4-Chloro­anilinium hydrogen (2R,3R)-tartrate monohydrate

Smith, G.; Wermuth, U.D.; White, J.M.

doi:10.1107/S1600536807032473

4-Chloroanilinium hydrogen (2R,3R)-tartrate monohydrate

In the structure of the hydrated 1:1 compound of 4-chloroaniline with L-tartaric acid, C₆H₇ClN⁺·C₄H₅O₆⁻·H₂O, determined at 130 K, the asymmetric unit comprises two 4-chloroanilinium cations, two hydrogen tartrate anions and two water molecules of solvation, and forms a two-dimensional duplex substructure comprising head-to-tail C₁¹(7) hydrogen-bonded hydrogen tartrate anions and water molecules. The π-associated 4-chloroanilinium cation pairs [ring centroid separation = 3.576 (4) Å; inter-ring dihedral angle = 0.5 (1)°] are accommodated within the channels of the substructure and are hydrogen-bonded to it peripherally.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032473/bt2426sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032473/bt2426Isup2.hkl Contains datablock I

CCDC reference: 657715

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Key indicators

Single-crystal X-ray study
T = 130 K
Mean (C-C) = 0.010 Å
R factor = 0.076
wR factor = 0.197
Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.89 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        N1A
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        N1B
PLAT417_ALERT_2_C Short Inter D-H..H-D       H21C   ..  H22W    ..       2.11 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               4197
           Count of symmetry unique reflns         2346
           Completeness (_total/calc)            178.90%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1851
           Fraction of Friedel pairs measured     0.789
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2C    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2D    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3C    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3D    = .          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The utility of L-tartaric acid as an agent for the introduction of chirality in organic compounds for the generation of crystalline materials with potentially useful nonlinear optical properties has been recognized (Aakeröy et al., 1992; Fuller et al., 1995; Renuka et al., 1995; Chen et al., 2005; Manivannan et al., 1995). The product from the 1:1 reaction with aniline (Chen et al., 2005), p-toluidine and m-anisidine (a monohydrate) (Renuka et al., 1995) have been determined so that our similar reaction of L-tartaric acid with 4-chloroaniline in aqueous propan-2-ol not unexpectedly gave good crystals of the proton-transfer compound 4-chloroanilinium hydrogen (2R,3R)-tartrate monohydrate C₆H₇ClN⁺ C₄H₅O₆^-.H₂O, (I) and the structure is reported here.

In (I), the asymmetric unit comprises two 4-chloroanilinium cations (A and B), two hydrogen L-tartarate anions (C and D) and two water molecules of solvation (O1W and O2W) (Fig. 1). The two hydrogen tartrate anions and the water molecules form duplex hydrogen-bonded substructures through homomeric A and B chain carboxylate interactions with other tartrate carboxylic acid and hydroxyl groups as well as with the water molecules (Table 1). These include the C₁¹(7) head-to-tail carboxylic acid–carboxylate associations (O11–H11···O42) which extend down the a cell direction in the unit cell (Figs. 2, 3). These carboxyl associations typify the hydrogen-bonded framework substructures in the majority of the anhydrous hydrogen tartrates (Aakeröy et al., 1992). The two independent 4-chloroanilinium cations in (I) form a π-associated dimer through partial overlapping of the offset benzene rings [ring centroid separation, 3.576 (4) Å; inter-ring dihedral angle, 0.5 (1)°]. However, the inter-dimer separation down the a cell direction [4.242 (4) Å] does not give stacks such as is found in the structure of quinolinium hydrogen-L-tartrate (Smith et al., 2006). In (I), these dimers are accommodated between the substructures and are peripherally hydrogen-bonded to them through aminium N⁺—H···O interactions with water and both carboxyl and hydroxyl O acceptors of the anions, including the R³₄(8) cyclic system seen in the asymmetric unit in Fig. 1. The result is a two-dimensional network structure.

The accepted (2R,3R) absolute configuration for the L-tartrate residues in (I) (Bijvoet et al., 1951) was assumed and both anions C and D adopt the common extended conformation. The intramolecular hydroxyl O–H···O(carboxyl) hydrogen bond which is also common in hydrogen tartrates is absent in the C anion but present in the D anion [O···O, [2.554 (6) Å]. In addition, in the D anion there is an unusual intramolecular hydroxyl–hydroxyl O–H···O contact [O···O, 2.936 (7) Å]. However, there are no significant conformational differences in the two anions, the O21–C2–C3–O31 torsion angles being -61.7 (7) ° (C) and -69.5 (6) ° (D), comparing with -66.8 (2) ° in sodium hydrogen L-tartrate monohydrate (Bott et al., 1993).

