4-Methyl-pyridinium 2-carb-oxy-4,5-dichloro-benzoate monohydrate.

In the structure of the 1:1 proton-transfer compound of 4-methyl-pyridine (γ-picoline) with 4,5-dichloro-phthalic acid, C(6)H(8)N(+)·C(8)H(3)Cl(2)O(4) (-)·H(2)O, determined at 200 K, the 4,5-dichloro-phthalate anions are bridged by the water mol-ecule through O-H⋯O(carbox-yl) hydrogen bonds, giving zigzag chains which extend along the c-axis direction. The 4-methyl-pyridinium cations are linked to the chains through single N-H⋯O(water) hydrogen bonds and occupy the voids within the chains in the one-dimensional structure. The anions have the common 'planar' conformation with a short intra-molecular O-H⋯O(carbox-yl) hydrogen bond.

Related literature

For the structures of other hydrogen 4,5-dichloro­phthalate salts, see: Mallinson et al. (2003 ▶); Bozkurt et al. (2006 ▶); Smith et al. (2007 ▶, 2008a ▶,b ▶, 2009 ▶, 2009a ▶,b ▶); Smith & Wermuth (2010a ▶,b ▶).

Experimental

Crystal data

C6H8N+·C8H3Cl2O4 −·H2O

M = 346.15

Monoclinic,

a = 3.8398 (3) Å

b = 29.5531 (17) Å

c = 12.9855 (7) Å

β = 90.054 (6)°

V = 1473.57 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.46 mm−1

T = 200 K

0.30 × 0.20 × 0.08 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.930, T max = 0.980

8898 measured reflections

2579 independent reflections

2156 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.129

S = 1.29

2579 reflections

215 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536810015503/jj2029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015503/jj2029Isup2.hkl

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

C6H8N+·C8H3Cl2O4−·H2O	F(000) = 712
Mr = 346.15	Dx = 1.560 Mg m−3
Monoclinic, P21/n	Melting point: 445 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 3.8398 (3) Å	Cell parameters from 4516 reflections
b = 29.5531 (17) Å	θ = 3.1–28.7°
c = 12.9855 (7) Å	µ = 0.46 mm−1
β = 90.054 (6)°	T = 200 K
V = 1473.57 (16) Å3	Plate, colourless
Z = 4	0.30 × 0.20 × 0.08 mm

Oxford Diffraction Gemini-S CCD-detector diffractometer	2579 independent reflections
Radiation source: Enhance (Mo) X-ray source	2156 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 16.08 pixels mm-1	θmax = 25.0°, θmin = 3.1°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −35→31
Tmin = 0.930, Tmax = 0.980	l = −15→15
8898 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)] = 0.045	Hydrogen site location: geom'
wR(F2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.29	w = 1/[σ2(Fo2) + (0.042P)2 + 1.7305P] where P = (Fo2 + 2Fc2)/3
2579 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.33 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 esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.1942 (3)	−0.02601 (3)	0.63754 (7)	0.0379 (3)
Cl5	−0.1079 (2)	0.00515 (3)	0.85706 (7)	0.0372 (3)
O11	0.0394 (8)	0.17470 (9)	0.8599 (2)	0.0471 (10)
O12	0.2068 (8)	0.20432 (9)	0.7127 (2)	0.0490 (10)
O21	0.4257 (8)	0.18118 (9)	0.5499 (2)	0.0504 (10)
O22	0.6118 (7)	0.11959 (9)	0.47323 (19)	0.0399 (9)
C1	0.1694 (8)	0.12249 (11)	0.7262 (2)	0.0233 (10)
C2	0.3066 (8)	0.10876 (11)	0.6304 (2)	0.0225 (10)
C3	0.3086 (8)	0.06268 (11)	0.6068 (2)	0.0249 (10)
C4	0.1817 (8)	0.03024 (11)	0.6731 (3)	0.0252 (10)
C5	0.0513 (8)	0.04386 (11)	0.7687 (2)	0.0252 (10)
C6	0.0428 (8)	0.08917 (11)	0.7929 (2)	0.0254 (10)
C11	0.1371 (9)	0.17020 (12)	0.7704 (3)	0.0328 (11)
C21	0.4622 (9)	0.13795 (12)	0.5446 (3)	0.0291 (11)
N1A	1.1032 (8)	0.19332 (11)	0.2708 (3)	0.0411 (11)
C2A	1.2276 (11)	0.21031 (13)	0.1826 (3)	0.0447 (14)
C3A	1.3735 (9)	0.18251 (13)	0.1103 (3)	0.0370 (12)
C4A	1.3940 (8)	0.13645 (12)	0.1288 (2)	0.0282 (10)
C5A	1.2671 (9)	0.12034 (12)	0.2211 (3)	0.0333 (11)
C6A	1.1180 (9)	0.14896 (14)	0.2913 (3)	0.0369 (11)
C41A	1.5391 (10)	0.10520 (15)	0.0494 (3)	0.0463 (14)
O1W	0.7863 (9)	0.23983 (11)	0.4193 (2)	0.0462 (10)
H3	0.39930	0.05350	0.54380	0.0300*
H6	−0.05070	0.09800	0.85580	0.0300*
H21	0.334 (15)	0.191 (2)	0.618 (5)	0.100 (19)*
H1A	1.012 (12)	0.211 (2)	0.315 (4)	0.049 (10)*
H2A	1.21470	0.24130	0.17040	0.0540*
H3A	1.45850	0.19450	0.04900	0.0450*
H5A	1.28280	0.08960	0.23580	0.0400*
H6A	1.02810	0.13770	0.35270	0.0440*
H41A	1.61710	0.12240	−0.00890	0.0560*
H42A	1.36170	0.08430	0.02790	0.0560*
H43A	1.73170	0.08870	0.07810	0.0560*
H11W	0.666 (13)	0.2227 (18)	0.449 (4)	0.065 (17)*
H12W	0.694 (11)	0.2626 (17)	0.405 (3)	0.046 (14)*

