Two- and three-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichloro­phthalic acid with the isomeric monoamino­benzoic acids

The crystal structures of the 1:1 proton-transfer compounds of 4,5-dichloro­phthalic acid with the three isomeric mono­amino­benzoic acids, namely the hydrate 2-carboxy­anilinium 2-car­b­oxy-4,5-dichloro­benzoate dihydrate, C₇H₈NO₂⁺·C₈H₃Cl₂O₄^-·2H₂O, (I), and the anhydrous salts 3-carboxy­anilinium 2-carb­oxy-4,5-dichloro­benzoate, C₇H₈NO₂⁺·C₈H₃Cl₂O₄^-, (II), and 4-carboxy­anilinium 2-carb­oxy-4,5-dichloro­benzoate, C₇H₈NO₂⁺·C₈H₃Cl₂O₄^-, (III), have been determined at 130 K. Compound (I) has a two-dimensional hydrogen-bonded sheet structure, while (II) and (III) are three-dimensional. All three compounds feature sheet substructures formed through anilinium N⁺-H...O_carbox­yl and anion carboxylic acid O-H...O_carboxyl inter­actions and, in the case of (I), additionally linked through the donor and acceptor associations of the solvent water mol­ecules. However, (II) and (III) have additional lateral extensions of these substructures though cyclic R²₂(8) associations involving the carboxylic acid groups of the cations. Also, (II) and (III) have cation-anion [pi]-[pi] aromatic ring inter­actions. This work provides further examples illustrating the regular formation of network substructures in the 1:1 proton-transfer salts of 4,5-dichloro­phthalic acid with the bifunctional aromatic amines.

S1. Comment

The known crystal structures of the anhydrous 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with nitrogen Lewis bases show a number of structural types. With the difunctional bases brucine (Smith et al., 2007) and 1,10-phenanthroline (Smith et al., 2008b), discrete cation–anion N⁺—H···O_carboxyl hydrogen-bonded units are found. With 2-aminopyrimidine (Smith et al., 2008b), discrete duplex cyclic hydrogen-bonded cation–anion units are found, while with the similar associative functional group-substituted but bicyclic heteroaromatic bases 8-hydroxyquinoline and 8-aminoquinoline (Smith et al., 2008a), the primary cation–anion units are extended into one-dimensional hydrogen-bonded chains through linear associations involving the second functional group of the cation species. In all of these examples, the DCPA anion species are essentially planar, having a short intramolecular O—H···O hydrogen bond (ca 1.4 Å) between the syn-related carboxylic acid H atom and the carboxyl group. This is also the case in the naphthalene-1,8-bis(dimethylammonium) salt of DCPA (Mallinson et al., 2003) and in the tetramethylammonium salt (Bozkurt et al., 2006), although in these compounds the structure is three-dimensional. However, in the unusual 1:1:1 adduct hydrate compound of DCPA with quinaldic acid (Smith et al., 2008a), the cation–anion units are extended into a two-dimensional sheet structure by linear S(n) (n = 6 or 7) (Etter et al., 1990) DCPA anion carboxylic acid O—H···O_carboxyl interactions. In these, the carboxylic acid and carboxylate groups of the DCPA anion are, of necessity, non-coplanar with the parent benzene ring. Similar two-dimensional sheet substructures are also found in the proton-transfer Lewis base salts of the nitro-substituted hydrogen phthalates and hydrogen isophthalates (Glidewell et al., 2003, 2005; Smith, Wermuth et al., 2008). The DCPA cation [anion?] is similarly nonplanar in bis(2-ethylanilinium) 4,5-dichlorophthalate (Büyükgüngör & Odabaşoğlu, 2007), but this involves DCPA as a dication [dianion?].

It has been found that, with the monoamino-substituted benzoic acids, three-dimensional framework structures are predominant in salts with strong aromatic carboxylic or sulfonic acids such as 3,5-dinitrosalicylic acid (Smith et al., 1995a), pyrazine-2,3-dicarboxylic acid (Smith et al., 1995b) and 5-sulfosalicylic acid (Smith, 2005). Common also in the structures of the aromatic Lewis base salts of these acids are π–π associations between alternating cation and anion ring systems. It was therefore of interest to observe the effect of combining the potential chain- and sheet-forming properties of the carboxylic acid and carboxylate groups of the DCPA anion with the structure-extending features of both the aminium and carboxylic acid groups of the protonated monoamino-substituted benzoic acids, such as are found in the series reported here.

The products from the 1:1 stoichiometric reaction of DCPA with the three isomeric aminobenzoic acids, namely 2-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate dihydrate, (I), 3-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate, (II), and 4-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate, (III), were expected to have higher-dimensional hydrogen-bonded structures. However, this was not the case in all three compounds, with the structure of the dihydrate, (I), found to be two-dimensional and significantly different from the three-dimensional structures of (II) and (III). All three compounds have at least one direct N⁺—H···O_carboxyl hydrogen-bonding interaction (Figs. 1–3); in the case of (III), this is a three-centre cyclic R²₁(7) N—H···O_{carboxylic acid},O_carboxylate association. Additionally, in (I) the two solvent water molecules act as double donors and acceptors in the extension of the structure into a two-dimensional sheet (Fig. 4). This involves carboxylic acid O—H···O_water, water O—H···O_carboxyl and water O—H···O_water associations.

Although the anhydrous compounds, (II) and (III), are structurally similar, (III) has a single cation–anion pair in the asymmetric unit (Fig. 3), whereas that of (II) comprises two independent but conformationally identical 2-carboxyanilinium cations (B and D) and two DCPA monoanions (A and C) (Fig. 2). In each compound, the substructures comprise a network of glide-related DCPA anions linked by common phthalate–carboxylic acid O—H···O_carboxyl hydrogen bonds, graph set S(7) [for (II), O12A—H···O22Aⁱ and O12C—H···O22Cⁱⁱⁱ (for symmetry codes, see Table 2); for (III), O12—H···O22ⁱⁱ (for symmetry code, see Table 3)]. The associated anilinium cations alternate with the DCPA anions down the a cell directions in the respective unit cells, giving sheet substructures which extend across ab (Figs. 5 and 6).

The cation and anion aromatic rings are π–π associated. For (II), the ring centroid separation (Cg···Cg) and inter-ring dihedral angle (α) for the planes C1B–C6B and C1A–C6A are 3.6357 (9) Å and 3.15 (1)°, respectively, while for the planes C1D–C6D and C1C–C6C, Cg···Cg = 3.5261 (9) Å and α = 3.81 (1)°. For (III), for the planes C1–C6 and C1A–C6A, Cg···Cg = 3.5867 (11) Å and α = 2.76 (1)°. This feature is absent in the structure of (I).

The three-dimensional structures in (II) and (III) are generated by classic (Leiserowitz, 1976) centrosymmetric head-to-head cyclic R²₂(8) associations through the carboxylic acid groups of the anilinium cations, which extend across the c axial directions in each. Also present in (II) and (III) but not in (I) are short intermolecular inversion-related Cl···Cl interactions: in (II), Cl4A···Cl4Aⁱⁱ = 3.3243 (6) and Cl5A···Cl5A^vii = 3.2295 Å [symmetry code: (vii) -x, -y + 1, -z], and in (III), Cl4···Cl4^v = 3.2488 (7) Å [symmetry code: (v) -x + 1, -y, -z + 1]. Similarly, there are unusual short intermolecular Cl···O_carboxyl interactions: in (II), Cl5A···O11D^viii = 3.2279 (14) Å [symmetry code: (viii) x, y - 1, z], and in (III), Cl4···O12A^vi = 2.2213 (15) Å [symmetry code: (vi) -x + 1/2, -y + 1/2, -z + 1].

Unlike the anion species found in the majority of the known structures of 1:1 acid salts of DCPA with aromatic Lewis bases, in which the presence of short intramolecular carboxylic acid O—H···O_carboxyl hydrogen bonds keeps the anions essentially planar, in compounds (I)–(III) this is not the case. The anion species in all three compounds are non-planar, with the two carboxyl groups rotated out of the plane of the benzene ring. The torsion angles associated with these groups, C2—C1—C11—O11 and C1—C2—C21—O22, are, respectively, for (I), -157.0 (2) and 70.7 (3)°; for (II), -24.0 (2) and -79.61 (19)° (anion A), and -15.9 (2) and -86.93 (19)° (anion B C ?); for (III), 20.0 (2) and 77.7 (2)°. The carboxylic acid substituent groups of the aminium cations in all three compounds are essentially coplanar with the aromatic rings: torsion angle C2—C1—C11—O12 for (I) -173.2 (2)°; for (II) 178.83 (14)° (cation B) and 176.65 (15)° (cation D); for (III) -179.66 (17)°.

