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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1574.
Published online 2010 June 5. doi:  10.1107/S1600536810018441
PMCID: PMC3006930

4-Methyl­anilinium 3,5-dinitro­benzoate

Abstract

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 [triangle]). For a related structure, see: Basaran et al. (1991 [triangle]).

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Object name is e-66-o1574-scheme1.jpg

Experimental

Crystal data

  • C7H10N+·C7H3N2O6
  • M r = 319.27
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1574-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.159
  • S = 0.96
  • 3360 reflections
  • 230 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

O3 and O6 atoms of the nitro groups were disordered over two sites with site occupancy factors 0.59 (5) and 0.41 (6). Positional parameters of all the H atoms were calculated geometrically and the H atoms were set to ride on the C and N atoms to which they are bonded with N—H = 0.89 Å and C—H = 0.93 and 0.96 Å for aryl and methyl H-atoms, respectively, with Uiso(H) = 1.2Ueq(C or N).

Figures

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.

Crystal data

C7H10N+·C7H3N2O6F(000) = 1328
Mr = 319.27Dx = 1.446 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 11511 reflections
a = 19.790 (4) Åθ = 3.0–27.5°
b = 7.2380 (14) ŵ = 0.12 mm1
c = 20.473 (4) ÅT = 293 K
V = 2932.5 (10) Å3Prism, colorless
Z = 80.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer3360 independent reflections
Radiation source: fine-focus sealed tube2368 reflections with I > 2.0 σ(I)
graphiteRint = 0.078
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scansh = −25→25
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.978, Tmax = 0.978l = −26→26
28284 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.159w = 1/[σ2(Fo2) + (0.0824P)2 + 0.969P] where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.026
3360 reflectionsΔρmax = 0.21 e Å3
230 parametersΔρmin = −0.22 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0065 (11)

Special details

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)

xyzUiso*/UeqOcc. (<1)
C130.05834 (9)0.8208 (3)0.03041 (9)0.0389 (4)
H130.03020.72350.04240.047*
O20.01845 (8)1.1416 (2)0.15941 (8)0.0607 (5)
C80.06408 (9)0.9758 (2)0.06998 (9)0.0355 (4)
O10.00415 (8)0.8407 (2)0.15781 (7)0.0572 (4)
C90.10590 (10)1.1195 (3)0.05077 (9)0.0424 (5)
H90.10961.22520.07630.051*
C120.09496 (10)0.8128 (3)−0.02711 (9)0.0418 (5)
C140.02558 (9)0.9872 (3)0.13409 (9)0.0397 (4)
O40.12095 (11)0.6430 (3)−0.11917 (9)0.0845 (6)
N20.08814 (12)0.6506 (3)−0.07003 (10)0.0655 (6)
C110.13792 (10)0.9514 (3)−0.04684 (9)0.0433 (5)
H110.16290.9426−0.08520.052*
N30.18743 (11)1.2557 (3)−0.02654 (9)0.0660 (6)
C100.14210 (10)1.1040 (3)−0.00676 (9)0.0441 (5)
O50.21377 (11)1.2487 (3)−0.07970 (9)0.0895 (7)
N10.03402 (8)0.4988 (2)0.21019 (8)0.0423 (4)
H1A0.02160.39540.18990.051*
H1B0.01880.59590.18800.051*
H1C0.01680.50010.25030.051*
C50.14494 (11)0.5352 (3)0.15756 (10)0.0464 (5)
H50.12320.55200.11770.056*
C40.10811 (10)0.5068 (2)0.21395 (9)0.0378 (4)
C10.24824 (11)0.5139 (3)0.22000 (10)0.0443 (5)
C30.13975 (11)0.4821 (3)0.27266 (10)0.0504 (5)
H30.11460.46240.31040.061*
C60.21460 (11)0.5381 (3)0.16134 (10)0.0501 (5)
H60.23960.55680.12340.060*
C20.20983 (11)0.4868 (3)0.27537 (10)0.0527 (6)
H20.23130.47130.31540.063*
C70.32394 (11)0.5136 (3)0.22312 (13)0.0601 (6)
H7A0.33820.52820.26760.072*
H7B0.34130.61370.19740.072*
H7C0.34080.39860.20640.072*
O60.1864 (11)1.4010 (15)0.0066 (7)0.079 (3)0.59 (5)
O30.0382 (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)

