., 2000).

Our attempted 1:1 stoichiometric reaction of 4-(phenyldiazenyl)aniline with a number of carboxylic acids in aqueous ethanol generally gave no new products, but with the isomeric 3- and 4-nitrophthalic acids, good crystals of the anhydrous proton-transfer compounds 4-(phenyldiazenyl)anilinium 2-carboxy-6-nitrobenzoate, (I), and 4-(phenyldiazenyl)anilinium 2-carboxy-4-nitrobenzoate, (II), both C₁₂H₁₂N₂⁺·C₈H₄N₂O₆^-, were obtained. With the third isomeric acid, 5-nitroisophthalic acid, the hydrated salt 4-(phenyldiazenyl)anilinium 3-carboxy-5-nitrobenzoate monohydrate, (III), C₁₂H₁₂N₂⁺·C₈H₄N₂O₆^-·H₂O, was obtained. The crystals of (I) and (II) are orange–yellow in colour, while (III) is red, suggesting that all were anilinium rather than azonium salts (which are typically dark red–black). The aim of this investigation was to confirm the presence of the anilinium species in each compound and to look for a common structural feature which favours the hydrogen phthalates for the formation of stable crystalline proton-transfer products with aniline yellow.

Although the aniline group is protonated in all three compounds, in (I) it is the 2-carboxylic acid substituent group of 3-nitrophthalic acid which is deprotonated (Fig. 1). This is also the case in other acid 3-nitrophthalate salts (Glidewell et al., 2003, 2005; Smith, Wermuth & Healy, 2007). With (II) it is the 1-carboxylic acid substituent group that is deprotonated (Fig. 2). The hydrated cation and anion species in (III) are shown in Fig. 3. It should also be noted that the 4-(phenyldiazenyl)anilinium cation in (I) shows a 0.799 (7):0.201 (7) longitudinal rotational disorder, similar to that which has been observed in an investigation of the structure of the parent aniline yellow (Smith, Wermuth & White, 2007).

In each of compounds (I)–(III), the anilinium group gives inter-species hydrogen bonding (Tables 1–3), resulting in two-dimensional sheet structures (Figs. 4–7). Similar two-dimensional structures are also found in the other aminium salts of aniline yellow (Mahmoudkhani & Langer, 2001b, 2002a,b). A feature of the hydrogen bonding in all three compounds is the presence of a substructure formed through strong head-to-tail carboxylic acid O—H···O_carboxylate interactions [graph set C(7) in (I) and (II), and C(8) in (III); Etter et al., 1990], with O···O separations of 2.5791 (18), 2.480 (3), 2.536 (4) Å for (I)–(III), respectively. These substructures (best seen in Fig. 6) incorporate the anilinium cations and, in the case of (III), additionally the water molecule of solvation, giving the sheet structures. With (I) and (II), the heteromeric interactions include similar C(6) infinite linear extensions involving both O acceptors of the carboxylate group of the anion [atoms O21 and O22 in (I), and atoms O11 and O12 in (II)] linked through two anilinium H atoms of the cation. These extend down the c axial direction in (I) and the a axial direction in (II) (see Figs. 4 and 5). With (III), the water molecule is central in the extension, acting in a bridging capacity as a dual donor linking separate anion carboxyl groups via atom O12A, and as a dual acceptor linking separate cation anilinium groups (see Fig. 7). The peripheral alternating cation and the anion aromatic ring residues form step features which lie between the sheets (see Figs. 4, 5 and 7). There are no hydrogen-bonding or π–π interactions between these residues; both the nitro-O and the diazenyl N atoms are unassociated, with a minimal number of aromatic C—H···O associations but with weak π–π aromatic ring interactions. In all three compounds, these take the form of partial ring overlap, in (I) and (II) between cation ring 1 (C1–C6) and anion ring 2 (C1A–C6A) [Cg1···Cg2 = 3.7310 (13) Å and 3.7701 (19) Å, respectively], while in (III) the interactions are cation–cation [Cg1···Cg1 = 3.796 (3) Å] and anion–anion [Cg2···Cg2 = 3.883 (3) Å].

With the cation species, the two phenyl rings are expected to be essentially coplanar, as has been found in the structures of the other aniline yellow compounds (Mahmoudkhani & Langer, 2001a,b, 2002a,b). The torsion angles C6—C1—N1—N11 and C21—C11—N11—N1 are 164.2 (2) and 169.1 (3)°, respectively, in (I), and -173.8 (4) and -167.4 (5)°, respectively, in (III), compared with 166.0 (3) and -173.7 (3)°, respectively, for the ordered molecular part of the cation in (I). With acid 3-nitrophthalate anions, it is more usual for the sterically encumbered 2-carboxylate group to be rotated significantly out of the plane of the benzene ring compared with the 1-carboxylic acid group. The associated torsion angles C1A—C2A—C21A—O22A [81.36 (17)°] and C2A—C1A—C11A—O11A [-152.97 (15)°] in (I) reflect this. With the absence of any hydrogen bonding associated with the nitro group in the structure, this group is almost coplanar with the benzene ring [torsion angle C2A—C3A—N3A—O32A = 175.40 (14)°]. The three equivalent torsion angles found in guanidinium 2-carboxy-6-nitrobenzoate monohydrate (Smith, Wermuth & Healy, 2007) are 101.2 (2), 173.3 (2) and 151.2 (2)°, respectively. With (II), there are fewer steric constraints except those associated with the ortho-related carboxyl groups [corresponding torsion angles 160.9 (3), -82.4 (3) and -176.4 (3)°], while in (III), the anion is essentially planar [torsion angles -176.5 (4), -173.5 (4) and -174.1 (5)°]. This is also the case in 5-nitroisophthalic acid (Colapietro et al., 1984) and its polymorphic monohydrate hydrate structures (Mahapatra et al., 1999; Saleh et al., 2006). With (III), there is also a short intramolecular aromatic C—H···O_carboxyl association [C2···O11A = 2.733 (5) Å].

It may be concluded that the hydrogen phthalate cations in the structures considered in this work have a strong influence upon the molecular assembly process, with their inherent ability to form primary substructures through head-to-tail hydrogen-bonding associations. The presence of the anilinium group rather than the azonium group in the cation (confirmed in all cases) is essential in the secondary assembly process, while the aromatic ring systems of both the phenyldiazenylaniline [-ium?] cations and the hydrogen phthalate anions act as peripheral and only weakly π-associated step features.

Related literature

For related literature, see: Colapietro et al. (1984); Etter et al. (1990); Glidewell et al. (2003, 2005); Mahapatra et al. (1999); Mahmoudkhani & Langer (2001a, 2001b, 2002a, 2002b); O'Neil (2001); Saleh et al. (2006); Smith, Wermuth & Healy (2007); Smith, Wermuth & White (2007); Yatsenko et al. (2000).

S2. Experimental

Compounds (I)–(III) were synthesized by heating together for 10 min under reflux 1 mmol quantities of 4-(phenyldiazenyl)aniline and, respectively, 3-nitrophthalic acid, 4-nitrophthalic acid or 5-nitroisophthalic acid in 80% ethanol–water (50 ml). Compounds (I) (m.p. 441 K) and (II) (m.p. 512–513 K) were obtained as orange–yellow needles after partial room-temperature evaporation of the solvents, while (III) was obtained as red needle prisms (m.p. 393 K). [CIF states brown blocks for (I) - please clarify]

S3. Refinement

The atoms of the disordered phenyldiazenylanilinium cation species in (I) (indicated by primed atom labels) were generally located by difference methods and the ring atoms were refined as a fixed groups with their common site occupancy determined by least-squares refinement [0.225 (8)]. These atoms were refined isotropically. H atoms potentially involved in hydrogen-bonding interactions in compounds (I)–(III) were located by difference methods and their positional and isotropic displacement parameters were refined. However, because of the poor data-to-refined-parameter ratio in (II), these atoms were constrained in the final refinement cycles. Other H atoms for all three compounds were included in calculated positions [C—H = 0.93–0.95 Å] and treated as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

