Methanaminium 3,4,5,6-tetra­chloro-2-(meth­oxy­carbon­yl)benzoate

Li, J.

doi:10.1107/S1600536811004351

organic compounds

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Volume 67| Part 3| March 2011| Page o605

doi:10.1107/S1600536811004351

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Methanaminium 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate

Jian Li ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ljwfu@163.com

(Received 22 January 2011; accepted 5 February 2011; online 12 February 2011)

In the crystal structure of the title compound, CH₆N⁺·C₉H₃Cl₄O₄⁻, the N atom of the methylamine molecule is protonated and hydrogen bonded to the carboxyl group of the 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate anion. The anions are linked by the cations via intermolecular N—H⋯O interactions into chains extending along the c axis.

Related literature

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

Experimental

Crystal data

CH₆N⁺·C₉H₃Cl₄O₄⁻
M_r = 348.98
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.092
S = 1.06
2413 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.26 e Å⁻³

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) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

Crystals of the title compound were obtained by accident by the reaction of 2-(methoxycarbonyl)-3,4,5,6-tetrachlorobenzoic acid and methanamine in methanol. To identify the product of this reaction a single crystal structure analysis was performed.

The asymmetric unit of the title compound (I) contains one methylammonium cation and one 2-(methoxycarbonyl)-3,4,5,6-tetrachlorobenzoate anion (Fig. 1). The bond lengths and angles are in agreement with those in ethylammonium 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate methanol solvate (Li, 2011) and in ethane-1,2-diammonium bis(2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate) methanol solvate (Liang, 2008). In the crystal structure the cations and anions are connected by intermolecular N—H···O hydrogen bonding into chains that elongate in the direction of the crystallographic c-axis (Fig. 2). Moreover, short distances between chlorine and oxygen atoms are found indicating for intermolecular Cl—O interactions (Fig. 2).

Related literature top

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

Experimental top

A mixture of 2-(methoxycarbonyl)-3,4,5,6-tetrachlorobenzoic acid (2.86 g, 0.01 mol) and methanol (15 ml) was refluxed for 0.5 h. Afterwards methanamine (0.45 g, 0.01 mol) was added and the mixture was stirred for 10 min at room temperature. The solution was kept at room temperature for 5 d. On solvent evaporation colourless single crystals of the title compound were obtained that are suitable for X-ray analysis.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with labelling and 30% probability ellipsoids.
	Fig. 2. Crystal structure of the title compound viewed along the c axis. Hydrogen bonding and Cl···O interactions are shown as dashed lines.

Methanaminium 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate top

Crystal data top

CH₆N⁺·C₉H₃Cl₄O₄⁻	F(000) = 704
M_r = 348.98	D_x = 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

Data collection top

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

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.036P)² + 0.764P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2413 reflections	Δρ_max = 0.27 e Å⁻³
176 parameters	Δρ_min = −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)

Crystal data top

CH₆N⁺·C₉H₃Cl₄O₄⁻	V = 1377.0 (2) Å³
M_r = 348.98	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.3138 (13) Å	µ = 0.87 mm⁻¹
b = 14.2231 (14) Å	T = 298 K
c = 6.7648 (7) Å	0.45 × 0.40 × 0.38 mm
β = 91.021 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2413 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1752 reflections with I > 2σ(I)
T_min = 0.697, T_max = 0.734	R_int = 0.034
6756 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.06	Δρ_max = 0.27 e Å⁻³
2413 reflections	Δρ_min = −0.26 e Å⁻³
176 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	CH₆N⁺·C₉H₃Cl₄O₄⁻
M_r	348.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.3138 (13), 14.2231 (14), 6.7648 (7)
β (°)	91.021 (1)
V (Å³)	1377.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.45 × 0.40 × 0.38

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.697, 0.734
No. of measured, independent and observed [I > 2σ(I)] reflections	6756, 2413, 1752
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.06
No. of reflections	2413
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.26

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2.

Acknowledgements

The author thanks Shandong Provincial Natural Science Foundation, China (ZR2009BL027) for support.

References

Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Liang, Z.-P. (2008). Acta Cryst. E64, o2416. Web of Science CSD CrossRef IUCr Journals Google Scholar
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