This present series provides further examples which demonstrate the utility of the hydrogen 4,5-dichlorophalate anion species in the stabilization of 1:1 hydrogen-bonded proton-transfer structures with aromatic Lewis base cations. In all three cases, the less common nonplanar DCPA anion type is observed, which gives structure extension in the anhydrous compounds through carboxylic acid···carboxylate hydrogen-bonding interactions and two-dimensional substructures. The secondary associative carboxylic acid substituent groups of the cations are also important in the formation of higher-order structure types.

S2. Experimental

Compounds (I)–(III) were synthesized by heating together, for 10 min under reflux, 1 mmol quantities of 4,5-dichlorophthalic acid and, respectively, 2-amino-, 3-amino- and 4-aminobenzoic acid in 50 ml of 50% ethanol–water for (I) or 80% methanol–water for (II) and (III). Compound (I) was obtained as large colourless needles [colourless blocks in CIF] (m.p. 437–438 K), compound (II) as colourless blocks [pale-brown blocks in CIF] and (III) as pale-brown plates [colourless blocks in CIF] (m.p. for both > 573 K), after partial room-temperature evaporation of solvents.

S3. Refinement

H atoms potentially involved in hydrogen-bonding interactions in all three compounds were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in calculated positions, with C—H = 0.93–0.95 Å, and treated as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007) for (I); SMART (Bruker, 2000) for (II), (III). Cell refinement: CrysAlis RED (Oxford Diffraction, 2007) for (I); SMART (Bruker, 2000) for (II), (III). Data reduction: CrysAlis RED (Oxford Diffraction, 2007) for (I); SAINT (Bruker, 1999) for (II), (III). For all compounds, 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 2-carboxyanilinium cation, the 2-carboxy-4,5-dichlorobenzoate anion and the two solvent water molecules of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Inter-species hydrogen bonds are shown as dashed lines.
	Fig. 2. The molecular configuration and atom-numbering scheme for the two 3-carboxyanilinium cations (B and D) and the two 2-carboxy-4,5-dichlorobenzoate anions (A and C) in the asymmetric unit of (II). 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.
	Fig. 3. The molecular configuration and atom-numbering scheme for the 4-carboxyanilinium cation and 2-carboxy-4,5-dichlorobenzoate anion in (III). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates the inter-species hydrogen bond.
	Fig. 4. Hydrogen bonding in the two-dimensional sheet structure in (I), viewed down the b axial direction, at x = 0. H atoms not involved in the hydrogen bonding have been omitted. Hydrogen bonds are shown as dashed lines. For symmetry codes, see Table 1.
	Fig. 5. The two-dimensional hydrogen-bonded cation–anion sheet structure in (II), viewed down the b axial direction, showing the cyclic inversion-related R^22(8) carboxylic acid dimeric links across c. H atoms not involved in the hydrogen bonding have been omitted. Hydrogen bonds are shown as dashed lines. For symmetry codes, see Table 2.
	Fig. 6. A view of the C(6) chain extension in the two-dimensional hydrogen-bonded sheet structure of (III), viewed down the b cell direction. H atoms not involved in the hydrogen bonding have been omitted. Hydrogen bonds are shown as dashed lines. For symmetry codes, see Table 3.

(I) 2-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate dihydrate

Crystal data

C7H8NO2^+·C8H3Cl2O4^−·2H2O	Z = 2
Mr = 408.18	F(000) = 420
Triclinic, P1	Dx = 1.607 Mg m^−3
Hall symbol: -P 1	Melting point = 437–438 K
a = 6.7684 (5) Å	Cu Kα radiation, λ = 1.5418 Å
b = 6.9561 (4) Å	Cell parameters from 3819 reflections
c = 18.0001 (14) Å	θ = 4.9–72.1°
α = 86.525 (6)°	µ = 3.90 mm^−1
β = 87.481 (6)°	T = 180 K
γ = 86.190 (6)°	Block, colourless
V = 843.37 (10) Å^3	0.40 × 0.26 × 0.14 mm

Data collection

Oxford Diffraction Gemini S Ultra CCD area-detector diffractometer	3190 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2691 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 16.0711 pixels mm^-1	θmax = 72.0°, θmin = 4.9°
ω scans	h = −8→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→5
Tmin = 0.260, Tmax = 0.580	l = −22→22
7458 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1194P)^2] where P = (Fo^2 + 2Fc^2)/3
3190 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.48 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
O11A	0.4333 (3)	0.8545 (3)	0.14119 (10)	0.0285 (5)
O12A	0.6581 (2)	0.7262 (3)	0.22102 (10)	0.0319 (5)
N2A	0.0530 (3)	0.8947 (3)	0.18242 (11)	0.0232 (6)
C1A	0.3332 (3)	0.8125 (3)	0.26804 (13)	0.0239 (6)
C2A	0.1327 (3)	0.8678 (3)	0.25686 (13)	0.0237 (6)
C3A	0.0000 (4)	0.8940 (3)	0.31681 (13)	0.0262 (7)
C4A	0.0635 (4)	0.8624 (4)	0.38925 (14)	0.0316 (7)
C5A	0.2604 (4)	0.8045 (4)	0.40128 (13)	0.0311 (7)
C6A	0.3920 (4)	0.7788 (4)	0.34113 (14)	0.0290 (7)
C11A	0.4911 (3)	0.7916 (3)	0.20785 (13)	0.0254 (7)
Cl4	−0.09069 (8)	0.39303 (9)	0.41255 (3)	0.0314 (2)
Cl5	0.34945 (9)	0.27447 (10)	0.45890 (3)	0.0351 (2)
O11	0.7137 (2)	0.1782 (2)	0.19595 (9)	0.0299 (5)
O12	0.5362 (3)	0.3751 (3)	0.11680 (10)	0.0296 (5)
O21	0.0981 (2)	0.5573 (2)	0.11045 (9)	0.0263 (5)
O22	0.1413 (2)	0.2385 (2)	0.10164 (9)	0.0243 (5)
C1	0.3977 (3)	0.3104 (3)	0.23672 (12)	0.0220 (6)
C2	0.2042 (3)	0.3667 (3)	0.21646 (12)	0.0219 (6)
C3	0.0560 (3)	0.3962 (3)	0.27106 (13)	0.0235 (6)
C4	0.0987 (3)	0.3639 (3)	0.34582 (13)	0.0241 (6)
C5	0.2914 (4)	0.3087 (3)	0.36611 (13)	0.0265 (7)
C6	0.4400 (3)	0.2805 (3)	0.31167 (13)	0.0248 (7)
C11	0.5658 (3)	0.2806 (3)	0.18095 (13)	0.0239 (6)
C21	0.1459 (3)	0.3906 (3)	0.13612 (12)	0.0226 (6)
O1W	−0.1909 (3)	0.2683 (3)	0.02211 (10)	0.0283 (5)
O2W	0.7176 (3)	0.8831 (3)	0.04216 (12)	0.0399 (6)
H3A	−0.13180	0.93280	0.30860	0.0310*
H4A	−0.02550	0.88010	0.42950	0.0380*
H5A	0.30370	0.78300	0.44960	0.0370*
H6A	0.52310	0.73800	0.34970	0.0350*
H11A	0.539 (7)	0.864 (6)	0.111 (3)	0.080 (15)*
H21A	0.074 (5)	0.783 (5)	0.1554 (18)	0.037 (8)*
H22A	−0.071 (5)	0.917 (4)	0.1878 (17)	0.028 (7)*
H23A	0.106 (4)	0.996 (5)	0.1535 (18)	0.034 (8)*
H3	−0.07180	0.43740	0.25770	0.0280*
H6	0.56810	0.24150	0.32520	0.0300*
H12	0.632 (7)	0.337 (6)	0.084 (3)	0.076 (14)*
H11W	−0.082 (7)	0.275 (6)	0.043 (2)	0.061 (11)*
H12W	−0.169 (6)	0.319 (6)	−0.017 (3)	0.058 (12)*
H21W	0.727 (6)	0.816 (6)	0.003 (3)	0.065 (12)*
H22W	0.741 (6)	1.005 (6)	0.026 (2)	0.060 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11A	0.0246 (8)	0.0355 (9)	0.0244 (9)	0.0020 (7)	0.0019 (7)	−0.0004 (7)
O12A	0.0240 (9)	0.0366 (9)	0.0339 (10)	0.0029 (7)	−0.0006 (7)	0.0011 (7)
N2A	0.0227 (10)	0.0254 (10)	0.0212 (10)	0.0024 (8)	−0.0004 (7)	−0.0031 (8)
C1A	0.0264 (11)	0.0212 (11)	0.0242 (11)	−0.0013 (8)	−0.0014 (9)	−0.0017 (8)
C2A	0.0295 (12)	0.0207 (10)	0.0205 (11)	0.0013 (8)	−0.0011 (9)	−0.0020 (8)
C3A	0.0285 (12)	0.0241 (11)	0.0251 (12)	0.0007 (9)	0.0040 (9)	−0.0016 (9)
C4A	0.0386 (13)	0.0323 (13)	0.0231 (12)	−0.0005 (10)	0.0063 (10)	−0.0035 (9)
C5A	0.0399 (14)	0.0327 (13)	0.0207 (11)	−0.0031 (10)	−0.0030 (10)	0.0001 (9)
C6A	0.0293 (12)	0.0287 (12)	0.0290 (13)	−0.0027 (9)	−0.0041 (10)	0.0010 (9)
C11A	0.0273 (12)	0.0230 (11)	0.0259 (12)	−0.0009 (9)	−0.0002 (9)	−0.0020 (9)
Cl4	0.0313 (4)	0.0415 (4)	0.0210 (3)	−0.0018 (2)	0.0063 (2)	−0.0038 (2)
Cl5	0.0390 (4)	0.0483 (4)	0.0177 (3)	−0.0001 (3)	−0.0038 (2)	−0.0006 (2)
O11	0.0272 (9)	0.0344 (9)	0.0270 (9)	0.0067 (7)	−0.0004 (7)	−0.0034 (7)
O12	0.0277 (9)	0.0356 (9)	0.0238 (8)	0.0041 (7)	0.0035 (7)	0.0016 (7)
O21	0.0343 (9)	0.0243 (8)	0.0193 (8)	0.0037 (6)	−0.0020 (6)	0.0007 (6)
O22	0.0298 (8)	0.0234 (8)	0.0192 (8)	0.0020 (6)	0.0004 (6)	−0.0027 (6)
C1	0.0264 (11)	0.0196 (10)	0.0199 (11)	0.0006 (8)	0.0006 (9)	−0.0027 (8)
C2	0.0272 (11)	0.0181 (10)	0.0203 (11)	0.0014 (8)	−0.0017 (8)	−0.0022 (8)
C3	0.0250 (11)	0.0230 (11)	0.0222 (11)	0.0001 (8)	0.0002 (9)	−0.0019 (8)
C4	0.0257 (11)	0.0239 (11)	0.0225 (11)	−0.0016 (8)	0.0034 (9)	−0.0028 (9)
C5	0.0335 (12)	0.0285 (12)	0.0170 (11)	−0.0003 (9)	−0.0022 (9)	0.0006 (8)
C6	0.0247 (11)	0.0239 (11)	0.0256 (12)	0.0006 (8)	−0.0034 (9)	−0.0016 (9)
C11	0.0252 (11)	0.0231 (11)	0.0235 (11)	−0.0006 (9)	0.0000 (9)	−0.0048 (8)
C21	0.0208 (10)	0.0260 (11)	0.0204 (11)	0.0014 (8)	0.0025 (8)	−0.0018 (8)
O1W	0.0277 (9)	0.0364 (9)	0.0200 (8)	0.0009 (7)	−0.0003 (7)	0.0001 (7)
O2W	0.0460 (11)	0.0368 (11)	0.0356 (11)	−0.0022 (8)	0.0164 (9)	−0.0058 (9)

