Bis(benzyl-aminium) 4,5-dichloro-benzene-1,2-dicarboxyl-ate monohydrate.

In the structure of the title salt, 2C(7)H(10)N(+)·C(8)H(2)Cl(2)O(4) (2-)·H(2)O, the two benzyl-aminium anions have different conformations, one being essentially planar and the other having the side chain rotated out of the benzene plane [minimum ring to side-chain C-C-C-N torsion angles = -3.6 (6) and 50.1 (5)°, respectively]. In the 4,5-dichloro-phthalate dianion, the carboxyl-ate groups make dihedral angles of 23.0 (2) and 76.5 (2)° with the benzene ring. In the crystal, aminium N-H⋯O and water O-H⋯O hydrogen-bonding associations with carboxyl-ate O-atom acceptors give a two-dimensional duplex sheet structure which extends along the (011) plane. Weak π-π inter-actions are also present between the benzene ring of the dianion and one of the cation rings [minimum ring centroid separation = 2.749 (3) Å].

Related literature

For the crystal structures of some 1:1 Lewis base salts of 4,5-dichloro­phthalic acid, see: Mattes & Dorau (1986 ▶); Smith et al. (2008 ▶). For crystal structures having dianionic 4,5-dichloro­phthalate species, see: Büyükgüngör & Odabaşoğlu (2007 ▶); Smith & Wermuth (2010 ▶, 2011 ▶).

Experimental

Crystal data

2C7H10N+·C8H2Cl2O4 2−·H2O

M = 467.33

Monoclinic,

a = 17.3005 (16) Å

b = 10.0084 (7) Å

c = 13.6990 (12) Å

β = 112.641 (11)°

V = 2189.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 200 K

0.33 × 0.22 × 0.12 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.86, T max = 0.98

12311 measured reflections

3842 independent reflections

3019 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.189

S = 1.19

3842 reflections

312 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812023458/wn2476sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023458/wn2476Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812023458/wn2476Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C7H10N+·C8H2Cl2O42−·H2O	F(000) = 976
Mr = 467.33	Dx = 1.418 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6279 reflections
a = 17.3005 (16) Å	θ = 3.2–28.7°
b = 10.0084 (7) Å	µ = 0.33 mm−1
c = 13.6990 (12) Å	T = 200 K
β = 112.641 (11)°	Plate, colourless
V = 2189.2 (4) Å3	0.33 × 0.22 × 0.12 mm
Z = 4

