4-Meth-oxy-anilinium 2-carb-oxy-4,5-di-chloro-benzoate.

In the title salt C7H10NO(+)·C8H3Cl2O4 (-) the benzene rings of the cation and anion are essentially parallel [inter-ring dihedral angle 4.8 (2)°]. In the anion the carb-oxy-lic acid and carboxyl-ate groups make dihedral angles of 19.0 (2) and 79.5 (2)°, respectively, with the benzene ring. Aminium N-H⋯O, carb-oxy-lic acid O-H⋯O and weak aromatic C-H⋯O hydrogen-bonding associations with carboxyl O-atom acceptors together with cation-anion π-π ring inter-actions [minimum ring centroid separation = 3.734 (3) Å] give rise to a sheet structure lying parallel to (001).

Related literature

For background to 4,5-di­chloro­phthalate salts, see: Mattes & Dorau (1986 ▶); Smith et al. (2008a ▶). For structures of some 1:1 anilinium salts of 4,5-di­chloro­phthalic acid, see: Odabaşoğlu & Büyükgüngör (2007 ▶); Smith et al. (2008b ▶); Smith et al. (2009 ▶). For the structure of a dianionic 4,5-di­chloro­phthalate salt, see: Smith & Wermuth (2012 ▶).

Experimental

Crystal data

C7H10NO+·C8H3Cl2O4 −

M = 358.16

Orthorhombic,

a = 7.5319 (8) Å

b = 12.9302 (14) Å

c = 32.3268 (18) Å

V = 3148.3 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.44 mm−1

T = 200 K

0.35 × 0.30 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO, Agilent, 2012 ▶) T min = 0.759, T max = 0.980

6518 measured reflections

2730 independent reflections

2620 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.117

S = 1.42

2730 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.33 e Å−3

Absolute structure: Flack (1983 ▶), 1569 Friedel pairs

Absolute structure parameter: 0.03 (13)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within ORTEP-3 for Windows (Farrugia, 2012 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813025014/sj5350sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025014/sj5350Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813025014/sj5350Isup3.cml

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

C7H10NO+·C8H3Cl2O4−	Dx = 1.511 Mg m−3
Mr = 358.16	Melting point: 473 K
Orthorhombic, C2221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 2436 reflections
a = 7.5319 (8) Å	θ = 3.7–28.1°
b = 12.9302 (14) Å	µ = 0.44 mm−1
c = 32.3268 (18) Å	T = 200 K
V = 3148.3 (5) Å3	Plate, colourless
Z = 8	0.35 × 0.30 × 0.15 mm
F(000) = 1472

Oxford Diffraction Gemini-S CCD-detector diffractometer	2730 independent reflections
Radiation source: Enhance (Mo) X-ray source	2620 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 16.077 pixels mm-1	θmax = 25.0°, θmin = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO, Agilent, 2012)	k = −15→16
Tmin = 0.759, Tmax = 0.980	l = −38→38
6518 measured reflections

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)] = 0.067	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0003P)2 + 10.2538P] where P = (Fo2 + 2Fc2)/3
S = 1.42	(Δ/σ)max = 0.001
2730 reflections	Δρmax = 0.32 e Å−3
208 parameters	Δρmin = −0.33 e Å−3
0 restraints	Absolute structure: Flack (1983), 1569 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (13)