Geometric parameters (Å, º)

Cl4—C4	1.728 (2)	C1A—C11A	1.495 (3)
Cl5—C5	1.731 (2)	C2A—C3A	1.386 (3)
O11A—C11A	1.319 (3)	C3A—C4A	1.391 (3)
O12A—C11A	1.218 (3)	C4A—C5A	1.389 (4)
O11A—H11A	0.88 (5)	C5A—C6A	1.384 (4)
O11—C11	1.220 (2)	C3A—H3A	0.9300
O12—C11	1.310 (3)	C4A—H4A	0.9300
O21—C21	1.250 (3)	C5A—H5A	0.9300
O22—C21	1.262 (3)	C6A—H6A	0.9300
O12—H12	0.90 (5)	C1—C11	1.496 (3)
O1W—H11W	0.85 (5)	C1—C2	1.399 (3)
O1W—H12W	0.78 (5)	C1—C6	1.392 (3)
O2W—H21W	0.87 (5)	C2—C3	1.387 (3)
O2W—H22W	0.90 (4)	C2—C21	1.512 (3)
N2A—C2A	1.463 (3)	C3—C4	1.391 (3)
N2A—H22A	0.85 (3)	C4—C5	1.393 (3)
N2A—H21A	0.94 (3)	C5—C6	1.386 (3)
N2A—H23A	0.93 (3)	C3—H3	0.9300
C1A—C2A	1.406 (3)	C6—H6	0.9300
C1A—C6A	1.393 (3)
C11A—O11A—H11A	109 (3)	C4A—C5A—H5A	120.00
C11—O12—H12	109 (3)	C5A—C6A—H6A	119.00
H11W—O1W—H12W	102 (4)	C1A—C6A—H6A	119.00
H21W—O2W—H22W	106 (4)	C2—C1—C6	119.82 (19)
H22A—N2A—H23A	109 (3)	C2—C1—C11	122.90 (19)
C2A—N2A—H23A	113.5 (19)	C6—C1—C11	117.28 (18)
H21A—N2A—H23A	107 (3)	C3—C2—C21	117.51 (18)
C2A—N2A—H22A	108 (2)	C1—C2—C3	120.0 (2)
H21A—N2A—H22A	107 (3)	C1—C2—C21	122.47 (19)
C2A—N2A—H21A	112 (2)	C2—C3—C4	119.91 (19)
C2A—C1A—C11A	125.4 (2)	C3—C4—C5	120.2 (2)
C6A—C1A—C11A	116.8 (2)	Cl4—C4—C5	120.89 (18)
C2A—C1A—C6A	117.8 (2)	Cl4—C4—C3	118.94 (16)
N2A—C2A—C1A	122.1 (2)	C4—C5—C6	120.0 (2)
C1A—C2A—C3A	120.9 (2)	Cl5—C5—C4	120.97 (19)
N2A—C2A—C3A	116.98 (19)	Cl5—C5—C6	119.04 (19)
C2A—C3A—C4A	120.1 (2)	C1—C6—C5	120.1 (2)
C3A—C4A—C5A	119.7 (2)	O11—C11—O12	125.1 (2)
C4A—C5A—C6A	119.8 (2)	O11—C11—C1	121.6 (2)
C1A—C6A—C5A	121.7 (2)	O12—C11—C1	113.23 (19)
O11A—C11A—C1A	113.86 (19)	O21—C21—O22	125.5 (2)
O11A—C11A—O12A	124.3 (2)	O21—C21—C2	117.65 (19)
O12A—C11A—C1A	121.8 (2)	O22—C21—C2	116.82 (18)
C4A—C3A—H3A	120.00	C2—C3—H3	120.00
C2A—C3A—H3A	120.00	C4—C3—H3	120.00
C5A—C4A—H4A	120.00	C5—C6—H6	120.00
C3A—C4A—H4A	120.00	C1—C6—H6	120.00
C6A—C5A—H5A	120.00
C6A—C1A—C2A—N2A	−176.0 (2)	C11—C1—C6—C5	178.97 (19)
C6A—C1A—C2A—C3A	2.1 (3)	C2—C1—C11—O11	−157.0 (2)
C11A—C1A—C2A—N2A	5.7 (3)	C2—C1—C11—O12	23.3 (3)
C11A—C1A—C2A—C3A	−176.2 (2)	C6—C1—C11—O11	23.2 (3)
C2A—C1A—C6A—C5A	−2.1 (4)	C6—C1—C11—O12	−156.4 (2)
C11A—C1A—C6A—C5A	176.3 (2)	C1—C2—C3—C4	−2.0 (3)
C2A—C1A—C11A—O11A	8.5 (3)	C21—C2—C3—C4	175.81 (19)
C2A—C1A—C11A—O12A	−173.2 (2)	C1—C2—C21—O21	−112.3 (2)
C6A—C1A—C11A—O11A	−169.8 (2)	C1—C2—C21—O22	70.7 (3)
C6A—C1A—C11A—O12A	8.5 (3)	C3—C2—C21—O21	69.9 (3)
N2A—C2A—C3A—C4A	177.1 (2)	C3—C2—C21—O22	−107.0 (2)
C1A—C2A—C3A—C4A	−1.1 (3)	C2—C3—C4—Cl4	−177.60 (16)
C2A—C3A—C4A—C5A	0.0 (4)	C2—C3—C4—C5	2.3 (3)
C3A—C4A—C5A—C6A	0.0 (4)	Cl4—C4—C5—Cl5	−2.0 (3)
C4A—C5A—C6A—C1A	1.0 (4)	Cl4—C4—C5—C6	178.06 (17)
C6—C1—C2—C3	1.3 (3)	C3—C4—C5—Cl5	178.12 (16)
C6—C1—C2—C21	−176.46 (19)	C3—C4—C5—C6	−1.8 (3)
C11—C1—C2—C3	−178.49 (19)	Cl5—C5—C6—C1	−178.88 (16)
C11—C1—C2—C21	3.8 (3)	C4—C5—C6—C1	1.1 (3)
C2—C1—C6—C5	−0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11A—H11A···O2W	0.88 (5)	1.70 (5)	2.574 (3)	171 (5)
O12—H12···O1W^i	0.90 (5)	1.67 (5)	2.562 (3)	179 (7)
O1W—H11W···O22	0.85 (5)	1.88 (4)	2.708 (2)	167 (4)
O1W—H12W···O21^ii	0.78 (5)	1.90 (5)	2.679 (2)	176 (5)
O2W—H21W···O22^iii	0.87 (5)	2.09 (5)	2.875 (3)	150 (4)
O2W—H22W···O1W^iv	0.90 (4)	1.92 (4)	2.789 (3)	163 (3)
N2A—H21A···O21	0.94 (3)	1.80 (3)	2.742 (3)	174 (3)
N2A—H22A···O11^v	0.85 (3)	2.26 (3)	2.938 (2)	137 (3)
N2A—H22A···O12A^vi	0.85 (3)	2.37 (3)	3.026 (3)	135 (2)
N2A—H23A···O22^vii	0.93 (3)	1.90 (3)	2.808 (3)	163 (3)
C6A—H6A···O12A	0.93	2.46	2.778 (3)	100