Oxford Diffraction Gemini-S CCD-detector diffractometer	3842 independent reflections
Radiation source: Enhance (Mo) X-ray source	3019 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 16.077 pixels mm-1	θmax = 25.0°, θmin = 3.2°
ω scans	h = −20→20
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.86, Tmax = 0.98	l = −16→16
12311 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189	H-atom parameters constrained
S = 1.19	w = 1/[σ2(Fo2) + (0.0794P)2 + 3.4869P] where P = (Fo2 + 2Fc2)/3
3842 reflections	(Δ/σ)max = 0.001
312 parameters	Δρmax = 0.79 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq
N11A	0.4026 (2)	0.4021 (3)	0.0987 (2)	0.0293 (11)
C1A	0.2474 (3)	0.4407 (4)	0.0233 (3)	0.0307 (11)
C2A	0.1790 (3)	0.5252 (5)	−0.0185 (4)	0.0460 (17)
C3A	0.0984 (3)	0.4801 (6)	−0.0447 (4)	0.0571 (19)
C4A	0.0838 (3)	0.3462 (6)	−0.0318 (4)	0.0515 (19)
C5A	0.1508 (3)	0.2619 (5)	0.0077 (4)	0.0443 (16)
C6A	0.2319 (3)	0.3065 (4)	0.0357 (3)	0.0353 (14)
C11A	0.3333 (3)	0.4980 (4)	0.0506 (3)	0.0322 (12)
N11B	0.5631 (2)	0.4462 (3)	0.4310 (2)	0.0270 (10)
C1B	0.6924 (3)	0.3655 (4)	0.5777 (3)	0.0295 (11)
C2B	0.7238 (3)	0.3664 (4)	0.6877 (3)	0.0378 (14)
C3B	0.8081 (3)	0.3812 (5)	0.7454 (4)	0.0446 (16)
C4B	0.8630 (3)	0.3963 (4)	0.6953 (4)	0.0431 (16)
C5B	0.8322 (3)	0.3971 (5)	0.5861 (4)	0.0443 (17)
C6B	0.7479 (3)	0.3822 (5)	0.5275 (4)	0.0392 (16)
C11B	0.6004 (3)	0.3454 (4)	0.5161 (3)	0.0329 (12)
Cl4	0.05397 (7)	0.26123 (11)	0.21573 (9)	0.0404 (4)
Cl5	0.06311 (7)	−0.04167 (12)	0.15221 (10)	0.0496 (4)
O11	0.38460 (19)	−0.0979 (3)	0.2378 (2)	0.0332 (9)
O12	0.45046 (18)	0.0453 (3)	0.3688 (2)	0.0394 (10)
O21	0.40882 (18)	0.3398 (3)	0.3058 (2)	0.0353 (9)
O22	0.39728 (17)	0.3096 (3)	0.4609 (2)	0.0285 (8)
C1	0.3039 (2)	0.0669 (4)	0.2786 (3)	0.0243 (11)
C2	0.2997 (2)	0.1997 (4)	0.3108 (3)	0.0232 (11)
C3	0.2221 (2)	0.2560 (4)	0.2924 (3)	0.0259 (11)
C4	0.1492 (2)	0.1842 (4)	0.2424 (3)	0.0283 (12)
C5	0.1534 (3)	0.0524 (4)	0.2126 (3)	0.0302 (12)
C6	0.2302 (3)	−0.0051 (4)	0.2304 (3)	0.0293 (12)
C11	0.3866 (3)	0.0005 (4)	0.2974 (3)	0.0278 (12)
C21	0.3755 (2)	0.2872 (4)	0.3636 (3)	0.0240 (11)
O1W	0.5248 (2)	0.1641 (3)	0.2253 (2)	0.0437 (11)
H2A	0.18780	0.61480	−0.02910	0.0550*
H3A	0.05360	0.53930	−0.07100	0.0690*
H4A	0.02950	0.31450	−0.04970	0.0620*
H5A	0.14150	0.17180	0.01590	0.0530*
H6A	0.27630	0.24680	0.06290	0.0420*
H11A	0.40280	0.37170	0.15800	0.0350*
H12A	0.44980	0.44770	0.10900	0.0350*
H13A	0.40080	0.33970	0.05300	0.0350*
H14A	0.33700	0.53380	−0.01330	0.0390*
H15A	0.34070	0.57180	0.09930	0.0390*
H2B	0.68730	0.35690	0.72240	0.0450*
H3B	0.82830	0.38090	0.81890	0.0540*
H4B	0.92010	0.40590	0.73450	0.0520*
H5B	0.86890	0.40780	0.55180	0.0530*
H6B	0.72790	0.38340	0.45400	0.0470*
H11B	0.58300	0.44510	0.38110	0.0320*
H12B	0.50500	0.42810	0.39110	0.0320*
H13B	0.57000	0.52010	0.45910	0.0320*
H14B	0.59160	0.25700	0.48470	0.0390*
H15B	0.57160	0.34930	0.56430	0.0390*
H3	0.21900	0.34330	0.31390	0.0310*
H6	0.23260	−0.09300	0.20990	0.0350*
H11W	0.55210	0.23660	0.23670	0.0650*
H12W	0.50510	0.15860	0.26570	0.0650*

	U11	U22	U33	U12	U13	U23
N11A	0.037 (2)	0.0257 (18)	0.0298 (17)	−0.0037 (15)	0.0179 (15)	−0.0026 (14)
C1A	0.040 (2)	0.030 (2)	0.0254 (19)	0.0025 (19)	0.0164 (18)	−0.0033 (16)
C2A	0.048 (3)	0.036 (3)	0.052 (3)	0.008 (2)	0.017 (2)	0.002 (2)
C3A	0.040 (3)	0.069 (4)	0.058 (3)	0.018 (3)	0.014 (2)	−0.002 (3)
C4A	0.039 (3)	0.079 (4)	0.040 (3)	−0.008 (3)	0.019 (2)	−0.004 (3)
C5A	0.045 (3)	0.050 (3)	0.041 (2)	−0.009 (2)	0.020 (2)	0.003 (2)
C6A	0.043 (3)	0.036 (2)	0.031 (2)	0.002 (2)	0.0188 (19)	0.0054 (18)
C11A	0.041 (2)	0.023 (2)	0.033 (2)	0.0014 (18)	0.0148 (18)	−0.0012 (17)
N11B	0.0371 (19)	0.0191 (16)	0.0293 (16)	−0.0034 (14)	0.0179 (15)	−0.0041 (13)
C1B	0.038 (2)	0.0147 (18)	0.041 (2)	0.0021 (17)	0.0210 (19)	0.0040 (16)
C2B	0.045 (3)	0.031 (2)	0.042 (2)	0.002 (2)	0.022 (2)	0.0070 (19)
C3B	0.049 (3)	0.040 (3)	0.041 (2)	0.002 (2)	0.013 (2)	0.004 (2)
C4B	0.034 (3)	0.027 (2)	0.064 (3)	0.0046 (19)	0.014 (2)	−0.001 (2)
C5B	0.041 (3)	0.039 (3)	0.062 (3)	0.004 (2)	0.030 (2)	0.003 (2)
C6B	0.042 (3)	0.040 (3)	0.041 (2)	0.004 (2)	0.022 (2)	0.005 (2)
C11B	0.041 (2)	0.021 (2)	0.043 (2)	0.0023 (18)	0.023 (2)	0.0063 (17)
Cl4	0.0307 (6)	0.0397 (6)	0.0530 (7)	0.0075 (5)	0.0185 (5)	0.0053 (5)
Cl5	0.0350 (6)	0.0422 (7)	0.0676 (8)	−0.0120 (5)	0.0155 (6)	−0.0114 (6)
O11	0.0445 (18)	0.0204 (14)	0.0431 (16)	0.0051 (13)	0.0262 (14)	−0.0038 (12)
O12	0.0333 (17)	0.0378 (17)	0.0430 (17)	0.0084 (14)	0.0103 (14)	−0.0079 (14)
O21	0.0378 (17)	0.0388 (17)	0.0327 (15)	−0.0107 (14)	0.0173 (13)	0.0040 (13)
O22	0.0405 (16)	0.0210 (14)	0.0276 (14)	−0.0035 (12)	0.0171 (12)	−0.0039 (11)
C1	0.035 (2)	0.0204 (19)	0.0226 (18)	−0.0011 (16)	0.0169 (16)	0.0002 (15)
C2	0.031 (2)	0.0222 (19)	0.0221 (17)	0.0015 (16)	0.0164 (16)	0.0029 (15)
C3	0.036 (2)	0.0210 (19)	0.0255 (19)	0.0025 (17)	0.0173 (17)	−0.0015 (15)
C4	0.030 (2)	0.032 (2)	0.029 (2)	0.0059 (18)	0.0180 (17)	0.0040 (17)
C5	0.035 (2)	0.025 (2)	0.032 (2)	−0.0073 (18)	0.0146 (18)	−0.0015 (16)
C6	0.038 (2)	0.024 (2)	0.031 (2)	−0.0005 (18)	0.0189 (18)	−0.0018 (16)
C11	0.034 (2)	0.023 (2)	0.032 (2)	0.0036 (17)	0.0188 (18)	0.0075 (17)
C21	0.029 (2)	0.0151 (18)	0.031 (2)	0.0028 (15)	0.0150 (17)	0.0032 (15)
O1W	0.059 (2)	0.0254 (16)	0.0577 (19)	−0.0065 (15)	0.0345 (17)	−0.0072 (14)