For all compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the 4-(phenyldiazenyl)anilinium cation and 2-carboxy-6-nitrobenzoate anion in (I). Displacement ellipsoids of the major-occupancy atoms are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. The inter-ion hydrogen bond is shown as a dashed line. The longitudinal rotationally disordered isotropic atoms of the cation [N1', N11', C1'–C6', C11'–C61' and their attached H atoms; site occupancy factor 0.225 (8)] are also joined by dashed lines.
	Fig. 2. The molecular configuration and atom-numbering scheme for the 4-(phenyldiazenyl)anilinium cation and 2-carboxy-4-nitrobenzoate anion in (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates an inter-ion hydrogen bond.
	Fig. 3. The molecular configuration and atom-numbering scheme for the 4-(phenyldiazenyl)anilinium cation, the 2-carboxy-5-nitrobenzoate anion and the water molecule of solvation in (III). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate the inter-species hydrogen bonds.
	Fig. 4. The C(6) hydrogen-bonded cation–anion extension in (I), viewed down the b axial direction. The disordered portion of the cation is omitted, as are H atoms not involved in these interactions. Hydrogen bonding is shown by dashed lines. [Symmetry codes: (vi) x, -y + 3/2, z - 1/2; (vii) x, y - 1/2, -z + 1/2; for other symmetry codes, see Table 1.]
	Fig. 5. A view of the C(6) chain extension in the two-dimensional hydrogen-bonded sheet structure of (II), down the b cell direction. H atoms not involved in these interactions have been omitted. [Symmetry codes: (v) x, y + 1, z; (vi) x + 1/2, y + 1/2, z; for other symmetry codes, see Table 2.]
	Fig. 6. A view of the undulating hydrogen-bonded anion substructure and its extension in the two-dimensional hydrogen-bonded sheet structure of (III), down the b axial direction of the cell. H atoms not involved in these interactions have been omitted. For symmetry codes, see Table 3.
	Fig. 7. The unit cell of (III), viewed down the approximate a cell direction, showing the water bridges in the two-dimensional sheets at z = 0, 1/2 and the interstitial cation–anion aromatic ring step features.

(I) 4-(phenyldiazenyl)anilinium 2-carboxy-6-nitrobenzoate

Crystal data

C12H12N3^+·C8H4NO6^−	F(000) = 848
Mr = 408.37	Dx = 1.445 Mg m^−3
Monoclinic, P21/c	Melting point: 441 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 17.873 (2) Å	Cell parameters from 3539 reflections
b = 7.9729 (10) Å	θ = 2.3–27.2°
c = 13.3054 (16) Å	µ = 0.11 mm^−1
β = 98.198 (2)°	T = 130 K
V = 1876.6 (4) Å^3	Needle cut from block, orange–yellow
Z = 4	0.55 × 0.30 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3306 independent reflections
Radiation source: sealed tube	2888 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 25.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −21→17
Tmin = 0.88, Tmax = 0.99	k = −9→9
9511 measured reflections	l = −15→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0506P)^2 + 0.5876P] where P = (Fo^2 + 2Fc^2)/3
3306 reflections	(Δ/σ)max < 0.001
320 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.18 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)
N1	0.16652 (16)	0.1941 (3)	0.61705 (14)	0.0343 (8)	0.775 (8)
N4	0.42531 (7)	0.58845 (17)	0.58646 (10)	0.0214 (4)
N11	0.17087 (14)	0.0416 (4)	0.59911 (15)	0.0355 (8)	0.775 (8)
C1	0.23519 (19)	0.2852 (5)	0.61061 (19)	0.0286 (9)	0.775 (8)
C2	0.3059 (2)	0.2105 (4)	0.6120 (2)	0.0286 (9)	0.775 (8)
C3	0.3675 (2)	0.3120 (5)	0.6047 (3)	0.0298 (9)	0.775 (8)
C4	0.3591 (3)	0.4821 (5)	0.5958 (4)	0.0212 (11)	0.775 (8)
C5	0.28978 (17)	0.5562 (7)	0.5953 (3)	0.0250 (9)	0.775 (8)
C6	0.22771 (15)	0.4571 (6)	0.6042 (2)	0.0308 (9)	0.775 (8)
C11	0.10308 (18)	−0.0511 (6)	0.6070 (2)	0.0355 (9)	0.775 (8)
C21	0.10199 (19)	−0.2117 (6)	0.5708 (3)	0.0580 (13)	0.775 (8)
C31	0.0405 (3)	−0.3127 (8)	0.5766 (5)	0.0727 (16)	0.775 (8)
C41	−0.02034 (17)	−0.2549 (4)	0.6186 (4)	0.0477 (13)	0.775 (8)
C51	−0.0195 (2)	−0.0934 (5)	0.6546 (5)	0.0567 (13)	0.775 (8)
C61	0.0419 (2)	0.0109 (4)	0.6479 (3)	0.0463 (10)	0.775 (8)
C1'	0.2519 (5)	0.2387 (12)	0.6042 (6)	0.017 (3)*	0.225 (8)
C2'	0.3263 (6)	0.1848 (10)	0.6096 (7)	0.030 (4)*	0.225 (8)
C3'	0.3837 (5)	0.3007 (14)	0.6037 (10)	0.027 (3)*	0.225 (8)
C4'	0.3666 (6)	0.4703 (12)	0.5925 (13)	0.021 (6)*	0.225 (8)
C5'	0.2921 (7)	0.5241 (10)	0.5872 (13)	0.042 (7)*	0.225 (8)
C6'	0.2348 (5)	0.4083 (13)	0.5930 (8)	0.030 (4)*	0.225 (8)
C11'	0.0830 (5)	0.0086 (12)	0.6148 (6)	0.024 (2)*	0.225 (8)
C21'	0.0932 (5)	−0.1467 (14)	0.5712 (7)	0.033 (3)*	0.225 (8)