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

(II) 3-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C7H8NO2^+·C8H3Cl2O4^−	F(000) = 1520
Mr = 372.15	Dx = 1.613 Mg m^−3
Monoclinic, P21/n	Melting point > 573 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.9028 (7) Å	Cell parameters from 8197 reflections
b = 7.4091 (4) Å	θ = 2.6–27.5°
c = 32.2323 (17) Å	µ = 0.46 mm^−1
β = 96.012 (1)°	T = 130 K
V = 3064.4 (3) Å^3	Block, pale brown
Z = 8	0.50 × 0.40 × 0.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer	6995 independent reflections
Radiation source: sealed tube	6125 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→13
Tmin = 0.74, Tmax = 0.85	k = −9→7
17962 measured reflections	l = −39→41

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0567P)^2 + 1.2365P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
6995 reflections	Δρmax = 0.45 e Å^−3
474 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00057 (17)

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
O11B	0.80317 (10)	0.31573 (17)	0.05268 (4)	0.0267 (4)
O12B	0.76409 (11)	0.04606 (18)	0.02395 (4)	0.0302 (4)
N3B	0.90063 (11)	0.1730 (2)	0.20638 (4)	0.0190 (4)
C1B	0.81462 (12)	0.0551 (2)	0.09589 (5)	0.0195 (4)
C2B	0.84861 (12)	0.1545 (2)	0.13134 (5)	0.0184 (4)
C3B	0.86747 (11)	0.0663 (2)	0.16919 (5)	0.0177 (4)
C4B	0.85311 (12)	−0.1182 (2)	0.17266 (5)	0.0204 (4)
C5B	0.81934 (13)	−0.2159 (2)	0.13694 (5)	0.0228 (5)
C6B	0.80012 (13)	−0.1306 (2)	0.09870 (5)	0.0225 (5)
C11B	0.79375 (12)	0.1516 (2)	0.05535 (5)	0.0217 (5)
O11D	0.27229 (10)	0.77527 (18)	0.04627 (4)	0.0270 (4)
O12D	0.25094 (11)	0.50101 (19)	0.01765 (4)	0.0308 (4)
N3D	0.39421 (11)	0.6618 (2)	0.19878 (4)	0.0194 (4)
C1D	0.30647 (12)	0.5200 (2)	0.08966 (5)	0.0211 (5)
C2D	0.33864 (12)	0.6284 (2)	0.12387 (5)	0.0194 (4)
C3D	0.36373 (11)	0.5484 (2)	0.16242 (5)	0.0187 (4)
C4D	0.35738 (12)	0.3633 (2)	0.16752 (5)	0.0217 (5)
C5D	0.32616 (13)	0.2566 (2)	0.13303 (5)	0.0241 (5)
C6D	0.30073 (13)	0.3337 (2)	0.09411 (5)	0.0234 (5)
C11D	0.27515 (12)	0.6104 (2)	0.04891 (5)	0.0228 (5)
Cl4A	0.53762 (3)	0.35754 (7)	0.03849 (1)	0.0309 (1)
Cl5A	0.50529 (4)	−0.06114 (7)	0.05278 (1)	0.0388 (2)
O11A	0.57562 (10)	−0.10779 (17)	0.21770 (4)	0.0293 (4)
O12A	0.68916 (9)	0.11528 (16)	0.23392 (4)	0.0209 (3)
O21A	0.59270 (9)	0.48350 (17)	0.21831 (4)	0.0236 (3)
O22A	0.75463 (8)	0.46135 (15)	0.19943 (3)	0.0184 (3)
C1A	0.59912 (11)	0.1174 (2)	0.16694 (5)	0.0172 (4)
C2A	0.61896 (11)	0.3009 (2)	0.16048 (5)	0.0163 (4)
C3A	0.59912 (12)	0.3723 (2)	0.12062 (5)	0.0190 (4)
C4A	0.56209 (12)	0.2631 (2)	0.08730 (5)	0.0212 (4)
C5A	0.54575 (12)	0.0803 (2)	0.09359 (5)	0.0223 (5)
C6A	0.56343 (12)	0.0093 (2)	0.13335 (5)	0.0203 (4)
C11A	0.61946 (12)	0.0309 (2)	0.20903 (5)	0.0185 (4)
C21A	0.65741 (12)	0.4251 (2)	0.19615 (5)	0.0169 (4)
Cl4C	0.05110 (3)	1.05825 (6)	0.05024 (1)	0.0287 (1)
Cl5C	−0.00872 (4)	0.64684 (7)	0.03649 (1)	0.0330 (2)
O11C	0.07635 (10)	0.38203 (17)	0.19032 (4)	0.0294 (4)
O12C	0.17700 (10)	0.59567 (17)	0.22301 (4)	0.0260 (4)
O21C	0.10158 (9)	0.98011 (16)	0.22782 (3)	0.0222 (3)
O22C	0.26417 (9)	0.94695 (15)	0.21001 (3)	0.0200 (3)
C1C	0.09780 (11)	0.6652 (2)	0.15704 (5)	0.0172 (4)
C2C	0.12307 (11)	0.8477 (2)	0.16299 (5)	0.0166 (4)
C3C	0.10632 (12)	0.9667 (2)	0.12971 (5)	0.0185 (4)
C4C	0.06740 (12)	0.9059 (2)	0.09071 (5)	0.0198 (4)
C5C	0.04204 (12)	0.7244 (2)	0.08472 (5)	0.0207 (4)
C6C	0.05676 (12)	0.6053 (2)	0.11775 (5)	0.0199 (4)
C11C	0.11511 (12)	0.5319 (2)	0.19210 (5)	0.0194 (4)
C21C	0.16542 (12)	0.9288 (2)	0.20422 (5)	0.0166 (4)
H2B	0.85870	0.28110	0.12960	0.0220*
H4B	0.86610	−0.17670	0.19890	0.0240*
H5B	0.80930	−0.34250	0.13880	0.0270*
H6B	0.77710	−0.19850	0.07450	0.0270*
H12B	0.754 (3)	0.110 (5)	−0.0019 (10)	0.062 (13)*
H31B	0.9665 (17)	0.217 (3)	0.2036 (7)	0.033 (6)*
H32B	0.9019 (17)	0.110 (3)	0.2288 (8)	0.036 (6)*
H33B	0.8555 (18)	0.276 (3)	0.2074 (7)	0.039 (6)*
H2D	0.34330	0.75550	0.12080	0.0230*
H4D	0.37410	0.31010	0.19420	0.0260*
H5D	0.32220	0.12940	0.13620	0.0290*
H6D	0.27950	0.25980	0.07070	0.0280*
H12D	0.229 (2)	0.563 (5)	−0.0063 (10)	0.050 (10)*
H31D	0.4595 (16)	0.704 (3)	0.1986 (6)	0.026 (5)*
H32D	0.3485 (18)	0.768 (3)	0.2001 (7)	0.042 (6)*
H33D	0.3909 (18)	0.597 (3)	0.2229 (8)	0.039 (6)*
H3A	0.61100	0.49700	0.11610	0.0230*
H6A	0.55100	−0.11530	0.13770	0.0240*
H12A	0.708 (2)	0.054 (4)	0.2604 (9)	0.048 (8)*
H3C	0.12180	1.09120	0.13380	0.0220*
H6C	0.03880	0.48170	0.11370	0.0240*
H12C	0.191 (2)	0.519 (4)	0.2481 (9)	0.051 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11B	0.0324 (6)	0.0272 (7)	0.0199 (6)	0.0001 (5)	−0.0005 (5)	0.0061 (5)
O12B	0.0418 (7)	0.0316 (7)	0.0160 (6)	−0.0016 (6)	−0.0022 (5)	0.0021 (5)
N3B	0.0192 (7)	0.0217 (7)	0.0160 (7)	−0.0001 (6)	0.0021 (5)	0.0013 (5)
C1B	0.0167 (7)	0.0257 (8)	0.0164 (8)	0.0026 (6)	0.0029 (6)	0.0017 (6)
C2B	0.0175 (7)	0.0191 (8)	0.0190 (8)	0.0018 (6)	0.0038 (6)	0.0023 (6)
C3B	0.0143 (7)	0.0225 (8)	0.0165 (7)	0.0012 (6)	0.0023 (6)	−0.0012 (6)
C4B	0.0211 (7)	0.0214 (8)	0.0188 (8)	0.0025 (6)	0.0027 (6)	0.0050 (6)
C5B	0.0242 (8)	0.0198 (8)	0.0249 (9)	0.0007 (6)	0.0046 (6)	0.0014 (6)
C6B	0.0231 (8)	0.0247 (9)	0.0197 (8)	0.0010 (7)	0.0030 (6)	−0.0023 (6)
C11B	0.0188 (7)	0.0291 (9)	0.0172 (8)	0.0015 (6)	0.0024 (6)	0.0028 (6)
O11D	0.0304 (6)	0.0303 (7)	0.0196 (6)	0.0009 (5)	−0.0012 (5)	0.0055 (5)
O12D	0.0396 (7)	0.0338 (7)	0.0180 (6)	0.0002 (6)	−0.0017 (5)	0.0009 (5)
N3D	0.0173 (7)	0.0243 (7)	0.0163 (7)	0.0008 (6)	0.0009 (5)	0.0034 (5)
C1D	0.0173 (7)	0.0277 (9)	0.0187 (8)	0.0008 (6)	0.0034 (6)	0.0029 (6)
C2D	0.0173 (7)	0.0239 (8)	0.0175 (8)	0.0013 (6)	0.0036 (6)	0.0032 (6)
C3D	0.0143 (7)	0.0247 (8)	0.0174 (8)	0.0022 (6)	0.0028 (6)	0.0011 (6)
C4D	0.0203 (8)	0.0249 (9)	0.0200 (8)	0.0021 (6)	0.0028 (6)	0.0058 (6)
C5D	0.0226 (8)	0.0219 (8)	0.0280 (9)	0.0003 (6)	0.0042 (7)	0.0027 (7)
C6D	0.0209 (8)	0.0279 (9)	0.0218 (8)	−0.0006 (7)	0.0037 (6)	−0.0015 (7)
C11D	0.0181 (7)	0.0329 (10)	0.0173 (8)	0.0003 (7)	0.0016 (6)	0.0026 (7)
Cl4A	0.0336 (2)	0.0439 (3)	0.0144 (2)	0.0036 (2)	−0.0012 (2)	0.0062 (2)
Cl5A	0.0495 (3)	0.0458 (3)	0.0202 (2)	−0.0189 (2)	−0.0001 (2)	−0.0118 (2)
O11A	0.0335 (7)	0.0257 (7)	0.0271 (7)	−0.0120 (5)	−0.0038 (5)	0.0079 (5)
O12A	0.0235 (6)	0.0208 (6)	0.0172 (6)	−0.0033 (5)	−0.0036 (4)	0.0038 (4)
O21A	0.0213 (6)	0.0281 (6)	0.0212 (6)	0.0036 (5)	0.0011 (5)	−0.0073 (5)
O22A	0.0193 (5)	0.0185 (6)	0.0171 (5)	−0.0017 (4)	0.0001 (4)	−0.0012 (4)
C1A	0.0155 (7)	0.0204 (8)	0.0155 (7)	0.0012 (6)	0.0014 (6)	0.0008 (6)
C2A	0.0149 (7)	0.0185 (7)	0.0152 (7)	0.0018 (6)	0.0008 (5)	−0.0010 (6)
C3A	0.0189 (7)	0.0206 (8)	0.0176 (8)	0.0029 (6)	0.0019 (6)	0.0021 (6)
C4A	0.0183 (7)	0.0314 (9)	0.0133 (7)	0.0022 (6)	−0.0004 (6)	0.0028 (6)
C5A	0.0195 (8)	0.0309 (9)	0.0163 (8)	−0.0043 (7)	0.0006 (6)	−0.0067 (7)
C6A	0.0199 (7)	0.0202 (8)	0.0211 (8)	−0.0031 (6)	0.0030 (6)	−0.0028 (6)
C11A	0.0188 (7)	0.0178 (8)	0.0189 (8)	0.0018 (6)	0.0020 (6)	0.0001 (6)
C21A	0.0225 (7)	0.0138 (7)	0.0140 (7)	0.0010 (6)	−0.0005 (6)	0.0016 (5)
Cl4C	0.0318 (2)	0.0368 (3)	0.0168 (2)	0.0014 (2)	−0.0011 (2)	0.0082 (2)
Cl5C	0.0379 (3)	0.0414 (3)	0.0180 (2)	−0.0025 (2)	−0.0057 (2)	−0.0100 (2)
O11C	0.0300 (7)	0.0224 (6)	0.0356 (7)	−0.0078 (5)	0.0026 (5)	0.0032 (5)
O12C	0.0320 (7)	0.0213 (6)	0.0226 (6)	−0.0034 (5)	−0.0075 (5)	0.0069 (5)
O21C	0.0238 (6)	0.0273 (6)	0.0154 (5)	0.0017 (5)	0.0018 (4)	−0.0051 (5)
O22C	0.0208 (5)	0.0212 (6)	0.0173 (5)	−0.0014 (4)	−0.0015 (4)	−0.0030 (4)
C1C	0.0150 (7)	0.0187 (8)	0.0178 (8)	0.0018 (6)	0.0020 (6)	−0.0015 (6)
C2C	0.0142 (7)	0.0208 (8)	0.0145 (7)	0.0017 (6)	0.0002 (5)	−0.0016 (6)
C3C	0.0189 (7)	0.0189 (8)	0.0175 (8)	0.0007 (6)	0.0013 (6)	−0.0013 (6)
C4C	0.0186 (7)	0.0269 (9)	0.0136 (7)	0.0028 (6)	0.0005 (6)	0.0023 (6)
C5C	0.0185 (7)	0.0292 (9)	0.0137 (7)	0.0006 (6)	−0.0011 (6)	−0.0070 (6)
C6C	0.0168 (7)	0.0210 (8)	0.0217 (8)	−0.0004 (6)	0.0008 (6)	−0.0039 (6)
C11C	0.0172 (7)	0.0196 (8)	0.0217 (8)	0.0010 (6)	0.0035 (6)	0.0003 (6)
C21C	0.0223 (7)	0.0133 (7)	0.0136 (7)	−0.0002 (6)	−0.0010 (6)	0.0012 (5)

Geometric parameters (Å, º)

