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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...Ocarbox­yl and anion carboxylic acid O-H...Ocarboxyl 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108027054/sf3087sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108027054/sf3087Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108027054/sf3087IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108027054/sf3087IIIsup4.hkl
Contains datablock III

CCDC references: 703748; 703749; 703750

Comment top

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···Ocarboxyl 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···Ocarboxyl 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 ππ 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···Ocarboxyl hydrogen-bonding interaction (Figs. 1–3); in the case of (III), this is a three-centre cyclic R21(7) N—H···Ocarboxylic acid,Ocarboxylate 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···Owater, water O—H···Ocarboxyl and water O—H···Owater 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···Ocarboxyl 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 ππ 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···Cl5Avii = 3.2295 Å [symmetry code: (vii) -x, -y + 1, -z], and in (III), Cl4···Cl4v = 3.2488 (7) Å [symmetry code: (v) -x + 1, -y, -z + 1]. Similarly, there are unusual short intermolecular Cl···Ocarboxyl interactions: in (II), Cl5A···O11Dviii = 3.2279 (14) Å [symmetry code: (viii) x, y - 1, z], and in (III), Cl4···O12Avi = 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···Ocarboxyl 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.

Experimental top

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.

Refinement top

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 Uiso(H) = 1.2Ueq(C).

Computing details top

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 top
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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.
[Figure 5] Fig. 5. The two-dimensional hydrogen-bonded cation–anion sheet structure in (II), viewed down the b axial direction, showing the cyclic inversion-related R22(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.
[Figure 6] 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 top
Crystal data top
C7H8NO2+·C8H3Cl2O4·2H2OZ = 2
Mr = 408.18F(000) = 420
Triclinic, P1Dx = 1.607 Mg m3
Hall symbol: -P 1Melting point = 437–438 K
a = 6.7684 (5) ÅCu Kα radiation, λ = 1.5418 Å
b = 6.9561 (4) ÅCell parameters from 3819 reflections
c = 18.0001 (14) Åθ = 4.9–72.1°
α = 86.525 (6)°µ = 3.90 mm1
β = 87.481 (6)°T = 180 K
γ = 86.190 (6)°Block, colourless
V = 843.37 (10) Å30.40 × 0.26 × 0.14 mm
Data collection top
Oxford Diffraction Gemini S Ultra CCD area-detector
diffractometer
3190 independent reflections
Radiation source: Enhance (Cu) X-ray Source2691 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 16.0711 pixels mm-1θmax = 72.0°, θmin = 4.9°
ω scansh = 87
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 85
Tmin = 0.260, Tmax = 0.580l = 2222
7458 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.1194P)2]
where P = (Fo2 + 2Fc2)/3
3190 reflections(Δ/σ)max < 0.001
271 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
C7H8NO2+·C8H3Cl2O4·2H2Oγ = 86.190 (6)°
Mr = 408.18V = 843.37 (10) Å3
Triclinic, P1Z = 2
a = 6.7684 (5) ÅCu Kα radiation
b = 6.9561 (4) ŵ = 3.90 mm1
c = 18.0001 (14) ÅT = 180 K
α = 86.525 (6)°0.40 × 0.26 × 0.14 mm
β = 87.481 (6)°
Data collection top
Oxford Diffraction Gemini S Ultra CCD area-detector
diffractometer
3190 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2691 reflections with I > 2σ(I)
Tmin = 0.260, Tmax = 0.580Rint = 0.039
7458 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.157H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.43 e Å3
3190 reflectionsΔρmin = 0.48 e Å3
271 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O11A0.4333 (3)0.8545 (3)0.14119 (10)0.0285 (5)
O12A0.6581 (2)0.7262 (3)0.22102 (10)0.0319 (5)
N2A0.0530 (3)0.8947 (3)0.18242 (11)0.0232 (6)
C1A0.3332 (3)0.8125 (3)0.26804 (13)0.0239 (6)
C2A0.1327 (3)0.8678 (3)0.25686 (13)0.0237 (6)
C3A0.0000 (4)0.8940 (3)0.31681 (13)0.0262 (7)
C4A0.0635 (4)0.8624 (4)0.38925 (14)0.0316 (7)
C5A0.2604 (4)0.8045 (4)0.40128 (13)0.0311 (7)
C6A0.3920 (4)0.7788 (4)0.34113 (14)0.0290 (7)
C11A0.4911 (3)0.7916 (3)0.20785 (13)0.0254 (7)
Cl40.09069 (8)0.39303 (9)0.41255 (3)0.0314 (2)
Cl50.34945 (9)0.27447 (10)0.45890 (3)0.0351 (2)
O110.7137 (2)0.1782 (2)0.19595 (9)0.0299 (5)
O120.5362 (3)0.3751 (3)0.11680 (10)0.0296 (5)
O210.0981 (2)0.5573 (2)0.11045 (9)0.0263 (5)
O220.1413 (2)0.2385 (2)0.10164 (9)0.0243 (5)
C10.3977 (3)0.3104 (3)0.23672 (12)0.0220 (6)
C20.2042 (3)0.3667 (3)0.21646 (12)0.0219 (6)
C30.0560 (3)0.3962 (3)0.27106 (13)0.0235 (6)
C40.0987 (3)0.3639 (3)0.34582 (13)0.0241 (6)
C50.2914 (4)0.3087 (3)0.36611 (13)0.0265 (7)
C60.4400 (3)0.2805 (3)0.31167 (13)0.0248 (7)
C110.5658 (3)0.2806 (3)0.18095 (13)0.0239 (6)
C210.1459 (3)0.3906 (3)0.13612 (12)0.0226 (6)
O1W0.1909 (3)0.2683 (3)0.02211 (10)0.0283 (5)
O2W0.7176 (3)0.8831 (3)0.04216 (12)0.0399 (6)
H3A0.131800.932800.308600.0310*
H4A0.025500.880100.429500.0380*
H5A0.303700.783000.449600.0370*
H6A0.523100.738000.349700.0350*
H11A0.539 (7)0.864 (6)0.111 (3)0.080 (15)*
H21A0.074 (5)0.783 (5)0.1554 (18)0.037 (8)*
H22A0.071 (5)0.917 (4)0.1878 (17)0.028 (7)*
H23A0.106 (4)0.996 (5)0.1535 (18)0.034 (8)*
H30.071800.437400.257700.0280*
H60.568100.241500.325200.0300*
H120.632 (7)0.337 (6)0.084 (3)0.076 (14)*
H11W0.082 (7)0.275 (6)0.043 (2)0.061 (11)*
H12W0.169 (6)0.319 (6)0.017 (3)0.058 (12)*
H21W0.727 (6)0.816 (6)0.003 (3)0.065 (12)*
H22W0.741 (6)1.005 (6)0.026 (2)0.060 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O11A0.0246 (8)0.0355 (9)0.0244 (9)0.0020 (7)0.0019 (7)0.0004 (7)
O12A0.0240 (9)0.0366 (9)0.0339 (10)0.0029 (7)0.0006 (7)0.0011 (7)
N2A0.0227 (10)0.0254 (10)0.0212 (10)0.0024 (8)0.0004 (7)0.0031 (8)
C1A0.0264 (11)0.0212 (11)0.0242 (11)0.0013 (8)0.0014 (9)0.0017 (8)
C2A0.0295 (12)0.0207 (10)0.0205 (11)0.0013 (8)0.0011 (9)0.0020 (8)
C3A0.0285 (12)0.0241 (11)0.0251 (12)0.0007 (9)0.0040 (9)0.0016 (9)
C4A0.0386 (13)0.0323 (13)0.0231 (12)0.0005 (10)0.0063 (10)0.0035 (9)
C5A0.0399 (14)0.0327 (13)0.0207 (11)0.0031 (10)0.0030 (10)0.0001 (9)
C6A0.0293 (12)0.0287 (12)0.0290 (13)0.0027 (9)0.0041 (10)0.0010 (9)
C11A0.0273 (12)0.0230 (11)0.0259 (12)0.0009 (9)0.0002 (9)0.0020 (9)
Cl40.0313 (4)0.0415 (4)0.0210 (3)0.0018 (2)0.0063 (2)0.0038 (2)
Cl50.0390 (4)0.0483 (4)0.0177 (3)0.0001 (3)0.0038 (2)0.0006 (2)
O110.0272 (9)0.0344 (9)0.0270 (9)0.0067 (7)0.0004 (7)0.0034 (7)
O120.0277 (9)0.0356 (9)0.0238 (8)0.0041 (7)0.0035 (7)0.0016 (7)
O210.0343 (9)0.0243 (8)0.0193 (8)0.0037 (6)0.0020 (6)0.0007 (6)
O220.0298 (8)0.0234 (8)0.0192 (8)0.0020 (6)0.0004 (6)0.0027 (6)
C10.0264 (11)0.0196 (10)0.0199 (11)0.0006 (8)0.0006 (9)0.0027 (8)
C20.0272 (11)0.0181 (10)0.0203 (11)0.0014 (8)0.0017 (8)0.0022 (8)
C30.0250 (11)0.0230 (11)0.0222 (11)0.0001 (8)0.0002 (9)0.0019 (8)
C40.0257 (11)0.0239 (11)0.0225 (11)0.0016 (8)0.0034 (9)0.0028 (9)
C50.0335 (12)0.0285 (12)0.0170 (11)0.0003 (9)0.0022 (9)0.0006 (8)
C60.0247 (11)0.0239 (11)0.0256 (12)0.0006 (8)0.0034 (9)0.0016 (9)
C110.0252 (11)0.0231 (11)0.0235 (11)0.0006 (9)0.0000 (9)0.0048 (8)
C210.0208 (10)0.0260 (11)0.0204 (11)0.0014 (8)0.0025 (8)0.0018 (8)
O1W0.0277 (9)0.0364 (9)0.0200 (8)0.0009 (7)0.0003 (7)0.0001 (7)
O2W0.0460 (11)0.0368 (11)0.0356 (11)0.0022 (8)0.0164 (9)0.0058 (9)
Geometric parameters (Å, º) top
Cl4—C41.728 (2)C1A—C11A1.495 (3)
Cl5—C51.731 (2)C2A—C3A1.386 (3)
O11A—C11A1.319 (3)C3A—C4A1.391 (3)
O12A—C11A1.218 (3)C4A—C5A1.389 (4)
O11A—H11A0.88 (5)C5A—C6A1.384 (4)
O11—C111.220 (2)C3A—H3A0.9300
O12—C111.310 (3)C4A—H4A0.9300
O21—C211.250 (3)C5A—H5A0.9300
O22—C211.262 (3)C6A—H6A0.9300
O12—H120.90 (5)C1—C111.496 (3)
O1W—H11W0.85 (5)C1—C21.399 (3)
O1W—H12W0.78 (5)C1—C61.392 (3)
O2W—H21W0.87 (5)C2—C31.387 (3)
O2W—H22W0.90 (4)C2—C211.512 (3)
N2A—C2A1.463 (3)C3—C41.391 (3)
N2A—H22A0.85 (3)C4—C51.393 (3)
N2A—H21A0.94 (3)C5—C61.386 (3)
N2A—H23A0.93 (3)C3—H30.9300
C1A—C2A1.406 (3)C6—H60.9300
C1A—C6A1.393 (3)
C11A—O11A—H11A109 (3)C4A—C5A—H5A120.00
C11—O12—H12109 (3)C5A—C6A—H6A119.00
H11W—O1W—H12W102 (4)C1A—C6A—H6A119.00
H21W—O2W—H22W106 (4)C2—C1—C6119.82 (19)
H22A—N2A—H23A109 (3)C2—C1—C11122.90 (19)
C2A—N2A—H23A113.5 (19)C6—C1—C11117.28 (18)
H21A—N2A—H23A107 (3)C3—C2—C21117.51 (18)
C2A—N2A—H22A108 (2)C1—C2—C3120.0 (2)
H21A—N2A—H22A107 (3)C1—C2—C21122.47 (19)
C2A—N2A—H21A112 (2)C2—C3—C4119.91 (19)
C2A—C1A—C11A125.4 (2)C3—C4—C5120.2 (2)
C6A—C1A—C11A116.8 (2)Cl4—C4—C5120.89 (18)
C2A—C1A—C6A117.8 (2)Cl4—C4—C3118.94 (16)
N2A—C2A—C1A122.1 (2)C4—C5—C6120.0 (2)
C1A—C2A—C3A120.9 (2)Cl5—C5—C4120.97 (19)
N2A—C2A—C3A116.98 (19)Cl5—C5—C6119.04 (19)
C2A—C3A—C4A120.1 (2)C1—C6—C5120.1 (2)
C3A—C4A—C5A119.7 (2)O11—C11—O12125.1 (2)
C4A—C5A—C6A119.8 (2)O11—C11—C1121.6 (2)
C1A—C6A—C5A121.7 (2)O12—C11—C1113.23 (19)
O11A—C11A—C1A113.86 (19)O21—C21—O22125.5 (2)
O11A—C11A—O12A124.3 (2)O21—C21—C2117.65 (19)
O12A—C11A—C1A121.8 (2)O22—C21—C2116.82 (18)
C4A—C3A—H3A120.00C2—C3—H3120.00
C2A—C3A—H3A120.00C4—C3—H3120.00
C5A—C4A—H4A120.00C5—C6—H6120.00
C3A—C4A—H4A120.00C1—C6—H6120.00
C6A—C5A—H5A120.00
C6A—C1A—C2A—N2A176.0 (2)C11—C1—C6—C5178.97 (19)
C6A—C1A—C2A—C3A2.1 (3)C2—C1—C11—O11157.0 (2)
C11A—C1A—C2A—N2A5.7 (3)C2—C1—C11—O1223.3 (3)
C11A—C1A—C2A—C3A176.2 (2)C6—C1—C11—O1123.2 (3)
C2A—C1A—C6A—C5A2.1 (4)C6—C1—C11—O12156.4 (2)
C11A—C1A—C6A—C5A176.3 (2)C1—C2—C3—C42.0 (3)
C2A—C1A—C11A—O11A8.5 (3)C21—C2—C3—C4175.81 (19)
C2A—C1A—C11A—O12A173.2 (2)C1—C2—C21—O21112.3 (2)
C6A—C1A—C11A—O11A169.8 (2)C1—C2—C21—O2270.7 (3)
C6A—C1A—C11A—O12A8.5 (3)C3—C2—C21—O2169.9 (3)
N2A—C2A—C3A—C4A177.1 (2)C3—C2—C21—O22107.0 (2)
C1A—C2A—C3A—C4A1.1 (3)C2—C3—C4—Cl4177.60 (16)
C2A—C3A—C4A—C5A0.0 (4)C2—C3—C4—C52.3 (3)
C3A—C4A—C5A—C6A0.0 (4)Cl4—C4—C5—Cl52.0 (3)
C4A—C5A—C6A—C1A1.0 (4)Cl4—C4—C5—C6178.06 (17)
C6—C1—C2—C31.3 (3)C3—C4—C5—Cl5178.12 (16)
C6—C1—C2—C21176.46 (19)C3—C4—C5—C61.8 (3)
C11—C1—C2—C3178.49 (19)Cl5—C5—C6—C1178.88 (16)
C11—C1—C2—C213.8 (3)C4—C5—C6—C11.1 (3)
C2—C1—C6—C50.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11A—H11A···O2W0.88 (5)1.70 (5)2.574 (3)171 (5)
O12—H12···O1Wi0.90 (5)1.67 (5)2.562 (3)179 (7)
O1W—H11W···O220.85 (5)1.88 (4)2.708 (2)167 (4)
O1W—H12W···O21ii0.78 (5)1.90 (5)2.679 (2)176 (5)
O2W—H21W···O22iii0.87 (5)2.09 (5)2.875 (3)150 (4)
O2W—H22W···O1Wiv0.90 (4)1.92 (4)2.789 (3)163 (3)
N2A—H21A···O210.94 (3)1.80 (3)2.742 (3)174 (3)
N2A—H22A···O11v0.85 (3)2.26 (3)2.938 (2)137 (3)
N2A—H22A···O12Avi0.85 (3)2.37 (3)3.026 (3)135 (2)
N2A—H23A···O22vii0.93 (3)1.90 (3)2.808 (3)163 (3)
C6A—H6A···O12A0.932.462.778 (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) x1, y+1, z; (vi) x1, y, z; (vii) x, y+1, z.
(II) 3-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate top
Crystal data top
C7H8NO2+·C8H3Cl2O4F(000) = 1520
Mr = 372.15Dx = 1.613 Mg m3
Monoclinic, P21/nMelting point > 573 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 12.9028 (7) ÅCell parameters from 8197 reflections
b = 7.4091 (4) Åθ = 2.6–27.5°
c = 32.2323 (17) ŵ = 0.46 mm1
β = 96.012 (1)°T = 130 K
V = 3064.4 (3) Å3Block, pale brown
Z = 80.50 × 0.40 × 0.35 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
6995 independent reflections
Radiation source: sealed tube6125 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1613
Tmin = 0.74, Tmax = 0.85k = 97
17962 measured reflectionsl = 3941
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0567P)2 + 1.2365P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
6995 reflectionsΔρmax = 0.45 e Å3
474 parametersΔρmin = 0.41 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00057 (17)
Crystal data top
C7H8NO2+·C8H3Cl2O4V = 3064.4 (3) Å3
Mr = 372.15Z = 8
Monoclinic, P21/nMo Kα radiation
a = 12.9028 (7) ŵ = 0.46 mm1
b = 7.4091 (4) ÅT = 130 K
c = 32.2323 (17) Å0.50 × 0.40 × 0.35 mm
β = 96.012 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
6995 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
6125 reflections with I > 2σ(I)
Tmin = 0.74, Tmax = 0.85Rint = 0.022
17962 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.45 e Å3
6995 reflectionsΔρmin = 0.41 e Å3
474 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O11B0.80317 (10)0.31573 (17)0.05268 (4)0.0267 (4)
O12B0.76409 (11)0.04606 (18)0.02395 (4)0.0302 (4)
N3B0.90063 (11)0.1730 (2)0.20638 (4)0.0190 (4)
C1B0.81462 (12)0.0551 (2)0.09589 (5)0.0195 (4)
C2B0.84861 (12)0.1545 (2)0.13134 (5)0.0184 (4)
C3B0.86747 (11)0.0663 (2)0.16919 (5)0.0177 (4)
C4B0.85311 (12)0.1182 (2)0.17266 (5)0.0204 (4)
C5B0.81934 (13)0.2159 (2)0.13694 (5)0.0228 (5)
C6B0.80012 (13)0.1306 (2)0.09870 (5)0.0225 (5)
C11B0.79375 (12)0.1516 (2)0.05535 (5)0.0217 (5)
O11D0.27229 (10)0.77527 (18)0.04627 (4)0.0270 (4)
O12D0.25094 (11)0.50101 (19)0.01765 (4)0.0308 (4)
N3D0.39421 (11)0.6618 (2)0.19878 (4)0.0194 (4)
C1D0.30647 (12)0.5200 (2)0.08966 (5)0.0211 (5)
C2D0.33864 (12)0.6284 (2)0.12387 (5)0.0194 (4)
C3D0.36373 (11)0.5484 (2)0.16242 (5)0.0187 (4)
C4D0.35738 (12)0.3633 (2)0.16752 (5)0.0217 (5)
C5D0.32616 (13)0.2566 (2)0.13303 (5)0.0241 (5)
C6D0.30073 (13)0.3337 (2)0.09411 (5)0.0234 (5)
C11D0.27515 (12)0.6104 (2)0.04891 (5)0.0228 (5)
Cl4A0.53762 (3)0.35754 (7)0.03849 (1)0.0309 (1)
Cl5A0.50529 (4)0.06114 (7)0.05278 (1)0.0388 (2)
O11A0.57562 (10)0.10779 (17)0.21770 (4)0.0293 (4)
O12A0.68916 (9)0.11528 (16)0.23392 (4)0.0209 (3)
O21A0.59270 (9)0.48350 (17)0.21831 (4)0.0236 (3)
O22A0.75463 (8)0.46135 (15)0.19943 (3)0.0184 (3)
C1A0.59912 (11)0.1174 (2)0.16694 (5)0.0172 (4)
C2A0.61896 (11)0.3009 (2)0.16048 (5)0.0163 (4)
C3A0.59912 (12)0.3723 (2)0.12062 (5)0.0190 (4)
C4A0.56209 (12)0.2631 (2)0.08730 (5)0.0212 (4)
C5A0.54575 (12)0.0803 (2)0.09359 (5)0.0223 (5)
C6A0.56343 (12)0.0093 (2)0.13335 (5)0.0203 (4)
C11A0.61946 (12)0.0309 (2)0.20903 (5)0.0185 (4)
C21A0.65741 (12)0.4251 (2)0.19615 (5)0.0169 (4)
Cl4C0.05110 (3)1.05825 (6)0.05024 (1)0.0287 (1)
Cl5C0.00872 (4)0.64684 (7)0.03649 (1)0.0330 (2)
O11C0.07635 (10)0.38203 (17)0.19032 (4)0.0294 (4)
O12C0.17700 (10)0.59567 (17)0.22301 (4)0.0260 (4)
O21C0.10158 (9)0.98011 (16)0.22782 (3)0.0222 (3)
O22C0.26417 (9)0.94695 (15)0.21001 (3)0.0200 (3)
C1C0.09780 (11)0.6652 (2)0.15704 (5)0.0172 (4)
C2C0.12307 (11)0.8477 (2)0.16299 (5)0.0166 (4)
C3C0.10632 (12)0.9667 (2)0.12971 (5)0.0185 (4)
C4C0.06740 (12)0.9059 (2)0.09071 (5)0.0198 (4)
C5C0.04204 (12)0.7244 (2)0.08472 (5)0.0207 (4)
C6C0.05676 (12)0.6053 (2)0.11775 (5)0.0199 (4)
C11C0.11511 (12)0.5319 (2)0.19210 (5)0.0194 (4)
C21C0.16542 (12)0.9288 (2)0.20422 (5)0.0166 (4)
H2B0.858700.281100.129600.0220*
H4B0.866100.176700.198900.0240*
H5B0.809300.342500.138800.0270*
H6B0.777100.198500.074500.0270*
H12B0.754 (3)0.110 (5)0.0019 (10)0.062 (13)*
H31B0.9665 (17)0.217 (3)0.2036 (7)0.033 (6)*
H32B0.9019 (17)0.110 (3)0.2288 (8)0.036 (6)*
H33B0.8555 (18)0.276 (3)0.2074 (7)0.039 (6)*
H2D0.343300.755500.120800.0230*
H4D0.374100.310100.194200.0260*
H5D0.322200.129400.136200.0290*
H6D0.279500.259800.070700.0280*
H12D0.229 (2)0.563 (5)0.0063 (10)0.050 (10)*
H31D0.4595 (16)0.704 (3)0.1986 (6)0.026 (5)*
H32D0.3485 (18)0.768 (3)0.2001 (7)0.042 (6)*
H33D0.3909 (18)0.597 (3)0.2229 (8)0.039 (6)*
H3A0.611000.497000.116100.0230*
H6A0.551000.115300.137700.0240*
H12A0.708 (2)0.054 (4)0.2604 (9)0.048 (8)*
H3C0.121801.091200.133800.0220*
H6C0.038800.481700.113700.0240*
H12C0.191 (2)0.519 (4)0.2481 (9)0.051 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O11B0.0324 (6)0.0272 (7)0.0199 (6)0.0001 (5)0.0005 (5)0.0061 (5)
O12B0.0418 (7)0.0316 (7)0.0160 (6)0.0016 (6)0.0022 (5)0.0021 (5)
N3B0.0192 (7)0.0217 (7)0.0160 (7)0.0001 (6)0.0021 (5)0.0013 (5)
C1B0.0167 (7)0.0257 (8)0.0164 (8)0.0026 (6)0.0029 (6)0.0017 (6)
C2B0.0175 (7)0.0191 (8)0.0190 (8)0.0018 (6)0.0038 (6)0.0023 (6)
C3B0.0143 (7)0.0225 (8)0.0165 (7)0.0012 (6)0.0023 (6)0.0012 (6)
C4B0.0211 (7)0.0214 (8)0.0188 (8)0.0025 (6)0.0027 (6)0.0050 (6)
C5B0.0242 (8)0.0198 (8)0.0249 (9)0.0007 (6)0.0046 (6)0.0014 (6)
C6B0.0231 (8)0.0247 (9)0.0197 (8)0.0010 (7)0.0030 (6)0.0023 (6)
C11B0.0188 (7)0.0291 (9)0.0172 (8)0.0015 (6)0.0024 (6)0.0028 (6)
O11D0.0304 (6)0.0303 (7)0.0196 (6)0.0009 (5)0.0012 (5)0.0055 (5)
O12D0.0396 (7)0.0338 (7)0.0180 (6)0.0002 (6)0.0017 (5)0.0009 (5)
N3D0.0173 (7)0.0243 (7)0.0163 (7)0.0008 (6)0.0009 (5)0.0034 (5)
C1D0.0173 (7)0.0277 (9)0.0187 (8)0.0008 (6)0.0034 (6)0.0029 (6)
C2D0.0173 (7)0.0239 (8)0.0175 (8)0.0013 (6)0.0036 (6)0.0032 (6)
C3D0.0143 (7)0.0247 (8)0.0174 (8)0.0022 (6)0.0028 (6)0.0011 (6)
C4D0.0203 (8)0.0249 (9)0.0200 (8)0.0021 (6)0.0028 (6)0.0058 (6)
C5D0.0226 (8)0.0219 (8)0.0280 (9)0.0003 (6)0.0042 (7)0.0027 (7)
C6D0.0209 (8)0.0279 (9)0.0218 (8)0.0006 (7)0.0037 (6)0.0015 (7)
C11D0.0181 (7)0.0329 (10)0.0173 (8)0.0003 (7)0.0016 (6)0.0026 (7)
Cl4A0.0336 (2)0.0439 (3)0.0144 (2)0.0036 (2)0.0012 (2)0.0062 (2)
Cl5A0.0495 (3)0.0458 (3)0.0202 (2)0.0189 (2)0.0001 (2)0.0118 (2)
O11A0.0335 (7)0.0257 (7)0.0271 (7)0.0120 (5)0.0038 (5)0.0079 (5)
O12A0.0235 (6)0.0208 (6)0.0172 (6)0.0033 (5)0.0036 (4)0.0038 (4)
O21A0.0213 (6)0.0281 (6)0.0212 (6)0.0036 (5)0.0011 (5)0.0073 (5)
O22A0.0193 (5)0.0185 (6)0.0171 (5)0.0017 (4)0.0001 (4)0.0012 (4)
C1A0.0155 (7)0.0204 (8)0.0155 (7)0.0012 (6)0.0014 (6)0.0008 (6)
C2A0.0149 (7)0.0185 (7)0.0152 (7)0.0018 (6)0.0008 (5)0.0010 (6)
C3A0.0189 (7)0.0206 (8)0.0176 (8)0.0029 (6)0.0019 (6)0.0021 (6)
C4A0.0183 (7)0.0314 (9)0.0133 (7)0.0022 (6)0.0004 (6)0.0028 (6)
C5A0.0195 (8)0.0309 (9)0.0163 (8)0.0043 (7)0.0006 (6)0.0067 (7)
C6A0.0199 (7)0.0202 (8)0.0211 (8)0.0031 (6)0.0030 (6)0.0028 (6)
C11A0.0188 (7)0.0178 (8)0.0189 (8)0.0018 (6)0.0020 (6)0.0001 (6)
C21A0.0225 (7)0.0138 (7)0.0140 (7)0.0010 (6)0.0005 (6)0.0016 (5)
Cl4C0.0318 (2)0.0368 (3)0.0168 (2)0.0014 (2)0.0011 (2)0.0082 (2)
Cl5C0.0379 (3)0.0414 (3)0.0180 (2)0.0025 (2)0.0057 (2)0.0100 (2)
O11C0.0300 (7)0.0224 (6)0.0356 (7)0.0078 (5)0.0026 (5)0.0032 (5)
O12C0.0320 (7)0.0213 (6)0.0226 (6)0.0034 (5)0.0075 (5)0.0069 (5)
O21C0.0238 (6)0.0273 (6)0.0154 (5)0.0017 (5)0.0018 (4)0.0051 (5)
O22C0.0208 (5)0.0212 (6)0.0173 (5)0.0014 (4)0.0015 (4)0.0030 (4)
C1C0.0150 (7)0.0187 (8)0.0178 (8)0.0018 (6)0.0020 (6)0.0015 (6)
C2C0.0142 (7)0.0208 (8)0.0145 (7)0.0017 (6)0.0002 (5)0.0016 (6)
C3C0.0189 (7)0.0189 (8)0.0175 (8)0.0007 (6)0.0013 (6)0.0013 (6)
C4C0.0186 (7)0.0269 (9)0.0136 (7)0.0028 (6)0.0005 (6)0.0023 (6)
C5C0.0185 (7)0.0292 (9)0.0137 (7)0.0006 (6)0.0011 (6)0.0070 (6)
C6C0.0168 (7)0.0210 (8)0.0217 (8)0.0004 (6)0.0008 (6)0.0039 (6)
C11C0.0172 (7)0.0196 (8)0.0217 (8)0.0010 (6)0.0035 (6)0.0003 (6)
C21C0.0223 (7)0.0133 (7)0.0136 (7)0.0002 (6)0.0010 (6)0.0012 (5)
Geometric parameters (Å, º) top
Cl4A—C4A1.7205 (16)C2B—H2B0.9500
Cl5A—C5A1.7198 (16)C4B—H4B0.9500
Cl4C—C4C1.7211 (16)C5B—H5B0.9500
Cl5C—C5C1.7213 (16)C6B—H6B0.9500
O11B—C11B1.2260 (19)C1D—C2D1.392 (2)
O12B—C11B1.304 (2)C1D—C11D1.492 (2)
O12B—H12B0.96 (3)C1D—C6D1.391 (2)
O11D—C11D1.225 (2)C2D—C3D1.384 (2)
O12D—C11D1.305 (2)C3D—C4D1.385 (2)
O12D—H12D0.92 (3)C4D—C5D1.389 (2)
O11A—C11A1.220 (2)C5D—C6D1.386 (2)
O12A—C11A1.301 (2)C2D—H2D0.9500
O21A—C21A1.233 (2)C4D—H4D0.9500
O22A—C21A1.2764 (19)C5D—H5D0.9500
O12A—H12A0.98 (3)C6D—H6D0.9500