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
Cl4	1.0614 (2)	0.04524 (14)	0.69649 (4)	0.0504 (5)
Cl5	0.6536 (2)	0.09989 (13)	0.70946 (4)	0.0482 (5)
O11	0.5402 (5)	0.1011 (3)	0.53015 (10)	0.0269 (11)
O12	0.5633 (4)	0.2669 (2)	0.54919 (9)	0.0213 (10)
O21	0.9047 (5)	0.1895 (3)	0.51574 (10)	0.0281 (11)
O22	1.1354 (5)	0.0921 (3)	0.53458 (11)	0.0380 (12)
C1	0.7212 (6)	0.1407 (3)	0.58796 (14)	0.0170 (14)
C2	0.9001 (5)	0.1197 (3)	0.58236 (14)	0.0147 (12)
C3	1.0023 (7)	0.0889 (4)	0.61632 (14)	0.0240 (16)
C4	0.9274 (7)	0.0827 (4)	0.65531 (15)	0.0270 (17)
C5	0.7505 (8)	0.1047 (4)	0.66078 (13)	0.0263 (16)
C6	0.6454 (7)	0.1346 (4)	0.62745 (13)	0.0233 (16)
C11	0.6000 (6)	0.1710 (4)	0.55224 (14)	0.0163 (12)
C21	0.9909 (6)	0.1314 (3)	0.54121 (15)	0.0200 (16)
O4A	1.2905 (6)	0.3233 (4)	0.67922 (14)	0.0607 (19)
N1A	0.8469 (5)	0.4080 (3)	0.54416 (11)	0.0233 (11)
C1A	0.9599 (6)	0.3876 (3)	0.58068 (14)	0.0203 (14)
C2A	1.1396 (7)	0.3733 (4)	0.57540 (15)	0.0270 (17)
C3A	1.2440 (8)	0.3499 (4)	0.60887 (18)	0.0350 (17)
C4A	1.1695 (8)	0.3463 (4)	0.64817 (18)	0.0333 (19)
C5A	0.9921 (8)	0.3605 (5)	0.65369 (16)	0.037 (2)
C6A	0.8838 (7)	0.3818 (4)	0.61917 (15)	0.0270 (17)
C41A	1.2233 (11)	0.3165 (6)	0.71999 (19)	0.072 (3)
H3	1.12410	0.07220	0.61260	0.0290*
H6	0.52360	0.15070	0.63140	0.0280*
H21	0.96620	0.20640	0.49100	0.0420*
H2A	1.19110	0.37960	0.54870	0.0320*
H3A	1.36690	0.33630	0.60520	0.0420*
H5A	0.94160	0.35610	0.68060	0.0450*
H6A	0.75970	0.39200	0.62250	0.0330*
H11A	0.80350	0.46520	0.54470	0.0280*
H12A	0.89410	0.40030	0.51980	0.0280*
H13A	0.75460	0.35580	0.54990	0.0280*
H41A	1.32010	0.29960	0.73910	0.1080*
H42A	1.13250	0.26230	0.72130	0.1080*
H43A	1.17060	0.38290	0.72790	0.1080*

	U11	U22	U33	U12	U13	U23
Cl4	0.0580 (10)	0.0630 (11)	0.0301 (7)	0.0060 (9)	−0.0209 (7)	0.0088 (7)
Cl5	0.0724 (11)	0.0539 (10)	0.0182 (6)	0.0038 (9)	0.0077 (7)	0.0036 (7)
O11	0.031 (2)	0.0218 (18)	0.0280 (17)	−0.0087 (16)	−0.0101 (16)	0.0035 (16)
O12	0.0197 (18)	0.0207 (18)	0.0236 (16)	0.0035 (15)	−0.0036 (15)	0.0038 (14)
O21	0.027 (2)	0.036 (2)	0.0213 (17)	0.0074 (17)	0.0072 (15)	0.0107 (15)
O22	0.030 (2)	0.044 (2)	0.040 (2)	0.017 (2)	0.0067 (18)	0.0123 (19)
C1	0.026 (3)	0.005 (2)	0.020 (2)	−0.0021 (19)	−0.003 (2)	0.0001 (19)
C2	0.010 (2)	0.006 (2)	0.028 (2)	0.0044 (18)	0.0030 (19)	0.0034 (18)
C3	0.028 (3)	0.014 (2)	0.030 (3)	−0.006 (2)	−0.008 (2)	0.001 (2)
C4	0.038 (3)	0.014 (3)	0.029 (3)	0.006 (2)	−0.016 (3)	0.003 (2)
C5	0.041 (3)	0.022 (3)	0.016 (2)	0.000 (3)	−0.002 (2)	0.002 (2)
C6	0.024 (3)	0.022 (3)	0.024 (2)	0.000 (2)	−0.001 (2)	0.000 (2)
C11	0.007 (2)	0.019 (2)	0.023 (2)	−0.0040 (19)	0.0051 (18)	0.005 (2)
C21	0.016 (3)	0.011 (2)	0.033 (3)	−0.003 (2)	0.002 (2)	0.006 (2)
O4A	0.061 (3)	0.075 (4)	0.046 (3)	0.013 (3)	−0.024 (2)	0.010 (2)
N1A	0.027 (2)	0.020 (2)	0.0228 (19)	−0.0015 (19)	0.0007 (18)	0.0026 (18)
C1A	0.028 (3)	0.007 (2)	0.026 (2)	−0.006 (2)	−0.003 (2)	−0.001 (2)
C2A	0.022 (3)	0.026 (3)	0.033 (3)	−0.001 (2)	0.003 (2)	0.002 (2)
C3A	0.030 (3)	0.027 (3)	0.048 (3)	−0.001 (3)	−0.004 (3)	0.000 (3)
C4A	0.039 (4)	0.019 (3)	0.042 (3)	−0.003 (3)	−0.018 (3)	0.004 (2)
C5A	0.054 (4)	0.038 (4)	0.020 (3)	−0.004 (3)	0.002 (2)	0.002 (2)
C6A	0.033 (3)	0.016 (3)	0.032 (3)	0.003 (2)	0.004 (2)	−0.002 (2)
C41A	0.108 (7)	0.065 (5)	0.043 (4)	−0.007 (5)	−0.030 (4)	0.016 (4)

Cl4—C4	1.739 (5)	C3—C4	1.383 (7)
Cl5—C5	1.736 (5)	C4—C5	1.374 (8)
O11—C11	1.237 (6)	C5—C6	1.392 (7)
O12—C11	1.274 (6)	C3—H3	0.9500
O21—C21	1.290 (6)	C6—H6	0.9500
O22—C21	1.220 (6)	C1A—C6A	1.372 (7)
O21—H21	0.9500	C1A—C2A	1.377 (7)
O4A—C41A	1.415 (8)	C2A—C3A	1.371 (8)
O4A—C4A	1.388 (7)	C3A—C4A	1.390 (8)
N1A—C1A	1.479 (6)	C4A—C5A	1.361 (9)
N1A—H13A	0.9900	C5A—C6A	1.409 (7)
N1A—H11A	0.8100	C2A—H2A	0.9500
N1A—H12A	0.8700	C3A—H3A	0.9500
C1—C11	1.523 (6)	C5A—H5A	0.9500
C1—C6	1.401 (6)	C6A—H6A	0.9500
C1—C2	1.386 (6)	C41A—H41A	0.9800
C2—C3	1.399 (6)	C41A—H42A	0.9800
C2—C21	1.503 (6)	C41A—H43A	0.9800
C21—O21—H21	115.00	C2—C3—H3	120.00
C4A—O4A—C41A	116.9 (5)	C4—C3—H3	120.00
H11A—N1A—H12A	107.00	C1—C6—H6	120.00
C1A—N1A—H13A	98.00	C5—C6—H6	120.00
H12A—N1A—H13A	112.00	C2A—C1A—C6A	121.1 (4)
H11A—N1A—H13A	110.00	N1A—C1A—C6A	119.6 (4)
C1A—N1A—H12A	118.00	N1A—C1A—C2A	119.4 (4)
C1A—N1A—H11A	112.00	C1A—C2A—C3A	119.7 (5)
C2—C1—C11	122.3 (4)	C2A—C3A—C4A	119.8 (5)
C6—C1—C11	117.5 (4)	O4A—C4A—C3A	113.8 (5)
C2—C1—C6	120.3 (4)	O4A—C4A—C5A	125.4 (5)
C1—C2—C21	122.5 (4)	C3A—C4A—C5A	120.8 (5)
C1—C2—C3	119.2 (4)	C4A—C5A—C6A	119.4 (5)
C3—C2—C21	118.2 (4)	C1A—C6A—C5A	119.1 (5)
C2—C3—C4	120.5 (5)	C1A—C2A—H2A	120.00
C3—C4—C5	120.1 (5)	C3A—C2A—H2A	120.00
Cl4—C4—C3	118.5 (4)	C2A—C3A—H3A	120.00
Cl4—C4—C5	121.5 (4)	C4A—C3A—H3A	120.00
Cl5—C5—C6	118.2 (4)	C4A—C5A—H5A	120.00
C4—C5—C6	120.6 (4)	C6A—C5A—H5A	120.00
Cl5—C5—C4	121.1 (4)	C1A—C6A—H6A	120.00
C1—C6—C5	119.3 (5)	C5A—C6A—H6A	120.00
O11—C11—O12	126.0 (4)	O4A—C41A—H41A	110.00
O11—C11—C1	117.9 (4)	O4A—C41A—H42A	110.00
