3-Methyl­anilinium nitrate

Rademeyer, M.; Liles, D.C.

doi:10.1107/S1600536810020738

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1685

doi:10.1107/S1600536810020738

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3-Methylanilinium nitrate

Melanie Rademeyer ^a ^* and David C. Liles ^a

^aDepartment of Chemistry, University of Pretoria, Pretoria 0002, South Africa
^*Correspondence e-mail: melanie.rademeyer@up.ac.za

(Received 28 April 2010; accepted 31 May 2010; online 16 June 2010)

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 , 2009 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₁₀N⁺·NO₃⁻
M_r = 170.17
Orthorhombic, P b c a
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 ) 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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.135
S = 1.06
1659 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.89	2.05	2.943 (2)	178
N1—H1A⋯O2ⁱ	0.89	2.51	3.130 (2)	127
N1—H1B⋯O3ⁱⁱ	0.89	2.15	3.0221 (19)	167
N1—H1B⋯O2ⁱⁱ	0.89	2.37	3.078 (2)	136
N1—H1C⋯O3ⁱⁱⁱ	0.89	2.01	2.879 (2)	166
N1—H1C⋯O1ⁱⁱⁱ	0.89	2.47	3.176 (2)	137
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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).

3-Methylanilinium nitrate top

Crystal data top

C₇H₁₀N⁺·NO₃⁻	F(000) = 720
M_r = 170.17	D_x = 1.322 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3320 reflections
a = 10.6599 (14) Å	θ = 2.5–26.0°
b = 9.7800 (13) Å	µ = 0.11 mm⁻¹
c = 16.401 (2) Å	T = 293 K
V = 1709.9 (4) Å³	Plate, colourless
Z = 8	0.40 × 0.32 × 0.05 mm

Data collection top

Bruker (Siemens) P4 diffractometer	1659 independent reflections
Radiation source: fine-focus sealed tube	1211 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→7
T_min = 0.968, T_max = 0.988	k = −9→11
8520 measured reflections	l = −18→20

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0693P)² + 0.2901P] where P = (F_o² + 2F_c²)/3
1659 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₇H₁₀N⁺·NO₃⁻	V = 1709.9 (4) Å³
M_r = 170.17	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.6599 (14) Å	µ = 0.11 mm⁻¹
b = 9.7800 (13) Å	T = 293 K
c = 16.401 (2) Å	0.40 × 0.32 × 0.05 mm

Data collection top

Bruker (Siemens) P4 diffractometer	1659 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1211 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.988	R_int = 0.032
8520 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.06	Δρ_max = 0.17 e Å⁻³
1659 reflections	Δρ_min = −0.14 e Å⁻³
111 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
N2	0.86066 (14)	0.20637 (15)	0.24233 (8)	0.0590 (4)
C4	0.62873 (17)	0.1314 (2)	0.08553 (12)	0.0704 (5)
H4	0.6324	0.1346	0.1421	0.084*
O2	0.95202 (13)	0.13478 (15)	0.22538 (9)	0.0824 (5)
C2	0.67695 (17)	0.01475 (19)	−0.03889 (11)	0.0659 (5)
H2	0.7116	−0.0593	−0.0665	0.079*
C6	0.57062 (16)	0.23133 (16)	−0.04117 (10)	0.0573 (4)
H6	0.5344	0.3018	−0.0711	0.069*
C5	0.57263 (16)	0.23767 (18)	0.04363 (11)	0.0619 (5)
C3	0.67905 (19)	0.0215 (2)	0.04542 (12)	0.0774 (6)
H3	0.7150	−0.0494	0.0751	0.093*
C7	0.5124 (3)	0.3551 (2)	0.08774 (13)	0.0914 (7)
H7A	0.4233	0.3413	0.0899	0.137*
H7B	0.5303	0.4387	0.0594	0.137*
H7C	0.5452	0.3603	0.1422	0.137*
O3	0.77282 (13)	0.15739 (14)	0.28406 (8)	0.0733 (4)
O1	0.85544 (14)	0.32743 (14)	0.22016 (8)	0.0765 (4)
N1	0.61546 (14)	0.11602 (14)	−0.17012 (8)	0.0608 (4)
H1A	0.5376	0.1350	−0.1862	0.091*
H1B	0.6366	0.0328	−0.1872	0.091*
H1C	0.6681	0.1772	−0.1911	0.091*
C1	0.62205 (14)	0.12107 (16)	−0.08055 (10)	0.0516 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0751 (10)	0.0567 (8)	0.0453 (7)	−0.0010 (7)	−0.0051 (7)	0.0024 (6)
C4	0.0682 (12)	0.0909 (14)	0.0520 (10)	−0.0142 (10)	−0.0053 (8)	0.0093 (9)
O2	0.0812 (10)	0.0760 (9)	0.0899 (11)	0.0165 (7)	0.0129 (7)	0.0099 (7)
C2	0.0653 (11)	0.0612 (10)	0.0712 (11)	0.0056 (8)	−0.0008 (9)	0.0071 (9)
C6	0.0678 (10)	0.0511 (9)	0.0531 (10)	−0.0049 (8)	0.0013 (7)	0.0044 (7)
C5	0.0663 (11)	0.0669 (11)	0.0524 (10)	−0.0152 (9)	0.0062 (8)	−0.0010 (8)
C3	0.0746 (12)	0.0840 (14)	0.0735 (12)	0.0043 (10)	−0.0102 (10)	0.0241 (11)
C7	0.1199 (18)	0.0888 (14)	0.0655 (12)	−0.0031 (13)	0.0233 (12)	−0.0117 (11)
O3	0.0808 (9)	0.0699 (8)	0.0692 (8)	−0.0048 (7)	0.0138 (7)	0.0074 (6)
O1	0.0983 (10)	0.0568 (8)	0.0746 (9)	0.0046 (7)	0.0019 (7)	0.0138 (6)
N1	0.0742 (10)	0.0545 (8)	0.0537 (8)	−0.0009 (7)	0.0008 (7)	−0.0042 (6)
C1	0.0550 (9)	0.0499 (9)	0.0501 (9)	−0.0075 (7)	−0.0011 (7)	0.0005 (7)