Related literature top

The structure of the title compound is different from those of the L-tartrates of the parent aniline (Chen et al., 2005), p-toluidine and m-anisidine (Renuka et al., 1995). For related literature, see: Aakeröy et al. (1992); Bijvoet et al. (1951); Bott et al. (1993); Fuller et al. (1995); Manivannan et al. (1995); Smith et al. (2006).

Experimental top

Compound (I) was synthesized by heating for 10 min under reflux, 1 mmol quantities of L-tartaric acid and 4-chloroaniline in 50 ml of 50% 2-propanol-water. Colourless needles (m.p. 443 K) were obtained after partial room-temperature evaporation of solvent.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top

	Fig. 1. The molecular configuration and atom-numbering scheme for the two 4-chloroanilinium cations (A and B), the two hydrogen L-tartrate anions (C and D) and the two water molecules of solvation in the asymmetric unit of (I). Inter- species hydrogen bonds are shown as dashed lines. Non-H atoms are shown as 40% probability displacement ellipsoids.
	Fig. 2. The homomeric C₁¹(7) hydrogen-bonded extension of the C– and D-anion structures in the two-dimensional duplex-chain substructure of (I), viewed perpendicular to the a axial direction. Hydrogen-bonding interactions are shown as dashed lines and non-interactive hydrogen atoms are omitted. For symmetry codes, see Table 1.
	Fig. 3. A perspective view of the packing of the two-dimensional structure of (I) in the unit cell showing the extension of the substructure along the a cell direction.

4-chloroanilinium hydrogen (2R,3R)-tartrate monohydrate top

Crystal data top

C₆H₇ClN⁺·C₄H₅O₆⁻·H₂O	F(000) = 616
M_r = 295.67	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁	Melting point: 443 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 7.3437 (15) Å	Cell parameters from 1450 reflections
b = 10.850 (2) Å	θ = 2.9–22.5°
c = 15.971 (3) Å	µ = 0.33 mm⁻¹
β = 97.880 (4)°	T = 130 K
V = 1260.5 (4) Å³	Needle, colourless
Z = 4	0.45 × 0.15 × 0.05 mm

Data collection top

Bruker SMART CCD diffractometer	4197 independent reflections
Radiation source: sealed tube	3319 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
φ and ω scans	θ_max = 25.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→8
T_min = 0.93, T_max = 0.98	k = −12→11
6196 measured reflections	l = −18→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.076	H-atom parameters not refined
wR(F²) = 0.197	w = 1/[σ²(F_o²) + (0.0989P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4197 reflections	Δρ_max = 0.79 e Å⁻³
342 parameters	Δρ_min = −0.59 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1857 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Crystal data top

C₆H₇ClN⁺·C₄H₅O₆⁻·H₂O	V = 1260.5 (4) Å³
M_r = 295.67	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 7.3437 (15) Å	µ = 0.33 mm⁻¹
b = 10.850 (2) Å	T = 130 K
c = 15.971 (3) Å	0.45 × 0.15 × 0.05 mm
β = 97.880 (4)°

Data collection top

Bruker SMART CCD diffractometer	4197 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	3319 reflections with I > 2σ(I)
T_min = 0.93, T_max = 0.98	R_int = 0.087
6196 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	H-atom parameters not refined
wR(F²) = 0.197	Δρ_max = 0.79 e Å⁻³
S = 1.06	Δρ_min = −0.59 e Å⁻³
4197 reflections	Absolute structure: Flack (1983), 1857 Friedel pairs
342 parameters	Absolute structure parameter: 0.02 (6)
1 restraint

