Methanaminium 3,4,5,6-tetra-chloro-2-(meth-oxy-carbon-yl)benzoate.

In the crystal structure of the title compound, CH(6)N(+)·C(9)H(3)Cl(4)O(4) (-), the N atom of the methyl-amine mol-ecule is protonated and hydrogen bonded to the carboxyl group of the 3,4,5,6-tetra-chloro-2-(meth-oxy-carbon-yl)benzoate anion. The anions are linked by the cations via inter-molecular N-H⋯O inter-actions into chains extending along the c axis.

Related literature

For related structures, see: Li (2011 ▶); Liang (2008 ▶).

Experimental

Crystal data

CH6N+·C9H3Cl4O4 −

M = 348.98

Monoclinic,

a = 14.3138 (13) Å

b = 14.2231 (14) Å

c = 6.7648 (7) Å

β = 91.021 (1)°

V = 1377.0 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.87 mm−1

T = 298 K

0.45 × 0.40 × 0.38 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.697, T max = 0.734

6756 measured reflections

2413 independent reflections

1752 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.092

S = 1.06

2413 reflections

176 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004351/nc2219sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004351/nc2219Isup2.hkl

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

CH6N+·C9H3Cl4O4−	F(000) = 704
Mr = 348.98	Dx = 1.683 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.3138 (13) Å	Cell parameters from 2427 reflections
b = 14.2231 (14) Å	θ = 2.9–27.9°
c = 6.7648 (7) Å	µ = 0.87 mm−1
β = 91.021 (1)°	T = 298 K
V = 1377.0 (2) Å3	Block, colorless
Z = 4	0.45 × 0.40 × 0.38 mm

Bruker SMART CCD area-detector diffractometer	2413 independent reflections
Radiation source: fine-focus sealed tube	1752 reflections with I > 2σ(I)
graphite	Rint = 0.034
phi and ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −10→17
Tmin = 0.697, Tmax = 0.734	k = −16→15
6756 measured reflections	l = −8→7

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)] = 0.034	H-atom parameters constrained
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.036P)2 + 0.764P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2413 reflections	Δρmax = 0.27 e Å−3
176 parameters	Δρmin = −0.26 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0169 (12)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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
Cl1	0.59548 (5)	0.44954 (5)	0.68418 (11)	0.0403 (2)
Cl2	0.75122 (6)	0.31368 (5)	0.83762 (13)	0.0504 (3)
Cl3	0.94431 (6)	0.31160 (6)	0.64018 (14)	0.0560 (3)
Cl4	0.97935 (5)	0.43587 (5)	0.26682 (13)	0.0498 (3)
N1	0.56810 (18)	0.82381 (16)	0.3492 (4)	0.0405 (6)
H1A	0.5878	0.8600	0.4489	0.061*
H1B	0.5950	0.8422	0.2382	0.061*
H1C	0.5832	0.7642	0.3743	0.061*
O1	0.82037 (15)	0.65000 (13)	0.1792 (3)	0.0405 (5)
O2	0.8307 (2)	0.52896 (16)	−0.0279 (3)	0.0647 (7)
O3	0.61656 (15)	0.57063 (15)	0.1743 (3)	0.0481 (6)
O4	0.62782 (14)	0.64439 (13)	0.4641 (3)	0.0408 (5)
C1	0.82003 (19)	0.5598 (2)	0.1337 (4)	0.0345 (7)
C2	0.64751 (19)	0.58072 (18)	0.3451 (4)	0.0303 (6)
C3	0.80417 (19)	0.50129 (17)	0.3163 (4)	0.0282 (6)
C4	0.71960 (19)	0.50884 (17)	0.4148 (4)	0.0269 (6)
C5	0.70398 (18)	0.44908 (17)	0.5740 (4)	0.0274 (6)
C6	0.77229 (19)	0.38691 (18)	0.6410 (4)	0.0303 (6)
C7	0.85805 (19)	0.38385 (18)	0.5494 (4)	0.0325 (7)
C8	0.87294 (19)	0.43961 (18)	0.3837 (4)	0.0327 (7)
C9	0.8303 (3)	0.7137 (2)	0.0141 (5)	0.0592 (10)
H9A	0.8873	0.7001	−0.0528	0.089*
H9B	0.8319	0.7773	0.0617	0.089*
H9C	0.7783	0.7061	−0.0760	0.089*
C10	0.4658 (2)	0.8321 (2)	0.3267 (5)	0.0543 (9)
H10A	0.4367	0.8127	0.4468	0.082*
H10B	0.4444	0.7928	0.2197	0.082*
H10C	0.4495	0.8963	0.2988	0.082*