O11C—C11C1.217 (2)C1A—C11A1.499 (2)
O12C—C11C1.299 (2)C1A—C6A1.386 (2)
O21C—C21C1.2381 (19)C1A—C2A1.403 (2)
O22C—C21C1.2754 (19)C2A—C3A1.388 (2)
O12C—H12C0.99 (3)C2A—C21A1.515 (2)
N3B—C3B1.462 (2)C3A—C4A1.389 (2)
N3B—H32B0.86 (2)C4A—C5A1.389 (2)
N3B—H31B0.92 (2)C5A—C6A1.382 (2)
N3B—H33B0.96 (2)C3A—H3A0.9500
N3D—C3D1.462 (2)C6A—H6A0.9500
N3D—H32D0.99 (2)C1C—C2C1.399 (2)
N3D—H33D0.92 (2)C1C—C11C1.500 (2)
N3D—H31D0.90 (2)C1C—C6C1.393 (2)
C1B—C6B1.393 (2)C2C—C3C1.388 (2)
C1B—C11B1.489 (2)C2C—C21C1.508 (2)
C1B—C2B1.391 (2)C3C—C4C1.380 (2)
C2B—C3B1.383 (2)C4C—C5C1.393 (2)
C3B—C4B1.386 (2)C5C—C6C1.381 (2)
C4B—C5B1.391 (2)C3C—H3C0.9500
C5B—C6B1.384 (2)C6C—H6C0.9500
C11B—O12B—H12B112 (2)C5D—C4D—H4D121.00
C11D—O12D—H12D112 (2)C6D—C5D—H5D120.00
C11A—O12A—H12A114.1 (17)C4D—C5D—H5D120.00
C11C—O12C—H12C117.6 (17)C5D—C6D—H6D120.00
H31B—N3B—H32B110 (2)C1D—C6D—H6D120.00
C3B—N3B—H33B109.3 (13)C2A—C1A—C11A122.10 (14)
C3B—N3B—H31B107.7 (14)C2A—C1A—C6A119.66 (14)
H32B—N3B—H33B111 (2)C6A—C1A—C11A118.19 (13)
C3B—N3B—H32B112.0 (16)C1A—C2A—C3A119.20 (14)
H31B—N3B—H33B106.8 (19)C3A—C2A—C21A119.00 (13)
H31D—N3D—H33D108.3 (19)C1A—C2A—C21A121.76 (14)
C3D—N3D—H32D112.4 (13)C2A—C3A—C4A120.59 (14)
C3D—N3D—H33D110.2 (15)Cl4A—C4A—C5A120.93 (12)
C3D—N3D—H31D111.6 (13)C3A—C4A—C5A120.03 (15)
H31D—N3D—H32D106.7 (19)Cl4A—C4A—C3A119.04 (12)
H32D—N3D—H33D107 (2)C4A—C5A—C6A119.59 (14)
C2B—C1B—C6B120.17 (14)Cl5A—C5A—C4A121.41 (12)
C2B—C1B—C11B118.62 (13)Cl5A—C5A—C6A119.00 (12)
C6B—C1B—C11B121.21 (14)C1A—C6A—C5A120.89 (14)
C1B—C2B—C3B119.05 (14)O11A—C11A—C1A121.76 (14)
C2B—C3B—C4B121.65 (15)O12A—C11A—C1A113.39 (13)
N3B—C3B—C4B119.83 (14)O11A—C11A—O12A124.82 (15)
N3B—C3B—C2B118.50 (13)O21A—C21A—C2A117.72 (14)
C3B—C4B—C5B118.66 (14)O22A—C21A—C2A115.57 (13)
C4B—C5B—C6B120.72 (14)O21A—C21A—O22A126.70 (15)
C1B—C6B—C5B119.75 (14)C2A—C3A—H3A120.00
O11B—C11B—C1B121.85 (14)C4A—C3A—H3A120.00
O12B—C11B—C1B113.86 (13)C5A—C6A—H6A120.00
O11B—C11B—O12B124.29 (15)C1A—C6A—H6A120.00
C3B—C2B—H2B120.00C2C—C1C—C6C119.56 (14)
C1B—C2B—H2B121.00C2C—C1C—C11C121.25 (14)
C5B—C4B—H4B121.00C6C—C1C—C11C119.18 (13)
C3B—C4B—H4B121.00C1C—C2C—C3C119.52 (14)
C6B—C5B—H5B120.00C1C—C2C—C21C124.30 (14)
C4B—C5B—H5B120.00C3C—C2C—C21C116.15 (13)
C1B—C6B—H6B120.00C2C—C3C—C4C120.61 (14)
C5B—C6B—H6B120.00Cl4C—C4C—C5C121.33 (12)
C2D—C1D—C6D120.38 (15)C3C—C4C—C5C119.96 (14)
C2D—C1D—C11D117.98 (13)Cl4C—C4C—C3C118.71 (12)
C6D—C1D—C11D121.60 (14)Cl5C—C5C—C6C119.46 (12)
C1D—C2D—C3D119.10 (14)C4C—C5C—C6C119.93 (15)
N3D—C3D—C4D119.23 (14)Cl5C—C5C—C4C120.61 (12)
C2D—C3D—C4D121.30 (14)C1C—C6C—C5C120.39 (14)
N3D—C3D—C2D119.44 (13)O11C—C11C—C1C122.51 (15)
C3D—C4D—C5D118.98 (14)O12C—C11C—C1C111.69 (13)
C4D—C5D—C6D120.74 (14)O11C—C11C—O12C125.79 (15)
C1D—C6D—C5D119.49 (14)O21C—C21C—C2C117.44 (13)
O11D—C11D—C1D120.82 (14)O22C—C21C—C2C115.80 (13)
O11D—C11D—O12D124.24 (15)O21C—C21C—O22C126.62 (14)
O12D—C11D—C1D114.94 (13)C2C—C3C—H3C120.00
C3D—C2D—H2D120.00C4C—C3C—H3C120.00
C1D—C2D—H2D120.00C1C—C6C—H6C120.00
C3D—C4D—H4D121.00C5C—C6C—H6C120.00
C6B—C1B—C2B—C3B0.1 (2)C1A—C2A—C3A—C4A1.3 (2)
C11B—C1B—C2B—C3B179.53 (14)C21A—C2A—C3A—C4A178.88 (14)
C2B—C1B—C6B—C5B0.2 (2)C1A—C2A—C21A—O21A79.61 (19)
C11B—C1B—C6B—C5B179.42 (15)C1A—C2A—C21A—O22A101.85 (17)
C2B—C1B—C11B—O11B1.9 (2)C3A—C2A—C21A—O21A97.91 (18)
C2B—C1B—C11B—O12B178.83 (14)C3A—C2A—C21A—O22A80.63 (18)
C6B—C1B—C11B—O11B177.75 (16)C2A—C3A—C4A—Cl4A179.51 (12)
C6B—C1B—C11B—O12B1.5 (2)C2A—C3A—C4A—C5A0.8 (2)
C1B—C2B—C3B—N3B178.48 (14)Cl4A—C4A—C5A—Cl5A2.5 (2)
C1B—C2B—C3B—C4B0.2 (2)Cl4A—C4A—C5A—C6A178.26 (12)
N3B—C3B—C4B—C5B178.61 (14)C3A—C4A—C5A—Cl5A177.19 (12)
C2B—C3B—C4B—C5B0.3 (2)C3A—C4A—C5A—C6A2.0 (2)
C3B—C4B—C5B—C6B0.2 (2)Cl5A—C5A—C6A—C1A178.03 (12)
C4B—C5B—C6B—C1B0.1 (2)C4A—C5A—C6A—C1A1.2 (2)
C6D—C1D—C2D—C3D0.7 (2)C6C—C1C—C2C—C3C0.4 (2)
C11D—C1D—C2D—C3D177.20 (14)C6C—C1C—C2C—C21C178.46 (14)
C2D—C1D—C6D—C5D0.7 (2)C11C—C1C—C2C—C3C179.71 (14)
C11D—C1D—C6D—C5D177.06 (15)C11C—C1C—C2C—C21C2.2 (2)
C2D—C1D—C11D—O11D4.0 (2)C2C—C1C—C6C—C5C0.7 (2)
C2D—C1D—C11D—O12D176.65 (15)C11C—C1C—C6C—C5C178.66 (14)
C6D—C1D—C11D—O11D173.82 (16)C2C—C1C—C11C—O11C165.56 (15)
C6D—C1D—C11D—O12D5.5 (2)C2C—C1C—C11C—O12C15.9 (2)
C1D—C2D—C3D—N3D177.95 (14)C6C—C1C—C11C—O11C15.1 (2)