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

	x	y	z	U_iso*/U_eq
Cl4A	0.9564 (3)	0.55789 (17)	0.48663 (12)	0.0366 (6)
N1A	0.6345 (8)	0.9058 (5)	0.2194 (3)	0.0197 (17)
C1A	0.7105 (9)	0.8202 (7)	0.2862 (4)	0.0203 (19)
C2A	0.7486 (10)	0.8612 (6)	0.3678 (5)	0.026 (2)
C3A	0.8266 (10)	0.7810 (6)	0.4301 (4)	0.024 (2)
C4A	0.8612 (10)	0.6607 (6)	0.4076 (4)	0.024 (2)
C5A	0.8207 (9)	0.6193 (6)	0.3260 (4)	0.025 (2)
C6A	0.7471 (9)	0.6994 (6)	0.2644 (4)	0.022 (2)
Cl4B	0.3364 (3)	0.82187 (19)	0.47195 (13)	0.0439 (7)
N1B	0.3270 (7)	0.4358 (5)	0.2080 (3)	0.0192 (17)
C1B	0.3282 (9)	0.5305 (6)	0.2730 (4)	0.020 (2)
C2B	0.2610 (10)	0.6462 (6)	0.2512 (5)	0.024 (2)
C3B	0.2671 (10)	0.7368 (7)	0.3126 (5)	0.028 (3)
C4B	0.3326 (10)	0.7061 (7)	0.3945 (5)	0.027 (3)
C5B	0.3993 (10)	0.5903 (7)	0.4180 (5)	0.031 (3)
C6B	0.3935 (10)	0.5014 (6)	0.3561 (5)	0.027 (2)
O11D	1.3279 (6)	0.1806 (4)	0.3335 (3)	0.0205 (14)
O12D	1.2998 (6)	0.0308 (4)	0.2370 (3)	0.0227 (16)
O21D	0.9331 (6)	0.0562 (5)	0.2059 (3)	0.0213 (16)
O31D	1.0026 (6)	0.3206 (4)	0.2331 (3)	0.0255 (16)
O41D	0.6701 (6)	0.1617 (4)	0.3335 (3)	0.0240 (16)
O42D	0.6568 (6)	0.3134 (5)	0.2385 (3)	0.0280 (17)
C1D	1.2342 (9)	0.1077 (6)	0.2827 (4)	0.0173 (19)
C2D	1.0252 (8)	0.1109 (6)	0.2818 (4)	0.0146 (17)
C3D	0.9500 (9)	0.2378 (6)	0.2957 (4)	0.0197 (19)
C4D	0.7397 (9)	0.2382 (6)	0.2880 (4)	0.020 (2)
O11C	0.7704 (6)	0.7011 (4)	−0.0581 (3)	0.0223 (14)
O12C	0.8064 (6)	0.7839 (5)	0.0707 (3)	0.0281 (16)
O21C	0.4577 (6)	0.8208 (5)	0.0689 (3)	0.0251 (17)
O31C	0.5071 (6)	0.5544 (5)	0.0801 (3)	0.0248 (17)
O41C	0.1507 (6)	0.5520 (5)	0.0570 (3)	0.0273 (16)
O42C	0.1257 (6)	0.6830 (4)	−0.0542 (3)	0.0197 (12)
C1C	0.7086 (9)	0.7465 (6)	0.0082 (4)	0.018 (2)
C2C	0.5001 (9)	0.7479 (6)	0.0013 (4)	0.0174 (17)
C3C	0.4269 (9)	0.6155 (6)	0.0054 (4)	0.0209 (19)
C4C	0.2190 (10)	0.6152 (6)	0.0028 (4)	0.021 (2)
O1W	0.8354 (7)	0.4453 (5)	0.0895 (3)	0.0276 (17)
O2W	0.1433 (8)	0.8814 (5)	0.1023 (4)	0.042 (2)
H2A	0.7218	0.9438	0.3816	0.032*
H3A	0.8558	0.8078	0.4869	0.029*
H5A	0.8435	0.5360	0.3125	0.030*
H6A	0.7213	0.6729	0.2073	0.026*
H11A	0.617	0.865	0.169	0.035*
H12A	0.714	0.970	0.215	0.036*
H13A	0.526	0.934	0.231	0.030*