C31'	0.0409 (8)	−0.2742 (11)	0.5765 (10)	0.050 (5)*	0.225 (8)
C41'	−0.0217 (7)	−0.2464 (15)	0.6255 (13)	0.068 (9)*	0.225 (8)
C51'	−0.0320 (6)	−0.0911 (17)	0.6690 (11)	0.046 (5)*	0.225 (8)
C61'	0.0204 (6)	0.0363 (12)	0.6637 (7)	0.040 (4)*	0.225 (8)
N1'	0.2004 (6)	0.1034 (11)	0.6076 (5)	0.027 (2)*	0.225 (8)
N11'	0.1326 (6)	0.1493 (11)	0.6172 (5)	0.031 (2)*	0.225 (8)
O11A	0.46342 (7)	1.15633 (15)	0.40898 (9)	0.0386 (4)
O12A	0.48397 (6)	0.95224 (13)	0.30108 (8)	0.0244 (3)
O21A	0.40177 (6)	0.63962 (12)	0.22058 (7)	0.0219 (3)
O22A	0.44206 (6)	0.60762 (13)	0.38640 (7)	0.0229 (3)
O31A	0.28656 (6)	0.47541 (14)	0.32131 (9)	0.0340 (4)
O32A	0.17511 (6)	0.55324 (16)	0.34617 (10)	0.0403 (4)
N3A	0.24065 (7)	0.58335 (17)	0.33526 (10)	0.0260 (4)
C1A	0.36304 (8)	0.96762 (19)	0.35585 (11)	0.0234 (4)
C2A	0.34187 (8)	0.79910 (18)	0.33696 (10)	0.0200 (4)
C3A	0.26627 (8)	0.75997 (19)	0.34180 (11)	0.0233 (5)
C4A	0.21249 (9)	0.8794 (2)	0.35647 (13)	0.0304 (5)
C5A	0.23415 (9)	1.0444 (2)	0.36972 (13)	0.0328 (5)
C6A	0.30919 (9)	1.0872 (2)	0.37215 (12)	0.0288 (5)
C11A	0.44208 (9)	1.03425 (19)	0.35914 (11)	0.0247 (5)
C21A	0.39964 (8)	0.66948 (18)	0.31315 (11)	0.0197 (4)
H61	0.04180	0.12350	0.67130	0.0560*	0.775 (8)
H2	0.31150	0.09230	0.61790	0.0340*	0.775 (8)
H3	0.41610	0.26330	0.60600	0.0360*	0.775 (8)
H5	0.28450	0.67440	0.58900	0.0300*	0.775 (8)
H6	0.17970	0.50750	0.60590	0.0370*	0.775 (8)
H21	0.14380	−0.25350	0.54170	0.0700*	0.775 (8)
H31	0.04010	−0.42410	0.55120	0.0870*	0.775 (8)
H41	−0.06250	−0.32570	0.62280	0.0570*	0.775 (8)
H42	0.4226 (10)	0.683 (3)	0.6239 (15)	0.038 (5)*
H43	0.4724 (12)	0.529 (3)	0.6100 (16)	0.049 (6)*
H44	0.4269 (10)	0.618 (2)	0.5182 (16)	0.041 (5)*
H51	−0.06120	−0.05270	0.68430	0.0680*	0.775 (8)
H2'	0.33800	0.06890	0.61720	0.0350*	0.225 (8)
H3'	0.43450	0.26390	0.60730	0.0280*	0.225 (8)
H5'	0.28050	0.64010	0.57950	0.0510*	0.225 (8)
H6'	0.18390	0.44510	0.58940	0.0360*	0.225 (8)
H21'	0.13600	−0.16570	0.53770	0.0390*	0.225 (8)
H31'	0.04790	−0.38030	0.54670	0.0600*	0.225 (8)
H41'	−0.05730	−0.33300	0.63270	0.0820*	0.225 (8)
H51'	−0.07480	−0.07220	0.70250	0.0550*	0.225 (8)
H61'	0.01330	0.14240	0.69350	0.0480*	0.225 (8)
H4A	0.16130	0.84770	0.35730	0.0360*
H5A	0.19760	1.12840	0.37720	0.0390*
H6A	0.32440	1.20030	0.38520	0.0350*
H12A	0.5272 (13)	1.018 (3)	0.2966 (17)	0.061 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0304 (15)	0.0379 (13)	0.0343 (11)	−0.0028 (11)	0.0034 (9)	0.0036 (9)
N4	0.0251 (7)	0.0193 (7)	0.0203 (7)	−0.0008 (5)	0.0050 (5)	−0.0008 (6)
N11	0.0334 (13)	0.0376 (15)	0.0357 (11)	−0.0084 (11)	0.0053 (8)	−0.0006 (9)
C1	0.0262 (13)	0.0348 (19)	0.0251 (13)	−0.0035 (14)	0.0045 (10)	−0.0003 (11)
C2	0.037 (2)	0.0207 (13)	0.0283 (15)	−0.0055 (13)	0.0052 (11)	−0.0003 (9)
C3	0.0264 (16)	0.0316 (17)	0.0320 (16)	0.0031 (14)	0.0066 (15)	−0.0024 (10)
C4	0.0244 (19)	0.0255 (19)	0.0143 (18)	−0.0028 (11)	0.0048 (11)	−0.0014 (9)
C5	0.0258 (18)	0.0254 (12)	0.0240 (16)	0.0013 (10)	0.0044 (9)	−0.0001 (13)
C6	0.0237 (14)	0.0369 (17)	0.0319 (15)	0.0026 (12)	0.0043 (9)	−0.0008 (13)
C11	0.0293 (14)	0.0395 (19)	0.0371 (15)	−0.0067 (15)	0.0026 (10)	0.0019 (13)
C21	0.0431 (17)	0.043 (2)	0.091 (3)	−0.0077 (16)	0.0205 (15)	−0.0078 (18)
C31	0.050 (2)	0.048 (2)	0.122 (4)	−0.0154 (17)	0.0184 (19)	−0.015 (2)
C41	0.0229 (17)	0.037 (2)	0.081 (3)	−0.0141 (11)	0.0003 (12)	0.0119 (14)
C51	0.0309 (16)	0.049 (2)	0.093 (3)	0.0007 (14)	0.0184 (19)	0.0128 (17)
C61	0.0421 (19)	0.0359 (16)	0.0622 (19)	−0.0065 (14)	0.0115 (17)	0.0007 (13)
O11A	0.0439 (7)	0.0316 (7)	0.0437 (7)	−0.0145 (5)	0.0183 (6)	−0.0185 (6)
O12A	0.0282 (6)	0.0216 (6)	0.0250 (6)	−0.0043 (5)	0.0093 (4)	−0.0026 (4)
O21A	0.0278 (6)	0.0187 (6)	0.0201 (5)	0.0011 (4)	0.0063 (4)	−0.0005 (4)
O22A	0.0255 (6)	0.0231 (6)	0.0207 (5)	0.0029 (4)	0.0049 (4)	0.0029 (4)
O31A	0.0335 (6)	0.0213 (6)	0.0489 (8)	0.0009 (5)	0.0122 (5)	0.0009 (5)
O32A	0.0249 (6)	0.0405 (8)	0.0569 (8)	−0.0085 (5)	0.0109 (5)	−0.0010 (6)
N3A	0.0267 (7)	0.0255 (7)	0.0260 (7)	−0.0014 (6)	0.0047 (5)	0.0017 (6)
C1A	0.0296 (8)	0.0235 (8)	0.0182 (7)	0.0005 (6)	0.0068 (6)	0.0009 (6)
C2A	0.0259 (8)	0.0211 (8)	0.0137 (7)	0.0012 (6)	0.0048 (6)	0.0013 (6)
C3A	0.0265 (8)	0.0232 (8)	0.0209 (8)	0.0003 (6)	0.0057 (6)	0.0003 (6)
C4A	0.0247 (8)	0.0346 (10)	0.0328 (9)	0.0036 (7)	0.0077 (7)	−0.0009 (7)
C5A	0.0324 (9)	0.0285 (9)	0.0386 (10)	0.0106 (7)	0.0088 (7)	−0.0025 (7)
C6A	0.0382 (9)	0.0209 (8)	0.0284 (8)	0.0028 (7)	0.0081 (7)	−0.0028 (7)
C11A	0.0325 (8)	0.0209 (8)	0.0217 (8)	−0.0012 (7)	0.0073 (6)	0.0019 (6)
C21A	0.0220 (7)	0.0155 (7)	0.0226 (8)	−0.0041 (6)	0.0068 (6)	0.0012 (6)

