One-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichloro­phthalic acid with 8-hydroxy­quinoline, 8-amino­quinoline and quinoline-2-carboxylic acid (quinaldic acid)

The structures of the 1:1 proton-transfer compounds of 4,5-di­chloro­phthalic acid with 8-hydroxy­quinoline, 8-amino­quinoline and quinoline-2-carboxylic acid (quinaldic acid), namely anhydrous 8-hydroxy­quinolinium 2-carb­oxy-4,5-di­chloro­benzoate, C₉H₈NO⁺·C₈H₃Cl₂O₄⁻, (I), 8-amino­quino­lin­ium 2-carb­oxy-4,5-dichloro­benzoate, C₉H₉N₂⁺·C₈H₃Cl₂O₄⁻, (II), and the adduct hydrate 2-car­boxy­quino­linium 2-car­boxy-4,5-dichloro­benzoate quinolinium-2-car­box­yl­ate mono­hy­drate, C₁₀H₈NO₂⁺·C₈H₃Cl₂O₄⁻·C₁₀H₇NO₂·H₂O, (III), have been determined at 130 K. Compounds (I) and (II) are isomorphous and all three compounds have one-dimensional hydrogen-bonded chain structures, formed in (I) through O—H...O_carboxyl extensions and in (II) through N⁺—H...O_carboxyl extensions of cation–anion pairs. In (III), a hydrogen-bonded cyclic R₂²(10) pseudo-dimer unit comprising a proton­ated quinaldic acid cation and a zwitterionic quinaldic acid adduct mol­ecule is found and is propagated through carboxylic acid O—H...O_carboxyl and water O—H...O_carboxyl inter­actions. In both (I) and (II), there are also cation–anion aromatic ring π–π associations. This work further illustrates the utility of both hydrogen phthalate anions and interactive-group-substituted quinoline cations in the formation of low-dimensional hydrogen-bonded structures.

S1. Comment

The crystal structures of the proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) are not common, being limited to tetramethylammonium hydrogen 4,5-dichlorophthalate (Bozkurt et al., 2006), naphthalene-1,8-bis(dimethylammonium) 4,5-dichlorophthalate (Mallinson et al., 2003), brucinium hydrogen 4,5-dichlorophthalate (Smith, Wermuth, Healy & White, 2007 or Smith, Wermuth & White, 2007 ?) and the 1:1 salts with 4-chloroaniline, 1,10-phenanthroline and the three isomeric monoaminobenzoic acids (Smith et al., 2008a). A non-transfer adduct with trans-cinnamamide is also known (Hosomi et al., 2000). In the hydrogen 4,5-dichlorophthalates, as well as other substituted hydrogen phthalate salts (Glidewell et al., 2003, 2005; Smith et al., 2008), low-dimensional hydrogen-bonded structures are common. It was considered that, combined with the heteroaromatic Lewis bases derived from quinoline, namely the interactive functional group-substituted analogues 8-hydroxyquinoline (quinolin-8-ol), 8-aminoquinoline and quinoline-2-carboxylic acid (quinaldic acid), DCPA would give one-dimensional 1:1 proton-transfer salts. This is found to be the case, with the determination of the structures of 8-hydroxyquinolinium 2-carboxy-4,5-dichlorobenzoate, C₉H₈NO⁺·C₈H₃Cl₂O₄^-, (I), 8-aminoquinolinium 2-carboxy-4,5-dichlorobenzoate, C₉H₉N₂⁺·C₈H₃Cl₂O₄^-, (II), and the adduct hydrate 2-carboxyquinolinium 2-carboxy-4,5-dichlorobenzoate quinolinium-2-carboxylate monohydrate, C₁₀H₈NO₂⁺·C₈H₃Cl₂O₄^-·C₁₀H₇NO₂·H₂O, (III), reported here.

In all three compounds, proton transfer has occurred, with the quinolinium group giving a primary N⁺—H···O_carboxyl hydrogen-bonding interaction (Tables 1–3). However, in (I) and (II), which are isomorphous, the association is heteromeric (Figs. 1 and 2), whereas in (III), the primary association is homomeric, forming a cation–adduct molecule pseudodimer (Fig. 3). All three compounds are extended into one-dimensional chain structures [graph set C(11) in (I) and (II), and C(13) in (III) (Etter et al., 1990)] by secondary hydrogen bonding involving the second functional groups of both the cation and anion, as well as, in the case of (III), the water molecule of solvation (Figs. 3–6). In (I), the single intermolecular cation–anion N⁺—H···O association is extended through the 8-hydroxy group of the cation, giving zigzag chains analogous to those found in other proton-transfer compounds of 8-hydroxyquinoline (Smith, Wermuth & White, 2001; Smith, Wermuth & Healy, 2004 or Smith, Wermuth & White, 2004 ?). There is also a short intramolecular N1A—H···O8A contact [2.689 (3) Å], common in these compounds. In (II), duplex asymmetric N⁺—H···O hydrogen bonds form a primary cyclic R₂²(9) association which encloses an intramolecular N⁺—H···N_amine contact [N1A—H···N8A = 2.829 (2) Å]. Propagation down a 2₁ screw axis in the unit cell [as is also found in (I)] is through a three-centre aminium N⁺—H···O,O'_carboxyl association. Again, this is analogous to the mode of propagation found in a number of other proton-transfer compounds of 8-aminoquinoline with aromatic carboxylic acids (Smith, Wermuth, Bott et al., 2001).

With the adduct hydrate, (III), the basic hydrogen-bonding pattern is quite different. The asymmetric unit comprises the protonated quinaldic acid cation, the hydrogen 4,5-dichlorophthalate anion, a zwitterionic quinaldic acid adduct molecule and a water molecule of solvation (Fig. 3). The two quinaldic acid species form a hydrogen-bonded cyclic pseudodimer through N⁺—H···O_carboxyl interactions [graph set R₂²(10)]. These units are similar to those found in the structures of the quinolinium-2-carboxylate adducts of the 1:1 proton-transfer salts of quinaldic acid with both 5-sulfosalicylic acid (Smith, Wermuth & Healy, 2004 or Smith, Wermuth & White, 2004 ?) and 2,4,6-trinitrobenzenesulfonic acid (Smith, Wermuth & White, 2007). The quinaldic acid adduct species is also found to be zwitterionic in both the parent acid structure (Dobrzyńska & Jerzykiewicz, 2004) and in the non-transfer adduct compound L-tartaric acid–quinaldic acid (1/2) (Smith et al., 2006). However, they are absent in the 1:1 proton-transfer compound 2-carboxyquinolinium 3,5-dinitrosalicylate (Smith, Wermuth, Healy & White, 2007).

With both (I) and (II) there are additional π–π interactions due to partial aromatic ring overlap of the anion (C1–C6) with C5A–C10A of the cation [ring centroid separation 3.6642 (13) Å and dihedral angle 1.29 (1)° in (I), compared with 3.6715 (9) Å and and 2.16 (1)° in (II)].

The anion species in (I) and (II) are conformationally similar but differ significantly from that found in (III). Both (I) and (II) have a short intramolecular carboxylic acid O—H···O_carboxylate hydrogen bond, resulting in the anions being essentially planar, with C2—C1—C11—O11 torsion angles of 171.3 (2)° in (I) and 175.88 (15)° in (II), and C1—C2—C21—O22 torsion angles of -176.6 (2)° in (I) and -174.38 (18)° in (II). With (III), the two carboxyl groups of the anion are rotated out of the plane of the benzene ring, with corresponding torsion angles of -38.2 (3) and 125.4 (2)°. In (III), the carboxylic acid groups of both quinaldic acid species (A and B) are essentially planar, with N1—C2—C21—O21 torsion angles of -177.7 (2) and 173.8 (2)°, respectively. In addition, there are solvent-accessible voids of 171 ų in the structure of (III).

Related literature

For related literature, see: Bozkurt et al. (2006); Dobrzyńska & Jerzykiewicz (2004); Etter et al. (1990); Glidewell et al. (2003, 2005); Hosomi et al. (2000); Mallinson et al. (2003); Smith et al. (2006, 2008, 2008a); Smith, Wermuth & Healy (2004); Smith, Wermuth & White (2001, 2004, 2007); Smith, Wermuth, Bott, White & Willis (2001); Smith, Wermuth, Healy & White (2007).

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, 8-hydroxyquinoline (quinolin-8-ol), 8-aminoquinoline and quinoline-2-carboxylic acid (quinaldic acid) in 50 ml of ethanol–water (8:2 v/v, 50 ml) for (I) and (III), or 95% ethanol (50 ml) for (II). Compound (I) was obtained as pale-yellow flat prismatic crystals (m.p. 499 K), (II) as pale-brown flat prisms (m.p. 471 K) and (III) as colourless prisms (m.p. 453–455 K), after partial room-temperature evaporation of solvent.

S3. Refinement

In all compounds, H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined, giving distance ranges N—H = 0.80 (2)–0.97 (3) Å and O—H = 0.84 (4)–1.01 (3) Å. All other H atoms were included at 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 8-hydroxyquinolinium cation and the 2-carboxy-4,5-dichlorobenzoate anion in (I). The interspecies hydrogen bond is shown as a dashed line. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular configuration and atom-numbering scheme for the 8-aminoquinolinium cation and the 2-carboxy-4,5-dichlorobenzoate anion in (II). The interspecies cyclic R2^2(9) hydrogen-bonding interaction and the intramolecular hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular configuration and atom-numbering scheme for the 2-carboxyquinolinium cation, the 2-carboxy-4,5-dichlorobenzoate anion, the quinolinium-2-carboxylate adduct molecule and the water molecule of solvation in (III). Dashed lines indicate the interspecies hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The hydrogen-bonded cation–anion chain structure in (I), viewed down the a-axis direction. Hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions have been omitted. [Symmetry code: (i) see Table 1; (ii) -x + 2, y - 1/2, -z + 3/2.]
	Fig. 5. A view of the chain extension in the one-dimensional hydrogen-bonded chain structure of (II), viewed down the a-axis direction. Hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions have been omitted. [Symmetry codes: (i) see Table 2; (ii) -x, y - 1/2, -z + 3/2.]
	Fig. 6. A perspective view of the chain extension in the one-dimensional hydrogen-bonded structure of (III). Hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions have been omitted. For symmetry codes, see Table 3.

(I) 8-hydroxyquinolinium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C9H8NO^+·C8H3Cl2O4^−	Dx = 1.632 Mg m^−3
Mr = 380.17	Melting point: 499 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3863 reflections
a = 6.8915 (3) Å	θ = 4.3–73.4°
b = 7.2887 (2) Å	µ = 4.06 mm^−1
c = 30.8009 (8) Å	T = 130 K
V = 1547.13 (9) Å^3	Prism, pale yellow
Z = 4	0.61 × 0.56 × 0.20 mm
F(000) = 776

Data collection

Oxford Diffraction Xcalibur KM4 CCD area-detector diffractometer	2506 independent reflections
Radiation source: Enhance (Cu) X-ray source	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 16.0711 pixels mm^-1	θmax = 73.4°, θmin = 5.8°
ϕ and ω scans	h = −8→6
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→8
Tmin = 0.112, Tmax = 0.443	l = −38→36
4879 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.078P)^2 + 0.296P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max = 0.002
S = 1.06	Δρmax = 0.40 e Å^−3
2506 reflections	Δρmin = −0.26 e Å^−3
239 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0072 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 662 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.035 (15)

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
O8A	0.6734 (2)	0.5914 (2)	0.82329 (5)	0.0201 (4)
N1A	0.3513 (3)	0.4331 (3)	0.79128 (6)	0.0172 (5)
C2A	0.1943 (3)	0.3654 (3)	0.77302 (7)	0.0210 (6)
C3A	0.0382 (3)	0.3079 (3)	0.79842 (8)	0.0233 (6)
C4A	0.0508 (3)	0.3210 (3)	0.84276 (8)	0.0208 (6)
C5A	0.2455 (3)	0.4051 (3)	0.90836 (7)	0.0210 (6)
C6A	0.4158 (4)	0.4736 (3)	0.92433 (7)	0.0217 (6)
C7A	0.5656 (3)	0.5351 (3)	0.89713 (7)	0.0192 (6)
C8A	0.5450 (3)	0.5278 (3)	0.85235 (7)	0.0151 (5)
C9A	0.3719 (3)	0.4502 (3)	0.83541 (7)	0.0155 (5)
C10A	0.2207 (3)	0.3908 (3)	0.86273 (7)	0.0175 (5)
Cl4	0.67789 (10)	0.41744 (10)	0.49719 (2)	0.0323 (2)
Cl5	0.28475 (9)	0.59039 (9)	0.53303 (2)	0.0324 (2)
O11	0.3598 (2)	0.5912 (3)	0.69516 (5)	0.0269 (5)
O12	0.6126 (3)	0.4418 (3)	0.72043 (5)	0.0258 (5)
O21	0.9054 (2)	0.3071 (2)	0.69386 (5)	0.0230 (4)
O22	1.0662 (2)	0.2720 (2)	0.63266 (5)	0.0230 (5)
C1	0.5745 (3)	0.4727 (3)	0.64188 (7)	0.0158 (5)
C2	0.7517 (3)	0.3985 (3)	0.62641 (7)	0.0151 (5)
C3	0.7780 (3)	0.3869 (3)	0.58140 (7)	0.0181 (6)
C4	0.6378 (3)	0.4416 (3)	0.55256 (7)	0.0193 (6)
C5	0.4640 (3)	0.5140 (3)	0.56761 (7)	0.0192 (6)
C6	0.4364 (3)	0.5285 (3)	0.61193 (7)	0.0184 (6)
C11	0.5097 (3)	0.5050 (3)	0.68868 (7)	0.0182 (6)
C21	0.9195 (3)	0.3225 (3)	0.65280 (7)	0.0164 (6)
H1A	0.461 (5)	0.473 (5)	0.7755 (10)	0.033 (9)*
H2A	0.18730	0.35580	0.74300	0.0250*
H3A	−0.07320	0.26120	0.78540	0.0280*
H4A	−0.05310	0.28380	0.85990	0.0250*
H5A	0.14720	0.36840	0.92710	0.0250*
H6A	0.43290	0.47950	0.95420	0.0260*
H7A	0.67940	0.58110	0.90920	0.0230*
H8A	0.758 (6)	0.657 (5)	0.8351 (12)	0.046 (10)*
H3	0.89430	0.34070	0.57070	0.0220*
H6	0.32040	0.57770	0.62210	0.0220*
H12	0.725 (6)	0.379 (6)	0.7100 (13)	0.041 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O8A	0.0126 (7)	0.0281 (8)	0.0197 (7)	−0.0062 (7)	0.0017 (6)	−0.0005 (7)
N1A	0.0144 (8)	0.0185 (9)	0.0187 (8)	0.0006 (7)	0.0003 (7)	−0.0001 (7)
C2A	0.0184 (10)	0.0193 (10)	0.0253 (10)	−0.0007 (8)	−0.0032 (9)	−0.0023 (8)
C3A	0.0152 (10)	0.0211 (11)	0.0337 (12)	−0.0042 (9)	−0.0027 (10)	−0.0009 (9)
C4A	0.0135 (10)	0.0171 (10)	0.0317 (11)	−0.0010 (9)	0.0044 (9)	0.0040 (9)
C5A	0.0207 (10)	0.0202 (10)	0.0222 (10)	0.0011 (9)	0.0080 (9)	0.0028 (9)
C6A	0.0257 (11)	0.0222 (11)	0.0172 (9)	0.0028 (9)	0.0011 (9)	0.0008 (8)
C7A	0.0185 (10)	0.0195 (10)	0.0197 (10)	0.0005 (8)	−0.0032 (9)	−0.0004 (8)
C8A	0.0127 (9)	0.0144 (10)	0.0183 (9)	0.0003 (8)	0.0009 (8)	0.0006 (7)
C9A	0.0133 (9)	0.0137 (9)	0.0195 (9)	0.0003 (8)	−0.0006 (8)	0.0003 (7)
C10A	0.0139 (9)	0.0124 (9)	0.0262 (10)	0.0018 (8)	0.0026 (9)	0.0004 (8)
Cl4	0.0387 (4)	0.0424 (4)	0.0157 (2)	0.0001 (3)	0.0020 (2)	−0.0017 (2)
Cl5	0.0304 (3)	0.0362 (3)	0.0307 (3)	−0.0070 (3)	−0.0156 (2)	−0.0031 (3)
O11	0.0217 (8)	0.0300 (9)	0.0290 (8)	−0.0082 (8)	0.0072 (7)	0.0018 (7)
O12	0.0202 (8)	0.0385 (10)	0.0186 (7)	−0.0019 (8)	−0.0002 (7)	0.0015 (7)
O21	0.0176 (7)	0.0298 (8)	0.0216 (7)	−0.0037 (7)	−0.0043 (7)	−0.0004 (7)
O22	0.0116 (7)	0.0293 (9)	0.0280 (8)	−0.0061 (7)	0.0020 (6)	−0.0011 (7)
C1	0.0145 (9)	0.0120 (9)	0.0209 (10)	0.0030 (8)	0.0010 (8)	0.0005 (7)
C2	0.0115 (9)	0.0135 (9)	0.0203 (10)	0.0014 (8)	−0.0004 (8)	0.0003 (8)
C3	0.0164 (10)	0.0162 (10)	0.0217 (10)	0.0003 (9)	0.0031 (8)	0.0005 (8)
C4	0.0223 (11)	0.0197 (10)	0.0158 (8)	0.0040 (9)	0.0025 (8)	−0.0024 (8)
C5	0.0199 (10)	0.0159 (10)	0.0219 (10)	0.0002 (9)	−0.0051 (9)	−0.0018 (8)
C6	0.0135 (9)	0.0176 (10)	0.0240 (10)	−0.0019 (8)	−0.0021 (8)	−0.0002 (8)
C11	0.0169 (10)	0.0172 (10)	0.0206 (10)	0.0029 (9)	0.0032 (9)	0.0019 (8)
C21	0.0132 (10)	0.0123 (10)	0.0238 (10)	0.0003 (8)	−0.0012 (9)	0.0007 (8)