H2B	0.2108	0.6637	0.1944	0.029*
H3B	0.2269	0.8183	0.2983	0.033*
H5B	0.4475	0.5725	0.4750	0.037*
H6B	0.4343	0.4201	0.3705	0.032*
H11B	0.375	0.366	0.233	0.029*
H12B	0.390	0.460	0.168	0.031*
H13B	0.209	0.424	0.183	0.033*
H2D	0.9973	0.0583	0.3298	0.018*
H3D	1.0024	0.2678	0.3532	0.024*
H11D	1.450	0.174	0.334	0.060*
H21D	0.908	0.108	0.176	0.070*
H31D	0.890	0.360	0.215	0.041*
H2C	0.4472	0.7867	−0.0534	0.021*
H3C	0.4585	0.5688	−0.0446	0.025*
H11C	0.893	0.695	−0.056	0.042*
H21C	0.345	0.842	0.058	0.051*
H31C	0.609	0.525	0.073	0.060*
H11W	0.847	0.364	0.079	0.062*
H12W	0.948	0.478	0.091	0.061*
H21W	0.031	0.873	0.099	0.040*
H22W	0.193	0.928	0.145	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl4A	0.0468 (12)	0.0268 (10)	0.0363 (11)	0.0033 (9)	0.0056 (9)	0.0137 (9)
N1A	0.021 (3)	0.016 (3)	0.024 (3)	−0.002 (2)	0.010 (2)	−0.002 (2)
C1A	0.020 (3)	0.017 (3)	0.023 (4)	−0.003 (3)	0.000 (3)	−0.001 (3)
C2A	0.034 (4)	0.018 (4)	0.028 (4)	−0.010 (3)	0.007 (3)	0.000 (3)
C3A	0.028 (4)	0.023 (4)	0.021 (4)	−0.007 (3)	0.005 (3)	−0.003 (3)
C4A	0.023 (4)	0.020 (4)	0.027 (4)	0.000 (3)	0.002 (3)	0.009 (3)
C5A	0.026 (4)	0.013 (3)	0.038 (4)	−0.004 (3)	0.011 (3)	−0.002 (3)
C6A	0.019 (4)	0.017 (4)	0.030 (4)	−0.004 (3)	0.007 (3)	−0.009 (3)
Cl4B	0.0475 (13)	0.0352 (11)	0.0515 (13)	−0.0046 (10)	0.0158 (10)	−0.0212 (10)
N1B	0.019 (3)	0.013 (3)	0.026 (3)	−0.003 (2)	0.005 (2)	0.001 (2)
C1B	0.019 (3)	0.019 (4)	0.022 (4)	−0.009 (3)	0.008 (3)	−0.001 (3)
C2B	0.033 (4)	0.019 (4)	0.024 (4)	−0.001 (3)	0.014 (3)	0.004 (3)
C3B	0.028 (4)	0.016 (4)	0.043 (5)	−0.001 (3)	0.017 (3)	−0.003 (3)
C4B	0.021 (4)	0.024 (4)	0.038 (5)	−0.006 (3)	0.012 (3)	−0.014 (3)
C5B	0.031 (4)	0.037 (5)	0.023 (4)	0.004 (3)	0.002 (3)	0.001 (3)
C6B	0.031 (4)	0.014 (3)	0.036 (4)	0.002 (3)	0.007 (3)	0.001 (3)
O11D	0.011 (2)	0.024 (2)	0.027 (3)	0.002 (2)	0.0040 (19)	−0.006 (2)
O12D	0.015 (2)	0.020 (3)	0.035 (3)	0.004 (2)	0.010 (2)	−0.003 (2)
O21D	0.020 (3)	0.014 (2)	0.028 (3)	0.002 (2)	−0.003 (2)	−0.005 (2)
O31D	0.029 (3)	0.011 (2)	0.039 (3)	0.002 (2)	0.014 (2)	0.000 (2)
O41D	0.026 (3)	0.016 (2)	0.032 (3)	0.007 (2)	0.011 (2)	0.001 (2)
O42D	0.023 (3)	0.026 (3)	0.036 (3)	0.004 (2)	0.008 (2)	0.006 (3)