Cl4A—C4A	1.7205 (16)	C2B—H2B	0.9500
Cl5A—C5A	1.7198 (16)	C4B—H4B	0.9500
Cl4C—C4C	1.7211 (16)	C5B—H5B	0.9500
Cl5C—C5C	1.7213 (16)	C6B—H6B	0.9500
O11B—C11B	1.2260 (19)	C1D—C2D	1.392 (2)
O12B—C11B	1.304 (2)	C1D—C11D	1.492 (2)
O12B—H12B	0.96 (3)	C1D—C6D	1.391 (2)
O11D—C11D	1.225 (2)	C2D—C3D	1.384 (2)
O12D—C11D	1.305 (2)	C3D—C4D	1.385 (2)
O12D—H12D	0.92 (3)	C4D—C5D	1.389 (2)
O11A—C11A	1.220 (2)	C5D—C6D	1.386 (2)
O12A—C11A	1.301 (2)	C2D—H2D	0.9500
O21A—C21A	1.233 (2)	C4D—H4D	0.9500
O22A—C21A	1.2764 (19)	C5D—H5D	0.9500
O12A—H12A	0.98 (3)	C6D—H6D	0.9500
O11C—C11C	1.217 (2)	C1A—C11A	1.499 (2)
O12C—C11C	1.299 (2)	C1A—C6A	1.386 (2)
O21C—C21C	1.2381 (19)	C1A—C2A	1.403 (2)
O22C—C21C	1.2754 (19)	C2A—C3A	1.388 (2)
O12C—H12C	0.99 (3)	C2A—C21A	1.515 (2)
N3B—C3B	1.462 (2)	C3A—C4A	1.389 (2)
N3B—H32B	0.86 (2)	C4A—C5A	1.389 (2)
N3B—H31B	0.92 (2)	C5A—C6A	1.382 (2)
N3B—H33B	0.96 (2)	C3A—H3A	0.9500
N3D—C3D	1.462 (2)	C6A—H6A	0.9500
N3D—H32D	0.99 (2)	C1C—C2C	1.399 (2)
N3D—H33D	0.92 (2)	C1C—C11C	1.500 (2)
N3D—H31D	0.90 (2)	C1C—C6C	1.393 (2)
C1B—C6B	1.393 (2)	C2C—C3C	1.388 (2)
C1B—C11B	1.489 (2)	C2C—C21C	1.508 (2)
C1B—C2B	1.391 (2)	C3C—C4C	1.380 (2)
C2B—C3B	1.383 (2)	C4C—C5C	1.393 (2)
C3B—C4B	1.386 (2)	C5C—C6C	1.381 (2)
C4B—C5B	1.391 (2)	C3C—H3C	0.9500
C5B—C6B	1.384 (2)	C6C—H6C	0.9500
C11B—O12B—H12B	112 (2)	C5D—C4D—H4D	121.00
C11D—O12D—H12D	112 (2)	C6D—C5D—H5D	120.00
C11A—O12A—H12A	114.1 (17)	C4D—C5D—H5D	120.00
C11C—O12C—H12C	117.6 (17)	C5D—C6D—H6D	120.00
H31B—N3B—H32B	110 (2)	C1D—C6D—H6D	120.00
C3B—N3B—H33B	109.3 (13)	C2A—C1A—C11A	122.10 (14)
C3B—N3B—H31B	107.7 (14)	C2A—C1A—C6A	119.66 (14)
H32B—N3B—H33B	111 (2)	C6A—C1A—C11A	118.19 (13)
C3B—N3B—H32B	112.0 (16)	C1A—C2A—C3A	119.20 (14)
H31B—N3B—H33B	106.8 (19)	C3A—C2A—C21A	119.00 (13)
H31D—N3D—H33D	108.3 (19)	C1A—C2A—C21A	121.76 (14)
C3D—N3D—H32D	112.4 (13)	C2A—C3A—C4A	120.59 (14)
C3D—N3D—H33D	110.2 (15)	Cl4A—C4A—C5A	120.93 (12)
C3D—N3D—H31D	111.6 (13)	C3A—C4A—C5A	120.03 (15)
H31D—N3D—H32D	106.7 (19)	Cl4A—C4A—C3A	119.04 (12)
H32D—N3D—H33D	107 (2)	C4A—C5A—C6A	119.59 (14)
C2B—C1B—C6B	120.17 (14)	Cl5A—C5A—C4A	121.41 (12)
C2B—C1B—C11B	118.62 (13)	Cl5A—C5A—C6A	119.00 (12)
C6B—C1B—C11B	121.21 (14)	C1A—C6A—C5A	120.89 (14)
C1B—C2B—C3B	119.05 (14)	O11A—C11A—C1A	121.76 (14)
C2B—C3B—C4B	121.65 (15)	O12A—C11A—C1A	113.39 (13)
N3B—C3B—C4B	119.83 (14)	O11A—C11A—O12A	124.82 (15)
N3B—C3B—C2B	118.50 (13)	O21A—C21A—C2A	117.72 (14)
C3B—C4B—C5B	118.66 (14)	O22A—C21A—C2A	115.57 (13)
C4B—C5B—C6B	120.72 (14)	O21A—C21A—O22A	126.70 (15)
C1B—C6B—C5B	119.75 (14)	C2A—C3A—H3A	120.00
O11B—C11B—C1B	121.85 (14)	C4A—C3A—H3A	120.00
O12B—C11B—C1B	113.86 (13)	C5A—C6A—H6A	120.00
O11B—C11B—O12B	124.29 (15)	C1A—C6A—H6A	120.00
C3B—C2B—H2B	120.00	C2C—C1C—C6C	119.56 (14)
C1B—C2B—H2B	121.00	C2C—C1C—C11C	121.25 (14)
C5B—C4B—H4B	121.00	C6C—C1C—C11C	119.18 (13)
C3B—C4B—H4B	121.00	C1C—C2C—C3C	119.52 (14)
C6B—C5B—H5B	120.00	C1C—C2C—C21C	124.30 (14)
C4B—C5B—H5B	120.00	C3C—C2C—C21C	116.15 (13)
C1B—C6B—H6B	120.00	C2C—C3C—C4C	120.61 (14)
C5B—C6B—H6B	120.00	Cl4C—C4C—C5C	121.33 (12)
C2D—C1D—C6D	120.38 (15)	C3C—C4C—C5C	119.96 (14)
C2D—C1D—C11D	117.98 (13)	Cl4C—C4C—C3C	118.71 (12)
C6D—C1D—C11D	121.60 (14)	Cl5C—C5C—C6C	119.46 (12)
C1D—C2D—C3D	119.10 (14)	C4C—C5C—C6C	119.93 (15)
N3D—C3D—C4D	119.23 (14)	Cl5C—C5C—C4C	120.61 (12)
C2D—C3D—C4D	121.30 (14)	C1C—C6C—C5C	120.39 (14)
N3D—C3D—C2D	119.44 (13)	O11C—C11C—C1C	122.51 (15)
C3D—C4D—C5D	118.98 (14)	O12C—C11C—C1C	111.69 (13)
C4D—C5D—C6D	120.74 (14)	O11C—C11C—O12C	125.79 (15)
C1D—C6D—C5D	119.49 (14)	O21C—C21C—C2C	117.44 (13)
O11D—C11D—C1D	120.82 (14)	O22C—C21C—C2C	115.80 (13)
O11D—C11D—O12D	124.24 (15)	O21C—C21C—O22C	126.62 (14)
O12D—C11D—C1D	114.94 (13)	C2C—C3C—H3C	120.00
C3D—C2D—H2D	120.00	C4C—C3C—H3C	120.00
C1D—C2D—H2D	120.00	C1C—C6C—H6C	120.00
C3D—C4D—H4D	121.00	C5C—C6C—H6C	120.00
C6B—C1B—C2B—C3B	−0.1 (2)	C1A—C2A—C3A—C4A	−1.3 (2)
C11B—C1B—C2B—C3B	179.53 (14)	C21A—C2A—C3A—C4A	−178.88 (14)
C2B—C1B—C6B—C5B	0.2 (2)	C1A—C2A—C21A—O21A	−79.61 (19)
C11B—C1B—C6B—C5B	−179.42 (15)	C1A—C2A—C21A—O22A	101.85 (17)
C2B—C1B—C11B—O11B	−1.9 (2)	C3A—C2A—C21A—O21A	97.91 (18)
C2B—C1B—C11B—O12B	178.83 (14)	C3A—C2A—C21A—O22A	−80.63 (18)
C6B—C1B—C11B—O11B	177.75 (16)	C2A—C3A—C4A—Cl4A	179.51 (12)
C6B—C1B—C11B—O12B	−1.5 (2)	C2A—C3A—C4A—C5A	−0.8 (2)
C1B—C2B—C3B—N3B	−178.48 (14)	Cl4A—C4A—C5A—Cl5A	2.5 (2)
C1B—C2B—C3B—C4B	−0.2 (2)	Cl4A—C4A—C5A—C6A	−178.26 (12)
N3B—C3B—C4B—C5B	178.61 (14)	C3A—C4A—C5A—Cl5A	−177.19 (12)
C2B—C3B—C4B—C5B	0.3 (2)	C3A—C4A—C5A—C6A	2.0 (2)
C3B—C4B—C5B—C6B	−0.2 (2)	Cl5A—C5A—C6A—C1A	178.03 (12)
C4B—C5B—C6B—C1B	−0.1 (2)	C4A—C5A—C6A—C1A	−1.2 (2)
C6D—C1D—C2D—C3D	−0.7 (2)	C6C—C1C—C2C—C3C	0.4 (2)
C11D—C1D—C2D—C3D	177.20 (14)	C6C—C1C—C2C—C21C	178.46 (14)
C2D—C1D—C6D—C5D	0.7 (2)	C11C—C1C—C2C—C3C	179.71 (14)
C11D—C1D—C6D—C5D	−177.06 (15)	C11C—C1C—C2C—C21C	−2.2 (2)
C2D—C1D—C11D—O11D	−4.0 (2)	C2C—C1C—C6C—C5C	0.7 (2)
C2D—C1D—C11D—O12D	176.65 (15)	C11C—C1C—C6C—C5C	−178.66 (14)
C6D—C1D—C11D—O11D	173.82 (16)	C2C—C1C—C11C—O11C	165.56 (15)
C6D—C1D—C11D—O12D	−5.5 (2)	C2C—C1C—C11C—O12C	−15.9 (2)
C1D—C2D—C3D—N3D	−177.95 (14)	C6C—C1C—C11C—O11C	−15.1 (2)
C1D—C2D—C3D—C4D	0.0 (2)	C6C—C1C—C11C—O12C	163.46 (14)
N3D—C3D—C4D—C5D	178.59 (14)	C1C—C2C—C3C—C4C	−1.5 (2)
C2D—C3D—C4D—C5D	0.7 (2)	C21C—C2C—C3C—C4C	−179.78 (14)
C3D—C4D—C5D—C6D	−0.6 (2)	C1C—C2C—C21C—O21C	−86.93 (19)
C4D—C5D—C6D—C1D	−0.1 (3)	C1C—C2C—C21C—O22C	97.07 (18)
C6A—C1A—C2A—C3A	2.1 (2)	C3C—C2C—C21C—O21C	91.22 (18)
C6A—C1A—C2A—C21A	179.63 (14)	C3C—C2C—C21C—O22C	−84.79 (17)
C11A—C1A—C2A—C3A	179.51 (14)	C2C—C3C—C4C—Cl4C	−178.43 (12)
C11A—C1A—C2A—C21A	−3.0 (2)	C2C—C3C—C4C—C5C	1.7 (2)
C2A—C1A—C6A—C5A	−0.9 (2)	Cl4C—C4C—C5C—Cl5C	−1.1 (2)
C11A—C1A—C6A—C5A	−178.37 (14)	Cl4C—C4C—C5C—C6C	179.51 (12)
C2A—C1A—C11A—O11A	157.84 (15)	C3C—C4C—C5C—Cl5C	178.87 (12)
C2A—C1A—C11A—O12A	−24.0 (2)	C3C—C4C—C5C—C6C	−0.6 (2)
C6A—C1A—C11A—O11A	−24.7 (2)	Cl5C—C5C—C6C—C1C	179.96 (11)
C6A—C1A—C11A—O12A	153.44 (14)	C4C—C5C—C6C—C1C	−0.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12A—H12A···O22A^i	0.98 (3)	1.50 (3)	2.4730 (16)	176 (3)
O12B—H12B···O11D^ii	0.96 (3)	1.67 (3)	2.6216 (18)	176 (4)
O12C—H12C···O22C^iii	0.99 (3)	1.51 (3)	2.4714 (16)	163 (3)
O12D—H12D···O11B^ii	0.92 (3)	1.76 (3)	2.6718 (18)	176 (3)
N3B—H31B···O11C^iv	0.92 (2)	1.95 (2)	2.8378 (19)	160 (2)
N3B—H31B···O21C^v	0.92 (2)	2.54 (2)	2.9778 (18)	109.6 (16)
N3D—H31D···O11A^vi	0.90 (2)	2.09 (2)	2.9097 (19)	150.8 (18)
N3D—H31D···O21A	0.90 (2)	2.41 (2)	2.8919 (19)	113.9 (17)
N3B—H32B···O21A^i	0.86 (2)	1.94 (2)	2.7977 (19)	176 (2)
N3D—H32D···O22C	0.99 (2)	1.77 (2)	2.7454 (19)	172 (2)
N3B—H33B···O22A	0.96 (2)	1.89 (2)	2.8416 (18)	169 (2)
N3D—H33D···O21C^iii	0.92 (2)	1.80 (2)	2.7176 (17)	174 (2)
C5B—H5B···O22A^vii	0.95	2.59	3.2901 (19)	131

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

(III) 4-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C7H8NO2^+·C8H3Cl2O4^−	F(000) = 1520
Mr = 372.15	Dx = 1.611 Mg m^−3
Monoclinic, C2/c	Melting point > 573 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 12.8552 (12) Å	Cell parameters from 2598 reflections
b = 7.5003 (7) Å	θ = 3.2–27.1°
c = 31.932 (3) Å	µ = 0.46 mm^−1
β = 94.785 (2)°	T = 130 K
V = 3068.1 (5) Å^3	Block, colourless
Z = 8	0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3467 independent reflections
Radiation source: sealed tube	2929 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 27.4°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→16
Tmin = 0.81, Tmax = 0.93	k = −9→9
9325 measured reflections	l = −38→41

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.50	w = 1/[σ^2(Fo^2) + (0.0195P)^2] where P = (Fo^2 + 2Fc^2)/3
3467 reflections	(Δ/σ)max = 0.001
237 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.32 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
O11A	0.22690 (12)	0.81678 (19)	0.44395 (4)	0.0308 (5)
O12A	0.22424 (11)	0.55873 (19)	0.47948 (4)	0.0288 (5)
N4A	0.09998 (13)	0.2735 (2)	0.29327 (5)	0.0167 (5)
C1A	0.18219 (14)	0.5536 (3)	0.40588 (5)	0.0193 (6)
C2A	0.16605 (14)	0.3701 (2)	0.40662 (5)	0.0201 (6)
C3A	0.13853 (14)	0.2790 (2)	0.36965 (5)	0.0188 (6)
C4A	0.12626 (13)	0.3735 (2)	0.33209 (5)	0.0163 (5)
C5A	0.14167 (14)	0.5555 (2)	0.33066 (5)	0.0188 (6)
C6A	0.17012 (14)	0.6458 (3)	0.36786 (5)	0.0196 (6)
C11A	0.21333 (14)	0.6439 (3)	0.44655 (6)	0.0212 (6)
Cl4	0.44163 (4)	0.12566 (7)	0.46386 (1)	0.0308 (2)
Cl5	0.47983 (4)	0.53547 (7)	0.44551 (1)	0.0290 (2)
O11	0.41110 (10)	0.56359 (18)	0.28022 (4)	0.0250 (4)
O12	0.30927 (10)	0.32711 (16)	0.26365 (4)	0.0189 (4)
O21	0.40833 (9)	−0.02857 (17)	0.28148 (4)	0.0210 (4)
O22	0.24592 (9)	−0.01692 (16)	0.30273 (4)	0.0171 (4)
C1	0.39522 (13)	0.3373 (2)	0.33163 (5)	0.0152 (5)
C2	0.37819 (13)	0.1557 (2)	0.33967 (5)	0.0148 (5)
C3	0.39404 (13)	0.0930 (2)	0.38055 (5)	0.0179 (5)
C4	0.42632 (14)	0.2080 (3)	0.41331 (5)	0.0196 (6)
C5	0.44277 (14)	0.3880 (2)	0.40524 (5)	0.0183 (6)
C6	0.42707 (13)	0.4512 (2)	0.36454 (5)	0.0175 (5)
C11	0.37326 (14)	0.4189 (2)	0.28895 (5)	0.0167 (5)
C21	0.34305 (14)	0.0266 (2)	0.30464 (5)	0.0161 (5)
H2A	0.17390	0.30730	0.43250	0.0240*
H3A	0.12820	0.15360	0.36990	0.0230*
H5A	0.13300	0.61790	0.30470	0.0230*
H6A	0.18140	0.77100	0.36740	0.0240*
H11A	0.244 (2)	0.856 (4)	0.4689 (8)	0.049 (9)*
H41A	0.0331 (15)	0.222 (3)	0.2922 (6)	0.026 (6)*
H42A	0.1506 (16)	0.183 (3)	0.2921 (6)	0.032 (6)*
H43A	0.1013 (17)	0.344 (3)	0.2690 (7)	0.046 (7)*
H3	0.38280	−0.02950	0.38630	0.0220*
H6	0.43820	0.57390	0.35900	0.0210*
H12	0.288 (2)	0.387 (4)	0.2380 (9)	0.059 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11A	0.0474 (10)	0.0244 (8)	0.0194 (7)	−0.0064 (7)	−0.0037 (7)	−0.0055 (6)
O12A	0.0392 (9)	0.0309 (8)	0.0159 (7)	−0.0093 (7)	0.0002 (6)	−0.0033 (6)
N4A	0.0181 (9)	0.0174 (9)	0.0143 (8)	−0.0008 (7)	−0.0002 (6)	−0.0035 (6)
C1A	0.0179 (10)	0.0223 (11)	0.0174 (9)	−0.0015 (8)	0.0004 (7)	−0.0037 (7)
C2A	0.0217 (10)	0.0234 (11)	0.0151 (9)	−0.0016 (8)	0.0005 (8)	0.0000 (7)
C3A	0.0196 (10)	0.0160 (10)	0.0211 (9)	−0.0022 (8)	0.0028 (8)	−0.0019 (7)
C4A	0.0144 (9)	0.0202 (10)	0.0142 (8)	0.0006 (7)	0.0010 (7)	−0.0046 (7)
C5A	0.0197 (10)	0.0188 (10)	0.0179 (9)	0.0016 (8)	0.0014 (7)	0.0002 (7)
C6A	0.0202 (10)	0.0179 (10)	0.0205 (9)	−0.0020 (8)	0.0003 (8)	−0.0021 (7)
C11A	0.0210 (10)	0.0235 (11)	0.0190 (9)	−0.0035 (8)	0.0012 (8)	−0.0048 (8)
Cl4	0.0434 (3)	0.0348 (3)	0.0131 (2)	−0.0055 (2)	−0.0037 (2)	0.0057 (2)
Cl5	0.0382 (3)	0.0311 (3)	0.0171 (2)	−0.0094 (2)	−0.0008 (2)	−0.0084 (2)
O11	0.0313 (8)	0.0220 (7)	0.0204 (7)	−0.0101 (6)	−0.0054 (6)	0.0071 (6)
O12	0.0223 (7)	0.0177 (7)	0.0153 (6)	−0.0035 (5)	−0.0062 (5)	0.0028 (5)
O21	0.0216 (7)	0.0227 (7)	0.0186 (6)	0.0030 (6)	0.0005 (6)	−0.0043 (5)
O22	0.0194 (7)	0.0165 (7)	0.0149 (6)	−0.0018 (5)	−0.0013 (5)	−0.0017 (5)
C1	0.0149 (9)	0.0169 (9)	0.0135 (8)	−0.0001 (7)	0.0001 (7)	0.0009 (7)
C2	0.0119 (9)	0.0173 (9)	0.0151 (8)	0.0011 (7)	0.0002 (7)	−0.0003 (7)
C3	0.0184 (10)	0.0161 (9)	0.0190 (9)	−0.0009 (8)	0.0000 (7)	0.0024 (7)
C4	0.0193 (10)	0.0264 (11)	0.0128 (9)	−0.0002 (8)	−0.0004 (7)	0.0031 (7)
C5	0.0182 (10)	0.0225 (10)	0.0140 (9)	−0.0022 (8)	0.0004 (7)	−0.0052 (7)
C6	0.0185 (10)	0.0145 (9)	0.0195 (9)	−0.0024 (7)	0.0008 (7)	−0.0004 (7)
C11	0.0152 (9)	0.0185 (10)	0.0164 (9)	0.0021 (7)	0.0011 (7)	0.0005 (7)
C21	0.0220 (10)	0.0129 (9)	0.0125 (8)	0.0020 (8)	−0.0031 (7)	0.0031 (7)