Cl4—C4	1.726 (4)	C6A—H6A	0.9300
Cl5—C5	1.737 (5)	C11A—H15A	0.9700
O11—C11	1.271 (5)	C11A—H14A	0.9700
O12—C11	1.244 (5)	C1B—C2B	1.391 (5)
O21—C21	1.260 (5)	C1B—C11B	1.501 (7)
O22—C21	1.258 (5)	C1B—C6B	1.390 (7)
O1W—H11W	0.8500	C2B—C3B	1.373 (7)
O1W—H12W	0.7600	C3B—C4B	1.378 (8)
N11A—C11A	1.478 (6)	C4B—C5B	1.381 (7)
N11A—H13A	0.8800	C5B—C6B	1.376 (8)
N11A—H11A	0.8700	C2B—H2B	0.9300
N11A—H12A	0.9000	C3B—H3B	0.9300
N11B—C11B	1.488 (5)	C4B—H4B	0.9300
N11B—H12B	0.9600	C5B—H5B	0.9300
N11B—H13B	0.8200	C6B—H6B	0.9300
N11B—H11B	0.8800	C11B—H15B	0.9700
C1A—C6A	1.393 (6)	C11B—H14B	0.9700
C1A—C2A	1.386 (7)	C1—C11	1.507 (6)
C1A—C11A	1.500 (7)	C1—C2	1.411 (6)
C2A—C3A	1.375 (8)	C1—C6	1.390 (6)
C3A—C4A	1.388 (8)	C2—C21	1.510 (5)
C4A—C5A	1.366 (8)	C2—C3	1.387 (5)
C5A—C6A	1.379 (8)	C3—C4	1.382 (5)
C2A—H2A	0.9300	C4—C5	1.391 (6)
C3A—H3A	0.9300	C5—C6	1.381 (7)
C4A—H4A	0.9300	C3—H3	0.9300
C5A—H5A	0.9300	C6—H6	0.9300
H11W—O1W—H12W	108.00	C4B—C5B—C6B	120.8 (5)
C11A—N11A—H13A	110.00	C1B—C6B—C5B	120.2 (5)
C11A—N11A—H11A	111.00	N11B—C11B—C1B	113.3 (4)
H12A—N11A—H13A	105.00	C1B—C2B—H2B	120.00
H11A—N11A—H13A	114.00	C3B—C2B—H2B	120.00
H11A—N11A—H12A	111.00	C4B—C3B—H3B	120.00
C11A—N11A—H12A	106.00	C2B—C3B—H3B	120.00
C11B—N11B—H11B	115.00	C3B—C4B—H4B	120.00
H12B—N11B—H13B	112.00	C5B—C4B—H4B	120.00
C11B—N11B—H13B	108.00	C4B—C5B—H5B	120.00
H11B—N11B—H13B	110.00	C6B—C5B—H5B	120.00
C11B—N11B—H12B	111.00	C5B—C6B—H6B	120.00
H11B—N11B—H12B	101.00	C1B—C6B—H6B	120.00
C6A—C1A—C11A	123.9 (4)	N11B—C11B—H15B	109.00
C2A—C1A—C11A	118.4 (4)	C1B—C11B—H14B	109.00
C2A—C1A—C6A	117.7 (5)	C1B—C11B—H15B	109.00
C1A—C2A—C3A	121.7 (5)	H14B—C11B—H15B	108.00
C2A—C3A—C4A	120.0 (5)	N11B—C11B—H14B	109.00
C3A—C4A—C5A	118.6 (5)	C2—C1—C6	119.2 (4)
C4A—C5A—C6A	121.9 (5)	C2—C1—C11	121.4 (3)
C1A—C6A—C5A	120.1 (4)	C6—C1—C11	119.3 (4)
N11A—C11A—C1A	114.8 (3)	C1—C2—C21	123.8 (3)
C3A—C2A—H2A	119.00	C3—C2—C21	116.9 (3)
C1A—C2A—H2A	119.00	C1—C2—C3	119.3 (4)
C2A—C3A—H3A	120.00	C2—C3—C4	120.9 (4)
C4A—C3A—H3A	120.00	Cl4—C4—C3	119.2 (3)
C3A—C4A—H4A	121.00	Cl4—C4—C5	121.0 (3)
C5A—C4A—H4A	121.00	C3—C4—C5	119.8 (4)
C4A—C5A—H5A	119.00	Cl5—C5—C6	119.1 (3)
C6A—C5A—H5A	119.00	C4—C5—C6	119.9 (4)
C1A—C6A—H6A	120.00	Cl5—C5—C4	121.0 (4)
C5A—C6A—H6A	120.00	C1—C6—C5	120.8 (4)
