4-Methyl­anilinium 3,5-dinitro­benzoate

Xu, R.

doi:10.1107/S1600536810018441

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1574

doi:10.1107/S1600536810018441

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4-Methylanilinium 3,5-dinitrobenzoate

Rui-jun Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: youyoubanzhen@126.com

(Received 7 May 2010; accepted 18 May 2010; online 5 June 2010)

The crystal structure of the title compound, C₇H₁₀N⁺·C₇H₃N₂O₆⁻, displays N—H⋯O hydrogen bonding between the ammonium groups and the O atoms of the 3,5-dinitrobenzoate anions. Intermolecular C—H⋯O interactions further stabilize the packing. An O atom of each of the nitro groups is disordered over two sites with site occupancy factors of 0.59 (5) and 0.41 (6).

Related literature

For dielectric–ferroelectric properties, see: Li et al. (2008 ). For a related structure, see: Basaran et al. (1991 ).

Experimental

Crystal data

C₇H₁₀N⁺·C₇H₃N₂O₆⁻
M_r = 319.27
Orthorhombic, P b c a
a = 19.790 (4) Å
b = 7.2380 (14) Å
c = 20.473 (4) Å
V = 2932.5 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.978, T_max = 0.978
28284 measured reflections
3360 independent reflections
2368 reflections with I > 2.0 σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.159
S = 0.96
3360 reflections
230 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	1.94	2.803 (2)	163
N1—H1B⋯O1	0.89	1.90	2.761 (2)	163
N1—H1C⋯O2ⁱⁱ	0.89	2.22	3.045 (2)	153
N1—H1C⋯O1ⁱⁱ	0.89	2.24	3.030 (2)	147
C3—H3⋯O1ⁱⁱ	0.93	2.59	3.344 (3)	138
C13—H13⋯O3ⁱⁱⁱ	0.93	2.43	3.351 (7)	173
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810018441/pv2280sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810018441/pv2280Isup2.hkl

checkCIF report

Comment top

Probing the dielectric-ferroelectric properties of organic ligands (Li et al., 2008), the title compound has been prepared in our laboratory. In this article, the preparation and crystal structure of the title compound have been presented. A related structure, that of 4-tethylanilinium dichloroacetate, has been reported previously (Basaran et al., 1991).

The asymmetric unit of the title compound composes of a (CH₃—C₆H₄—NH₃⁺) cation and an (2(NO₂)-C₆H₃—COO^-) anion (Fig. 1). The strong N—H···O hydrogen bonds involving H1A and H1B (N1···O2 2.803 (2) and N1···O1 2.761 (2) Å) and the bifurcated hydrogen bonds involving H1C (N1···O2 3.045 (2) and N1···O1 3.030 (2) Å) are beneficial to the stability of the crystal structure (Fig. 2 and Tab. 1). Hydrogen bonds of the type C—H···O further stabilize the crystal structure.

Related literature top

For the dielectric–ferroelectric properties of organic ligands, see: Li et al. (2008). For a related structure, see: Basaran et al. (1991).

Experimental top

The title compound was obtained by the addition of 3,5-dinitrobenzoic acid (4.66 g, 0.022 mol) to a solution of 4-methylaniline (2.14 g, 0.02 mol) in ethanol, in the stoichiometric ratio 1.1:1. After two weeks, good quality single crystals were obtained by slow evaporation.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. O3' and O6' representing the smaller fractions of the disordered atoms have been excluded.
	Fig. 2. A view of the packing of the title compound, stacking along the b-axis. Dashed lines indicate hydrogen bonds.

4-methylanilinium 3,5-dinitrobenzoate top

Crystal data top

C₇H₁₀N⁺·C₇H₃N₂O₆⁻	F(000) = 1328
M_r = 319.27	D_x = 1.446 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 11511 reflections
a = 19.790 (4) Å	θ = 3.0–27.5°
b = 7.2380 (14) Å	µ = 0.12 mm⁻¹
c = 20.473 (4) Å	T = 293 K
V = 2932.5 (10) Å³	Prism, colorless
Z = 8	0.2 × 0.2 × 0.2 mm

Data collection top

Rigaku Mercury2 diffractometer	3360 independent reflections
Radiation source: fine-focus sealed tube	2368 reflections with I > 2.0 σ(I)
Graphite monochromator	R_int = 0.078
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −25→25
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.978, T_max = 0.978	l = −26→26
28284 measured reflections