C1D—C2D—C3D—C4D0.0 (2)C6C—C1C—C11C—O12C163.46 (14)
N3D—C3D—C4D—C5D178.59 (14)C1C—C2C—C3C—C4C1.5 (2)
C2D—C3D—C4D—C5D0.7 (2)C21C—C2C—C3C—C4C179.78 (14)
C3D—C4D—C5D—C6D0.6 (2)C1C—C2C—C21C—O21C86.93 (19)
C4D—C5D—C6D—C1D0.1 (3)C1C—C2C—C21C—O22C97.07 (18)
C6A—C1A—C2A—C3A2.1 (2)C3C—C2C—C21C—O21C91.22 (18)
C6A—C1A—C2A—C21A179.63 (14)C3C—C2C—C21C—O22C84.79 (17)
C11A—C1A—C2A—C3A179.51 (14)C2C—C3C—C4C—Cl4C178.43 (12)
C11A—C1A—C2A—C21A3.0 (2)C2C—C3C—C4C—C5C1.7 (2)
C2A—C1A—C6A—C5A0.9 (2)Cl4C—C4C—C5C—Cl5C1.1 (2)
C11A—C1A—C6A—C5A178.37 (14)Cl4C—C4C—C5C—C6C179.51 (12)
C2A—C1A—C11A—O11A157.84 (15)C3C—C4C—C5C—Cl5C178.87 (12)
C2A—C1A—C11A—O12A24.0 (2)C3C—C4C—C5C—C6C0.6 (2)
C6A—C1A—C11A—O11A24.7 (2)Cl5C—C5C—C6C—C1C179.96 (11)
C6A—C1A—C11A—O12A153.44 (14)C4C—C5C—C6C—C1C0.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12A—H12A···O22Ai0.98 (3)1.50 (3)2.4730 (16)176 (3)
O12B—H12B···O11Dii0.96 (3)1.67 (3)2.6216 (18)176 (4)
O12C—H12C···O22Ciii0.99 (3)1.51 (3)2.4714 (16)163 (3)
O12D—H12D···O11Bii0.92 (3)1.76 (3)2.6718 (18)176 (3)
N3B—H31B···O11Civ0.92 (2)1.95 (2)2.8378 (19)160 (2)
N3B—H31B···O21Cv0.92 (2)2.54 (2)2.9778 (18)109.6 (16)
N3D—H31D···O11Avi0.90 (2)2.09 (2)2.9097 (19)150.8 (18)
N3D—H31D···O21A0.90 (2)2.41 (2)2.8919 (19)113.9 (17)
N3B—H32B···O21Ai0.86 (2)1.94 (2)2.7977 (19)176 (2)
N3D—H32D···O22C0.99 (2)1.77 (2)2.7454 (19)172 (2)
N3B—H33B···O22A0.96 (2)1.89 (2)2.8416 (18)169 (2)
N3D—H33D···O21Ciii0.92 (2)1.80 (2)2.7176 (17)174 (2)
C5B—H5B···O22Avii0.952.593.2901 (19)131
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x+1/2, y1/2, z+1/2; (iv) x+1, y, z; (v) x+1, y1, z; (vi) x, y+1, z; (vii) x, y1, z.
(III) 4-carboxyanilinium 2-carboxy-4,5-dichlorobenzoate top
Crystal data top
C7H8NO2+·C8H3Cl2O4F(000) = 1520
Mr = 372.15Dx = 1.611 Mg m3
Monoclinic, C2/cMelting point > 573 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 12.8552 (12) ÅCell parameters from 2598 reflections
b = 7.5003 (7) Åθ = 3.2–27.1°
c = 31.932 (3) ŵ = 0.46 mm1
β = 94.785 (2)°T = 130 K
V = 3068.1 (5) Å3Block, colourless
Z = 80.25 × 0.20 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3467 independent reflections
Radiation source: sealed tube2929 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 27.4°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1416
Tmin = 0.81, Tmax = 0.93k = 99
9325 measured reflectionsl = 3841
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.50 w = 1/[σ2(Fo2) + (0.0195P)2]
where P = (Fo2 + 2Fc2)/3
3467 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C7H8NO2+·C8H3Cl2O4V = 3068.1 (5) Å3
Mr = 372.15Z = 8
Monoclinic, C2/cMo Kα radiation
a = 12.8552 (12) ŵ = 0.46 mm1
b = 7.5003 (7) ÅT = 130 K
c = 31.932 (3) Å0.25 × 0.20 × 0.15 mm
β = 94.785 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3467 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2929 reflections with I > 2σ(I)
Tmin = 0.81, Tmax = 0.93Rint = 0.031
9325 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.50Δρmax = 0.31 e Å3
3467 reflectionsΔρmin = 0.32 e Å3
237 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O11A0.22690 (12)0.81678 (19)0.44395 (4)0.0308 (5)
O12A0.22424 (11)0.55873 (19)0.47948 (4)0.0288 (5)
N4A0.09998 (13)0.2735 (2)0.29327 (5)0.0167 (5)
C1A0.18219 (14)0.5536 (3)0.40588 (5)0.0193 (6)
C2A0.16605 (14)0.3701 (2)0.40662 (5)0.0201 (6)
C3A0.13853 (14)0.2790 (2)0.36965 (5)0.0188 (6)
C4A0.12626 (13)0.3735 (2)0.33209 (5)0.0163 (5)
C5A0.14167 (14)0.5555 (2)0.33066 (5)0.0188 (6)
C6A0.17012 (14)0.6458 (3)0.36786 (5)0.0196 (6)
C11A0.21333 (14)0.6439 (3)0.44655 (6)0.0212 (6)
Cl40.44163 (4)0.12566 (7)0.46386 (1)0.0308 (2)
Cl50.47983 (4)0.53547 (7)0.44551 (1)0.0290 (2)
O110.41110 (10)0.56359 (18)0.28022 (4)0.0250 (4)
O120.30927 (10)0.32711 (16)0.26365 (4)0.0189 (4)
O210.40833 (9)0.02857 (17)0.28148 (4)0.0210 (4)
O220.24592 (9)0.01692 (16)0.30273 (4)0.0171 (4)
C10.39522 (13)0.3373 (2)0.33163 (5)0.0152 (5)
C20.37819 (13)0.1557 (2)0.33967 (5)0.0148 (5)
C30.39404 (13)0.0930 (2)0.38055 (5)0.0179 (5)
C40.42632 (14)0.2080 (3)0.41331 (5)0.0196 (6)
C50.44277 (14)0.3880 (2)0.40524 (5)0.0183 (6)
C60.42707 (13)0.4512 (2)0.36454 (5)0.0175 (5)
C110.37326 (14)0.4189 (2)0.28895 (5)0.0167 (5)
C210.34305 (14)0.0266 (2)0.30464 (5)0.0161 (5)
H2A0.173900.307300.432500.0240*
H3A0.128200.153600.369900.0230*
H5A0.133000.617900.304700.0230*
H6A0.181400.771000.367400.0240*
H11A0.244 (2)0.856 (4)0.4689 (8)0.049 (9)*
H41A0.0331 (15)0.222 (3)0.2922 (6)0.026 (6)*
H42A0.1506 (16)0.183 (3)0.2921 (6)0.032 (6)*
H43A0.1013 (17)0.344 (3)0.2690 (7)0.046 (7)*
H30.382800.029500.386300.0220*
H60.438200.573900.359000.0210*
H120.288 (2)0.387 (4)0.2380 (9)0.059 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O11A0.0474 (10)0.0244 (8)0.0194 (7)0.0064 (7)0.0037 (7)0.0055 (6)
O12A0.0392 (9)0.0309 (8)0.0159 (7)0.0093 (7)0.0002 (6)0.0033 (6)
N4A0.0181 (9)0.0174 (9)0.0143 (8)0.0008 (7)0.0002 (6)0.0035 (6)
C1A0.0179 (10)0.0223 (11)0.0174 (9)0.0015 (8)0.0004 (7)0.0037 (7)
C2A0.0217 (10)0.0234 (11)0.0151 (9)0.0016 (8)0.0005 (8)0.0000 (7)
C3A0.0196 (10)0.0160 (10)0.0211 (9)0.0022 (8)0.0028 (8)0.0019 (7)
C4A0.0144 (9)0.0202 (10)0.0142 (8)0.0006 (7)0.0010 (7)0.0046 (7)
C5A0.0197 (10)0.0188 (10)0.0179 (9)0.0016 (8)0.0014 (7)0.0002 (7)
C6A0.0202 (10)0.0179 (10)0.0205 (9)0.0020 (8)0.0003 (8)0.0021 (7)
C11A0.0210 (10)0.0235 (11)0.0190 (9)0.0035 (8)0.0012 (8)0.0048 (8)
Cl40.0434 (3)0.0348 (3)0.0131 (2)0.0055 (2)0.0037 (2)0.0057 (2)
Cl50.0382 (3)0.0311 (3)0.0171 (2)0.0094 (2)0.0008 (2)0.0084 (2)
O110.0313 (8)0.0220 (7)0.0204 (7)0.0101 (6)0.0054 (6)0.0071 (6)
O120.0223 (7)0.0177 (7)0.0153 (6)0.0035 (5)0.0062 (5)0.0028 (5)
O210.0216 (7)0.0227 (7)0.0186 (6)0.0030 (6)0.0005 (6)0.0043 (5)
O220.0194 (7)0.0165 (7)0.0149 (6)0.0018 (5)0.0013 (5)0.0017 (5)
C10.0149 (9)0.0169 (9)0.0135 (8)0.0001 (7)0.0001 (7)0.0009 (7)
C20.0119 (9)0.0173 (9)0.0151 (8)0.0011 (7)0.0002 (7)0.0003 (7)
C30.0184 (10)0.0161 (9)0.0190 (9)0.0009 (8)0.0000 (7)0.0024 (7)
C40.0193 (10)0.0264 (11)0.0128 (9)0.0002 (8)0.0004 (7)0.0031 (7)
C50.0182 (10)0.0225 (10)0.0140 (9)0.0022 (8)0.0004 (7)0.0052 (7)
C60.0185 (10)0.0145 (9)0.0195 (9)0.0024 (7)0.0008 (7)0.0004 (7)
C110.0152 (9)0.0185 (10)0.0164 (9)0.0021 (7)0.0011 (7)0.0005 (7)
C210.0220 (10)0.0129 (9)0.0125 (8)0.0020 (8)0.0031 (7)0.0031 (7)
Geometric parameters (Å, º) top
Cl4—C41.7241 (18)C3A—C4A1.391 (2)
Cl5—C51.7326 (16)C4A—C5A1.381 (2)
O11A—C11A1.312 (3)C5A—C6A1.390 (2)
O12A—C11A1.228 (2)C2A—H2A0.9500
O11A—H11A0.86 (3)C3A—H3A0.9500
O11—C111.231 (2)C5A—H5A0.9500
O12—C111.301 (2)C6A—H6A0.9500
O21—C211.235 (2)C1—C21.407 (2)
O22—C211.287 (2)C1—C111.499 (2)
O12—H120.95 (3)C1—C61.389 (2)
N4A—C4A1.464 (2)C2—C31.387 (2)
N4A—H42A0.94 (2)C2—C211.519 (2)
N4A—H43A0.94 (2)C3—C41.392 (2)
N4A—H41A0.94 (2)C4—C51.394 (3)
C1A—C2A1.392 (3)C5—C61.382 (2)
C1A—C6A1.395 (3)C3—H30.9500
C1A—C11A1.490 (3)C6—H60.9500
C2A—C3A1.384 (2)
C11A—O11A—H11A107.7 (19)C5A—C6A—H6A120.00
C11—O12—H12113.9 (17)C1A—C6A—H6A120.00
C4A—N4A—H43A113.0 (14)C2—C1—C6119.86 (14)
C4A—N4A—H42A106.9 (12)C2—C1—C11122.74 (14)
H42A—N4A—H43A108.2 (18)C6—C1—C11117.25 (13)
H41A—N4A—H42A109.6 (19)C1—C2—C3119.17 (14)
H41A—N4A—H43A106.3 (18)C1—C2—C21121.60 (14)
C4A—N4A—H41A112.8 (12)C3—C2—C21119.23 (13)
C2A—C1A—C6A119.94 (17)C2—C3—C4120.57 (15)
C2A—C1A—C11A117.66 (16)Cl4—C4—C5120.85 (14)
C6A—C1A—C11A122.4 (2)C3—C4—C5120.10 (15)
C1A—C2A—C3A120.09 (14)Cl4—C4—C3119.02 (16)
C2A—C3A—C4A119.11 (14)Cl5—C5—C6119.24 (12)
N4A—C4A—C5A120.14 (14)C4—C5—C6119.57 (14)
C3A—C4A—C5A121.75 (15)Cl5—C5—C4121.18 (12)
N4A—C4A—C3A118.08 (14)C1—C6—C5120.73 (14)
C4A—C5A—C6A118.81 (16)O11—C11—C1121.19 (15)
C1A—C6A—C5A120.31 (19)O12—C11—C1114.20 (14)
O11A—C11A—O12A124.19 (18)O11—C11—O12124.57 (15)
O11A—C11A—C1A114.94 (17)O21—C21—C2118.63 (15)
O12A—C11A—C1A120.9 (2)O22—C21—C2115.10 (14)
C3A—C2A—H2A120.00O21—C21—O22126.26 (15)
C1A—C2A—H2A120.00C2—C3—H3120.00
C2A—C3A—H3A120.00C4—C3—H3120.00
C4A—C3A—H3A120.00C1—C6—H6120.00
C4A—C5A—H5A121.00C5—C6—H6120.00
C6A—C5A—H5A121.00
C6A—C1A—C2A—C3A0.3 (3)C11—C1—C6—C5176.09 (16)
C11A—C1A—C2A—C3A179.04 (17)C2—C1—C11—O11162.33 (17)
C2A—C1A—C6A—C5A0.2 (3)C2—C1—C11—O1220.0 (2)
C11A—C1A—C6A—C5A179.53 (17)C6—C1—C11—O1122.0 (2)
C2A—C1A—C11A—O11A179.66 (17)C6—C1—C11—O12155.63 (15)
C2A—C1A—C11A—O12A0.0 (3)C1—C2—C3—C40.1 (2)
C6A—C1A—C11A—O11A1.0 (3)C21—C2—C3—C4179.94 (16)
C6A—C1A—C11A—O12A179.34 (18)C1—C2—C21—O2177.7 (2)
C1A—C2A—C3A—C4A0.7 (3)C1—C2—C21—O22103.48 (18)