C1D	0.025 (4)	0.014 (3)	0.013 (3)	−0.003 (3)	0.003 (3)	0.002 (3)
C2D	0.018 (3)	0.013 (3)	0.013 (3)	−0.004 (3)	0.003 (3)	−0.004 (3)
C3D	0.021 (3)	0.011 (3)	0.027 (4)	−0.001 (3)	0.003 (3)	−0.005 (3)
C4D	0.025 (4)	0.012 (3)	0.025 (4)	0.002 (3)	0.006 (3)	−0.003 (3)
O11C	0.021 (2)	0.025 (3)	0.022 (2)	−0.001 (2)	0.007 (2)	−0.006 (2)
O12C	0.016 (2)	0.044 (3)	0.024 (3)	−0.001 (2)	0.002 (2)	−0.009 (2)
O21C	0.020 (3)	0.026 (3)	0.030 (3)	0.010 (2)	0.006 (2)	−0.008 (2)
O31C	0.021 (3)	0.024 (3)	0.031 (3)	0.006 (2)	0.009 (2)	0.007 (2)
O41C	0.020 (2)	0.030 (3)	0.032 (3)	−0.006 (2)	0.004 (2)	0.005 (2)
O42C	0.018 (2)	0.021 (2)	0.019 (2)	0.004 (2)	−0.0018 (19)	−0.003 (2)
C1C	0.025 (4)	0.014 (3)	0.018 (4)	0.004 (3)	0.013 (3)	0.003 (3)
C2C	0.020 (3)	0.014 (3)	0.020 (3)	0.005 (3)	0.009 (3)	−0.005 (3)
C3C	0.029 (4)	0.018 (3)	0.017 (3)	0.006 (3)	0.008 (3)	0.001 (3)
C4C	0.032 (4)	0.011 (3)	0.021 (4)	0.000 (3)	0.011 (3)	−0.006 (3)
O1W	0.022 (3)	0.027 (3)	0.034 (3)	−0.004 (2)	0.005 (2)	0.001 (2)
O2W	0.036 (3)	0.044 (4)	0.045 (4)	−0.001 (3)	0.007 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Cl4A—C4A	1.756 (7)	N1B—H11B	0.90
Cl4B—C4B	1.760 (8)	C1A—C2A	1.369 (10)
O11C—C1C	1.305 (8)	C1A—C6A	1.392 (10)
O12C—C1C	1.217 (8)	C2A—C3A	1.385 (10)
O21C—C2C	1.407 (8)	C3A—C4A	1.387 (9)
O31C—C3C	1.420 (8)	C4A—C5A	1.372 (9)
O41C—C4C	1.261 (8)	C5A—C6A	1.367 (9)
O42C—C4C	1.292 (8)	C2A—H2A	0.9500
O11C—H11C	0.90	C3A—H3A	0.9500
O21C—H21C	0.85	C5A—H5A	0.9500
O31C—H31C	0.84	C6A—H6A	0.9500
O11D—C1D	1.267 (8)	C1B—C6B	1.384 (10)
O12D—C1D	1.248 (8)	C1B—C2B	1.376 (9)
O21D—C2D	1.433 (8)	C2B—C3B	1.385 (11)
O31D—C3D	1.436 (8)	C3B—C4B	1.371 (11)
O41D—C4D	1.257 (8)	C4B—C5B	1.382 (11)
O42D—C4D	1.237 (8)	C5B—C6B	1.378 (11)
O11D—H11D	0.90	C2B—H2B	0.9500
O21D—H21D	0.74	C3B—H3B	0.9500
O31D—H31D	0.94	C5B—H5B	0.9500
O1W—H11W	0.90	C6B—H6B	0.9500
O1W—H12W	0.90	C1C—C2C	1.520 (9)
N1A—C1A	1.466 (9)	C2C—C3C	1.538 (9)
N1A—H11A	0.91	C3C—C4C	1.522 (10)
N1A—H13A	0.90	C2C—H2C	1.0000
N1A—H12A	0.92	C3C—H3C	1.0000
O2W—H21W	0.82	C1D—C2D	1.533 (9)
O2W—H22W	0.89	C2D—C3D	1.511 (9)
N1B—C1B	1.460 (8)	C3D—C4D	1.532 (9)
N1B—H13B	0.91	C2D—H2D	1.0000
N1B—H12B	0.88	C3D—H3D	1.0000

C1C—O11C—H11C	117	C4B—C5B—C6B	117.8 (7)
C2C—O21C—H21C	108	C1B—C6B—C5B	120.1 (6)
C3C—O31C—H31C	110	C3B—C2B—H2B	120.00
C1D—O11D—H11D	114	C1B—C2B—H2B	120.00
C2D—O21D—H21D	106	C4B—C3B—H3B	121.00
C3D—O31D—H31D	101	C2B—C3B—H3B	121.00
H11W—O1W—H12W	106	C6B—C5B—H5B	121.00
H12A—N1A—H13A	110	C4B—C5B—H5B	121.00
H11A—N1A—H13A	109	C1B—C6B—H6B	120.00
H11A—N1A—H12A	108	C5B—C6B—H6B	120.00
C1A—N1A—H11A	109	O11C—C1C—C2C	113.8 (5)
C1A—N1A—H12A	111	O12C—C1C—C2C	122.1 (6)
C1A—N1A—H13A	109	O11C—C1C—O12C	124.1 (6)
H21W—O2W—H22W	115	O21C—C2C—C3C	112.1 (5)
H12B—N1B—H13B	107	C1C—C2C—C3C	110.0 (5)
C1B—N1B—H11B	108	O21C—C2C—C1C	106.1 (5)
C1B—N1B—H12B	111	C2C—C3C—C4C	110.9 (5)
H11B—N1B—H12B	111	O31C—C3C—C4C	108.7 (5)
H11B—N1B—H13B	111	O31C—C3C—C2C	111.4 (5)
C1B—N1B—H13B	109	O41C—C4C—C3C	118.3 (6)
N1A—C1A—C2A	119.6 (6)	O41C—C4C—O42C	124.8 (7)
N1A—C1A—C6A	118.8 (6)	O42C—C4C—C3C	116.8 (6)
C2A—C1A—C6A	121.5 (6)	C1C—C2C—H2C	110.00
C1A—C2A—C3A	119.3 (6)	C3C—C2C—H2C	110.00
C2A—C3A—C4A	118.5 (6)	O21C—C2C—H2C	109.00
C3A—C4A—C5A	122.1 (6)	C4C—C3C—H3C	109.00
Cl4A—C4A—C5A	119.2 (5)	O31C—C3C—H3C	109.00
Cl4A—C4A—C3A	118.7 (5)	C2C—C3C—H3C	109.00
C4A—C5A—C6A	119.2 (6)	O12D—C1D—C2D	118.4 (6)
C1A—C6A—C5A	119.3 (6)	O11D—C1D—C2D	116.6 (6)
C3A—C2A—H2A	120.00	O11D—C1D—O12D	124.9 (6)
C1A—C2A—H2A	120.00	O21D—C2D—C1D	110.8 (5)
C4A—C3A—H3A	121.00	C1D—C2D—C3D	113.9 (5)
C2A—C3A—H3A	121.00	O21D—C2D—C3D	111.2 (5)
C6A—C5A—H5A	120.00	C2D—C3D—C4D	112.1 (5)
C4A—C5A—H5A	120.00	O31D—C3D—C4D	107.9 (5)
C5A—C6A—H6A	120.00	O31D—C3D—C2D	109.2 (5)
C1A—C6A—H6A	120.00	O41D—C4D—C3D	115.9 (6)
C2B—C1B—C6B	121.0 (6)	O42D—C4D—C3D	117.1 (6)
N1B—C1B—C6B	119.3 (6)	O41D—C4D—O42D	127.0 (6)
N1B—C1B—C2B	119.7 (6)	C1D—C2D—H2D	107.00
C1B—C2B—C3B	119.5 (7)	C3D—C2D—H2D	107.00
C2B—C3B—C4B	118.4 (7)	O21D—C2D—H2D	107.00
Cl4B—C4B—C3B	117.8 (6)	C4D—C3D—H3D	109.00
C3B—C4B—C5B	123.0 (7)	O31D—C3D—H3D	109.00
Cl4B—C4B—C5B	119.2 (6)	C2D—C3D—H3D	109.00