Geometric parameters (Å, º) top

N2—O2	1.2312 (19)	C6—H6	0.9300
N2—O1	1.2398 (19)	C5—C7	1.501 (3)
N2—O3	1.2550 (18)	C3—H3	0.9300
C4—C3	1.370 (3)	C7—H7A	0.9600
C4—C5	1.382 (3)	C7—H7B	0.9600
C4—H4	0.9300	C7—H7C	0.9600
C2—C1	1.375 (2)	N1—C1	1.472 (2)
C2—C3	1.385 (3)	N1—H1A	0.8900
C2—H2	0.9300	N1—H1B	0.8900
C6—C1	1.371 (2)	N1—H1C	0.8900
C6—C5	1.392 (2)

O2—N2—O1	120.82 (16)	C2—C3—H3	119.7
O2—N2—O3	119.76 (15)	C5—C7—H7A	109.5
O1—N2—O3	119.40 (16)	C5—C7—H7B	109.5
C3—C4—C5	121.40 (18)	H7A—C7—H7B	109.5
C3—C4—H4	119.3	C5—C7—H7C	109.5
C5—C4—H4	119.3	H7A—C7—H7C	109.5
C1—C2—C3	117.87 (17)	H7B—C7—H7C	109.5
C1—C2—H2	121.1	C1—N1—H1A	109.5
C3—C2—H2	121.1	C1—N1—H1B	109.5
C1—C6—C5	119.96 (16)	H1A—N1—H1B	109.5
C1—C6—H6	120.0	C1—N1—H1C	109.5
C5—C6—H6	120.0	H1A—N1—H1C	109.5
C4—C5—C6	118.03 (17)	H1B—N1—H1C	109.5
C4—C5—C7	121.37 (18)	C6—C1—C2	122.05 (16)
C6—C5—C7	120.59 (17)	C6—C1—N1	118.52 (14)
C4—C3—C2	120.68 (18)	C2—C1—N1	119.41 (15)
C4—C3—H3	119.7

C3—C4—C5—C6	−1.2 (3)	C1—C2—C3—C4	−0.5 (3)
C3—C4—C5—C7	177.24 (19)	C5—C6—C1—C2	−0.2 (2)
C1—C6—C5—C4	0.8 (2)	C5—C6—C1—N1	178.47 (14)
C1—C6—C5—C7	−177.68 (17)	C3—C2—C1—C6	0.1 (3)
C5—C4—C3—C2	1.1 (3)	C3—C2—C1—N1	−178.60 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.89	2.05	2.943 (2)	178
N1—H1A···O2ⁱ	0.89	2.51	3.130 (2)	127
N1—H1B···O3ⁱⁱ	0.89	2.15	3.0221 (19)	167
N1—H1B···O2ⁱⁱ	0.89	2.37	3.078 (2)	136
N1—H1C···O3ⁱⁱⁱ	0.89	2.01	2.879 (2)	166
N1—H1C···O1ⁱⁱⁱ	0.89	2.47	3.176 (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.

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·NO₃⁻
M_r	170.17
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.6599 (14), 9.7800 (13), 16.401 (2)
V (Å³)	1709.9 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.32 × 0.05

Data collection
Diffractometer	Bruker (Siemens) P4 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.968, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	8520, 1659, 1211
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.135, 1.06
No. of reflections	1659
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.14

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.89	2.05	2.943 (2)	177.6
N1—H1A···O2ⁱ	0.89	2.51	3.130 (2)	126.9
N1—H1B···O3ⁱⁱ	0.89	2.15	3.0221 (19)	167.2
N1—H1B···O2ⁱⁱ	0.89	2.37	3.078 (2)	136.1
N1—H1C···O3ⁱⁱⁱ	0.89	2.01	2.879 (2)	166.3
N1—H1C···O1ⁱⁱⁱ	0.89	2.47	3.176 (2)	136.5

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.

Acknowledgements

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

References

Benali-Cherif, N., Boussekine, H., Boutobba, Z. & Dadda, N. (2009). Acta Cryst. E65, o2744. Web of Science CrossRef IUCr Journals Google Scholar
Benali-Cherif, N., Kateb, A., Boussekine, H., Boutobba, Z. & Messai, A. (2007). Acta Cryst. E63, o3251. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar