PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1685.
Published online 2010 June 16. doi:  10.1107/S1600536810020738
PMCID: PMC3006795

3-Methyl­anilinium nitrate

Abstract

In the title compound, C7H10N+·NO3 , the 3-methyl­anilinium cations inter­act with the nitrate anions through strong bifurcated N+—H(...)(O,O) hydrogen bonds, forming a two-dimensional hydrogen-bonded network.

Related literature

For related structures, see: Benali-Cherif et al. (2007 [triangle], 2009 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1685-scheme1.jpg

Experimental

Crystal data

  • C7H10N+·NO3
  • M r = 170.17
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1685-efi1.jpg
  • a = 10.6599 (14) Å
  • b = 9.7800 (13) Å
  • c = 16.401 (2) Å
  • V = 1709.9 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 293 K
  • 0.40 × 0.32 × 0.05 mm

Data collection

  • Bruker (Siemens) P4 diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.968, T max = 0.988
  • 8520 measured reflections
  • 1659 independent reflections
  • 1211 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.135
  • S = 1.06
  • 1659 reflections
  • 111 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]) and WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020738/kj2146sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020738/kj2146Isup2.hkl

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

Acknowledgments

Funding received for this work from the University of Pretoria and the National Research Foundation (GUN: 2054350) is acknowledged.

supplementary crystallographic information

Comment

A fundamental understanding of the role of oxyanion geometry on molecular packing and non-covalent interactions in salt crystal structures is central to the fields of both molecular recognition and crystal engineering. The crystal structure of the title compound was determined as part of a project focusing on the role of anions when combined with alkylammonium or arylammonium cations. The structures of the related compounds p-toluidinium nitrate (Benali-Cherif et al., 2009) and o-toluidinium nitrate (Benali-Cherif et al., 2007) have been reported in the literature.

The molecular geometry and labelling scheme of the title compound is illustrated in Fig. 1. The asymmetric unit contains one 3-methylanilinium cation and one trigonal planar nitrate anion. A layered structure consisting of alternating organic and inorganic layers is exhibited by the title compound. The organic layers contain the hydrophobic part of the cation, while the inorganic layers comprise the ammonium groups and nitrate anions. The molecular packing of the title compound, viewed down the b-axis, is illustrated in Fig 2(a). In the organic layer pairs of cations alternate in orientation, with all the aromatic groups packing in a single row. Aromatic interactions are present between pairs of parallel cations, packing in a head-to-tail, offset π-stacking fashion, with a centroid-to-centroid distance of 3.6347 (12) Å. Neighbouring parallel cation pairs pack with aromatic planes at an angle of 57 °. The ammonium groups of pairs of parallel cations point to pairs of nitrate anions, interacting through strong, charge assisted N+—H···O- hydrogen bonds, listed in Table 1. Each ammonium group is hydrogen bonded to three different nitrate anions through three bifurcated hydrogen bonds to six different oxygen atoms, as illustrated in Fig. 2(b). In each bifurcated hydrogen bond, one of the interactions displays an N+—H···O- interaction angle closer to 180 °, while the angle of the second interaction deviates significantly more from linearity. In addition, for each bifurcated interaction, the two N+—H···O- angles and the -O—HO- angle add up to approximately 360°. Each nitrate anion accepts three bifurcated hydrogen bonds from three different ammonium groups. The oxygen atom, O3, which accepts two approximately linear hydrogen bonds, exhibits a shorter N—O bond distance compared to the other N—O bonds.

The hydrogen bonding interactions result in a two-dimensional hydrogen bonded sheet, parallel to the ab-plane, as illustrated in Fig. 2(b). Two types of hydrogen bonded rings are present in the sheet. The larger of the two can be described by the graph set notation R36(12), while the smaller ring is described by R21(4) (Bernstein et al., 1995).