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)] = 0.054	H-atom parameters constrained
wR(F²) = 0.159	w = 1/[σ²(F_o²) + (0.0824P)² + 0.969P] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.026
3360 reflections	Δρ_max = 0.21 e Å⁻³
230 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (11)

Crystal data top

C₇H₁₀N⁺·C₇H₃N₂O₆⁻	V = 2932.5 (10) Å³
M_r = 319.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 19.790 (4) Å	µ = 0.12 mm⁻¹
b = 7.2380 (14) Å	T = 293 K
c = 20.473 (4) Å	0.2 × 0.2 × 0.2 mm

Data collection top

Rigaku Mercury2 diffractometer	3360 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2368 reflections with I > 2.0 σ(I)
T_min = 0.978, T_max = 0.978	R_int = 0.078
28284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 0.96	Δρ_max = 0.21 e Å⁻³
3360 reflections	Δρ_min = −0.22 e Å⁻³
230 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
C13	0.05834 (9)	0.8208 (3)	0.03041 (9)	0.0389 (4)
H13	0.0302	0.7235	0.0424	0.047*
O2	0.01845 (8)	1.1416 (2)	0.15941 (8)	0.0607 (5)
C8	0.06408 (9)	0.9758 (2)	0.06998 (9)	0.0355 (4)
O1	0.00415 (8)	0.8407 (2)	0.15781 (7)	0.0572 (4)
C9	0.10590 (10)	1.1195 (3)	0.05077 (9)	0.0424 (5)
H9	0.1096	1.2252	0.0763	0.051*
C12	0.09496 (10)	0.8128 (3)	−0.02711 (9)	0.0418 (5)
C14	0.02558 (9)	0.9872 (3)	0.13409 (9)	0.0397 (4)
O4	0.12095 (11)	0.6430 (3)	−0.11917 (9)	0.0845 (6)
N2	0.08814 (12)	0.6506 (3)	−0.07003 (10)	0.0655 (6)
C11	0.13792 (10)	0.9514 (3)	−0.04684 (9)	0.0433 (5)
H11	0.1629	0.9426	−0.0852	0.052*
N3	0.18743 (11)	1.2557 (3)	−0.02654 (9)	0.0660 (6)
C10	0.14210 (10)	1.1040 (3)	−0.00676 (9)	0.0441 (5)
O5	0.21377 (11)	1.2487 (3)	−0.07970 (9)	0.0895 (7)
N1	0.03402 (8)	0.4988 (2)	0.21019 (8)	0.0423 (4)
H1A	0.0216	0.3954	0.1899	0.051*
H1B	0.0188	0.5959	0.1880	0.051*
H1C	0.0168	0.5001	0.2503	0.051*
C5	0.14494 (11)	0.5352 (3)	0.15756 (10)	0.0464 (5)
H5	0.1232	0.5520	0.1177	0.056*
C4	0.10811 (10)	0.5068 (2)	0.21395 (9)	0.0378 (4)
C1	0.24824 (11)	0.5139 (3)	0.22000 (10)	0.0443 (5)
C3	0.13975 (11)	0.4821 (3)	0.27266 (10)	0.0504 (5)
H3	0.1146	0.4624	0.3104	0.061*
C6	0.21460 (11)	0.5381 (3)	0.16134 (10)	0.0501 (5)
H6	0.2396	0.5568	0.1234	0.060*
C2	0.20983 (11)	0.4868 (3)	0.27537 (10)	0.0527 (6)
H2	0.2313	0.4713	0.3154	0.063*
C7	0.32394 (11)	0.5136 (3)	0.22312 (13)	0.0601 (6)
H7A	0.3382	0.5282	0.2676	0.072*
H7B	0.3413	0.6137	0.1974	0.072*
H7C	0.3408	0.3986	0.2064	0.072*
O6	0.1864 (11)	1.4010 (15)	0.0066 (7)	0.079 (3)	0.59 (5)
O3	0.0382 (13)	0.549 (3)	−0.0614 (5)	0.086 (4)	0.59 (5)
O6'	0.2092 (15)	1.351 (5)	0.0179 (11)	0.090 (7)	0.41 (5)
O3'	0.0653 (14)	0.5080 (19)	−0.0405 (18)	0.086 (6)	0.41 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C13	0.0403 (10)	0.0373 (10)	0.0390 (10)	0.0003 (8)	0.0010 (8)	0.0025 (8)
O2	0.0577 (10)	0.0609 (10)	0.0635 (10)	−0.0064 (7)	0.0159 (7)	−0.0254 (8)
C8	0.0338 (9)	0.0401 (10)	0.0327 (9)	0.0041 (7)	−0.0020 (7)	0.0007 (8)
O1	0.0631 (9)	0.0534 (9)	0.0552 (9)	0.0088 (7)	0.0223 (7)	0.0144 (7)
C9	0.0473 (11)	0.0409 (10)	0.0389 (10)	−0.0035 (8)	0.0004 (8)	−0.0036 (8)
C12	0.0492 (11)	0.0382 (10)	0.0380 (10)	0.0028 (8)	0.0002 (8)	−0.0046 (8)
C14	0.0317 (9)	0.0499 (12)	0.0374 (10)	0.0033 (8)	0.0000 (7)	−0.0025 (9)
O4	0.1219 (17)	0.0742 (12)	0.0575 (11)	−0.0063 (11)	0.0326 (11)	−0.0238 (9)
N2	0.0895 (16)	0.0515 (12)	0.0554 (12)	−0.0094 (11)	0.0180 (11)	−0.0127 (10)
C11	0.0471 (11)	0.0500 (11)	0.0327 (9)	0.0016 (9)	0.0043 (8)	0.0012 (8)
N3	0.0785 (14)	0.0701 (14)	0.0492 (11)	−0.0299 (11)	0.0148 (10)	−0.0049 (10)
C10	0.0443 (11)	0.0499 (12)	0.0382 (10)	−0.0098 (9)	0.0005 (8)	0.0027 (8)
O5	0.1144 (16)	0.0894 (14)	0.0647 (11)	−0.0438 (12)	0.0420 (11)	−0.0088 (10)
N1	0.0482 (10)	0.0403 (9)	0.0384 (9)	−0.0019 (7)	0.0036 (7)	−0.0038 (7)
C5	0.0577 (13)	0.0461 (11)	0.0356 (10)	0.0011 (9)	0.0045 (9)	0.0038 (8)
C4	0.0462 (11)	0.0303 (9)	0.0370 (10)	−0.0013 (7)	0.0048 (8)	−0.0041 (7)
C1	0.0465 (11)	0.0357 (10)	0.0506 (11)	−0.0015 (8)	0.0078 (9)	−0.0041 (8)
C3	0.0491 (12)	0.0672 (14)	0.0350 (10)	−0.0064 (10)	0.0089 (9)	−0.0023 (9)
C6	0.0572 (13)	0.0497 (12)	0.0434 (11)	−0.0016 (9)	0.0184 (10)	0.0024 (9)
C2	0.0507 (12)	0.0687 (15)	0.0387 (11)	−0.0048 (10)	0.0010 (9)	0.0003 (10)
C7	0.0497 (13)	0.0572 (14)	0.0735 (16)	−0.0016 (10)	0.0103 (11)	−0.0026 (12)
O6	0.116 (7)	0.063 (4)	0.058 (4)	−0.037 (4)	0.013 (4)	−0.006 (2)
O3	0.136 (9)	0.064 (5)	0.058 (3)	−0.053 (5)	0.016 (4)	−0.014 (3)
O6'	0.105 (10)	0.107 (13)	0.058 (6)	−0.068 (9)	0.016 (6)	−0.023 (7)
O3'	0.113 (9)	0.055 (4)	0.090 (12)	−0.017 (5)	0.034 (7)	−0.022 (5)