Geometric parameters (Å, º)

Cl4—C4	1.737 (2)	C8A—C9A	1.420 (3)
Cl5—C5	1.724 (2)	C9A—C10A	1.408 (3)
O8A—C8A	1.341 (3)	C2A—H2A	0.9300
O8A—H8A	0.84 (4)	C3A—H3A	0.9300
O11—C11	1.226 (3)	C4A—H4A	0.9300
O12—C11	1.293 (3)	C5A—H5A	0.9300
O21—C21	1.273 (3)	C6A—H6A	0.9300
O22—C21	1.242 (3)	C7A—H7A	0.9300
O12—H12	0.96 (4)	C1—C2	1.418 (3)
N1A—C2A	1.316 (3)	C1—C11	1.527 (3)
N1A—C9A	1.372 (3)	C1—C6	1.386 (3)
N1A—H1A	0.95 (3)	C2—C21	1.518 (3)
C2A—C3A	1.395 (3)	C2—C3	1.401 (3)
C3A—C4A	1.372 (3)	C3—C4	1.372 (3)
C4A—C10A	1.417 (3)	C4—C5	1.389 (3)
C5A—C10A	1.420 (3)	C5—C6	1.382 (3)
C5A—C6A	1.367 (3)	C3—H3	0.9300
C6A—C7A	1.403 (3)	C6—H6	0.9300
C7A—C8A	1.388 (3)
C8A—O8A—H8A	112 (3)	C7A—C6A—H6A	119.00
C11—O12—H12	111 (2)	C5A—C6A—H6A	119.00
C2A—N1A—C9A	122.9 (2)	C8A—C7A—H7A	120.00
C2A—N1A—H1A	123.6 (19)	C6A—C7A—H7A	120.00
C9A—N1A—H1A	114 (2)	C2—C1—C11	128.88 (19)
N1A—C2A—C3A	120.5 (2)	C2—C1—C6	118.7 (2)
C2A—C3A—C4A	119.3 (2)	C6—C1—C11	112.46 (18)
C3A—C4A—C10A	120.6 (2)	C1—C2—C21	127.97 (19)
C6A—C5A—C10A	119.1 (2)	C1—C2—C3	117.84 (19)
C5A—C6A—C7A	122.2 (2)	C3—C2—C21	114.16 (18)
C6A—C7A—C8A	120.4 (2)	C2—C3—C4	122.2 (2)
O8A—C8A—C9A	116.54 (19)	Cl4—C4—C5	120.24 (16)
O8A—C8A—C7A	125.63 (19)	C3—C4—C5	120.1 (2)
C7A—C8A—C9A	117.81 (19)	Cl4—C4—C3	119.63 (16)
C8A—C9A—C10A	121.7 (2)	C4—C5—C6	118.52 (19)
N1A—C9A—C10A	119.18 (19)	Cl5—C5—C4	122.33 (17)
N1A—C9A—C8A	119.16 (19)	Cl5—C5—C6	119.14 (16)
C5A—C10A—C9A	118.70 (19)	C1—C6—C5	122.7 (2)
C4A—C10A—C5A	123.8 (2)	O11—C11—C1	118.63 (19)
C4A—C10A—C9A	117.6 (2)	O12—C11—C1	119.91 (19)
N1A—C2A—H2A	120.00	O11—C11—O12	121.5 (2)
C3A—C2A—H2A	120.00	O22—C21—C2	117.44 (19)
C2A—C3A—H3A	120.00	O21—C21—O22	122.15 (19)
C4A—C3A—H3A	120.00	O21—C21—C2	120.38 (18)
C10A—C4A—H4A	120.00	C2—C3—H3	119.00
C3A—C4A—H4A	120.00	C4—C3—H3	119.00
C6A—C5A—H5A	120.00	C1—C6—H6	119.00
C10A—C5A—H5A	120.00	C5—C6—H6	119.00
C9A—N1A—C2A—C3A	0.4 (3)	C11—C1—C2—C3	−178.5 (2)
C2A—N1A—C9A—C8A	−178.9 (2)	C11—C1—C2—C21	3.5 (4)
C2A—N1A—C9A—C10A	1.0 (3)	C2—C1—C6—C5	0.3 (3)
N1A—C2A—C3A—C4A	−0.6 (3)	C11—C1—C6—C5	179.4 (2)
C2A—C3A—C4A—C10A	−0.5 (3)	C2—C1—C11—O11	171.3 (2)
C3A—C4A—C10A—C5A	−178.8 (2)	C2—C1—C11—O12	−8.7 (4)
C3A—C4A—C10A—C9A	1.7 (3)	C6—C1—C11—O11	−7.7 (3)
C10A—C5A—C6A—C7A	1.7 (3)	C6—C1—C11—O12	172.3 (2)
C6A—C5A—C10A—C4A	179.7 (2)	C1—C2—C3—C4	−1.1 (3)
C6A—C5A—C10A—C9A	−0.9 (3)	C21—C2—C3—C4	177.1 (2)
C5A—C6A—C7A—C8A	−0.1 (3)	C1—C2—C21—O21	5.5 (3)
C6A—C7A—C8A—O8A	176.2 (2)	C1—C2—C21—O22	−176.6 (2)
C6A—C7A—C8A—C9A	−2.4 (3)	C3—C2—C21—O21	−172.6 (2)
O8A—C8A—C9A—N1A	4.4 (3)	C3—C2—C21—O22	5.4 (3)
O8A—C8A—C9A—C10A	−175.46 (19)	C2—C3—C4—Cl4	−178.26 (17)
C7A—C8A—C9A—N1A	−176.9 (2)	C2—C3—C4—C5	1.0 (3)
C7A—C8A—C9A—C10A	3.2 (3)	Cl4—C4—C5—Cl5	−2.4 (3)
N1A—C9A—C10A—C4A	−2.0 (3)	Cl4—C4—C5—C6	179.04 (17)
N1A—C9A—C10A—C5A	178.5 (2)	C3—C4—C5—Cl5	178.36 (17)
C8A—C9A—C10A—C4A	177.9 (2)	C3—C4—C5—C6	−0.3 (3)
C8A—C9A—C10A—C5A	−1.7 (3)	Cl5—C5—C6—C1	−179.07 (17)
C6—C1—C2—C3	0.5 (3)	C4—C5—C6—C1	−0.4 (3)
C6—C1—C2—C21	−177.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O8A	0.95 (3)	2.25 (3)	2.689 (3)	108 (2)
N1A—H1A···O12	0.95 (3)	2.01 (3)	2.830 (3)	145 (3)
O8A—H8A···O22^i	0.84 (4)	1.78 (4)	2.607 (2)	171 (4)
O12—H12···O21	0.96 (4)	1.44 (4)	2.389 (2)	173 (4)
C2A—H2A···O11	0.93	2.56	3.124 (3)	120
C2A—H2A···O21^ii	0.93	2.49	3.176 (3)	131
C3—H3···O22	0.93	2.30	2.672 (3)	103
C3A—H3A···O11^iii	0.93	2.41	3.171 (3)	139
C6—H6···O11	0.93	2.27	2.657 (3)	104
C7A—H7A···O22^i	0.93	2.58	3.203 (3)	125

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

(II) 8-aminoquinolinium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C9H9N2^+·C8H3Cl2O4^−	Dx = 1.627 Mg m^−3
Mr = 379.19	Melting point: 471 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5985 reflections
a = 7.2003 (6) Å	θ = 2.8–27.5°
b = 7.3039 (6) Å	µ = 0.45 mm^−1
c = 29.438 (3) Å	T = 130 K
V = 1548.2 (2) Å^3	Cut plate, pale brown
Z = 4	0.45 × 0.40 × 0.10 mm
F(000) = 776

Data collection

Bruker CCD area-detector diffractometer	3529 independent reflections
Radiation source: sealed tube	3425 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 27.6°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→4
Tmin = 0.842, Tmax = 0.956	k = −9→9
9645 measured reflections	l = −37→38

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 0.3288P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3529 reflections	Δρmax = 0.31 e Å^−3
242 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (5)

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
N1A	0.30022 (19)	0.4127 (2)	0.79305 (5)	0.0177 (3)
N8A	0.6450 (2)	0.5704 (2)	0.81739 (5)	0.0201 (4)
C2A	0.1402 (2)	0.3402 (2)	0.77963 (6)	0.0222 (5)
C3A	0.0133 (2)	0.2717 (2)	0.81111 (7)	0.0232 (5)
C4A	0.0552 (2)	0.2849 (2)	0.85632 (6)	0.0218 (5)
C5A	0.2733 (2)	0.3763 (2)	0.91764 (6)	0.0201 (5)
C6A	0.4420 (2)	0.4512 (2)	0.92918 (5)	0.0208 (5)
C7A	0.5679 (2)	0.5105 (2)	0.89594 (6)	0.0186 (4)
C8A	0.5286 (2)	0.4997 (2)	0.84991 (6)	0.0168 (4)
C9A	0.3525 (2)	0.4239 (2)	0.83767 (5)	0.0161 (4)
C10A	0.2259 (2)	0.3606 (2)	0.87131 (6)	0.0177 (4)
Cl4	0.60192 (6)	0.42315 (7)	0.49219 (1)	0.0275 (1)
Cl5	0.24836 (6)	0.57856 (6)	0.54397 (1)	0.0257 (1)
O11	0.41286 (18)	0.53291 (17)	0.71080 (4)	0.0240 (3)
O12	0.67963 (18)	0.39657 (19)	0.72501 (4)	0.0273 (4)
O21	0.94065 (18)	0.26731 (18)	0.68629 (4)	0.0254 (4)
O22	1.05293 (18)	0.2509 (2)	0.61728 (5)	0.0309 (4)
C1	0.5875 (2)	0.4385 (2)	0.64629 (5)	0.0161 (4)
C2	0.7469 (2)	0.37106 (19)	0.62314 (5)	0.0157 (4)
C3	0.7462 (2)	0.3702 (2)	0.57580 (6)	0.0175 (4)
C4	0.5946 (2)	0.4311 (2)	0.55079 (5)	0.0174 (4)
C5	0.4386 (2)	0.4959 (2)	0.57347 (6)	0.0181 (4)
C6	0.4368 (2)	0.4990 (2)	0.62025 (5)	0.0182 (4)
C11	0.5566 (2)	0.4572 (2)	0.69732 (5)	0.0198 (4)
C21	0.9274 (2)	0.2923 (2)	0.64275 (6)	0.0187 (4)
H1A	0.366 (3)	0.466 (3)	0.7723 (8)	0.030 (6)*
H2A	0.11170	0.33500	0.74810	0.0270*
H3A	−0.09970	0.21710	0.80140	0.0280*
H4A	−0.03190	0.24230	0.87810	0.0260*
H5A	0.18990	0.33560	0.94050	0.0240*
H6A	0.47390	0.46310	0.96030	0.0250*
H7A	0.68400	0.55960	0.90530	0.0220*
H81A	0.648 (4)	0.524 (3)	0.7928 (8)	0.036 (7)*
H82A	0.748 (3)	0.615 (3)	0.8268 (7)	0.024 (5)*
H3	0.85270	0.32660	0.56010	0.0220*
H6	0.32940	0.54360	0.63540	0.0210*
H21	0.827 (5)	0.315 (4)	0.7022 (9)	0.058 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0162 (6)	0.0194 (6)	0.0175 (6)	−0.0013 (6)	−0.0003 (5)	−0.0010 (5)
N8A	0.0169 (7)	0.0258 (7)	0.0176 (7)	0.0045 (6)	0.0002 (5)	−0.0032 (6)
C2A	0.0193 (8)	0.0240 (8)	0.0233 (8)	−0.0021 (7)	0.0045 (7)	−0.0050 (7)
C3A	0.0150 (8)	0.0220 (8)	0.0327 (9)	0.0016 (7)	0.0050 (7)	−0.0022 (7)
C4A	0.0184 (8)	0.0183 (7)	0.0288 (9)	−0.0003 (7)	−0.0043 (7)	0.0022 (7)
C5A	0.0212 (8)	0.0194 (8)	0.0198 (8)	−0.0026 (7)	−0.0047 (6)	0.0021 (6)
C6A	0.0261 (9)	0.0211 (8)	0.0153 (7)	−0.0040 (7)	0.0021 (7)	−0.0001 (6)
C7A	0.0167 (8)	0.0183 (7)	0.0207 (8)	−0.0006 (6)	0.0033 (6)	0.0002 (6)
C8A	0.0165 (7)	0.0144 (7)	0.0196 (8)	−0.0027 (6)	−0.0001 (6)	−0.0002 (6)
C9A	0.0174 (7)	0.0136 (7)	0.0172 (7)	−0.0022 (7)	−0.0002 (6)	−0.0017 (6)
C10A	0.0180 (8)	0.0140 (7)	0.0212 (8)	−0.0029 (6)	−0.0026 (6)	0.0007 (6)
Cl4	0.0290 (2)	0.0397 (2)	0.0138 (2)	0.0021 (2)	−0.0015 (2)	−0.0005 (2)
Cl5	0.0212 (2)	0.0350 (2)	0.0210 (2)	0.0067 (2)	0.0061 (2)	−0.0017 (2)
O11	0.0262 (6)	0.0280 (6)	0.0178 (6)	0.0051 (5)	−0.0037 (5)	0.0021 (5)
O12	0.0256 (6)	0.0391 (8)	0.0173 (6)	0.0031 (6)	0.0036 (5)	−0.0004 (5)
O21	0.0221 (6)	0.0316 (7)	0.0225 (6)	0.0049 (6)	0.0069 (5)	0.0007 (5)
O22	0.0182 (6)	0.0429 (8)	0.0316 (7)	0.0097 (6)	−0.0015 (5)	−0.0027 (6)
C1	0.0143 (7)	0.0140 (7)	0.0199 (7)	−0.0025 (6)	0.0015 (6)	−0.0008 (5)
C2	0.0163 (7)	0.0136 (7)	0.0171 (7)	−0.0019 (6)	0.0009 (6)	−0.0002 (6)
C3	0.0160 (8)	0.0174 (7)	0.0192 (8)	−0.0001 (6)	−0.0008 (6)	0.0013 (6)
C4	0.0150 (7)	0.0175 (7)	0.0198 (8)	0.0002 (6)	0.0040 (6)	−0.0021 (6)
C5	0.0216 (8)	0.0190 (7)	0.0138 (7)	−0.0020 (7)	−0.0001 (6)	−0.0005 (6)
C6	0.0159 (7)	0.0181 (7)	0.0207 (7)	−0.0018 (7)	−0.0014 (6)	0.0006 (6)
C11	0.0168 (8)	0.0164 (7)	0.0262 (8)	−0.0012 (6)	0.0045 (7)	0.0003 (6)
C21	0.0211 (8)	0.0179 (8)	0.0171 (7)	−0.0047 (7)	0.0000 (6)	−0.0001 (6)

Geometric parameters (Å, º)

Cl4—C4	1.7269 (15)	C7A—C8A	1.387 (2)
Cl5—C5	1.7306 (16)	C8A—C9A	1.430 (2)
O11—C11	1.2387 (19)	C9A—C10A	1.423 (2)
O12—C11	1.2827 (19)	C2A—H2A	0.9500
O21—C21	1.298 (2)	C3A—H3A	0.9500
O22—C21	1.213 (2)	C4A—H4A	0.9500
O21—H21	1.01 (3)	C5A—H5A	0.9500
N1A—C2A	1.328 (2)	C6A—H6A	0.9500
N1A—C9A	1.369 (2)	C7A—H7A	0.9500
N8A—C8A	1.373 (2)	C1—C2	1.423 (2)
N1A—H1A	0.87 (2)	C1—C11	1.525 (2)
N8A—H81A	0.80 (2)	C1—C6	1.400 (2)
N8A—H82A	0.86 (2)	C2—C21	1.534 (2)
C2A—C3A	1.394 (2)	C2—C3	1.394 (2)
C3A—C4A	1.368 (3)	C3—C4	1.390 (2)
C4A—C10A	1.418 (2)	C4—C5	1.390 (2)
C5A—C6A	1.375 (2)	C5—C6	1.377 (2)
C5A—C10A	1.411 (2)	C3—H3	0.9500
C6A—C7A	1.403 (2)	C6—H6	0.9500
C21—O21—H21	110.6 (16)	C10A—C5A—H5A	120.00
C2A—N1A—C9A	123.22 (14)	C7A—C6A—H6A	119.00
C9A—N1A—H1A	120.0 (15)	C5A—C6A—H6A	119.00
C2A—N1A—H1A	116.4 (15)	C8A—C7A—H7A	119.00
C8A—N8A—H81A	119.2 (18)	C6A—C7A—H7A	119.00
C8A—N8A—H82A	116.5 (14)	C2—C1—C11	128.36 (13)
H81A—N8A—H82A	116 (2)	C2—C1—C6	118.18 (13)
N1A—C2A—C3A	120.92 (16)	C6—C1—C11	113.46 (12)
C2A—C3A—C4A	118.48 (14)	C1—C2—C21	129.27 (14)
C3A—C4A—C10A	121.42 (15)	C1—C2—C3	118.53 (13)
C6A—C5A—C10A	119.01 (14)	C3—C2—C21	112.19 (13)
C5A—C6A—C7A	121.44 (14)	C2—C3—C4	122.08 (14)
C6A—C7A—C8A	122.17 (14)	Cl4—C4—C5	121.07 (12)
N8A—C8A—C9A	120.75 (15)	C3—C4—C5	119.30 (14)
N8A—C8A—C7A	122.37 (14)	Cl4—C4—C3	119.64 (12)
C7A—C8A—C9A	116.70 (14)	C4—C5—C6	119.57 (14)
N1A—C9A—C8A	120.59 (14)	Cl5—C5—C4	121.16 (13)
N1A—C9A—C10A	118.18 (13)	Cl5—C5—C6	119.24 (12)
C8A—C9A—C10A	121.23 (14)	C1—C6—C5	122.34 (13)
C4A—C10A—C9A	117.73 (15)	O11—C11—C1	118.52 (13)
C5A—C10A—C9A	119.43 (13)	O12—C11—C1	119.63 (13)
C4A—C10A—C5A	122.84 (15)	O11—C11—O12	121.84 (14)
N1A—C2A—H2A	120.00	O22—C21—C2	119.49 (15)
C3A—C2A—H2A	120.00	O21—C21—O22	121.37 (15)
C2A—C3A—H3A	121.00	O21—C21—C2	119.11 (13)
C4A—C3A—H3A	121.00	C2—C3—H3	119.00
C10A—C4A—H4A	119.00	C4—C3—H3	119.00
C3A—C4A—H4A	119.00	C1—C6—H6	119.00
C6A—C5A—H5A	121.00	C5—C6—H6	119.00
C9A—N1A—C2A—C3A	0.7 (2)	C11—C1—C2—C3	−178.55 (14)
C2A—N1A—C9A—C8A	178.55 (14)	C11—C1—C2—C21	2.6 (2)
C2A—N1A—C9A—C10A	−2.3 (2)	C2—C1—C6—C5	−0.3 (2)
N1A—C2A—C3A—C4A	1.6 (2)	C11—C1—C6—C5	179.05 (13)
C2A—C3A—C4A—C10A	−2.1 (2)	C2—C1—C11—O11	174.38 (15)
C3A—C4A—C10A—C5A	179.95 (14)	C2—C1—C11—O12	−4.9 (2)
C3A—C4A—C10A—C9A	0.4 (2)	C6—C1—C11—O11	−4.9 (2)
C10A—C5A—C6A—C7A	−0.6 (2)	C6—C1—C11—O12	175.87 (14)
C6A—C5A—C10A—C4A	179.90 (14)	C1—C2—C3—C4	−0.7 (2)
C6A—C5A—C10A—C9A	−0.6 (2)	C21—C2—C3—C4	178.36 (13)
C5A—C6A—C7A—C8A	1.0 (2)	C1—C2—C21—O21	5.8 (2)
C6A—C7A—C8A—N8A	174.84 (14)	C1—C2—C21—O22	−175.88 (15)
C6A—C7A—C8A—C9A	−0.3 (2)	C3—C2—C21—O21	−173.16 (14)
N8A—C8A—C9A—N1A	3.0 (2)	C3—C2—C21—O22	5.2 (2)
N8A—C8A—C9A—C10A	−176.07 (14)	C2—C3—C4—Cl4	−179.08 (12)
C7A—C8A—C9A—N1A	178.21 (14)	C2—C3—C4—C5	0.3 (2)
C7A—C8A—C9A—C10A	−0.9 (2)	Cl4—C4—C5—Cl5	−2.23 (18)
N1A—C9A—C10A—C4A	1.8 (2)	Cl4—C4—C5—C6	179.48 (11)
N1A—C9A—C10A—C5A	−177.81 (14)	C3—C4—C5—Cl5	178.39 (11)
C8A—C9A—C10A—C4A	−179.13 (14)	C3—C4—C5—C6	0.1 (2)
C8A—C9A—C10A—C5A	1.3 (2)	Cl5—C5—C6—C1	−178.44 (12)
C6—C1—C2—C3	0.7 (2)	C4—C5—C6—C1	−0.1 (2)
C6—C1—C2—C21	−178.21 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H12···O12	1.01 (3)	1.39 (3)	2.3922 (18)	174 (3)
N1A—H1A···O11	0.87 (2)	1.91 (2)	2.7002 (19)	152 (2)
N8A—H81A···O12	0.80 (2)	2.21 (2)	3.0116 (19)	176 (3)
N8A—H82A···O21^i	0.86 (2)	2.53 (2)	3.314 (2)	152.2 (18)
N8A—H82A···O22^i	0.86 (2)	2.40 (2)	3.189 (2)	153.8 (18)
C2A—H2A···O21^ii	0.95	2.25	3.146 (2)	156
C3—H3···O22	0.95	2.28	2.670 (2)	103
C6—H6···O11	0.95	2.30	2.6826 (19)	103
C7A—H7A···O22^i	0.95	2.45	3.269 (2)	145

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

(III) 2-carboxyquinolinium 2-carboxy-4,5-dichlorobenzoate quinolinium 2-carboxylate monohydrate

Crystal data

C10H8NO2^+·C8H3Cl2O4^−·C10H7NO2·H2O	Z = 2
Mr = 599.36	F(000) = 616
Triclinic, P1	Dx = 1.407 Mg m^−3
Hall symbol: -P 1	Melting point: 455 K
a = 7.1893 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1172 (13) Å	Cell parameters from 2565 reflections
c = 19.520 (3) Å	θ = 3–25°
α = 87.558 (2)°	µ = 0.29 mm^−1
β = 88.577 (2)°	T = 130 K
γ = 83.996 (2)°	Prism, colourless
V = 1410.4 (3) Å^3	0.40 × 0.30 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4878 independent reflections
Radiation source: sealed tube	3980 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
ϕ and ω scans	θmax = 25.0°, θmin = 1.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.865, Tmax = 0.931	k = −12→9
6939 measured reflections	l = −17→23

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1022P)^2] where P = (Fo^2 + 2Fc^2)/3
4878 reflections	(Δ/σ)max = 0.002
390 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.51 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
O21A	0.6202 (3)	−0.26013 (17)	0.38453 (8)	0.0313 (6)
O22A	0.6907 (3)	−0.05882 (17)	0.41323 (9)	0.0328 (6)
N1A	0.6843 (3)	−0.1319 (2)	0.54646 (10)	0.0237 (6)
C2A	0.6535 (3)	−0.2210 (2)	0.50092 (12)	0.0227 (7)
C3A	0.6174 (4)	−0.3493 (2)	0.52295 (13)	0.0260 (8)
C4A	0.6132 (4)	−0.3814 (3)	0.59198 (13)	0.0276 (8)
C5A	0.6397 (4)	−0.3142 (3)	0.71237 (13)	0.0312 (8)
C6A	0.6690 (4)	−0.2180 (3)	0.75589 (13)	0.0320 (8)
C7A	0.7045 (4)	−0.0909 (3)	0.73113 (13)	0.0323 (8)
C8A	0.7106 (4)	−0.0590 (3)	0.66192 (13)	0.0297 (8)
C9A	0.6807 (3)	−0.1583 (3)	0.61645 (12)	0.0249 (8)
C10A	0.6436 (3)	−0.2872 (3)	0.64041 (12)	0.0250 (8)
C21A	0.6560 (4)	−0.1747 (2)	0.42600 (12)	0.0248 (8)
O21B	0.8848 (3)	0.3200 (2)	0.55248 (9)	0.0436 (7)
O22B	0.7896 (3)	0.12477 (19)	0.52688 (9)	0.0369 (7)
N1B	0.8280 (3)	0.1844 (2)	0.39254 (10)	0.0244 (7)
C2B	0.8547 (3)	0.2770 (3)	0.43689 (12)	0.0256 (8)
C3B	0.8867 (4)	0.4046 (3)	0.41316 (13)	0.0294 (8)
C4B	0.8820 (4)	0.4360 (3)	0.34454 (13)	0.0302 (8)
C5B	0.8531 (4)	0.3625 (3)	0.22533 (13)	0.0309 (8)
C6B	0.8292 (4)	0.2637 (3)	0.18274 (13)	0.0305 (8)
C7B	0.8055 (4)	0.1340 (3)	0.20960 (13)	0.0288 (8)
C8B	0.8058 (4)	0.1057 (2)	0.27853 (13)	0.0272 (8)
C9B	0.8297 (3)	0.2075 (2)	0.32263 (12)	0.0241 (8)
C10B	0.8553 (3)	0.3381 (2)	0.29723 (13)	0.0254 (8)
C21B	0.8426 (4)	0.2353 (3)	0.51320 (13)	0.0282 (8)
Cl4	0.59274 (10)	0.16384 (7)	1.03271 (3)	0.0350 (2)
Cl5	0.17722 (10)	0.11042 (7)	1.07312 (3)	0.0347 (2)
O11	0.0013 (3)	0.32387 (18)	0.77895 (10)	0.0330 (6)
O12	−0.1359 (3)	0.15182 (18)	0.82527 (9)	0.0327 (6)
O21	0.3468 (3)	0.17710 (18)	0.73890 (9)	0.0350 (6)
O22	0.4659 (3)	0.36120 (17)	0.76824 (9)	0.0307 (6)
C1	0.1439 (4)	0.2071 (2)	0.87320 (12)	0.0235 (7)
C2	0.3284 (4)	0.2281 (2)	0.85538 (12)	0.0239 (7)
C3	0.4653 (4)	0.2136 (2)	0.90452 (13)	0.0279 (8)
C4	0.4187 (4)	0.1793 (2)	0.97204 (12)	0.0271 (8)
C5	0.2378 (4)	0.1581 (2)	0.98994 (12)	0.0261 (8)
C6	0.1002 (4)	0.1717 (2)	0.94129 (12)	0.0251 (8)
C11	−0.0116 (4)	0.2228 (2)	0.82307 (12)	0.0239 (7)
C21	0.3865 (3)	0.2625 (2)	0.78261 (12)	0.0242 (8)
O1W	0.7776 (4)	0.3400 (3)	0.68150 (13)	0.0508 (9)
H1A	0.731 (5)	−0.048 (4)	0.5342 (18)	0.064 (11)*
H3A	0.59580	−0.41430	0.49100	0.0310*
H4A	0.58950	−0.46850	0.60730	0.0330*
H5A	0.61650	−0.40010	0.73010	0.0370*
H6A	0.66540	−0.23700	0.80400	0.0380*
H7A	0.72490	−0.02530	0.76280	0.0390*
H8A	0.73430	0.02750	0.64540	0.0360*
H21A	0.632 (6)	−0.230 (4)	0.341 (2)	0.040 (10)*
H1B	0.794 (4)	0.096 (3)	0.4080 (16)	0.046 (9)*
H3B	0.91170	0.46930	0.44460	0.0350*
H4B	0.89670	0.52430	0.32840	0.0360*
H5B	0.86860	0.44910	0.20670	0.0370*
H6B	0.82830	0.28140	0.13460	0.0370*
H7B	0.78900	0.06570	0.17910	0.0340*
H8B	0.79000	0.01860	0.29620	0.0330*
H3	0.59080	0.22710	0.89220	0.0330*
H6	−0.02450	0.15690	0.95410	0.0300*
H11	−0.095 (6)	0.330 (4)	0.754 (2)	0.072 (13)*
H1W	0.643 (6)	0.347 (5)	0.693 (2)	0.062 (16)*
H2W	0.800 (6)	0.333 (4)	0.635 (2)	0.059 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O21A	0.0479 (12)	0.0293 (10)	0.0187 (9)	−0.0139 (9)	0.0080 (8)	−0.0041 (7)
O22A	0.0498 (12)	0.0275 (10)	0.0232 (9)	−0.0160 (9)	0.0038 (8)	0.0007 (7)
N1A	0.0265 (11)	0.0260 (11)	0.0191 (10)	−0.0060 (9)	0.0060 (8)	−0.0027 (9)
C2A	0.0223 (13)	0.0249 (12)	0.0212 (12)	−0.0037 (10)	0.0061 (10)	−0.0038 (10)
C3A	0.0263 (14)	0.0271 (13)	0.0245 (13)	−0.0046 (10)	0.0055 (10)	−0.0005 (10)
C4A	0.0307 (14)	0.0263 (13)	0.0252 (13)	−0.0023 (11)	0.0053 (11)	0.0014 (10)
C5A	0.0327 (15)	0.0359 (15)	0.0240 (13)	−0.0009 (12)	0.0058 (11)	0.0009 (11)
C6A	0.0289 (14)	0.0463 (16)	0.0199 (13)	−0.0009 (12)	0.0065 (11)	−0.0018 (11)
C7A	0.0314 (15)	0.0444 (16)	0.0215 (13)	−0.0034 (12)	0.0056 (11)	−0.0113 (11)
C8A	0.0308 (14)	0.0308 (14)	0.0277 (14)	−0.0042 (11)	0.0040 (11)	−0.0053 (11)
C9A	0.0230 (13)	0.0339 (14)	0.0175 (12)	−0.0020 (11)	0.0046 (10)	−0.0016 (10)
C10A	0.0216 (13)	0.0291 (13)	0.0233 (13)	0.0012 (10)	0.0035 (10)	−0.0012 (10)
C21A	0.0290 (14)	0.0260 (13)	0.0200 (12)	−0.0066 (11)	0.0054 (10)	−0.0011 (10)
O21B	0.0674 (15)	0.0452 (12)	0.0237 (10)	−0.0302 (11)	0.0112 (9)	−0.0122 (9)
O22B	0.0542 (13)	0.0334 (11)	0.0260 (10)	−0.0192 (9)	0.0095 (9)	−0.0042 (8)
N1B	0.0269 (12)	0.0231 (11)	0.0241 (11)	−0.0065 (9)	0.0074 (9)	−0.0064 (9)
C2B	0.0223 (13)	0.0323 (14)	0.0234 (13)	−0.0086 (11)	0.0092 (10)	−0.0082 (10)
C3B	0.0292 (14)	0.0289 (14)	0.0319 (14)	−0.0108 (11)	0.0117 (11)	−0.0117 (11)
C4B	0.0314 (15)	0.0287 (14)	0.0314 (14)	−0.0098 (11)	0.0124 (11)	−0.0035 (11)
C5B	0.0371 (15)	0.0250 (13)	0.0306 (14)	−0.0067 (11)	0.0089 (11)	0.0017 (11)
C6B	0.0357 (15)	0.0328 (14)	0.0234 (13)	−0.0078 (12)	0.0073 (11)	−0.0003 (11)
C7B	0.0324 (15)	0.0296 (14)	0.0252 (13)	−0.0071 (11)	0.0065 (11)	−0.0065 (11)
C8B	0.0307 (14)	0.0230 (13)	0.0285 (14)	−0.0064 (11)	0.0066 (11)	−0.0036 (10)
C9B	0.0223 (13)	0.0267 (13)	0.0239 (13)	−0.0058 (10)	0.0083 (10)	−0.0044 (10)
C10B	0.0250 (13)	0.0217 (12)	0.0302 (14)	−0.0072 (10)	0.0091 (10)	−0.0041 (10)
C21B	0.0300 (14)	0.0321 (14)	0.0243 (13)	−0.0121 (11)	0.0109 (11)	−0.0062 (11)
Cl4	0.0399 (4)	0.0388 (4)	0.0273 (4)	−0.0104 (3)	−0.0014 (3)	0.0034 (3)
Cl5	0.0460 (4)	0.0428 (4)	0.0167 (3)	−0.0154 (3)	0.0103 (3)	0.0018 (3)
O11	0.0414 (12)	0.0330 (10)	0.0267 (10)	−0.0184 (9)	0.0004 (9)	0.0097 (8)
O12	0.0363 (11)	0.0366 (10)	0.0276 (10)	−0.0198 (9)	0.0039 (8)	0.0060 (8)
O21	0.0536 (12)	0.0333 (10)	0.0209 (9)	−0.0191 (9)	0.0141 (8)	−0.0070 (8)
O22	0.0367 (10)	0.0319 (10)	0.0254 (9)	−0.0156 (8)	0.0093 (8)	0.0006 (8)
C1	0.0326 (14)	0.0194 (12)	0.0196 (12)	−0.0095 (10)	0.0092 (10)	−0.0027 (9)
C2	0.0325 (14)	0.0203 (12)	0.0198 (12)	−0.0092 (10)	0.0098 (10)	−0.0031 (9)
C3	0.0280 (14)	0.0305 (14)	0.0262 (13)	−0.0110 (11)	0.0103 (11)	−0.0004 (10)
C4	0.0385 (15)	0.0231 (13)	0.0202 (13)	−0.0067 (11)	0.0033 (11)	−0.0010 (10)
C5	0.0393 (15)	0.0220 (12)	0.0178 (12)	−0.0102 (11)	0.0122 (11)	−0.0009 (9)
C6	0.0304 (14)	0.0245 (13)	0.0212 (12)	−0.0090 (11)	0.0104 (10)	−0.0007 (10)
C11	0.0315 (14)	0.0216 (12)	0.0189 (12)	−0.0072 (11)	0.0125 (10)	−0.0021 (10)
C21	0.0238 (13)	0.0251 (13)	0.0241 (13)	−0.0072 (10)	0.0099 (10)	−0.0003 (10)
O1W	0.0384 (14)	0.091 (2)	0.0241 (12)	−0.0167 (13)	0.0112 (10)	0.0041 (13)