	U11	U22	U33	U12	U13	U23
Cl1	0.0319 (4)	0.0426 (4)	0.0470 (5)	0.0041 (3)	0.0120 (3)	0.0124 (3)
Cl2	0.0489 (5)	0.0470 (5)	0.0554 (5)	0.0046 (4)	0.0012 (4)	0.0251 (4)
Cl3	0.0397 (5)	0.0524 (5)	0.0758 (6)	0.0189 (4)	−0.0053 (4)	0.0093 (4)
Cl4	0.0323 (4)	0.0515 (5)	0.0660 (6)	0.0021 (4)	0.0166 (4)	−0.0093 (4)
N1	0.0551 (17)	0.0323 (13)	0.0341 (14)	0.0043 (12)	−0.0040 (12)	−0.0006 (11)
O1	0.0548 (14)	0.0320 (11)	0.0350 (11)	−0.0030 (10)	0.0087 (10)	0.0036 (9)
O2	0.097 (2)	0.0604 (15)	0.0369 (14)	−0.0146 (14)	0.0208 (13)	−0.0099 (11)
O3	0.0471 (13)	0.0616 (14)	0.0352 (12)	0.0050 (11)	−0.0105 (10)	0.0095 (10)
O4	0.0451 (13)	0.0313 (11)	0.0462 (13)	0.0112 (9)	0.0059 (10)	0.0040 (9)
C1	0.0297 (16)	0.0423 (17)	0.0317 (17)	−0.0031 (13)	0.0049 (13)	−0.0011 (13)
C2	0.0264 (15)	0.0295 (15)	0.0352 (17)	0.0005 (12)	0.0043 (13)	0.0089 (13)
C3	0.0310 (15)	0.0240 (13)	0.0295 (15)	−0.0035 (12)	0.0012 (12)	−0.0042 (11)
C4	0.0284 (15)	0.0263 (14)	0.0261 (14)	−0.0004 (12)	−0.0011 (12)	−0.0018 (11)
C5	0.0226 (14)	0.0283 (14)	0.0314 (15)	−0.0005 (12)	0.0022 (12)	−0.0028 (12)
C6	0.0341 (16)	0.0252 (14)	0.0315 (15)	−0.0017 (12)	−0.0027 (13)	0.0011 (11)
C7	0.0260 (15)	0.0258 (14)	0.0454 (17)	0.0046 (12)	−0.0043 (13)	−0.0050 (12)
C8	0.0296 (15)	0.0294 (14)	0.0391 (17)	−0.0011 (12)	0.0060 (13)	−0.0095 (13)
C9	0.074 (3)	0.051 (2)	0.054 (2)	−0.0026 (19)	0.0147 (19)	0.0210 (17)
C10	0.055 (2)	0.054 (2)	0.053 (2)	0.0031 (17)	−0.0051 (18)	0.0001 (16)