U11U22U33U12U13U23
C130.0403 (10)0.0373 (10)0.0390 (10)0.0003 (8)0.0010 (8)0.0025 (8)
O20.0577 (10)0.0609 (10)0.0635 (10)−0.0064 (7)0.0159 (7)−0.0254 (8)
C80.0338 (9)0.0401 (10)0.0327 (9)0.0041 (7)−0.0020 (7)0.0007 (8)
O10.0631 (9)0.0534 (9)0.0552 (9)0.0088 (7)0.0223 (7)0.0144 (7)
C90.0473 (11)0.0409 (10)0.0389 (10)−0.0035 (8)0.0004 (8)−0.0036 (8)
C120.0492 (11)0.0382 (10)0.0380 (10)0.0028 (8)0.0002 (8)−0.0046 (8)
C140.0317 (9)0.0499 (12)0.0374 (10)0.0033 (8)0.0000 (7)−0.0025 (9)
O40.1219 (17)0.0742 (12)0.0575 (11)−0.0063 (11)0.0326 (11)−0.0238 (9)
N20.0895 (16)0.0515 (12)0.0554 (12)−0.0094 (11)0.0180 (11)−0.0127 (10)
C110.0471 (11)0.0500 (11)0.0327 (9)0.0016 (9)0.0043 (8)0.0012 (8)
N30.0785 (14)0.0701 (14)0.0492 (11)−0.0299 (11)0.0148 (10)−0.0049 (10)
C100.0443 (11)0.0499 (12)0.0382 (10)−0.0098 (9)0.0005 (8)0.0027 (8)
O50.1144 (16)0.0894 (14)0.0647 (11)−0.0438 (12)0.0420 (11)−0.0088 (10)
N10.0482 (10)0.0403 (9)0.0384 (9)−0.0019 (7)0.0036 (7)−0.0038 (7)
C50.0577 (13)0.0461 (11)0.0356 (10)0.0011 (9)0.0045 (9)0.0038 (8)
C40.0462 (11)0.0303 (9)0.0370 (10)−0.0013 (7)0.0048 (8)−0.0041 (7)
C10.0465 (11)0.0357 (10)0.0506 (11)−0.0015 (8)0.0078 (9)−0.0041 (8)
C30.0491 (12)0.0672 (14)0.0350 (10)−0.0064 (10)0.0089 (9)−0.0023 (9)
C60.0572 (13)0.0497 (12)0.0434 (11)−0.0016 (9)0.0184 (10)0.0024 (9)
C20.0507 (12)0.0687 (15)0.0387 (11)−0.0048 (10)0.0010 (9)0.0003 (10)
C70.0497 (13)0.0572 (14)0.0735 (16)−0.0016 (10)0.0103 (11)−0.0026 (12)
O60.116 (7)0.063 (4)0.058 (4)−0.037 (4)0.013 (4)−0.006 (2)
O30.136 (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, °)

C13—C121.384 (3)N3—C101.475 (3)
C13—C81.389 (3)N1—C41.469 (3)
C13—H130.9300N1—H1A0.8900
O2—C141.240 (2)N1—H1B0.8900
C8—C91.386 (3)N1—H1C0.8900
C8—C141.520 (3)C5—C41.381 (3)
O1—C141.241 (2)C5—C61.381 (3)
C9—C101.383 (3)C5—H50.9300
C9—H90.9300C4—C31.367 (3)
C12—C111.376 (3)C1—C21.379 (3)
C12—N21.473 (3)C1—C61.384 (3)
O4—N21.199 (2)C1—C71.499 (3)
N2—O31.242 (12)C3—C21.388 (3)
N2—O3'1.279 (19)C3—H30.9300
C11—C101.378 (3)C6—H60.9300
C11—H110.9300C2—H20.9300
N3—O51.208 (2)C7—H7A0.9600
N3—O6'1.218 (16)C7—H7B0.9600
N3—O61.252 (12)C7—H7C0.9600
C12—C13—C8119.15 (17)C9—C10—N3119.25 (18)
C12—C13—H13120.4C4—N1—H1A109.5
C8—C13—H13120.4C4—N1—H1B109.5
C9—C8—C13119.31 (17)H1A—N1—H1B109.5
C9—C8—C14120.25 (16)C4—N1—H1C109.5
C13—C8—C14120.43 (16)H1A—N1—H1C109.5
C10—C9—C8119.36 (18)H1B—N1—H1C109.5
C10—C9—H9120.3C4—C5—C6118.84 (19)
C8—C9—H9120.3C4—C5—H5120.6
C11—C12—C13122.91 (18)C6—C5—H5120.6
C11—C12—N2117.56 (18)C3—C4—C5120.86 (19)
C13—C12—N2119.53 (18)C3—C4—N1119.86 (16)
O2—C14—O1124.57 (18)C5—C4—N1119.26 (17)
O2—C14—C8117.84 (17)C2—C1—C6117.8 (2)
O1—C14—C8117.58 (17)C2—C1—C7121.0 (2)
O4—N2—O3121.6 (4)C6—C1—C7121.17 (19)
O4—N2—O3'123.5 (6)C4—C3—C2119.30 (18)
O3—N2—O3'34.5 (6)C4—C3—H3120.3
O4—N2—C12119.18 (19)C2—C3—H3120.3
O3—N2—C12117.2 (6)C5—C6—C1121.78 (18)
O3'—N2—C12113.2 (12)C5—C6—H6119.1
C12—C11—C10116.52 (18)C1—C6—H6119.1
C12—C11—H11121.7C1—C2—C3121.4 (2)
C10—C11—H11121.7C1—C2—H2119.3
O5—N3—O6'122.9 (8)C3—C2—H2119.3
O5—N3—O6122.1 (6)C1—C7—H7A109.5
O6'—N3—O629.2 (15)C1—C7—H7B109.5
O5—N3—C10118.59 (19)H7A—C7—H7B109.5
O6'—N3—C10115.5 (11)C1—C7—H7C109.5
O6—N3—C10117.9 (7)H7A—C7—H7C109.5
C11—C10—C9122.73 (18)H7B—C7—H7C109.5
C11—C10—N3118.01 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.891.942.803 (2)163
N1—H1B···O10.891.902.761 (2)163
N1—H1C···O2ii0.892.223.045 (2)153
N1—H1C···O1ii0.892.243.030 (2)147
C3—H3···O1ii0.932.593.344 (3)138
C13—H13···O3iii0.932.433.351 (7)173

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2280).

References

  • Basaran, R., Dou, S. & Weiss, A. (1991). Ber. Bunsenges. Phys. Chem.95, 46–57.
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem, 11, 1959–1962
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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