Geometric parameters (Å, º)

Cl4—C4	1.735 (3)	C4A—H4A	0.9500
Cl5—C5	1.732 (2)	C5A—H5A	0.9500
O21A—C21A	1.259 (3)	C6A—H6A	0.9500
O22A—C21A	1.238 (3)	C7A—H7A	0.9500
O21A—H21A	0.90 (4)	C8A—H8A	0.9500
O21B—C21B	1.239 (3)	C2B—C21B	1.534 (4)
O22B—C21B	1.235 (4)	C2B—C3B	1.393 (4)
O11—C11	1.318 (3)	C3B—C4B	1.364 (4)
O12—C11	1.202 (3)	C4B—C10B	1.413 (4)
O21—C21	1.297 (3)	C5B—C6B	1.354 (4)
O22—C21	1.220 (3)	C5B—C10B	1.415 (4)
O11—H11	0.85 (4)	C6B—C7B	1.418 (4)
O1W—H2W	0.92 (4)	C7B—C8B	1.364 (4)
O1W—H1W	0.98 (4)	C8B—C9B	1.397 (3)
N1A—C2A	1.331 (3)	C9B—C10B	1.420 (3)
N1A—C9A	1.381 (3)	C3B—H3B	0.9500
N1A—H1A	0.96 (4)	C4B—H4B	0.9500
N1B—C2B	1.334 (3)	C5B—H5B	0.9500
N1B—C9B	1.375 (3)	C6B—H6B	0.9500
N1B—H1B	0.99 (3)	C7B—H7B	0.9500
C2A—C3A	1.398 (3)	C8B—H8B	0.9500
C2A—C21A	1.517 (3)	C1—C2	1.398 (4)
C3A—C4A	1.373 (4)	C1—C11	1.496 (4)
C4A—C10A	1.407 (4)	C1—C6	1.399 (3)
C5A—C6A	1.355 (4)	C2—C3	1.384 (4)
C5A—C10A	1.420 (3)	C2—C21	1.507 (3)
C6A—C7A	1.401 (4)	C3—C4	1.390 (3)
C7A—C8A	1.376 (4)	C4—C5	1.374 (4)
C8A—C9A	1.405 (4)	C5—C6	1.381 (4)
C9A—C10A	1.416 (4)	C3—H3	0.9500
C3A—H3A	0.9500	C6—H6	0.9500
C21A—O21A—H21A	111 (3)	C7B—C8B—C9B	118.7 (2)
C11—O11—H11	107 (3)	N1B—C9B—C10B	117.7 (2)
H1W—O1W—H2W	112 (4)	C8B—C9B—C10B	121.6 (2)
C2A—N1A—C9A	123.3 (2)	N1B—C9B—C8B	120.8 (2)
C9A—N1A—H1A	113 (2)	C4B—C10B—C9B	118.7 (2)
C2A—N1A—H1A	124 (2)	C4B—C10B—C5B	123.7 (2)
C2B—N1B—C9B	123.3 (2)	C5B—C10B—C9B	117.6 (2)
C9B—N1B—H1B	114.8 (18)	O21B—C21B—C2B	114.3 (2)
C2B—N1B—H1B	121.7 (18)	O22B—C21B—C2B	116.3 (2)
N1A—C2A—C21A	116.71 (18)	O21B—C21B—O22B	129.4 (2)
N1A—C2A—C3A	120.2 (2)	C4B—C3B—H3B	120.00
C3A—C2A—C21A	123.1 (2)	C2B—C3B—H3B	120.00
C2A—C3A—C4A	119.1 (2)	C3B—C4B—H4B	120.00
C3A—C4A—C10A	121.0 (3)	C10B—C4B—H4B	120.00
C6A—C5A—C10A	120.2 (3)	C10B—C5B—H5B	120.00
C5A—C6A—C7A	121.0 (2)	C6B—C5B—H5B	120.00
C6A—C7A—C8A	121.4 (3)	C5B—C6B—H6B	120.00
C7A—C8A—C9A	117.9 (3)	C7B—C6B—H6B	120.00
N1A—C9A—C10A	117.9 (2)	C8B—C7B—H7B	119.00
C8A—C9A—C10A	121.6 (2)	C6B—C7B—H7B	119.00
N1A—C9A—C8A	120.5 (2)	C9B—C8B—H8B	121.00
C4A—C10A—C5A	123.6 (3)	C7B—C8B—H8B	121.00
C5A—C10A—C9A	117.9 (2)	C2—C1—C11	123.2 (2)
C4A—C10A—C9A	118.6 (2)	C2—C1—C6	119.0 (2)
O22A—C21A—C2A	116.8 (2)	C6—C1—C11	117.8 (2)
O21A—C21A—O22A	128.2 (2)	C1—C2—C21	121.8 (2)
O21A—C21A—C2A	114.99 (19)	C3—C2—C21	117.9 (2)
C4A—C3A—H3A	120.00	C1—C2—C3	120.3 (2)
C2A—C3A—H3A	121.00	C2—C3—C4	119.8 (3)
C3A—C4A—H4A	120.00	Cl4—C4—C5	120.98 (18)
C10A—C4A—H4A	119.00	C3—C4—C5	120.3 (2)
C10A—C5A—H5A	120.00	Cl4—C4—C3	118.8 (2)
C6A—C5A—H5A	120.00	Cl5—C5—C6	118.3 (2)
C7A—C6A—H6A	119.00	C4—C5—C6	120.4 (2)
C5A—C6A—H6A	120.00	Cl5—C5—C4	121.2 (2)
C6A—C7A—H7A	119.00	C1—C6—C5	120.2 (3)
C8A—C7A—H7A	119.00	O12—C11—C1	122.4 (2)
C9A—C8A—H8A	121.00	O11—C11—O12	125.0 (2)
C7A—C8A—H8A	121.00	O11—C11—C1	112.6 (2)
N1B—C2B—C21B	116.4 (2)	O22—C21—C2	121.5 (2)
C3B—C2B—C21B	123.4 (2)	O21—C21—O22	124.8 (2)
N1B—C2B—C3B	120.1 (2)	O21—C21—C2	113.66 (19)
C2B—C3B—C4B	119.6 (3)	C2—C3—H3	120.00
C3B—C4B—C10B	120.5 (3)	C4—C3—H3	120.00
C6B—C5B—C10B	120.7 (3)	C1—C6—H6	120.00
C5B—C6B—C7B	120.4 (2)	C5—C6—H6	120.00
C6B—C7B—C8B	121.1 (2)
C9A—N1A—C2A—C3A	−0.8 (4)	C3B—C4B—C10B—C9B	1.3 (4)
C9A—N1A—C2A—C21A	178.0 (2)	C10B—C5B—C6B—C7B	0.2 (4)
C2A—N1A—C9A—C8A	−178.7 (2)	C6B—C5B—C10B—C4B	179.2 (3)
C2A—N1A—C9A—C10A	0.5 (3)	C6B—C5B—C10B—C9B	−0.7 (4)
C2B—N1B—C9B—C8B	178.3 (2)	C5B—C6B—C7B—C8B	0.1 (4)
C2B—N1B—C9B—C10B	−2.1 (3)	C6B—C7B—C8B—C9B	0.1 (4)
C9B—N1B—C2B—C3B	−0.1 (4)	C7B—C8B—C9B—N1B	179.0 (2)
C9B—N1B—C2B—C21B	178.3 (2)	C7B—C8B—C9B—C10B	−0.6 (4)
C3A—C2A—C21A—O21A	1.0 (4)	N1B—C9B—C10B—C4B	1.5 (3)
N1A—C2A—C21A—O21A	−177.7 (2)	N1B—C9B—C10B—C5B	−178.7 (2)
N1A—C2A—C21A—O22A	1.6 (3)	C8B—C9B—C10B—C4B	−178.9 (2)
N1A—C2A—C3A—C4A	0.4 (4)	C8B—C9B—C10B—C5B	0.9 (3)
C21A—C2A—C3A—C4A	−178.3 (2)	C6—C1—C2—C3	0.2 (3)
C3A—C2A—C21A—O22A	−179.7 (2)	C6—C1—C2—C21	178.17 (19)
C2A—C3A—C4A—C10A	0.3 (4)	C11—C1—C2—C3	179.12 (19)
C3A—C4A—C10A—C9A	−0.6 (4)	C11—C1—C2—C21	−2.9 (3)
C3A—C4A—C10A—C5A	179.6 (3)	C2—C1—C6—C5	0.1 (3)
C6A—C5A—C10A—C4A	−179.5 (3)	C11—C1—C6—C5	−178.89 (19)
C6A—C5A—C10A—C9A	0.7 (4)	C2—C1—C11—O11	−38.2 (3)
C10A—C5A—C6A—C7A	−0.3 (4)	C2—C1—C11—O12	143.8 (2)
C5A—C6A—C7A—C8A	0.1 (5)	C6—C1—C11—O11	140.8 (2)
C6A—C7A—C8A—C9A	−0.2 (4)	C6—C1—C11—O12	−37.2 (3)
C7A—C8A—C9A—N1A	179.7 (2)	C1—C2—C3—C4	−0.7 (3)
C7A—C8A—C9A—C10A	0.6 (4)	C21—C2—C3—C4	−178.72 (18)
N1A—C9A—C10A—C5A	−179.9 (2)	C1—C2—C21—O21	−55.7 (3)
C8A—C9A—C10A—C4A	179.4 (2)	C1—C2—C21—O22	125.4 (2)
C8A—C9A—C10A—C5A	−0.8 (4)	C3—C2—C21—O21	122.4 (2)
N1A—C9A—C10A—C4A	0.2 (3)	C3—C2—C21—O22	−56.5 (3)
N1B—C2B—C3B—C4B	3.0 (4)	C2—C3—C4—Cl4	−179.22 (16)
C21B—C2B—C3B—C4B	−175.3 (3)	C2—C3—C4—C5	0.8 (3)
N1B—C2B—C21B—O21B	173.8 (2)	Cl4—C4—C5—Cl5	−1.9 (3)
N1B—C2B—C21B—O22B	−7.5 (4)	Cl4—C4—C5—C6	179.50 (16)
C3B—C2B—C21B—O21B	−7.9 (4)	C3—C4—C5—Cl5	178.05 (16)
C3B—C2B—C21B—O22B	170.9 (3)	C3—C4—C5—C6	−0.6 (3)
C2B—C3B—C4B—C10B	−3.5 (4)	Cl5—C5—C6—C1	−178.56 (16)
C3B—C4B—C10B—C5B	−178.5 (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
O11—H11···O1W^i	0.85 (4)	1.70 (4)	2.510 (3)	159 (4)
O21A—H21A···O21^ii	0.90 (4)	1.64 (4)	2.531 (2)	179 (5)
N1A—H1A···O22B	0.96 (4)	1.84 (4)	2.788 (3)	168 (3)
N1B—H1B···O22A	0.99 (3)	1.80 (3)	2.756 (3)	163 (3)
O1W—H1W···O22	0.98 (4)	1.92 (4)	2.771 (3)	143 (4)
O1W—H2W···O21B	0.92 (4)	1.71 (4)	2.625 (3)	169 (4)
C3—H3···O12^iii	0.95	2.41	3.239 (3)	146
C5B—H5B···O11^iv	0.95	2.60	3.441 (4)	148
C7A—H7A···O12^iii	0.95	2.51	3.435 (3)	163
C8A—H8A···O22B	0.95	2.51	3.234 (3)	133
C8B—H8B···O22A	0.95	2.50	3.190 (3)	130
C8B—H8B···O21^ii	0.95	2.43	3.204 (3)	138

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