Cl1—C5	1.734 (3)	C2—C4	1.521 (4)
Cl2—C6	1.720 (3)	C3—C8	1.389 (4)
Cl3—C7	1.712 (3)	C3—C4	1.396 (4)
Cl4—C8	1.729 (3)	C4—C5	1.393 (4)
N1—C10	1.475 (4)	C5—C6	1.388 (4)
N1—H1A	0.8900	C6—C7	1.386 (4)
N1—H1B	0.8900	C7—C8	1.393 (4)
N1—H1C	0.8900	C9—H9A	0.9600
O1—C1	1.319 (3)	C9—H9B	0.9600
O1—C9	1.447 (3)	C9—H9C	0.9600
O2—C1	1.191 (3)	C10—H10A	0.9600
O3—C2	1.238 (3)	C10—H10B	0.9600
O4—C2	1.247 (3)	C10—H10C	0.9600
C1—C3	1.510 (4)
C10—N1—H1A	109.5	C7—C6—C5	119.9 (2)
C10—N1—H1B	109.5	C7—C6—Cl2	119.7 (2)
H1A—N1—H1B	109.5	C5—C6—Cl2	120.4 (2)
C10—N1—H1C	109.5	C6—C7—C8	119.5 (3)
H1A—N1—H1C	109.5	C6—C7—Cl3	119.8 (2)
H1B—N1—H1C	109.5	C8—C7—Cl3	120.7 (2)
C1—O1—C9	115.4 (2)	C3—C8—C7	120.4 (2)
O2—C1—O1	124.9 (3)	C3—C8—Cl4	119.6 (2)
O2—C1—C3	124.9 (3)	C7—C8—Cl4	119.9 (2)
O1—C1—C3	110.2 (2)	O1—C9—H9A	109.5
O3—C2—O4	127.2 (3)	O1—C9—H9B	109.5
O3—C2—C4	116.1 (2)	H9A—C9—H9B	109.5
O4—C2—C4	116.6 (2)	O1—C9—H9C	109.5
C8—C3—C4	120.5 (2)	H9A—C9—H9C	109.5
C8—C3—C1	120.0 (2)	H9B—C9—H9C	109.5
C4—C3—C1	119.5 (2)	N1—C10—H10A	109.5
C5—C4—C3	118.3 (2)	N1—C10—H10B	109.5
C5—C4—C2	122.1 (2)	H10A—C10—H10B	109.5
C3—C4—C2	119.5 (2)	N1—C10—H10C	109.5
C6—C5—C4	121.3 (2)	H10A—C10—H10C	109.5
C6—C5—Cl1	119.5 (2)	H10B—C10—H10C	109.5
C4—C5—Cl1	119.2 (2)
C9—O1—C1—O2	3.0 (5)	C2—C4—C5—Cl1	5.4 (4)
C9—O1—C1—C3	−177.0 (3)	C4—C5—C6—C7	0.2 (4)
O2—C1—C3—C8	63.3 (4)	Cl1—C5—C6—C7	177.8 (2)
O1—C1—C3—C8	−116.7 (3)	C4—C5—C6—Cl2	−179.9 (2)
O2—C1—C3—C4	−115.9 (3)	Cl1—C5—C6—Cl2	−2.3 (3)
O1—C1—C3—C4	64.1 (3)	C5—C6—C7—C8	−3.6 (4)
C8—C3—C4—C5	−3.9 (4)	Cl2—C6—C7—C8	176.5 (2)
C1—C3—C4—C5	175.3 (2)	C5—C6—C7—Cl3	176.6 (2)
C8—C3—C4—C2	176.6 (2)	Cl2—C6—C7—Cl3	−3.3 (3)
C1—C3—C4—C2	−4.2 (4)	C4—C3—C8—C7	0.6 (4)
O3—C2—C4—C5	−118.0 (3)	C1—C3—C8—C7	−178.6 (2)
O4—C2—C4—C5	63.7 (3)	C4—C3—C8—Cl4	−176.7 (2)
O3—C2—C4—C3	61.5 (3)	C1—C3—C8—Cl4	4.1 (3)
O4—C2—C4—C3	−116.8 (3)	C6—C7—C8—C3	3.2 (4)
C3—C4—C5—C6	3.5 (4)	Cl3—C7—C8—C3	−177.0 (2)
C2—C4—C5—C6	−177.0 (2)	C6—C7—C8—Cl4	−179.5 (2)
C3—C4—C5—Cl1	−174.1 (2)	Cl3—C7—C8—Cl4	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3i	0.89	1.86	2.742 (3)	173
N1—H1B···O4ii	0.89	1.93	2.794 (3)	163
N1—H1C···O4	0.89	1.92	2.797 (3)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.89	1.86	2.742 (3)	173
N1—H1B⋯O4ii	0.89	1.93	2.794 (3)	163
N1—H1C⋯O4	0.89	1.92	2.797 (3)	170

Symmetry codes: (i) ; (ii) .