	U11	U22	U33	U12	U13	U23
Cl4	0.0516 (6)	0.0224 (4)	0.0396 (5)	−0.0018 (4)	0.0113 (4)	−0.0043 (4)
Cl5	0.0483 (5)	0.0316 (5)	0.0318 (5)	−0.0034 (4)	0.0108 (4)	0.0091 (4)
O11	0.074 (2)	0.0310 (15)	0.0363 (16)	−0.0029 (13)	0.0195 (14)	−0.0095 (12)
O12	0.084 (2)	0.0225 (14)	0.0406 (16)	0.0024 (13)	0.0133 (15)	0.0012 (12)
O21	0.083 (2)	0.0280 (15)	0.0403 (17)	−0.0001 (14)	0.0222 (15)	0.0098 (12)
O22	0.0534 (16)	0.0394 (15)	0.0269 (14)	0.0010 (12)	0.0122 (12)	0.0059 (11)
C1	0.0232 (17)	0.0233 (17)	0.0234 (17)	0.0009 (13)	−0.0027 (13)	0.0001 (13)
C2	0.0225 (16)	0.0244 (17)	0.0206 (17)	0.0021 (13)	−0.0019 (13)	0.0042 (13)
C3	0.0273 (17)	0.0264 (18)	0.0209 (16)	0.0014 (13)	0.0039 (13)	−0.0017 (13)
C4	0.0281 (17)	0.0212 (17)	0.0264 (17)	0.0023 (13)	0.0023 (13)	−0.0015 (13)
C5	0.0268 (17)	0.0249 (17)	0.0240 (17)	0.0002 (13)	0.0028 (13)	0.0057 (14)
C6	0.0256 (17)	0.0327 (19)	0.0179 (16)	0.0014 (14)	0.0017 (13)	−0.0036 (14)
C11	0.039 (2)	0.0253 (19)	0.034 (2)	0.0018 (15)	0.0015 (16)	−0.0026 (15)
C21	0.0315 (19)	0.032 (2)	0.0237 (18)	−0.0023 (14)	0.0016 (14)	0.0051 (15)
N1A	0.0374 (18)	0.043 (2)	0.043 (2)	0.0010 (14)	−0.0022 (15)	−0.0190 (16)
C2A	0.046 (2)	0.029 (2)	0.059 (3)	−0.0040 (17)	0.001 (2)	0.0014 (19)
C3A	0.037 (2)	0.040 (2)	0.034 (2)	−0.0036 (16)	0.0039 (16)	0.0114 (17)
C4A	0.0237 (17)	0.038 (2)	0.0228 (17)	−0.0011 (14)	−0.0019 (13)	−0.0018 (15)
C5A	0.0339 (19)	0.032 (2)	0.034 (2)	−0.0021 (15)	−0.0002 (16)	0.0050 (16)
C6A	0.036 (2)	0.050 (2)	0.0248 (19)	−0.0044 (17)	0.0016 (15)	0.0032 (17)
C41A	0.037 (2)	0.059 (3)	0.043 (2)	0.0042 (19)	0.0065 (18)	−0.013 (2)
O1W	0.078 (2)	0.0254 (16)	0.0352 (16)	0.0033 (16)	0.0159 (15)	0.0043 (13)

Cl4—C4	1.726 (3)	C3—C4	1.378 (5)
Cl5—C5	1.732 (3)	C4—C5	1.398 (5)
O11—C11	1.229 (5)	C5—C6	1.376 (5)
O12—C11	1.285 (5)	C3—H3	0.9300
O21—C21	1.287 (4)	C6—H6	0.9300
O22—C21	1.218 (5)	C2A—C3A	1.368 (5)
O21—H21	1.00 (6)	C3A—C4A	1.385 (5)
O1W—H12W	0.78 (5)	C4A—C5A	1.379 (5)
O1W—H11W	0.79 (5)	C4A—C41A	1.493 (5)
N1A—C6A	1.339 (5)	C5A—C6A	1.369 (5)
N1A—C2A	1.339 (5)	C2A—H2A	0.9300
N1A—H1A	0.85 (5)	C3A—H3A	0.9300
C1—C11	1.527 (5)	C5A—H5A	0.9300
C1—C6	1.399 (4)	C6A—H6A	0.9300
C1—C2	1.411 (4)	C41A—H43A	0.9600
C2—C3	1.396 (5)	C41A—H41A	0.9600
C2—C21	1.531 (5)	C41A—H42A	0.9600
C21—O21—H21	112 (3)	C4—C3—H3	119.00
H11W—O1W—H12W	114 (5)	C2—C3—H3	119.00
C2A—N1A—C6A	121.5 (4)	C1—C6—H6	119.00
C2A—N1A—H1A	120 (4)	C5—C6—H6	119.00
C6A—N1A—H1A	119 (4)	N1A—C2A—C3A	120.6 (4)
C2—C1—C11	128.9 (3)	C2A—C3A—C4A	119.7 (3)
C6—C1—C11	112.9 (3)	C3A—C4A—C41A	120.7 (3)
C2—C1—C6	118.3 (3)	C3A—C4A—C5A	118.1 (3)
C1—C2—C21	128.8 (3)	C5A—C4A—C41A	121.3 (3)
C3—C2—C21	112.8 (3)	C4A—C5A—C6A	120.9 (3)
C1—C2—C3	118.4 (3)	N1A—C6A—C5A	119.4 (4)
C2—C3—C4	122.7 (3)	C3A—C2A—H2A	120.00
C3—C4—C5	118.8 (3)	N1A—C2A—H2A	120.00
Cl4—C4—C3	119.5 (3)	C2A—C3A—H3A	120.00
Cl4—C4—C5	121.7 (3)	C4A—C3A—H3A	120.00
Cl5—C5—C4	121.7 (3)	C6A—C5A—H5A	120.00
C4—C5—C6	119.4 (3)	C4A—C5A—H5A	120.00
Cl5—C5—C6	118.9 (2)	N1A—C6A—H6A	120.00
C1—C6—C5	122.4 (3)	C5A—C6A—H6A	120.00
O12—C11—C1	119.2 (3)	C4A—C41A—H42A	109.00
O11—C11—C1	118.7 (3)	C4A—C41A—H43A	109.00
O11—C11—O12	122.1 (3)	C4A—C41A—H41A	110.00
O21—C21—O22	122.3 (3)	H41A—C41A—H43A	110.00
O21—C21—C2	118.5 (3)	H42A—C41A—H43A	109.00
O22—C21—C2	119.2 (3)	H41A—C41A—H42A	109.00
C2A—N1A—C6A—C5A	0.7 (5)	C1—C2—C21—O22	169.9 (3)
C6A—N1A—C2A—C3A	0.2 (6)	C1—C2—C3—C4	0.1 (5)
C6—C1—C2—C21	−179.6 (3)	C2—C3—C4—C5	−1.2 (5)
C11—C1—C2—C21	0.3 (5)	C2—C3—C4—Cl4	180.0 (3)
C2—C1—C6—C5	0.7 (5)	C3—C4—C5—Cl5	−179.2 (2)
C11—C1—C6—C5	−179.1 (3)	Cl4—C4—C5—Cl5	−0.4 (4)
C2—C1—C11—O11	−173.2 (3)	Cl4—C4—C5—C6	−179.2 (2)
C2—C1—C11—O12	8.0 (5)	C3—C4—C5—C6	2.0 (5)
C6—C1—C11—O11	6.7 (4)	C4—C5—C6—C1	−1.8 (5)
C11—C1—C2—C3	180.0 (3)	Cl5—C5—C6—C1	179.4 (2)
C6—C1—C11—O12	−172.2 (3)	N1A—C2A—C3A—C4A	−0.3 (6)
C6—C1—C2—C3	0.1 (4)	C2A—C3A—C4A—C5A	−0.5 (5)
C21—C2—C3—C4	179.9 (3)	C2A—C3A—C4A—C41A	177.6 (3)
C1—C2—C21—O21	−11.1 (5)	C41A—C4A—C5A—C6A	−176.6 (3)
C3—C2—C21—O21	169.2 (3)	C3A—C4A—C5A—C6A	1.5 (5)
C3—C2—C21—O22	−9.8 (4)	C4A—C5A—C6A—N1A	−1.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1W	0.85 (5)	1.82 (5)	2.663 (5)	170 (5)
O1W—H11W···O21	0.79 (5)	2.02 (5)	2.793 (4)	168 (5)
O1W—H12W···O11i	0.78 (5)	2.03 (5)	2.806 (4)	170 (4)
O21—H21···O12	1.00 (6)	1.38 (6)	2.376 (4)	180 (8)
C2A—H2A···O12i	0.93	2.59	3.243 (5)	128
C2A—H2A···O12ii	0.93	2.54	3.147 (5)	123
C6A—H6A···O22	0.93	2.30	3.181 (5)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O1W	0.85 (5)	1.82 (5)	2.663 (5)	170 (5)
O1W—H11W⋯O21	0.79 (5)	2.02 (5)	2.793 (4)	168 (5)
O1W—H12W⋯O11i	0.78 (5)	2.03 (5)	2.806 (4)	170 (4)
O21—H21⋯O12	1.00 (6)	1.38 (6)	2.376 (4)	180 (8)

Symmetry code: (i) .