Geometric parameters (Å, º)

O11A—C11A	1.2085 (19)	C21'—C31'	1.3896
O12A—C11A	1.3228 (19)	C31—C41	1.371 (7)
O21A—C21A	1.2604 (17)	C31'—C41'	1.3907
O22A—C21A	1.2479 (18)	C41—C51	1.373 (6)
O31A—N3A	1.2214 (17)	C41'—C51'	1.3901
O32A—N3A	1.2245 (17)	C51—C61	1.390 (5)
O12A—H12A	0.94 (2)	C51'—C61'	1.3902
N1—N11	1.244 (4)	C2—H2	0.9500
N1—C1	1.439 (5)	C2'—H2'	0.9500
N1'—N11'	1.290 (15)	C3—H3	0.9500
N1'—C1'	1.423 (13)	C3'—H3'	0.9500
N4—C4'	1.421 (10)	C5—H5	0.9500
N4—C4	1.475 (5)	C5'—H5'	0.9500
N11—C11	1.436 (5)	C6—H6	0.9500
N11'—C11'	1.427 (13)	C6'—H6'	0.9500
N4—H44	0.94 (2)	C21—H21	0.9500
N4—H42	0.91 (2)	C21'—H21'	0.9500
N4—H43	0.98 (2)	C31—H31	0.9500
N3A—C3A	1.480 (2)	C31'—H31'	0.9500
C1—C2	1.395 (5)	C41—H41	0.9500
C1—C6	1.379 (6)	C41'—H41'	0.9500
C1'—C2'	1.3895	C51—H51	0.9500
C1'—C6'	1.3896	C51'—H51'	0.9500
C2—C3	1.381 (5)	C61—H61	0.9500
C2'—C3'	1.3912	C61'—H61'	0.9500
C3—C4	1.368 (6)	C1A—C2A	1.409 (2)
C3'—C4'	1.3896	C1A—C11A	1.504 (2)
C4—C5	1.372 (6)	C1A—C6A	1.394 (2)
C4'—C5'	1.3911	C2A—C3A	1.397 (2)
C5—C6	1.381 (5)	C2A—C21A	1.526 (2)
C5'—C6'	1.3891	C3A—C4A	1.386 (2)
C11—C61	1.381 (5)	C4A—C5A	1.376 (2)
C11—C21	1.367 (7)	C5A—C6A	1.380 (2)
C11'—C61'	1.3898	C4A—H4A	0.9500
C11'—C21'	1.3903	C5A—H5A	0.9500
C21—C31	1.374 (7)	C6A—H6A	0.9500
C11A—O12A—H12A	107.4 (14)	C2—C3—H3	120.00
N11—N1—C1	113.9 (3)	C4—C3—H3	120.00
N11'—N1'—C1'	114.2 (8)	C2'—C3'—H3'	120.00
N1—N11—C11	114.4 (3)	C4'—C3'—H3'	120.00
N1'—N11'—C11'	111.4 (8)	C4—C5—H5	120.00
C4—N4—H44	111.1 (11)	C6—C5—H5	120.00
C4'—N4—H44	110.1 (13)	C4'—C5'—H5'	120.00
C4'—N4—H42	114.9 (13)	C6'—C5'—H5'	120.00
H43—N4—H44	106.7 (16)	C1—C6—H6	120.00
C4—N4—H43	111.0 (14)	C5—C6—H6	120.00
H42—N4—H44	109.4 (16)	C1'—C6'—H6'	120.00
C4—N4—H42	108.9 (12)	C5'—C6'—H6'	120.00
C4'—N4—H43	105.6 (14)	C31—C21—H21	120.00
H42—N4—H43	109.7 (18)	C11—C21—H21	120.00
O31A—N3A—O32A	123.69 (14)	C31'—C21'—H21'	120.00
O32A—N3A—C3A	118.23 (13)	C11'—C21'—H21'	120.00
O31A—N3A—C3A	118.07 (12)	C21—C31—H31	120.00
C2—C1—C6	120.3 (3)	C41—C31—H31	120.00
N1—C1—C6	115.4 (3)	C41'—C31'—H31'	120.00
N1—C1—C2	124.2 (3)	C21'—C31'—H31'	120.00
C2'—C1'—C6'	120.05	C51—C41—H41	120.00
N1'—C1'—C6'	127.4 (9)	C31—C41—H41	120.00
N1'—C1'—C2'	112.5 (8)	C51'—C41'—H41'	118.00
C1—C2—C3	118.6 (3)	C31'—C41'—H41'	122.00
C1'—C2'—C3'	119.97	C61—C51—H51	120.00
C2—C3—C4	120.6 (4)	C41—C51—H51	120.00
C2'—C3'—C4'	119.98	C41'—C51'—H51'	120.00
N4—C4—C5	119.1 (4)	C61'—C51'—H51'	120.00
C3—C4—C5	121.0 (4)	C51—C61—H61	120.00
N4—C4—C3	119.9 (4)	C11—C61—H61	120.00
C3'—C4'—C5'	119.98	C11'—C61'—H61'	120.00
N4—C4'—C5'	120.1 (8)	C51'—C61'—H61'	120.00
N4—C4'—C3'	119.9 (9)	C2A—C1A—C11A	124.70 (13)
C4—C5—C6	119.3 (5)	C6A—C1A—C11A	114.87 (13)
C4'—C5'—C6'	120.01	C2A—C1A—C6A	120.43 (14)
C1—C6—C5	120.2 (3)	C1A—C2A—C21A	120.70 (13)
C1'—C6'—C5'	120.00	C3A—C2A—C21A	123.09 (13)
N11—C11—C21	115.2 (3)	C1A—C2A—C3A	116.21 (13)
N11—C11—C61	124.7 (4)	N3A—C3A—C2A	120.20 (13)
C21—C11—C61	120.1 (3)	N3A—C3A—C4A	116.55 (13)
C21'—C11'—C61'	119.94	C2A—C3A—C4A	123.20 (14)
N11'—C11'—C21'	126.3 (8)	C3A—C4A—C5A	119.13 (15)
N11'—C11'—C61'	113.8 (8)	C4A—C5A—C6A	119.63 (15)
C11—C21—C31	120.0 (4)	C1A—C6A—C5A	121.18 (15)
C11'—C21'—C31'	120.08	O11A—C11A—C1A	121.47 (14)
C21—C31—C41	120.9 (5)	O12A—C11A—C1A	114.58 (13)
C21'—C31'—C41'	119.95	O11A—C11A—O12A	123.91 (15)
C31—C41—C51	119.2 (4)	O21A—C21A—C2A	116.52 (12)
C31'—C41'—C51'	120.02	O22A—C21A—C2A	117.34 (12)
C41—C51—C61	120.5 (4)	O21A—C21A—O22A	126.08 (13)
C41'—C51'—C61'	119.97	C3A—C4A—H4A	120.00
C11—C61—C51	119.2 (4)	C5A—C4A—H4A	120.00
C11'—C61'—C51'	120.05	C4A—C5A—H5A	120.00
C3—C2—H2	121.00	C6A—C5A—H5A	120.00
C1—C2—H2	121.00	C1A—C6A—H6A	119.00
C3'—C2'—H2'	120.00	C5A—C6A—H6A	119.00
C1'—C2'—H2'	120.00
C1—N1—N11—C11	179.0 (2)	C31—C41—C51—C61	0.5 (8)
N11—N1—C1—C2	−16.8 (3)	C41—C51—C61—C11	−1.7 (7)
N11—N1—C1—C6	164.2 (2)	C6A—C1A—C2A—C21A	176.53 (13)
N1—N11—C11—C21	169.1 (3)	C11A—C1A—C2A—C3A	177.04 (13)
N1—N11—C11—C61	−11.2 (4)	C6A—C1A—C2A—C3A	−3.7 (2)
O31A—N3A—C3A—C4A	179.26 (14)	C2A—C1A—C11A—O12A	29.2 (2)
O31A—N3A—C3A—C2A	−3.1 (2)	C6A—C1A—C11A—O11A	27.7 (2)
O32A—N3A—C3A—C2A	175.50 (14)	C6A—C1A—C11A—O12A	−150.09 (14)
O32A—N3A—C3A—C4A	−2.2 (2)	C11A—C1A—C6A—C5A	179.00 (14)
N1—C1—C6—C5	−178.5 (3)	C11A—C1A—C2A—C21A	−2.8 (2)
N1—C1—C2—C3	179.6 (3)	C2A—C1A—C6A—C5A	−0.4 (2)
C6—C1—C2—C3	−1.3 (4)	C2A—C1A—C11A—O11A	−152.97 (15)
C2—C1—C6—C5	2.4 (4)	C1A—C2A—C3A—N3A	−172.71 (13)
C1—C2—C3—C4	−0.3 (5)	C1A—C2A—C21A—O22A	81.36 (17)
C2—C3—C4—C5	0.9 (7)	C3A—C2A—C21A—O21A	84.13 (17)
C2—C3—C4—N4	−179.0 (3)	C3A—C2A—C21A—O22A	−98.41 (17)
N4—C4—C5—C6	−179.9 (3)	C1A—C2A—C3A—C4A	4.8 (2)
C3—C4—C5—C6	0.2 (7)	C21A—C2A—C3A—N3A	7.1 (2)
C4—C5—C6—C1	−1.8 (5)	C21A—C2A—C3A—C4A	−175.40 (14)
C61—C11—C21—C31	−1.1 (6)	C1A—C2A—C21A—O21A	−96.10 (16)
N11—C11—C61—C51	−177.7 (4)	N3A—C3A—C4A—C5A	175.82 (14)
C21—C11—C61—C51	2.0 (6)	C2A—C3A—C4A—C5A	−1.8 (2)
N11—C11—C21—C31	178.6 (4)	C3A—C4A—C5A—C6A	−2.5 (3)
C11—C21—C31—C41	−0.1 (8)	C4A—C5A—C6A—C1A	3.6 (2)
C21—C31—C41—C51	0.4 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12A—H12A···O21A^i	0.94 (2)	1.64 (2)	2.5794 (15)	175 (2)
N4—H42···O11A^ii	0.91 (2)	2.50 (2)	2.8399 (18)	102.8 (13)
N4—H42···O21A^iii	0.91 (2)	1.98 (2)	2.8768 (17)	167.7 (19)
N4—H43···O22A^iv	0.98 (2)	1.87 (2)	2.8194 (17)	162.3 (19)
N4—H43···O12A^iii	0.98 (2)	2.53 (2)	2.9164 (17)	103.7 (14)
N4—H44···O22A	0.94 (2)	1.81 (2)	2.7250 (16)	161.7 (15)
C6A—H6A···O31A^v	0.95	2.41	3.182 (2)	138

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

(II) 4-(phenyldiazenyl)anilinium 2-carboxy-4-nitrobenzoate

Crystal data

C12H12N3^+·C8H4NO6^−	F(000) = 848
Mr = 408.37	Dx = 1.455 Mg m^−3
Monoclinic, C2	Melting point = 511–513 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 12.950 (3) Å	Cell parameters from 1103 reflections
b = 7.5571 (18) Å	θ = 3.1–22.8°
c = 19.364 (5) Å	µ = 0.11 mm^−1
β = 100.371 (5)°	T = 130 K
V = 1864.1 (8) Å^3	Needle, orange-yellow
Z = 4	0.45 × 0.05 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1766 independent reflections
Radiation source: sealed tube	1564 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ and ω scans	θmax = 25.0°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −15→13
Tmin = 0.98, Tmax = 0.99	k = −7→8
4865 measured reflections	l = −22→20