H14A—C11A—H15A	108.00	O11—C11—C1	116.3 (4)
N11A—C11A—H14A	109.00	O12—C11—C1	118.2 (4)
N11A—C11A—H15A	109.00	O11—C11—O12	125.5 (5)
C1A—C11A—H14A	109.00	O21—C21—C2	117.7 (3)
C1A—C11A—H15A	109.00	O22—C21—C2	117.5 (3)
C2B—C1B—C6B	118.6 (5)	O21—C21—O22	124.7 (4)
C2B—C1B—C11B	119.8 (4)	C2—C3—H3	120.00
C6B—C1B—C11B	121.6 (4)	C4—C3—H3	119.00
C1B—C2B—C3B	120.6 (5)	C1—C6—H6	120.00
C2B—C3B—C4B	120.5 (5)	C5—C6—H6	120.00
C3B—C4B—C5B	119.2 (5)
C6A—C1A—C2A—C3A	1.6 (7)	C11—C1—C2—C3	−179.5 (4)
C11A—C1A—C2A—C3A	−179.5 (4)	C11—C1—C2—C21	1.4 (6)
C2A—C1A—C6A—C5A	−0.6 (6)	C2—C1—C6—C5	0.9 (6)
C11A—C1A—C6A—C5A	−179.4 (4)	C11—C1—C6—C5	179.6 (4)
C2A—C1A—C11A—N11A	177.6 (4)	C2—C1—C11—O11	−157.7 (4)
C6A—C1A—C11A—N11A	−3.6 (6)	C2—C1—C11—O12	22.4 (6)
C1A—C2A—C3A—C4A	−1.5 (8)	C6—C1—C11—O11	23.6 (6)
C2A—C3A—C4A—C5A	0.4 (8)	C6—C1—C11—O12	−156.3 (4)
C3A—C4A—C5A—C6A	0.6 (8)	C1—C2—C3—C4	−0.5 (6)
C4A—C5A—C6A—C1A	−0.5 (7)	C21—C2—C3—C4	178.6 (3)
C6B—C1B—C2B—C3B	−1.1 (6)	C1—C2—C21—O21	78.1 (5)
C11B—C1B—C2B—C3B	178.3 (4)	C1—C2—C21—O22	−106.7 (5)
C2B—C1B—C6B—C5B	1.0 (7)	C3—C2—C21—O21	−101.0 (4)
C11B—C1B—C6B—C5B	−178.4 (4)	C3—C2—C21—O22	74.2 (5)
C2B—C1B—C11B—N11B	130.6 (4)	C2—C3—C4—Cl4	−177.0 (3)
C6B—C1B—C11B—N11B	−50.1 (5)	C2—C3—C4—C5	1.8 (6)
C1B—C2B—C3B—C4B	0.4 (7)	Cl4—C4—C5—Cl5	−2.6 (5)
C2B—C3B—C4B—C5B	0.3 (7)	Cl4—C4—C5—C6	177.0 (3)
C3B—C4B—C5B—C6B	−0.4 (7)	C3—C4—C5—Cl5	178.6 (3)
C4B—C5B—C6B—C1B	−0.3 (7)	C3—C4—C5—C6	−1.8 (6)
C6—C1—C2—C3	−0.8 (6)	Cl5—C5—C6—C1	−180.0 (3)
C6—C1—C2—C21	−179.9 (4)	C4—C5—C6—C1	0.4 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N11A—H11A···O21	0.87	2.01	2.866 (4)	168
N11A—H12A···O12i	0.90	1.90	2.801 (5)	180
N11A—H13A···O22ii	0.88	1.94	2.816 (4)	175
N11B—H11B···O11i	0.88	1.96	2.823 (4)	167
N11B—H12B···O21	0.96	1.85	2.770 (4)	160
N11B—H13B···O22iii	0.82	1.99	2.803 (4)	172
O1W—H11W···O11i	0.85	1.94	2.789 (4)	179
O1W—H12W···O12	0.76	2.28	2.980 (4)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11A—H11A⋯O21	0.87	2.01	2.866 (4)	168
N11A—H12A⋯O12i	0.90	1.90	2.801 (5)	180
N11A—H13A⋯O22ii	0.88	1.94	2.816 (4)	175
N11B—H11B⋯O11i	0.88	1.96	2.823 (4)	167
N11B—H12B⋯O21	0.96	1.85	2.770 (4)	160
N11B—H13B⋯O22iii	0.82	1.99	2.803 (4)	172
O1W—H11W⋯O11i	0.85	1.94	2.789 (4)	179
O1W—H12W⋯O12	0.76	2.28	2.980 (4)	154

Symmetry codes: (i) ; (ii) ; (iii) .