O12—C11—C1	116.0 (4)	O4A—C41A—H43A	109.00
O21—C21—O22	125.4 (5)	H41A—C41A—H42A	109.00
O21—C21—C2	113.2 (4)	H41A—C41A—H43A	109.00
O22—C21—C2	121.3 (4)	H42A—C41A—H43A	109.00
C41A—O4A—C4A—C5A	−1.5 (9)	C2—C3—C4—Cl4	−179.4 (4)
C41A—O4A—C4A—C3A	−178.9 (5)	C2—C3—C4—C5	1.4 (8)
C6—C1—C2—C21	−176.1 (4)	Cl4—C4—C5—C6	180.0 (4)
C6—C1—C2—C3	2.2 (6)	C3—C4—C5—Cl5	−178.8 (4)
C2—C1—C6—C5	−1.6 (7)	Cl4—C4—C5—Cl5	2.0 (7)
C11—C1—C6—C5	178.4 (4)	C3—C4—C5—C6	−0.8 (8)
C2—C1—C11—O11	81.2 (6)	C4—C5—C6—C1	0.9 (8)
C2—C1—C11—O12	−101.9 (5)	Cl5—C5—C6—C1	179.0 (4)
C6—C1—C11—O11	−98.9 (5)	N1A—C1A—C2A—C3A	−177.2 (4)
C11—C1—C2—C3	−177.8 (4)	C6A—C1A—C2A—C3A	1.9 (7)
C11—C1—C2—C21	3.8 (6)	N1A—C1A—C6A—C5A	178.9 (5)
C6—C1—C11—O12	78.0 (5)	C2A—C1A—C6A—C5A	−0.2 (7)
C1—C2—C21—O21	19.1 (6)	C1A—C2A—C3A—C4A	−3.5 (8)
C1—C2—C21—O22	−163.9 (4)	C2A—C3A—C4A—O4A	−179.1 (5)
C21—C2—C3—C4	176.3 (4)	C2A—C3A—C4A—C5A	3.4 (8)
C3—C2—C21—O22	17.8 (6)	O4A—C4A—C5A—C6A	−178.9 (5)
C3—C2—C21—O21	−159.3 (4)	C3A—C4A—C5A—C6A	−1.7 (9)
C1—C2—C3—C4	−2.1 (7)	C4A—C5A—C6A—C1A	0.1 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11i	0.81	2.55	2.926 (5)	110
N1A—H11A···O22ii	0.81	2.10	2.881 (5)	163
N1A—H12A···O11iii	0.87	1.95	2.811 (5)	168
N1A—H13A···O12	0.99	1.84	2.814 (5)	167
O21—H21···O12iii	0.95	1.53	2.480 (4)	179
C3A—H3A···O12iv	0.95	2.50	3.265 (7)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H11A⋯O22i	0.81	2.10	2.881 (5)	163
N1A—H12A⋯O11ii	0.87	1.95	2.811 (5)	168
N1A—H13A⋯O12	0.99	1.84	2.814 (5)	167
O21—H21⋯O12ii	0.95	1.53	2.480 (4)	179
C3A—H3A⋯O12iii	0.95	2.50	3.265 (7)	137

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