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters not refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0409P)^2] where P = (Fo^2 + 2Fc^2)/3
1766 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.26 e Å^−3
1 restraint	Δρmin = −0.21 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
N1	0.2479 (2)	0.0790 (4)	0.29899 (14)	0.0362 (10)
N4	0.11130 (18)	0.5521 (3)	0.07349 (12)	0.0201 (8)
N11	0.2892 (2)	0.1422 (4)	0.35540 (15)	0.0351 (10)
C1	0.2144 (2)	0.2131 (4)	0.24523 (16)	0.0274 (11)
C2	0.2039 (2)	0.3941 (4)	0.25726 (16)	0.0278 (10)
C3	0.1695 (2)	0.5059 (4)	0.20060 (15)	0.0260 (10)
C4	0.1459 (2)	0.4358 (4)	0.13358 (15)	0.0204 (9)
C5	0.1566 (2)	0.2568 (4)	0.12197 (15)	0.0239 (10)
C6	0.1901 (2)	0.1456 (4)	0.17809 (16)	0.0265 (10)
C11	0.3202 (2)	0.0058 (4)	0.40853 (17)	0.0323 (11)
C21	0.3574 (2)	0.0680 (5)	0.47489 (17)	0.0373 (11)
C31	0.3850 (3)	−0.0494 (5)	0.52975 (17)	0.0367 (11)
C41	0.3783 (2)	−0.2291 (5)	0.51785 (17)	0.0362 (11)
C51	0.3428 (2)	−0.2937 (5)	0.45042 (17)	0.0363 (11)
C61	0.3125 (2)	−0.1760 (5)	0.39561 (16)	0.0357 (11)
O11A	0.41526 (14)	0.8566 (2)	0.05343 (9)	0.0230 (7)
O12A	0.25676 (14)	0.8309 (3)	0.08423 (9)	0.0199 (6)
O21A	0.31481 (14)	0.4916 (2)	0.02563 (10)	0.0209 (6)
O22A	0.42168 (15)	0.2602 (3)	0.05663 (10)	0.0271 (7)
O41A	0.53126 (19)	0.1819 (3)	0.31060 (11)	0.0431 (9)
O42A	0.53465 (19)	0.4019 (3)	0.38214 (11)	0.0408 (9)
N4A	0.5181 (2)	0.3399 (4)	0.32290 (13)	0.0297 (9)
C1A	0.3989 (2)	0.6736 (4)	0.15072 (14)	0.0173 (9)
C2A	0.4146 (2)	0.4903 (4)	0.14021 (14)	0.0184 (9)
C3A	0.4541 (2)	0.3839 (4)	0.19709 (14)	0.0207 (10)
C4A	0.4782 (2)	0.4568 (4)	0.26329 (15)	0.0362 (11)
C5A	0.4646 (2)	0.6362 (4)	0.27563 (15)	0.0235 (9)
C6A	0.4257 (2)	0.7418 (4)	0.21851 (14)	0.0217 (9)
C11A	0.3551 (2)	0.7957 (3)	0.09052 (14)	0.0184 (9)
C21A	0.3846 (2)	0.4033 (4)	0.06952 (14)	0.0176 (9)
H2	0.21970	0.43930	0.30260	0.0330*
H3	0.16250	0.62670	0.20770	0.0310*
H5	0.14140	0.21160	0.07660	0.0290*
H6	0.19630	0.02480	0.17060	0.0320*
H21	0.36400	0.18920	0.48290	0.0450*
H31	0.40840	−0.00690	0.57490	0.0440*
H41	0.39750	−0.30740	0.55500	0.0430*
H42	0.041	0.603	0.0728	0.043*
H43	0.103	0.490	0.0322	0.057*
H44	0.160	0.640	0.0730	0.040*
H51	0.33940	−0.41500	0.44220	0.0440*
H61	0.28720	−0.21780	0.35060	0.0430*
H3A	0.46420	0.26370	0.19060	0.0250*
H5A	0.48120	0.68330	0.32060	0.0280*
H6A	0.41700	0.86220	0.22550	0.0260*
H21A	0.288	0.434	−0.014	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0315 (16)	0.0432 (17)	0.0356 (17)	−0.0026 (14)	0.0104 (13)	−0.0065 (15)
N4	0.0131 (13)	0.0211 (14)	0.0258 (15)	−0.0009 (12)	0.0027 (10)	0.0040 (12)
N11	0.0328 (17)	0.0367 (17)	0.0367 (17)	0.0001 (13)	0.0089 (13)	−0.0057 (14)
C1	0.0194 (16)	0.032 (2)	0.0321 (19)	0.0047 (14)	0.0080 (13)	0.0108 (15)
C2	0.0278 (17)	0.035 (2)	0.0208 (17)	0.0011 (14)	0.0051 (13)	0.0007 (14)
C3	0.0203 (15)	0.0298 (19)	0.0284 (18)	−0.0035 (13)	0.0056 (13)	−0.0023 (14)
C4	0.0144 (15)	0.0216 (17)	0.0265 (17)	−0.0008 (12)	0.0072 (12)	0.0017 (13)
C5	0.0194 (16)	0.0275 (17)	0.0252 (17)	−0.0006 (14)	0.0048 (12)	−0.0015 (14)
C6	0.0273 (18)	0.0192 (17)	0.0343 (19)	0.0007 (13)	0.0089 (14)	0.0031 (15)
C11	0.0271 (17)	0.037 (2)	0.035 (2)	0.0063 (14)	0.0118 (14)	0.0112 (16)
C21	0.0347 (19)	0.043 (2)	0.036 (2)	0.0068 (17)	0.0112 (15)	0.0045 (18)
C31	0.034 (2)	0.049 (2)	0.0276 (19)	0.0046 (16)	0.0070 (15)	0.0062 (17)
C41	0.0278 (18)	0.049 (2)	0.032 (2)	−0.0026 (14)	0.0058 (14)	0.0171 (17)
C51	0.0310 (19)	0.038 (2)	0.040 (2)	0.0002 (15)	0.0065 (15)	0.0084 (17)
C61	0.0254 (17)	0.056 (2)	0.0258 (18)	0.0012 (17)	0.0048 (13)	0.0062 (18)
O11A	0.0194 (11)	0.0232 (12)	0.0271 (11)	−0.0027 (9)	0.0064 (9)	0.0022 (9)
O12A	0.0173 (10)	0.0194 (10)	0.0228 (11)	0.0020 (8)	0.0031 (8)	0.0017 (9)
O21A	0.0235 (10)	0.0173 (10)	0.0204 (11)	0.0041 (8)	−0.0002 (8)	0.0000 (9)
O22A	0.0275 (12)	0.0231 (12)	0.0291 (12)	0.0102 (10)	0.0009 (9)	−0.0045 (9)
O41A	0.0663 (18)	0.0267 (14)	0.0363 (14)	0.0208 (12)	0.0092 (12)	0.0065 (11)
O42A	0.0575 (17)	0.0397 (14)	0.0223 (13)	0.0012 (12)	−0.0007 (11)	0.0025 (11)
N4A	0.0342 (15)	0.0340 (16)	0.0208 (15)	0.0046 (13)	0.0051 (11)	0.0048 (13)
C1A	0.0129 (14)	0.0175 (16)	0.0225 (16)	0.0008 (11)	0.0057 (12)	0.0002 (12)
C2A	0.0129 (14)	0.0212 (15)	0.0211 (16)	−0.0007 (12)	0.0035 (11)	0.0024 (13)
C3A	0.0224 (16)	0.0145 (17)	0.0272 (17)	0.0001 (12)	0.0100 (13)	−0.0010 (13)
C4A	0.0278 (18)	0.049 (2)	0.032 (2)	0.0031 (16)	0.0058 (14)	0.0171 (17)
C5A	0.0244 (16)	0.0268 (17)	0.0186 (16)	−0.0013 (13)	0.0021 (13)	−0.0045 (13)
C6A	0.0197 (16)	0.0187 (16)	0.0273 (17)	0.0038 (13)	0.0055 (12)	−0.0006 (14)
C11A	0.0212 (16)	0.0107 (16)	0.0233 (16)	−0.0015 (11)	0.0044 (12)	−0.0052 (12)
C21A	0.0155 (15)	0.0144 (15)	0.0238 (16)	−0.0023 (12)	0.0064 (12)	0.0033 (12)