Geometric parameters (Å, º)

Cl4—C4	1.7241 (18)	C3A—C4A	1.391 (2)
Cl5—C5	1.7326 (16)	C4A—C5A	1.381 (2)
O11A—C11A	1.312 (3)	C5A—C6A	1.390 (2)
O12A—C11A	1.228 (2)	C2A—H2A	0.9500
O11A—H11A	0.86 (3)	C3A—H3A	0.9500
O11—C11	1.231 (2)	C5A—H5A	0.9500
O12—C11	1.301 (2)	C6A—H6A	0.9500
O21—C21	1.235 (2)	C1—C2	1.407 (2)
O22—C21	1.287 (2)	C1—C11	1.499 (2)
O12—H12	0.95 (3)	C1—C6	1.389 (2)
N4A—C4A	1.464 (2)	C2—C3	1.387 (2)
N4A—H42A	0.94 (2)	C2—C21	1.519 (2)
N4A—H43A	0.94 (2)	C3—C4	1.392 (2)
N4A—H41A	0.94 (2)	C4—C5	1.394 (3)
C1A—C2A	1.392 (3)	C5—C6	1.382 (2)
C1A—C6A	1.395 (3)	C3—H3	0.9500
C1A—C11A	1.490 (3)	C6—H6	0.9500
C2A—C3A	1.384 (2)
C11A—O11A—H11A	107.7 (19)	C5A—C6A—H6A	120.00
C11—O12—H12	113.9 (17)	C1A—C6A—H6A	120.00
C4A—N4A—H43A	113.0 (14)	C2—C1—C6	119.86 (14)
C4A—N4A—H42A	106.9 (12)	C2—C1—C11	122.74 (14)
H42A—N4A—H43A	108.2 (18)	C6—C1—C11	117.25 (13)
H41A—N4A—H42A	109.6 (19)	C1—C2—C3	119.17 (14)
H41A—N4A—H43A	106.3 (18)	C1—C2—C21	121.60 (14)
C4A—N4A—H41A	112.8 (12)	C3—C2—C21	119.23 (13)
C2A—C1A—C6A	119.94 (17)	C2—C3—C4	120.57 (15)
C2A—C1A—C11A	117.66 (16)	Cl4—C4—C5	120.85 (14)
C6A—C1A—C11A	122.4 (2)	C3—C4—C5	120.10 (15)
C1A—C2A—C3A	120.09 (14)	Cl4—C4—C3	119.02 (16)
C2A—C3A—C4A	119.11 (14)	Cl5—C5—C6	119.24 (12)
N4A—C4A—C5A	120.14 (14)	C4—C5—C6	119.57 (14)
C3A—C4A—C5A	121.75 (15)	Cl5—C5—C4	121.18 (12)
N4A—C4A—C3A	118.08 (14)	C1—C6—C5	120.73 (14)
C4A—C5A—C6A	118.81 (16)	O11—C11—C1	121.19 (15)
C1A—C6A—C5A	120.31 (19)	O12—C11—C1	114.20 (14)
O11A—C11A—O12A	124.19 (18)	O11—C11—O12	124.57 (15)
O11A—C11A—C1A	114.94 (17)	O21—C21—C2	118.63 (15)
O12A—C11A—C1A	120.9 (2)	O22—C21—C2	115.10 (14)
C3A—C2A—H2A	120.00	O21—C21—O22	126.26 (15)
C1A—C2A—H2A	120.00	C2—C3—H3	120.00
C2A—C3A—H3A	120.00	C4—C3—H3	120.00
C4A—C3A—H3A	120.00	C1—C6—H6	120.00
C4A—C5A—H5A	121.00	C5—C6—H6	120.00
C6A—C5A—H5A	121.00
C6A—C1A—C2A—C3A	0.3 (3)	C11—C1—C6—C5	176.09 (16)
C11A—C1A—C2A—C3A	−179.04 (17)	C2—C1—C11—O11	−162.33 (17)
C2A—C1A—C6A—C5A	0.2 (3)	C2—C1—C11—O12	20.0 (2)
C11A—C1A—C6A—C5A	179.53 (17)	C6—C1—C11—O11	22.0 (2)
C2A—C1A—C11A—O11A	−179.66 (17)	C6—C1—C11—O12	−155.63 (15)
C2A—C1A—C11A—O12A	0.0 (3)	C1—C2—C3—C4	0.1 (2)
C6A—C1A—C11A—O11A	1.0 (3)	C21—C2—C3—C4	179.94 (16)
C6A—C1A—C11A—O12A	−179.34 (18)	C1—C2—C21—O21	77.7 (2)
C1A—C2A—C3A—C4A	−0.7 (3)	C1—C2—C21—O22	−103.48 (18)
C2A—C3A—C4A—N4A	178.33 (16)	C3—C2—C21—O21	−102.23 (19)
C2A—C3A—C4A—C5A	0.6 (3)	C3—C2—C21—O22	76.6 (2)
N4A—C4A—C5A—C6A	−177.77 (16)	C2—C3—C4—Cl4	178.24 (13)
C3A—C4A—C5A—C6A	0.0 (3)	C2—C3—C4—C5	0.2 (3)
C4A—C5A—C6A—C1A	−0.4 (3)	Cl4—C4—C5—Cl5	0.4 (2)
C6—C1—C2—C3	−0.3 (2)	Cl4—C4—C5—C6	−178.19 (14)
C6—C1—C2—C21	179.83 (16)	C3—C4—C5—Cl5	178.39 (14)
C11—C1—C2—C3	−175.84 (16)	C3—C4—C5—C6	−0.2 (3)
C11—C1—C2—C21	4.3 (3)	Cl5—C5—C6—C1	−178.65 (13)
C2—C1—C6—C5	0.3 (3)	C4—C5—C6—C1	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11A—H11A···O12A^i	0.86 (3)	1.78 (3)	2.6435 (19)	178 (2)
O12—H12···O22^ii	0.95 (3)	1.52 (3)	2.4726 (18)	180 (4)
N4A—H41A···O11^iii	0.94 (2)	1.98 (2)	2.895 (2)	163.9 (19)
N4A—H41A···O21^iv	0.94 (2)	2.47 (2)	2.874 (2)	106.0 (16)
N4A—H42A···O12	0.94 (2)	2.54 (2)	2.953 (2)	106.6 (16)
N4A—H42A···O22	0.94 (2)	1.95 (2)	2.874 (2)	166.6 (18)
N4A—H43A···O21^ii	0.94 (2)	1.87 (2)	2.805 (2)	174 (2)

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