Experimental

3-Methylanilinium nitrate was prepared by the dropwise addition of excess concentrated nitric acid (0.90 ml, 70%, Saarchem) to a solution of m-toluidine (0.50 ml, 99%, Aldrich) in 20 ml chloroform (99%, Saarchem). Slow evaporation of the chloroform solution at room temperature gave colourless crystals.

Refinement

All H atoms were refined using a riding model (HFIX 33 for N1 and C7), with C—H distances either 0.93 or 0.96 Å and N—H distances of 0.89 Å, and Uiso(H) = 1.5Ueq(C) or 1.2Ueq(C) or 1.2Ueq(N). The highest residual peak was 0.95 Å from atom H7B.

Figures

Fig. 1.
The asymmetric unit of the title compound showing the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level.
Fig. 2.
(a) Packing diagram of the title compound viewed down the b-axis.(b) N—H···O hydrogen bonding network in the title compound (dashed lines indicate hydrogen bonds).

Crystal data

C7H10N+·NO3F(000) = 720
Mr = 170.17Dx = 1.322 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3320 reflections
a = 10.6599 (14) Åθ = 2.5–26.0°
b = 9.7800 (13) ŵ = 0.11 mm1
c = 16.401 (2) ÅT = 293 K
V = 1709.9 (4) Å3Plate, colourless
Z = 80.40 × 0.32 × 0.05 mm

Data collection

Bruker (Siemens) P4 diffractometer1659 independent reflections
Radiation source: fine-focus sealed tube1211 reflections with I > 2σ(I)
graphiteRint = 0.032
[var phi] and ω scansθmax = 26.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −13→7
Tmin = 0.968, Tmax = 0.988k = −9→11
8520 measured reflectionsl = −18→20

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0693P)2 + 0.2901P] where P = (Fo2 + 2Fc2)/3
1659 reflections(Δ/σ)max < 0.001
111 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = −0.14 e Å3

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*/Ueq
N20.86066 (14)0.20637 (15)0.24233 (8)0.0590 (4)
C40.62873 (17)0.1314 (2)0.08553 (12)0.0704 (5)
H40.63240.13460.14210.084*
O20.95202 (13)0.13478 (15)0.22538 (9)0.0824 (5)
C20.67695 (17)0.01475 (19)−0.03889 (11)0.0659 (5)
H20.7116−0.0593−0.06650.079*
C60.57062 (16)0.23133 (16)−0.04117 (10)0.0573 (4)
H60.53440.3018−0.07110.069*
C50.57263 (16)0.23767 (18)0.04363 (11)0.0619 (5)
C30.67905 (19)0.0215 (2)0.04542 (12)0.0774 (6)
H30.7150−0.04940.07510.093*
C70.5124 (3)0.3551 (2)0.08774 (13)0.0914 (7)
H7A0.42330.34130.08990.137*
H7B0.53030.43870.05940.137*
H7C0.54520.36030.14220.137*
O30.77282 (13)0.15739 (14)0.28406 (8)0.0733 (4)
O10.85544 (14)0.32743 (14)0.22016 (8)0.0765 (4)
N10.61546 (14)0.11602 (14)−0.17012 (8)0.0608 (4)
H1A0.53760.1350−0.18620.091*
H1B0.63660.0328−0.18720.091*
H1C0.66810.1772−0.19110.091*
C10.62205 (14)0.12107 (16)−0.08055 (10)0.0516 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N20.0751 (10)0.0567 (8)0.0453 (7)−0.0010 (7)−0.0051 (7)0.0024 (6)
C40.0682 (12)0.0909 (14)0.0520 (10)−0.0142 (10)−0.0053 (8)0.0093 (9)
O20.0812 (10)0.0760 (9)0.0899 (11)0.0165 (7)0.0129 (7)0.0099 (7)
C20.0653 (11)0.0612 (10)0.0712 (11)0.0056 (8)−0.0008 (9)0.0071 (9)
C60.0678 (10)0.0511 (9)0.0531 (10)−0.0049 (8)0.0013 (7)0.0044 (7)
C50.0663 (11)0.0669 (11)0.0524 (10)−0.0152 (9)0.0062 (8)−0.0010 (8)
C30.0746 (12)0.0840 (14)0.0735 (12)0.0043 (10)−0.0102 (10)0.0241 (11)
C70.1199 (18)0.0888 (14)0.0655 (12)−0.0031 (13)0.0233 (12)−0.0117 (11)
O30.0808 (9)0.0699 (8)0.0692 (8)−0.0048 (7)0.0138 (7)0.0074 (6)
O10.0983 (10)0.0568 (8)0.0746 (9)0.0046 (7)0.0019 (7)0.0138 (6)
N10.0742 (10)0.0545 (8)0.0537 (8)−0.0009 (7)0.0008 (7)−0.0042 (6)
C10.0550 (9)0.0499 (9)0.0501 (9)−0.0075 (7)−0.0011 (7)0.0005 (7)