Geometric parameters (Å, º)

O11A—C11A	1.239 (3)	C31—C41	1.378 (5)
O12A—C11A	1.285 (3)	C41—C51	1.392 (5)
O21A—C21A	1.307 (3)	C51—C61	1.386 (5)
O22A—C21A	1.227 (4)	C2—H2	0.9300
O41A—N4A	1.235 (4)	C3—H3	0.9300
O42A—N4A	1.222 (3)	C5—H5	0.9300
O21A—H21A	0.90	C6—H6	0.9300
N1—C1	1.462 (4)	C21—H21	0.9300
N1—N11	1.224 (4)	C31—H31	0.9300
N4—C4	1.463 (4)	C41—H41	0.9300
N11—C11	1.461 (4)	C51—H51	0.9300
N4—H43	0.92	C61—H61	0.9300
N4—H44	0.92	C1A—C2A	1.420 (4)
N4—H42	0.99	C1A—C11A	1.515 (4)
N4A—C4A	1.471 (4)	C1A—C6A	1.395 (4)
C1—C6	1.379 (4)	C2A—C3A	1.385 (4)
C1—C2	1.398 (4)	C2A—C21A	1.505 (4)
C2—C3	1.393 (4)	C3A—C4A	1.379 (4)
C3—C4	1.384 (4)	C4A—C5A	1.393 (4)
C4—C5	1.382 (4)	C5A—C6A	1.383 (4)
C5—C6	1.380 (4)	C3A—H3A	0.9300
C11—C21	1.372 (5)	C5A—H5A	0.9300
C11—C61	1.397 (5)	C6A—H6A	0.9300
C21—C31	1.381 (5)
C21A—O21A—H21A	115	C5—C6—H6	120.00
N11—N1—C1	113.0 (3)	C1—C6—H6	120.00
N1—N11—C11	112.0 (3)	C31—C21—H21	120.00
H43—N4—H44	110	C11—C21—H21	120.00
C4—N4—H44	109.3	C21—C31—H31	120.00
C4—N4—H42	113.3	C41—C31—H31	120.00
C4—N4—H43	111	C31—C41—H41	120.00
H42—N4—H43	103	C51—C41—H41	120.00
H42—N4—H44	111	C61—C51—H51	120.00
O41A—N4A—O42A	123.0 (3)	C41—C51—H51	120.00
O41A—N4A—C4A	118.1 (2)	C11—C61—H61	120.00
O42A—N4A—C4A	118.9 (3)	C51—C61—H61	120.00
C2—C1—C6	120.4 (3)	C2A—C1A—C11A	121.8 (2)
N1—C1—C6	113.8 (3)	C6A—C1A—C11A	119.6 (3)
N1—C1—C2	125.8 (3)	C2A—C1A—C6A	118.5 (3)
C1—C2—C3	119.3 (3)	C1A—C2A—C21A	122.4 (2)
C2—C3—C4	119.5 (3)	C3A—C2A—C21A	117.9 (3)
N4—C4—C5	118.9 (2)	C1A—C2A—C3A	119.6 (3)
C3—C4—C5	121.0 (3)	C2A—C3A—C4A	119.8 (3)
N4—C4—C3	120.0 (3)	N4A—C4A—C3A	118.6 (3)
C4—C5—C6	119.6 (3)	C3A—C4A—C5A	122.3 (3)
C1—C6—C5	120.2 (3)	N4A—C4A—C5A	119.2 (3)
N11—C11—C21	115.1 (3)	C4A—C5A—C6A	117.6 (3)
C21—C11—C61	120.4 (3)	C1A—C6A—C5A	122.2 (3)
N11—C11—C61	124.5 (3)	O11A—C11A—C1A	119.0 (2)
C11—C21—C31	119.9 (3)	O12A—C11A—C1A	115.2 (2)
C21—C31—C41	120.3 (3)	O11A—C11A—O12A	125.7 (2)
C31—C41—C51	120.2 (3)	O21A—C21A—C2A	113.8 (2)
C41—C51—C61	119.6 (3)	O22A—C21A—C2A	121.6 (2)
C11—C61—C51	119.5 (3)	O21A—C21A—O22A	124.6 (2)
C1—C2—H2	120.00	C2A—C3A—H3A	120.00
C3—C2—H2	120.00	C4A—C3A—H3A	120.00
C2—C3—H3	120.00	C4A—C5A—H5A	121.00
C4—C3—H3	120.00	C6A—C5A—H5A	121.00
C6—C5—H5	120.00	C1A—C6A—H6A	119.00
C4—C5—H5	120.00	C5A—C6A—H6A	119.00
C1—N1—N11—C11	179.0 (2)	C21—C31—C41—C51	−0.5 (5)
N11—N1—C1—C2	−15.5 (4)	C31—C41—C51—C61	−1.1 (4)
N11—N1—C1—C6	166.0 (3)	C41—C51—C61—C11	1.4 (4)
N1—N11—C11—C21	−173.7 (3)	C6A—C1A—C2A—C3A	1.1 (4)
N1—N11—C11—C61	5.3 (4)	C6A—C1A—C2A—C21A	177.8 (2)
O41A—N4A—C4A—C3A	2.2 (4)	C11A—C1A—C2A—C3A	−179.5 (2)
O41A—N4A—C4A—C5A	−178.8 (3)	C11A—C1A—C2A—C21A	−2.8 (4)
O42A—N4A—C4A—C3A	−176.4 (3)	C2A—C1A—C6A—C5A	−1.5 (4)
O42A—N4A—C4A—C5A	2.7 (4)	C11A—C1A—C6A—C5A	179.1 (2)
C6—C1—C2—C3	−0.6 (4)	C2A—C1A—C11A—O11A	−82.4 (3)
N1—C1—C6—C5	179.6 (2)	C2A—C1A—C11A—O12A	99.6 (3)
N1—C1—C2—C3	−179.0 (3)	C6A—C1A—C11A—O11A	97.0 (3)
C2—C1—C6—C5	1.0 (4)	C6A—C1A—C11A—O12A	−80.9 (3)
C1—C2—C3—C4	0.3 (4)	C1A—C2A—C3A—C4A	−0.3 (4)
C2—C3—C4—C5	−0.4 (4)	C21A—C2A—C3A—C4A	−177.1 (2)
C2—C3—C4—N4	−179.0 (2)	C1A—C2A—C21A—O21A	−20.9 (4)
C3—C4—C5—C6	0.8 (4)	C1A—C2A—C21A—O22A	160.9 (3)
N4—C4—C5—C6	179.4 (2)	C3A—C2A—C21A—O21A	155.9 (2)
C4—C5—C6—C1	−1.1 (4)	C3A—C2A—C21A—O22A	−22.3 (4)
N11—C11—C21—C31	177.4 (3)	C2A—C3A—C4A—N4A	178.8 (2)
C61—C11—C21—C31	−1.6 (4)	C2A—C3A—C4A—C5A	−0.2 (4)
N11—C11—C61—C51	−179.0 (3)	N4A—C4A—C5A—C6A	−179.2 (2)
C21—C11—C61—C51	0.0 (4)	C3A—C4A—C5A—C6A	−0.2 (4)
C11—C21—C31—C41	1.9 (5)	C4A—C5A—C6A—C1A	1.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21A—H21A···O12A^i	0.90	1.58	2.480 (3)	179
N4—H42···O11A^ii	0.99	2.46	2.902 (3)	107
N4—H42···O22A^iii	0.99	1.93	2.885 (3)	162
N4—H43···O11A^i	0.92	1.92	2.835 (3)	179
N4—H44···O12A	0.92	1.90	2.809 (3)	172
C6—H6···O12A^iv	0.93	2.46	3.205 (4)	138
C41—H41···O42A^v	0.93	2.59	3.466 (4)	158

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

(III) 4-(phenyldiazenyl)anilinium 3-carboxy-5-nitrobenzoate monohydrate

Crystal data

C12H12N3^+·C8H4NO6^−·H2O	Dx = 1.379 Mg m^−3
Mr = 426.38	Melting point: 393 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3315 reflections
a = 14.0965 (15) Å	θ = 2.4–25.4°
b = 6.7602 (7) Å	µ = 0.11 mm^−1
c = 43.091 (5) Å	T = 130 K
V = 4106.4 (8) Å^3	Needle, red
Z = 8	0.50 × 0.15 × 0.15 mm
F(000) = 1776

Data collection

Bruker SMART CCD area-detector diffractometer	2720 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.096
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
ϕ and ω scans	h = −13→16
20144 measured reflections	k = −8→7
3612 independent reflections	l = −51→42

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)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.211	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ^2(Fo^2) + (0.P)^2 + 14.8749P] where P = (Fo^2 + 2Fc^2)/3
3612 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.28 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	0.7409 (3)	0.7594 (6)	0.18617 (9)	0.0357 (14)
N4	0.6279 (4)	0.7422 (7)	0.06108 (10)	0.0363 (16)
N11	0.8281 (3)	0.7834 (6)	0.19166 (10)	0.0390 (16)
C1	0.7194 (3)	0.7529 (7)	0.15412 (11)	0.0303 (16)
C2	0.7849 (3)	0.7528 (6)	0.13009 (11)	0.0290 (14)
C3	0.7550 (3)	0.7490 (7)	0.09974 (11)	0.0297 (16)
C4	0.6583 (3)	0.7474 (7)	0.09334 (11)	0.0273 (16)
C5	0.5918 (4)	0.7462 (7)	0.11685 (12)	0.0363 (17)
C6	0.6227 (3)	0.7468 (8)	0.14728 (11)	0.0353 (17)
C11	0.8511 (4)	0.7887 (7)	0.22392 (13)	0.0430 (19)
C21	0.9417 (5)	0.8544 (9)	0.23093 (15)	0.056 (2)
C31	0.9690 (5)	0.8677 (10)	0.26147 (17)	0.068 (3)
C41	0.9082 (6)	0.8142 (10)	0.28480 (16)	0.069 (3)
C51	0.8184 (5)	0.7438 (10)	0.27790 (15)	0.065 (3)
C61	0.7894 (4)	0.7324 (8)	0.24733 (13)	0.0500 (19)
O11A	0.4375 (2)	0.8187 (5)	0.06107 (8)	0.0397 (12)
O12A	0.3634 (2)	0.7778 (5)	0.01579 (7)	0.0301 (10)
O31A	0.0232 (2)	0.7423 (5)	0.01107 (8)	0.0342 (11)
O32A	−0.0683 (2)	0.8198 (6)	0.05154 (9)	0.0477 (14)
O51A	0.0952 (4)	0.9375 (10)	0.15158 (11)	0.094 (3)
O52A	0.2474 (4)	0.9688 (7)	0.15270 (9)	0.0720 (18)
N5A	0.1738 (4)	0.9320 (8)	0.13951 (11)	0.0527 (19)
C1A	0.2698 (3)	0.8203 (6)	0.06086 (11)	0.0263 (16)
C2A	0.1865 (3)	0.7948 (6)	0.04427 (11)	0.0260 (14)
C3A	0.0991 (3)	0.8107 (6)	0.05857 (11)	0.0280 (16)
C4A	0.0943 (4)	0.8520 (7)	0.09006 (11)	0.0340 (17)
C5A	0.1772 (4)	0.8766 (7)	0.10612 (11)	0.0340 (16)
C6A	0.2661 (4)	0.8620 (7)	0.09240 (11)	0.0310 (16)
C11A	0.3650 (3)	0.8046 (6)	0.04523 (11)	0.0280 (16)
C31A	0.0101 (4)	0.7900 (7)	0.04039 (12)	0.0330 (17)
O1W	0.7467 (3)	0.9794 (5)	0.02378 (8)	0.0322 (11)
H2	0.84940	0.75530	0.13460	0.0350*
H3	0.79890	0.74750	0.08360	0.0350*
H5	0.52740	0.74500	0.11230	0.0440*
H6	0.57870	0.74310	0.16330	0.0420*
H21	0.98350	0.88910	0.21510	0.0680*
H31	1.02940	0.91350	0.26630	0.0820*
H41	0.92740	0.82520	0.30540	0.0830*
H42	0.660 (4)	0.821 (8)	0.0501 (12)	0.041 (15)*
H43	0.639 (5)	0.622 (8)	0.0530 (12)	0.050 (16)*
H44	0.564 (4)	0.766 (7)	0.0596 (11)	0.044 (14)*
H51	0.77790	0.70440	0.29380	0.0780*
H61	0.72890	0.68730	0.24250	0.0600*
H2A	0.18940	0.76650	0.02320	0.0310*
H4A	0.03600	0.86270	0.10000	0.0410*
H6A	0.32130	0.87960	0.10390	0.0380*
H31A	−0.037 (5)	0.759 (11)	0.0001 (16)	0.08 (2)*
H1W	0.708 (3)	1.049 (7)	0.0119 (11)	0.043 (13)*
H2W	0.782 (6)	0.903 (14)	0.0086 (19)	0.042 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.044 (3)	0.027 (2)	0.036 (2)	0.000 (2)	−0.003 (2)	0.0036 (18)
N4	0.037 (3)	0.034 (2)	0.038 (3)	0.001 (2)	0.001 (2)	0.008 (2)
N11	0.044 (3)	0.026 (2)	0.047 (3)	−0.001 (2)	−0.008 (2)	0.003 (2)
C1	0.037 (3)	0.020 (2)	0.034 (3)	−0.006 (2)	−0.001 (2)	0.003 (2)
C2	0.027 (2)	0.018 (2)	0.042 (3)	−0.003 (2)	−0.004 (2)	0.002 (2)
C3	0.037 (3)	0.018 (2)	0.034 (3)	−0.002 (2)	0.008 (2)	0.002 (2)
C4	0.030 (3)	0.018 (2)	0.034 (3)	−0.0029 (19)	−0.001 (2)	0.002 (2)
C5	0.033 (3)	0.034 (3)	0.042 (3)	0.005 (2)	0.000 (2)	−0.001 (2)
C6	0.036 (3)	0.037 (3)	0.033 (3)	−0.008 (2)	0.008 (2)	−0.001 (2)
C11	0.058 (4)	0.024 (3)	0.047 (3)	−0.002 (3)	−0.013 (3)	0.003 (2)
C21	0.062 (4)	0.043 (3)	0.064 (4)	−0.004 (3)	−0.020 (3)	0.002 (3)
C31	0.075 (5)	0.050 (4)	0.079 (5)	−0.007 (4)	−0.042 (4)	−0.003 (4)
C41	0.097 (6)	0.057 (4)	0.053 (4)	0.003 (4)	−0.041 (4)	−0.001 (3)
C51	0.093 (5)	0.057 (4)	0.045 (4)	0.001 (4)	−0.015 (4)	0.007 (3)
C61	0.069 (4)	0.037 (3)	0.044 (3)	−0.002 (3)	−0.017 (3)	0.004 (3)
O11A	0.037 (2)	0.038 (2)	0.044 (2)	0.0017 (16)	−0.0121 (18)	0.0004 (17)
O12A	0.0309 (18)	0.0260 (17)	0.0335 (19)	0.0022 (15)	−0.0018 (14)	0.0023 (15)
O31A	0.0266 (18)	0.041 (2)	0.035 (2)	0.0057 (16)	0.0025 (15)	−0.0042 (16)
O32A	0.032 (2)	0.063 (3)	0.048 (2)	0.0025 (19)	0.0134 (18)	0.000 (2)
O51A	0.086 (4)	0.156 (6)	0.040 (3)	0.028 (4)	0.012 (3)	−0.019 (3)
O52A	0.101 (4)	0.077 (3)	0.038 (2)	0.003 (3)	−0.017 (3)	−0.014 (2)
N5A	0.070 (4)	0.060 (3)	0.028 (3)	0.015 (3)	0.002 (3)	−0.005 (2)
C1A	0.037 (3)	0.013 (2)	0.029 (3)	−0.0004 (19)	0.000 (2)	0.0013 (19)
C2A	0.037 (3)	0.013 (2)	0.028 (2)	0.0025 (19)	0.001 (2)	0.0013 (18)
C3A	0.035 (3)	0.020 (2)	0.029 (3)	0.003 (2)	0.006 (2)	0.0012 (19)
C4A	0.039 (3)	0.027 (3)	0.036 (3)	0.010 (2)	0.012 (2)	0.002 (2)
C5A	0.054 (3)	0.025 (3)	0.023 (2)	0.005 (2)	0.000 (2)	−0.001 (2)
C6A	0.041 (3)	0.018 (2)	0.034 (3)	0.002 (2)	−0.011 (2)	0.002 (2)
C11A	0.033 (3)	0.018 (2)	0.033 (3)	−0.001 (2)	−0.010 (2)	0.001 (2)
C31A	0.037 (3)	0.024 (3)	0.038 (3)	0.003 (2)	0.011 (2)	0.004 (2)
O1W	0.040 (2)	0.0243 (18)	0.0322 (19)	0.0046 (16)	−0.0078 (18)	−0.0001 (16)

Geometric parameters (Å, º)

O11A—C11A	1.233 (5)	C21—C31	1.374 (10)
O12A—C11A	1.282 (6)	C31—C41	1.370 (10)
O31A—C31A	1.317 (6)	C41—C51	1.385 (11)
O32A—C31A	1.222 (6)	C51—C61	1.381 (9)
O51A—N5A	1.225 (8)	C2—H2	0.9300
O52A—N5A	1.209 (8)	C3—H3	0.9300
O31A—H31A	0.98 (7)	C5—H5	0.9300
O1W—H2W	0.97 (8)	C6—H6	0.9300
O1W—H1W	0.88 (5)	C21—H21	0.9300
N1—C1	1.415 (6)	C31—H31	0.9300
N1—N11	1.262 (6)	C41—H41	0.9300
N4—C4	1.455 (6)	C51—H51	0.9300
N11—C11	1.428 (7)	C61—H61	0.9300
N4—H44	0.92 (6)	C1A—C2A	1.386 (6)
N4—H43	0.90 (5)	C1A—C11A	1.505 (6)
N4—H42	0.84 (6)	C1A—C6A	1.389 (7)
N5A—C5A	1.488 (7)	C2A—C3A	1.382 (6)
C1—C6	1.395 (6)	C3A—C4A	1.387 (7)
C1—C2	1.387 (6)	C3A—C31A	1.486 (7)
C2—C3	1.374 (7)	C4A—C5A	1.368 (8)
C3—C4	1.391 (6)	C5A—C6A	1.389 (8)
C4—C5	1.380 (7)	C2A—H2A	0.9300
C5—C6	1.382 (7)	C4A—H4A	0.9300
C11—C61	1.385 (8)	C6A—H6A	0.9300
C11—C21	1.386 (9)
C31A—O31A—H31A	108 (4)	C5—C6—H6	120.00
H1W—O1W—H2W	102 (6)	C1—C6—H6	120.00
N11—N1—C1	113.3 (4)	C11—C21—H21	120.00
N1—N11—C11	114.0 (4)	C31—C21—H21	121.00
C4—N4—H44	111 (3)	C21—C31—H31	120.00
C4—N4—H42	111 (4)	C41—C31—H31	120.00
H43—N4—H44	108 (5)	C31—C41—H41	120.00
H42—N4—H44	112 (5)	C51—C41—H41	120.00
H42—N4—H43	105 (5)	C61—C51—H51	120.00
C4—N4—H43	110 (4)	C41—C51—H51	120.00
O51A—N5A—O52A	124.8 (5)	C51—C61—H61	120.00
O51A—N5A—C5A	116.6 (5)	C11—C61—H61	120.00
O52A—N5A—C5A	118.6 (5)	C6A—C1A—C11A	119.1 (4)
C2—C1—C6	119.5 (4)	C2A—C1A—C6A	119.9 (4)
N1—C1—C6	114.6 (4)	C2A—C1A—C11A	121.1 (4)
N1—C1—C2	125.9 (4)	C1A—C2A—C3A	121.1 (4)
C1—C2—C3	120.4 (4)	C2A—C3A—C31A	120.7 (4)
C2—C3—C4	119.3 (4)	C4A—C3A—C31A	119.6 (4)
N4—C4—C5	120.1 (4)	C2A—C3A—C4A	119.7 (4)
N4—C4—C3	118.6 (4)	C3A—C4A—C5A	118.5 (5)
C3—C4—C5	121.3 (5)	N5A—C5A—C6A	117.3 (5)
C4—C5—C6	118.8 (5)	N5A—C5A—C4A	119.5 (5)
C1—C6—C5	120.6 (4)	C4A—C5A—C6A	123.1 (5)
C21—C11—C61	120.5 (5)	C1A—C6A—C5A	117.7 (5)
N11—C11—C21	115.4 (5)	O12A—C11A—C1A	115.9 (4)
N11—C11—C61	124.0 (5)	O11A—C11A—O12A	125.0 (4)
C11—C21—C31	119.2 (6)	O11A—C11A—C1A	119.1 (4)
C21—C31—C41	120.7 (7)	O32A—C31A—C3A	122.8 (5)
C31—C41—C51	120.4 (6)	O31A—C31A—O32A	123.0 (5)
C41—C51—C61	119.6 (6)	O31A—C31A—C3A	114.2 (4)
C11—C61—C51	119.6 (5)	C3A—C2A—H2A	119.00
C3—C2—H2	120.00	C1A—C2A—H2A	120.00
C1—C2—H2	120.00	C3A—C4A—H4A	121.00
C2—C3—H3	120.00	C5A—C4A—H4A	121.00
C4—C3—H3	120.00	C1A—C6A—H6A	121.00
C6—C5—H5	121.00	C5A—C6A—H6A	121.00
C4—C5—H5	121.00
C1—N1—N11—C11	−179.5 (4)	C21—C31—C41—C51	0.7 (11)
N11—N1—C1—C2	6.0 (7)	C31—C41—C51—C61	−1.6 (10)
N11—N1—C1—C6	−173.8 (4)	C41—C51—C61—C11	1.0 (9)
N1—N11—C11—C21	−167.4 (5)	C6A—C1A—C2A—C3A	0.2 (6)
N1—N11—C11—C61	13.0 (7)	C11A—C1A—C2A—C3A	−179.5 (4)
O51A—N5A—C5A—C4A	5.6 (8)	C2A—C1A—C6A—C5A	0.0 (6)
O51A—N5A—C5A—C6A	−177.5 (5)	C11A—C1A—C6A—C5A	179.7 (4)
O52A—N5A—C5A—C4A	−174.1 (5)	C2A—C1A—C11A—O11A	−176.5 (4)
O52A—N5A—C5A—C6A	2.8 (7)	C2A—C1A—C11A—O12A	3.8 (6)
C6—C1—C2—C3	0.7 (7)	C6A—C1A—C11A—O11A	3.8 (6)
N1—C1—C6—C5	178.0 (5)	C6A—C1A—C11A—O12A	−175.9 (4)
N1—C1—C2—C3	−179.1 (4)	C1A—C2A—C3A—C4A	−0.3 (6)
C2—C1—C6—C5	−1.8 (7)	C1A—C2A—C3A—C31A	177.9 (4)
C1—C2—C3—C4	0.7 (7)	C2A—C3A—C4A—C5A	0.2 (7)
C2—C3—C4—C5	−1.1 (7)	C31A—C3A—C4A—C5A	−178.0 (4)
C2—C3—C4—N4	−179.6 (4)	C2A—C3A—C31A—O31A	4.7 (6)
C3—C4—C5—C6	0.1 (7)	C2A—C3A—C31A—O32A	−173.5 (4)
N4—C4—C5—C6	178.6 (5)	C4A—C3A—C31A—O31A	−177.2 (4)
C4—C5—C6—C1	1.4 (8)	C4A—C3A—C31A—O32A	4.6 (7)
N11—C11—C21—C31	178.8 (5)	C3A—C4A—C5A—N5A	176.6 (4)
C61—C11—C21—C31	−1.6 (9)	C3A—C4A—C5A—C6A	−0.1 (7)
N11—C11—C61—C51	−179.7 (5)	N5A—C5A—C6A—C1A	−176.8 (4)
C21—C11—C61—C51	0.6 (8)	C4A—C5A—C6A—C1A	0.0 (7)
C11—C21—C31—C41	0.9 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31A—H31A···O12A^i	0.98 (7)	1.58 (7)	2.536 (4)	164 (7)
O1W—H1W···O12A^ii	0.88 (5)	1.95 (5)	2.830 (5)	173 (4)
O1W—H2W···O12A^iii	0.97 (8)	1.98 (9)	2.939 (5)	170 (8)
N4—H42···O1W	0.84 (6)	1.98 (5)	2.821 (6)	173 (5)
N4—H43···O1W^iv	0.90 (5)	2.26 (6)	2.977 (6)	137 (5)
N4—H43···O32A^v	0.90 (5)	2.27 (6)	3.005 (6)	138 (6)
N4—H44···O11A	0.92 (6)	1.82 (6)	2.733 (6)	174 (4)
C3—H3···O32A^vi	0.93	2.38	3.278 (6)	163
C5—H5···O11A	0.93	2.59	3.279 (6)	131

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