Geometric parameters (Å, º) top

C13—C12	1.384 (3)	N3—C10	1.475 (3)
C13—C8	1.389 (3)	N1—C4	1.469 (3)
C13—H13	0.9300	N1—H1A	0.8900
O2—C14	1.240 (2)	N1—H1B	0.8900
C8—C9	1.386 (3)	N1—H1C	0.8900
C8—C14	1.520 (3)	C5—C4	1.381 (3)
O1—C14	1.241 (2)	C5—C6	1.381 (3)
C9—C10	1.383 (3)	C5—H5	0.9300
C9—H9	0.9300	C4—C3	1.367 (3)
C12—C11	1.376 (3)	C1—C2	1.379 (3)
C12—N2	1.473 (3)	C1—C6	1.384 (3)
O4—N2	1.199 (2)	C1—C7	1.499 (3)
N2—O3	1.242 (12)	C3—C2	1.388 (3)
N2—O3'	1.279 (19)	C3—H3	0.9300
C11—C10	1.378 (3)	C6—H6	0.9300
C11—H11	0.9300	C2—H2	0.9300
N3—O5	1.208 (2)	C7—H7A	0.9600
N3—O6'	1.218 (16)	C7—H7B	0.9600
N3—O6	1.252 (12)	C7—H7C	0.9600

C12—C13—C8	119.15 (17)	C9—C10—N3	119.25 (18)
C12—C13—H13	120.4	C4—N1—H1A	109.5
C8—C13—H13	120.4	C4—N1—H1B	109.5
C9—C8—C13	119.31 (17)	H1A—N1—H1B	109.5
C9—C8—C14	120.25 (16)	C4—N1—H1C	109.5
C13—C8—C14	120.43 (16)	H1A—N1—H1C	109.5
C10—C9—C8	119.36 (18)	H1B—N1—H1C	109.5
C10—C9—H9	120.3	C4—C5—C6	118.84 (19)
C8—C9—H9	120.3	C4—C5—H5	120.6
C11—C12—C13	122.91 (18)	C6—C5—H5	120.6
C11—C12—N2	117.56 (18)	C3—C4—C5	120.86 (19)
C13—C12—N2	119.53 (18)	C3—C4—N1	119.86 (16)
O2—C14—O1	124.57 (18)	C5—C4—N1	119.26 (17)
O2—C14—C8	117.84 (17)	C2—C1—C6	117.8 (2)
O1—C14—C8	117.58 (17)	C2—C1—C7	121.0 (2)
O4—N2—O3	121.6 (4)	C6—C1—C7	121.17 (19)
O4—N2—O3'	123.5 (6)	C4—C3—C2	119.30 (18)
O3—N2—O3'	34.5 (6)	C4—C3—H3	120.3
O4—N2—C12	119.18 (19)	C2—C3—H3	120.3
O3—N2—C12	117.2 (6)	C5—C6—C1	121.78 (18)
O3'—N2—C12	113.2 (12)	C5—C6—H6	119.1
C12—C11—C10	116.52 (18)	C1—C6—H6	119.1
C12—C11—H11	121.7	C1—C2—C3	121.4 (2)
C10—C11—H11	121.7	C1—C2—H2	119.3
O5—N3—O6'	122.9 (8)	C3—C2—H2	119.3
O5—N3—O6	122.1 (6)	C1—C7—H7A	109.5
O6'—N3—O6	29.2 (15)	C1—C7—H7B	109.5
O5—N3—C10	118.59 (19)	H7A—C7—H7B	109.5
O6'—N3—C10	115.5 (11)	C1—C7—H7C	109.5
O6—N3—C10	117.9 (7)	H7A—C7—H7C	109.5
C11—C10—C9	122.73 (18)	H7B—C7—H7C	109.5
C11—C10—N3	118.01 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.94	2.803 (2)	163
N1—H1B···O1	0.89	1.90	2.761 (2)	163
N1—H1C···O2ⁱⁱ	0.89	2.22	3.045 (2)	153
N1—H1C···O1ⁱⁱ	0.89	2.24	3.030 (2)	147
C3—H3···O1ⁱⁱ	0.93	2.59	3.344 (3)	138
C13—H13···O3ⁱⁱⁱ	0.93	2.43	3.351 (7)	173

Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·C₇H₃N₂O₆⁻
M_r	319.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	19.790 (4), 7.2380 (14), 20.473 (4)
V (Å³)	2932.5 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.978, 0.978
No. of measured, independent and observed [I > 2.0 σ(I)] reflections	28284, 3360, 2368
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.159, 0.96
No. of reflections	3360
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.94	2.803 (2)	162.6
N1—H1B···O1	0.89	1.90	2.761 (2)	162.8
N1—H1C···O2ⁱⁱ	0.89	2.22	3.045 (2)	153.1
N1—H1C···O1ⁱⁱ	0.89	2.24	3.030 (2)	147.0
C3—H3···O1ⁱⁱ	0.93	2.59	3.344 (3)	138.2
C13—H13···O3ⁱⁱⁱ	0.93	2.43	3.351 (7)	172.8

Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z.

References

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1574

doi:10.1107/S1600536810018441

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