C2A—C3A—C4A—N4A178.33 (16)C3—C2—C21—O21102.23 (19)
C2A—C3A—C4A—C5A0.6 (3)C3—C2—C21—O2276.6 (2)
N4A—C4A—C5A—C6A177.77 (16)C2—C3—C4—Cl4178.24 (13)
C3A—C4A—C5A—C6A0.0 (3)C2—C3—C4—C50.2 (3)
C4A—C5A—C6A—C1A0.4 (3)Cl4—C4—C5—Cl50.4 (2)
C6—C1—C2—C30.3 (2)Cl4—C4—C5—C6178.19 (14)
C6—C1—C2—C21179.83 (16)C3—C4—C5—Cl5178.39 (14)
C11—C1—C2—C3175.84 (16)C3—C4—C5—C60.2 (3)
C11—C1—C2—C214.3 (3)Cl5—C5—C6—C1178.65 (13)
C2—C1—C6—C50.3 (3)C4—C5—C6—C10.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11A—H11A···O12Ai0.86 (3)1.78 (3)2.6435 (19)178 (2)
O12—H12···O22ii0.95 (3)1.52 (3)2.4726 (18)180 (4)
N4A—H41A···O11iii0.94 (2)1.98 (2)2.895 (2)163.9 (19)
N4A—H41A···O21iv0.94 (2)2.47 (2)2.874 (2)106.0 (16)
N4A—H42A···O120.94 (2)2.54 (2)2.953 (2)106.6 (16)
N4A—H42A···O220.94 (2)1.95 (2)2.874 (2)166.6 (18)
N4A—H43A···O21ii0.94 (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) x1/2, y1/2, z; (iv) x1/2, y+1/2, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC7H8NO2+·C8H3Cl2O4·2H2OC7H8NO2+·C8H3Cl2O4C7H8NO2+·C8H3Cl2O4
Mr408.18372.15372.15
Crystal system, space groupTriclinic, P1Monoclinic, P21/nMonoclinic, C2/c
Temperature (K)180130130
a, b, c (Å)6.7684 (5), 6.9561 (4), 18.0001 (14)12.9028 (7), 7.4091 (4), 32.2323 (17)12.8552 (12), 7.5003 (7), 31.932 (3)
α, β, γ (°)86.525 (6), 87.481 (6), 86.190 (6)90, 96.012 (1), 9090, 94.785 (2), 90
V3)843.37 (10)3064.4 (3)3068.1 (5)
Z288
Radiation typeCu KαMo KαMo Kα
µ (mm1)3.900.460.46
Crystal size (mm)0.40 × 0.26 × 0.140.50 × 0.40 × 0.350.25 × 0.20 × 0.15
Data collection
DiffractometerOxford Diffraction Gemini S Ultra CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.260, 0.5800.74, 0.850.81, 0.93
No. of measured, independent and
observed [I > 2σ(I)] reflections
7458, 3190, 2691 17962, 6995, 6125 9325, 3467, 2929
Rint0.0390.0220.031
(sin θ/λ)max1)0.6170.6500.647
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.157, 1.09 0.040, 0.104, 1.06 0.042, 0.086, 1.50
No. of reflections319069953467
No. of parameters271474237
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.480.45, 0.410.31, 0.32

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), SMART (Bruker, 2000), CrysAlis RED (Oxford Diffraction, 2007), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O11A—H11A···O2W0.88 (5)1.70 (5)2.574 (3)171 (5)
O12—H12···O1Wi0.90 (5)1.67 (5)2.562 (3)179 (7)
O1W—H11W···O220.85 (5)1.88 (4)2.708 (2)167 (4)
O1W—H12W···O21ii0.78 (5)1.90 (5)2.679 (2)176 (5)
O2W—H21W···O22iii0.87 (5)2.09 (5)2.875 (3)150 (4)
O2W—H22W···O1Wiv0.90 (4)1.92 (4)2.789 (3)163 (3)
N2A—H21A···O210.94 (3)1.80 (3)2.742 (3)174 (3)
N2A—H22A···O11v0.85 (3)2.26 (3)2.938 (2)137 (3)
N2A—H22A···O12Avi0.85 (3)2.37 (3)3.026 (3)135 (2)
N2A—H23A···O22vii0.93 (3)1.90 (3)2.808 (3)163 (3)
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) x1, y+1, z; (vi) x1, y, z; (vii) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O12A—H12A···O22Ai0.98 (3)1.50 (3)2.4730 (16)176 (3)
O12B—H12B···O11Dii0.96 (3)1.67 (3)2.6216 (18)176 (4)
O12C—H12C···O22Ciii0.99 (3)1.51 (3)2.4714 (16)163 (3)
O12D—H12D···O11Bii0.92 (3)1.76 (3)2.6718 (18)176 (3)
N3B—H31B···O11Civ0.92 (2)1.95 (2)2.8378 (19)160 (2)
N3B—H31B···O21Cv0.92 (2)2.54 (2)2.9778 (18)109.6 (16)
N3D—H31D···O11Avi0.90 (2)2.09 (2)2.9097 (19)150.8 (18)
N3D—H31D···O21A0.90 (2)2.41 (2)2.8919 (19)113.9 (17)
N3B—H32B···O21Ai0.86 (2)1.94 (2)2.7977 (19)176 (2)
N3D—H32D···O22C0.99 (2)1.77 (2)2.7454 (19)172 (2)
N3B—H33B···O22A0.96 (2)1.89 (2)2.8416 (18)169 (2)
N3D—H33D···O21Ciii0.92 (2)1.80 (2)2.7176 (17)174 (2)
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x+1/2, y1/2, z+1/2; (iv) x+1, y, z; (v) x+1, y1, z; (vi) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O11A—H11A···O12Ai0.86 (3)1.78 (3)2.6435 (19)178 (2)
O12—H12···O22ii0.95 (3)1.52 (3)2.4726 (18)180 (4)
N4A—H41A···O11iii0.94 (2)1.98 (2)2.895 (2)163.9 (19)
N4A—H41A···O21iv0.94 (2)2.47 (2)2.874 (2)106.0 (16)
N4A—H42A···O120.94 (2)2.54 (2)2.953 (2)106.6 (16)
N4A—H42A···O220.94 (2)1.95 (2)2.874 (2)166.6 (18)
N4A—H43A···O21ii0.94 (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) x1/2, y1/2, z; (iv) x1/2, y+1/2, z.
 

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