2-Methyl-anilinium 3,4,5,6-tetra-bromo-2-(meth-oxy-carbon-yl)benzoate methanol monosolvate.

In the anion of the title compound, C(7)H(10)N(+)·C(9)H(3)Br(4)O(4) (-)·CH(3)O, the dihedral angles formed by the benzene ring and the mean planes of the carboxyl-ate and meth-oxy-carbonyl groups are 74.8 (5) and 75.0 (5)°, respectively. In the crystal, inter-molecular N-H⋯O and O-H⋯O hydrogen bonds link the components into chains along [100]. Additional stabilization is provided by weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

C7H10N+·C9H3Br4O4 −·CH4O

M = 634.96

Monoclinic,

a = 8.1909 (8) Å

b = 13.5551 (12) Å

c = 19.5082 (16) Å

β = 90.371 (1)°

V = 2165.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 7.46 mm−1

T = 298 K

0.40 × 0.32 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.154, T max = 0.229

10672 measured reflections

3811 independent reflections

2507 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.072

S = 1.07

3811 reflections

248 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −0.59 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008543/lh5212sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008543/lh5212Isup2.hkl

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

C7H10N+·C9H3Br4O4−·CH4O	F(000) = 1224
Mr = 634.96	Dx = 1.947 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2873 reflections
a = 8.1909 (8) Å	θ = 2.6–23.9°
b = 13.5551 (12) Å	µ = 7.46 mm−1
c = 19.5082 (16) Å	T = 298 K
β = 90.371 (1)°	Block, colorless
V = 2165.9 (3) Å3	0.40 × 0.32 × 0.28 mm
Z = 4

Bruker SMART CCD diffractometer	3811 independent reflections
Radiation source: fine-focus sealed tube	2507 reflections with I > 2σ(I)
graphite	Rint = 0.055
φ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→9
Tmin = 0.154, Tmax = 0.229	k = −13→16
10672 measured reflections	l = −23→21

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0232P)2] where P = (Fo2 + 2Fc2)/3
3811 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

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
Br1	0.03655 (7)	0.49170 (4)	0.40325 (2)	0.03923 (16)
Br2	0.02019 (8)	0.40894 (4)	0.24560 (2)	0.05302 (19)
Br3	0.15610 (7)	0.18668 (4)	0.20996 (2)	0.05158 (18)
Br4	0.29944 (7)	0.04678 (4)	0.33723 (3)	0.05207 (19)
N1	0.3657 (5)	0.8858 (3)	0.05060 (18)	0.0390 (11)
H1A	0.3027	0.8481	0.0241	0.058*
H1B	0.4659	0.8882	0.0333	0.058*
H1C	0.3243	0.9464	0.0524	0.058*
O1	0.1935 (5)	0.0866 (3)	0.49814 (18)	0.0577 (11)
O2	0.4329 (5)	0.1646 (3)	0.5033 (2)	0.0712 (13)
O3	0.1279 (4)	0.3275 (2)	0.55173 (15)	0.0374 (9)
O4	0.3365 (4)	0.4141 (2)	0.51013 (15)	0.0386 (9)
O5	0.8267 (5)	0.2644 (3)	0.5294 (2)	0.0714 (12)
H5	0.9166	0.2887	0.5373	0.107*
C1	0.3034 (8)	0.1514 (4)	0.4786 (2)	0.0398 (14)
C2	0.2195 (6)	0.3546 (3)	0.5050 (2)	0.0268 (11)
C3	0.2381 (5)	0.2138 (3)	0.4200 (2)	0.0265 (11)
C4	0.1913 (5)	0.3107 (3)	0.4340 (2)	0.0242 (11)
C5	0.1213 (6)	0.3663 (3)	0.3820 (2)	0.0293 (12)
C6	0.1100 (6)	0.3289 (3)	0.3151 (2)	0.0297 (12)
C7	0.1649 (6)	0.2341 (4)	0.3009 (2)	0.0315 (12)
C8	0.2249 (6)	0.1765 (3)	0.3535 (2)	0.0326 (12)
C9	0.2418 (9)	0.0245 (5)	0.5563 (3)	0.104 (3)
H9A	0.3277	−0.0193	0.5425	0.156*
H9B	0.1496	−0.0134	0.5712	0.156*
H9C	0.2798	0.0654	0.5932	0.156*
C10	0.3726 (6)	0.8439 (4)	0.1201 (3)	0.0410 (14)
C11	0.4507 (7)	0.8936 (4)	0.1712 (3)	0.0450 (15)
C12	0.4626 (8)	0.8472 (5)	0.2352 (3)	0.0645 (19)
H12	0.5158	0.8790	0.2712	0.077*
C13	0.3973 (9)	0.7565 (6)	0.2453 (3)	0.078 (2)
H13	0.4090	0.7263	0.2878	0.094*
C14	0.3140 (9)	0.7084 (5)	0.1937 (4)	0.080 (2)
H14	0.2653	0.6475	0.2017	0.096*
C15	0.3040 (7)	0.7521 (4)	0.1297 (3)	0.0584 (17)
H15	0.2517	0.7199	0.0936	0.070*
C16	0.5220 (7)	0.9958 (4)	0.1608 (3)	0.0619 (17)
H16A	0.5957	0.9947	0.1227	0.093*
H16B	0.5799	1.0156	0.2015	0.093*
H16C	0.4354	1.0418	0.1516	0.093*
C17	0.7840 (9)	0.2058 (7)	0.5817 (4)	0.159 (5)
H17A	0.8389	0.1435	0.5776	0.238*
H17B	0.6681	0.1954	0.5806	0.238*
H17C	0.8145	0.2365	0.6242	0.238*

	U11	U22	U33	U12	U13	U23
Br1	0.0555 (4)	0.0286 (3)	0.0336 (3)	0.0129 (3)	0.0007 (2)	−0.0035 (2)
Br2	0.0803 (5)	0.0476 (4)	0.0309 (3)	0.0160 (3)	−0.0143 (3)	0.0012 (3)
Br3	0.0688 (4)	0.0524 (4)	0.0334 (3)	0.0099 (3)	−0.0113 (3)	−0.0209 (3)
Br4	0.0709 (5)	0.0284 (3)	0.0568 (4)	0.0109 (3)	−0.0097 (3)	−0.0151 (3)
N1	0.037 (3)	0.034 (3)	0.046 (3)	0.006 (2)	0.002 (2)	0.004 (2)
O1	0.076 (3)	0.041 (2)	0.056 (2)	−0.002 (2)	0.000 (2)	0.023 (2)
O2	0.066 (3)	0.076 (3)	0.071 (3)	0.000 (3)	−0.030 (2)	0.010 (2)
O3	0.046 (2)	0.037 (2)	0.0284 (18)	−0.0014 (17)	0.0035 (17)	0.0013 (16)
O4	0.042 (2)	0.038 (2)	0.0355 (19)	−0.0106 (19)	0.0016 (16)	−0.0121 (16)
O5	0.055 (3)	0.071 (3)	0.088 (3)	−0.016 (2)	−0.018 (2)	0.027 (3)
C1	0.053 (4)	0.030 (3)	0.036 (3)	0.004 (3)	−0.009 (3)	−0.009 (3)
C2	0.031 (3)	0.023 (3)	0.026 (3)	0.007 (3)	−0.004 (2)	−0.003 (2)
C3	0.029 (3)	0.022 (3)	0.029 (3)	−0.002 (2)	−0.005 (2)	−0.003 (2)
C4	0.023 (3)	0.026 (3)	0.023 (2)	−0.007 (2)	0.003 (2)	0.000 (2)
C5	0.029 (3)	0.029 (3)	0.029 (3)	−0.003 (2)	0.005 (2)	−0.001 (2)
C6	0.034 (3)	0.034 (3)	0.021 (2)	0.000 (2)	−0.003 (2)	0.000 (2)
C7	0.038 (3)	0.034 (3)	0.022 (2)	−0.004 (3)	−0.005 (2)	−0.013 (2)
C8	0.035 (3)	0.023 (3)	0.039 (3)	−0.003 (2)	−0.003 (2)	−0.005 (2)
C9	0.150 (8)	0.073 (5)	0.088 (5)	0.021 (5)	0.012 (5)	0.053 (4)
C10	0.036 (3)	0.044 (4)	0.043 (3)	0.015 (3)	0.012 (3)	0.009 (3)
C11	0.041 (4)	0.052 (4)	0.042 (3)	0.024 (3)	0.005 (3)	0.001 (3)
C12	0.081 (5)	0.066 (5)	0.047 (4)	0.033 (4)	0.008 (3)	0.000 (3)
C13	0.104 (6)	0.077 (6)	0.054 (4)	0.035 (5)	0.016 (4)	0.019 (4)
C14	0.085 (6)	0.055 (5)	0.100 (6)	0.006 (4)	0.031 (5)	0.031 (4)
C15	0.066 (5)	0.050 (4)	0.060 (4)	0.002 (3)	0.011 (3)	0.009 (3)
C16	0.061 (4)	0.065 (4)	0.060 (4)	0.010 (3)	−0.006 (3)	−0.011 (3)
C17	0.097 (7)	0.290 (13)	0.089 (6)	−0.103 (8)	−0.040 (5)	0.090 (7)

Br1—C5	1.883 (5)	C7—C8	1.376 (6)
Br2—C6	1.883 (4)	C9—H9A	0.9600
Br3—C7	1.889 (4)	C9—H9B	0.9600
Br4—C8	1.889 (5)	C9—H9C	0.9600
N1—C10	1.471 (6)	C10—C11	1.359 (7)
N1—H1A	0.8900	C10—C15	1.379 (7)
N1—H1B	0.8900	C11—C12	1.402 (7)
N1—H1C	0.8900	C11—C16	1.518 (7)
O1—C1	1.315 (6)	C12—C13	1.356 (8)
O1—C9	1.464 (6)	C12—H12	0.9300
O2—C1	1.176 (6)	C13—C14	1.377 (9)
O3—C2	1.239 (5)	C13—H13	0.9300
O4—C2	1.256 (5)	C14—C15	1.383 (8)
O5—C17	1.341 (7)	C14—H14	0.9300
O5—H5	0.8200	C15—H15	0.9300
C1—C3	1.517 (6)	C16—H16A	0.9600
C2—C4	1.525 (6)	C16—H16B	0.9600
C3—C4	1.395 (6)	C16—H16C	0.9600
C3—C8	1.397 (6)	C17—H17A	0.9600
C4—C5	1.385 (6)	C17—H17B	0.9600
C5—C6	1.403 (6)	C17—H17C	0.9600
C6—C7	1.390 (6)
C10—N1—H1A	109.5	H9A—C9—H9B	109.5
C10—N1—H1B	109.5	O1—C9—H9C	109.5
H1A—N1—H1B	109.5	H9A—C9—H9C	109.5
C10—N1—H1C	109.5	H9B—C9—H9C	109.5
H1A—N1—H1C	109.5	C11—C10—C15	122.6 (5)
H1B—N1—H1C	109.5	C11—C10—N1	120.0 (5)
C1—O1—C9	115.2 (5)	C15—C10—N1	117.4 (5)
C17—O5—H5	109.5	C10—C11—C12	117.4 (5)
O2—C1—O1	126.9 (5)	C10—C11—C16	122.3 (5)
O2—C1—C3	122.4 (5)	C12—C11—C16	120.3 (6)
O1—C1—C3	110.6 (5)	C13—C12—C11	120.7 (6)
O3—C2—O4	126.6 (4)	C13—C12—H12	119.7
O3—C2—C4	117.7 (4)	C11—C12—H12	119.7
O4—C2—C4	115.7 (4)	C12—C13—C14	121.2 (6)
C4—C3—C8	120.1 (4)	C12—C13—H13	119.4
C4—C3—C1	118.3 (4)	C14—C13—H13	119.4
C8—C3—C1	121.6 (4)	C13—C14—C15	118.9 (6)
C5—C4—C3	118.9 (4)	C13—C14—H14	120.6
C5—C4—C2	120.8 (4)	C15—C14—H14	120.6
C3—C4—C2	120.3 (4)	C10—C15—C14	119.2 (6)
C4—C5—C6	120.6 (4)	C10—C15—H15	120.4
C4—C5—Br1	118.8 (3)	C14—C15—H15	120.4
C6—C5—Br1	120.6 (3)	C11—C16—H16A	109.5
C7—C6—C5	120.0 (4)	C11—C16—H16B	109.5
C7—C6—Br2	121.0 (3)	H16A—C16—H16B	109.5
C5—C6—Br2	119.0 (3)	C11—C16—H16C	109.5
C8—C7—C6	119.4 (4)	H16A—C16—H16C	109.5
C8—C7—Br3	121.2 (4)	H16B—C16—H16C	109.5
C6—C7—Br3	119.4 (3)	O5—C17—H17A	109.5
C7—C8—C3	120.8 (4)	O5—C17—H17B	109.5
C7—C8—Br4	121.1 (3)	H17A—C17—H17B	109.5
C3—C8—Br4	118.0 (3)	O5—C17—H17C	109.5
O1—C9—H9A	109.5	H17A—C17—H17C	109.5
O1—C9—H9B	109.5	H17B—C17—H17C	109.5
C9—O1—C1—O2	−0.9 (8)	Br2—C6—C7—C8	−177.9 (4)
C9—O1—C1—C3	−178.0 (4)	C5—C6—C7—Br3	−177.7 (3)
O2—C1—C3—C4	−72.0 (7)	Br2—C6—C7—Br3	2.2 (6)
O1—C1—C3—C4	105.2 (5)	C6—C7—C8—C3	−2.9 (7)
O2—C1—C3—C8	107.7 (6)	Br3—C7—C8—C3	177.0 (3)
O1—C1—C3—C8	−75.1 (6)	C6—C7—C8—Br4	179.5 (3)
C8—C3—C4—C5	4.5 (7)	Br3—C7—C8—Br4	−0.6 (6)
C1—C3—C4—C5	−175.7 (4)	C4—C3—C8—C7	−0.5 (7)
C8—C3—C4—C2	−174.5 (4)	C1—C3—C8—C7	179.8 (5)
C1—C3—C4—C2	5.2 (7)	C4—C3—C8—Br4	177.2 (3)
O3—C2—C4—C5	106.2 (5)	C1—C3—C8—Br4	−2.5 (6)
O4—C2—C4—C5	−74.8 (6)	C15—C10—C11—C12	1.1 (8)
O3—C2—C4—C3	−74.8 (6)	N1—C10—C11—C12	−176.0 (4)
O4—C2—C4—C3	104.2 (5)	C15—C10—C11—C16	−178.3 (5)
C3—C4—C5—C6	−5.2 (7)	N1—C10—C11—C16	4.6 (8)
C2—C4—C5—C6	173.8 (4)	C10—C11—C12—C13	−0.4 (8)
C3—C4—C5—Br1	173.1 (3)	C16—C11—C12—C13	179.1 (6)
C2—C4—C5—Br1	−7.8 (6)	C11—C12—C13—C14	−1.7 (10)
C4—C5—C6—C7	1.9 (7)	C12—C13—C14—C15	3.0 (10)
Br1—C5—C6—C7	−176.4 (3)	C11—C10—C15—C14	0.2 (8)
C4—C5—C6—Br2	−178.0 (3)	N1—C10—C15—C14	177.4 (5)
Br1—C5—C6—Br2	3.7 (5)	C13—C14—C15—C10	−2.2 (9)
C5—C6—C7—C8	2.2 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5i	0.89	1.87	2.756 (6)	178
N1—H1B···O4i	0.89	1.87	2.746 (5)	170
O5—H5···O3ii	0.82	1.83	2.645 (5)	173
C15—H15···O5i	0.93	2.55	3.281 (7)	135
C17—H17B···O2	0.96	2.47	3.296 (9)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O5i	0.89	1.87	2.756 (6)	178
N1—H1B⋯O4i	0.89	1.87	2.746 (5)	170
O5—H5⋯O3ii	0.82	1.83	2.645 (5)	173
C15—H15⋯O5i	0.93	2.55	3.281 (7)	135
C17—H17B⋯O2	0.96	2.47	3.296 (9)	144

Symmetry codes: (i) ; (ii) .