N1A—C1A—C2A—C3A	−177.7 (6)	O12C—C1C—C2C—O21C	12.0 (9)
C6A—C1A—C2A—C3A	0.5 (11)	O12C—C1C—C2C—C3C	−109.5 (7)
N1A—C1A—C6A—C5A	179.0 (6)	O21C—C2C—C3C—O31C	−61.7 (7)
C2A—C1A—C6A—C5A	0.8 (10)	O21C—C2C—C3C—C4C	59.6 (7)
C1A—C2A—C3A—C4A	−0.9 (11)	C1C—C2C—C3C—O31C	56.1 (7)
C2A—C3A—C4A—Cl4A	−178.9 (6)	C1C—C2C—C3C—C4C	177.3 (5)
C2A—C3A—C4A—C5A	0.0 (11)	O31C—C3C—C4C—O41C	−8.5 (8)
Cl4A—C4A—C5A—C6A	−179.8 (5)	O31C—C3C—C4C—O42C	169.8 (5)
C3A—C4A—C5A—C6A	1.3 (11)	C2C—C3C—C4C—O41C	−131.2 (6)
C4A—C5A—C6A—C1A	−1.7 (10)	C2C—C3C—C4C—O42C	47.1 (7)
N1B—C1B—C2B—C3B	−178.2 (6)	O11D—C1D—C2D—O21D	161.6 (5)
C6B—C1B—C2B—C3B	3.2 (11)	O11D—C1D—C2D—C3D	35.4 (8)
N1B—C1B—C6B—C5B	178.6 (6)	O12D—C1D—C2D—O21D	−21.6 (8)
C2B—C1B—C6B—C5B	−2.8 (11)	O12D—C1D—C2D—C3D	−147.8 (6)
C1B—C2B—C3B—C4B	−3.1 (11)	O21D—C2D—C3D—O31D	−69.5 (6)
C2B—C3B—C4B—Cl4B	−179.1 (6)	O21D—C2D—C3D—C4D	49.9 (7)
C2B—C3B—C4B—C5B	2.6 (12)	C1D—C2D—C3D—O31D	56.5 (7)
Cl4B—C4B—C5B—C6B	179.6 (6)	C1D—C2D—C3D—C4D	175.9 (5)
C3B—C4B—C5B—C6B	−2.1 (11)	O31D—C3D—C4D—O41D	173.8 (5)
C4B—C5B—C6B—C1B	2.2 (11)	O31D—C3D—C4D—O42D	−6.5 (8)
O11C—C1C—C2C—O21C	−168.5 (5)	C2D—C3D—C4D—O41D	53.6 (7)
O11C—C1C—C2C—C3C	70.0 (7)	C2D—C3D—C4D—O42D	−126.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O12C	0.91	2.40	3.131 (7)	137
N1A—H11A···O21C	0.91	1.91	2.731 (7)	149
N1A—H12A···O21Dⁱ	0.92	1.889	2.765 (8)	160
N1A—H13A···O12Dⁱⁱ	0.90	1.98	2.855 (7)	165
N1B—H11B···O42D	0.90	2.14	2.747 (7)	124
N1B—H12B···O31C	0.88	2.02	2.884 (7)	166
N1B—H12B···O41C	0.88	2.52	2.868 (7)	104
N1B—H13B···O31Dⁱⁱⁱ	0.91	2.13	2.768 (7)	126
N1B—H13B···O41C	0.91	2.43	2.868 (7)	109
O11C—H11C···O42C^iv	0.90	1.71	2.609 (6)	179
O11D—H11D···O41D^iv	0.90	1.62	2.521 (6)	179
O21C—H21C···O2W	0.85	1.78	2.527 (7)	145
O31C—H31C···O1W	0.84	1.86	2.672 (7)	163
O21D—H21D···O31D	0.74	2.54	2.936 (7)	115
O21D—H21D···O42C^v	0.74	2.09	2.768 (7)	151
O31D—H31D···O1W	0.94	2.19	2.798 (7)	121
O31D—H31D···O42D	0.94	1.87	2.554 (6)	127
O1W—H11W···O42C^v	0.90	2.02	2.923 (7)	179
O1W—H12W···O41C^iv	0.90	1.84	2.702 (7)	161
O2W—H21W···O12Cⁱⁱⁱ	0.82	1.91	2.674 (8)	153
O2W—H22W···O12Dⁱⁱ	0.89	1.92	2.810 (8)	179
C2A—H2A···O41Dⁱ	0.95	2.50	3.343 (8)	148
C2B—H2B···O41C	0.95	2.49	3.261 (9)	138
C3B—H3B···O12Dⁱⁱ	0.95	2.59	3.431 (9)	148

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

Experimental details

Crystal data
Chemical formula	C₆H₇ClN⁺·C₄H₅O₆⁻·H₂O
M_r	295.67
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	130
a, b, c (Å)	7.3437 (15), 10.850 (2), 15.971 (3)
β (°)	97.880 (4)
V (Å³)	1260.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.45 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.93, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	6196, 4197, 3319
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.197, 1.06
No. of reflections	4197
No. of parameters	342
No. of restraints	1
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.59
Absolute structure	Flack (1983), 1857 Friedel pairs
Absolute structure parameter	0.02 (6)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 1999), SAINT, SHELXS97 Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.