Geometric parameters (Å, °)

N2—O21.2312 (19)C6—H60.9300
N2—O11.2398 (19)C5—C71.501 (3)
N2—O31.2550 (18)C3—H30.9300
C4—C31.370 (3)C7—H7A0.9600
C4—C51.382 (3)C7—H7B0.9600
C4—H40.9300C7—H7C0.9600
C2—C11.375 (2)N1—C11.472 (2)
C2—C31.385 (3)N1—H1A0.8900
C2—H20.9300N1—H1B0.8900
C6—C11.371 (2)N1—H1C0.8900
C6—C51.392 (2)
O2—N2—O1120.82 (16)C2—C3—H3119.7
O2—N2—O3119.76 (15)C5—C7—H7A109.5
O1—N2—O3119.40 (16)C5—C7—H7B109.5
C3—C4—C5121.40 (18)H7A—C7—H7B109.5
C3—C4—H4119.3C5—C7—H7C109.5
C5—C4—H4119.3H7A—C7—H7C109.5
C1—C2—C3117.87 (17)H7B—C7—H7C109.5
C1—C2—H2121.1C1—N1—H1A109.5
C3—C2—H2121.1C1—N1—H1B109.5
C1—C6—C5119.96 (16)H1A—N1—H1B109.5
C1—C6—H6120.0C1—N1—H1C109.5
C5—C6—H6120.0H1A—N1—H1C109.5
C4—C5—C6118.03 (17)H1B—N1—H1C109.5
C4—C5—C7121.37 (18)C6—C1—C2122.05 (16)
C6—C5—C7120.59 (17)C6—C1—N1118.52 (14)
C4—C3—C2120.68 (18)C2—C1—N1119.41 (15)
C4—C3—H3119.7
C3—C4—C5—C6−1.2 (3)C1—C2—C3—C4−0.5 (3)
C3—C4—C5—C7177.24 (19)C5—C6—C1—C2−0.2 (2)
C1—C6—C5—C40.8 (2)C5—C6—C1—N1178.47 (14)
C1—C6—C5—C7−177.68 (17)C3—C2—C1—C60.1 (3)
C5—C4—C3—C21.1 (3)C3—C2—C1—N1−178.60 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.892.052.943 (2)178
N1—H1A···O2i0.892.513.130 (2)127
N1—H1B···O3ii0.892.153.0221 (19)167
N1—H1B···O2ii0.892.373.078 (2)136
N1—H1C···O3iii0.892.012.879 (2)166
N1—H1C···O1iii0.892.473.176 (2)137

Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x+3/2, −y, z−1/2; (iii) x, −y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2146).

References

  • Benali-Cherif, N., Boussekine, H., Boutobba, Z. & Dadda, N. (2009). Acta Cryst. E65, o2744. [PMC free article] [PubMed]
  • Benali-Cherif, N., Kateb, A., Boussekine, H., Boutobba, Z. & Messai, A. (2007). Acta Cryst. E63, o3251.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2001). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography