2,3-Xylidinium nitrate

Kefi, C.; Marouani, H.; Rzaigui, M.

doi:10.1107/S1600536813023465

organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1475

doi:10.1107/S1600536813023465

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2,3-Xylidinium nitrate

Chourouk Kefi,^a Houda Marouani ^a ^* and Mohamed Rzaigui ^a

^aLaboratoire de chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: houda_marouani@voila.fr

(Received 18 August 2013; accepted 20 August 2013; online 23 August 2013)

In the crystal structure of the title compound, C₈H₁₂N⁺·NO₃⁻, the 2,3-xylidinium (2,3-dimethylanilinium) cations are connected to the nitrate anions through bifurcated N—H⋯(O,O) and weak C—H⋯O hydrogen bonds, generating corrugated layers parallel to (001) at z = 0.25 and 0.75. These layers are connected via C—H⋯O interactions, giving rise to a three-dimensional network.

Related literature

For related structures, see: Marouani et al. (2010 , 2012 ). For graph-set notation of hydrogen-bonding motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₁₂N⁺·NO₃⁻
M_r = 184.20
Orthorhombic, P b c a
a = 10.889 (2) Å
b = 10.110 (2) Å
c = 17.010 (3) Å
V = 1872.5 (6) Å³
Z = 8
Ag Kα radiation
λ = 0.56083 Å
μ = 0.06 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
8719 measured reflections
4541 independent reflections
1933 reflections with I > 2σ(I)
R_int = 0.056
2 standard reflections every 120 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.178
S = 0.86
4541 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3	0.89	2.03	2.915 (2)	177
N2—H2A⋯O2	0.89	2.64	3.296 (2)	131
N2—H2B⋯O1ⁱ	0.89	2.11	2.995 (2)	171
N2—H2B⋯O2ⁱ	0.89	2.46	3.148 (2)	134
N2—H2C⋯O3ⁱⁱ	0.89	2.15	2.973 (2)	153
N2—H2C⋯O1ⁱⁱ	0.89	2.36	3.158 (2)	149
C4—H4⋯O2ⁱⁱⁱ	0.93	2.57	3.439 (3)	156
C7—H7A⋯O1ⁱⁱ	0.96	2.63	3.522 (3)	155
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) -x, -y+1, -z+1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Putz 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813023465/pv2645sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023465/pv2645Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813023465/pv2645Isup3.cml

checkCIF report

Comment top

As a part of our study of crystal packing containing the 2,3-xylidinium cation (Marouani, et al., 2010), we report here the preparation and the crystal structure of the title compound (I).

The asymmetric unit of (I) is composed of nitrate anion and 2,3-xylidinium cation (Fig. 1). The bond distances and angles in the anion and the cation agree very well with the corresponding bond distances and angles reported earlier for the anion (Marouani et al., 2012) and the cation (Marouani et al., 2010). The aromatic ring of the cation is essentially planar with an r.m.s deviation of 0.0017 Å. The interplanar distance between the rings of the cations is in the vicinity of 3.569 Å, indicating the formation of π–π interactions.

The cations are connected to the anions through bifurcated N—H···O(O) and weak C7—H7A···O1 hydrogen bonds (Table 1), generating a corrugated layers parallel to the (001) plane at z = 0.25 and 0.75 (Fig. 2). These layers are connected via C4—H4···O2 interactions, giving rise to a three-dimensional network. Each cation is bonded to three different nitrate anions through six N—H···O hydrogen bonds forming R₆³(12) and R₁²(4) motifs in the graph-set notation (Fig. 3) (Bernstein et al., 1995). All the hydrogen bonds, the van der Waals contacts, and electrostatic interactions between the different entities give rise to a three-dimensional network in the structure and add stability to the compound.

Related literature top

For related structures, see: Marouani et al. (2010, 2012). For graph-set notation of hydrogen-bonding motifs, see: Bernstein et al. (1995).

Experimental top

Single crystals of the title compound were prepared at room temperature from an aqueous mixture of 2,3-xylidine ( 1 mmol) and nitric acid (1 mmol). The mixture was stirred for 15 min then slowly evaporated at room temperature until the formation of good quality pink prismatic single crystals.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dotted lines.
	Fig. 2. Projection of (I) along the b axis. The H-atoms not involved in H-bonding are omitted.
	Fig. 3. Hydrogen bond motifs in (I).

2,3-Dimethylanilinium nitrate top

Crystal data top

C₈H₁₂N⁺·NO₃⁻	F(000) = 784
M_r = 184.20	D_x = 1.307 Mg m⁻³
Orthorhombic, Pbca	Ag Kα radiation, λ = 0.56083 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 10.889 (2) Å	θ = 8–10°
b = 10.110 (2) Å	µ = 0.06 mm⁻¹
c = 17.010 (3) Å	T = 293 K
V = 1872.5 (6) Å³	Prism, pink
Z = 8	0.4 × 0.3 × 0.2 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.056
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.4°
Graphite monochromator	h = −18→3
non–profiled ω scans	k = −5→16
8719 measured reflections	l = −2→28
4541 independent reflections	2 standard reflections every 120 min
1933 reflections with I > 2σ(I)	intensity decay: 2%

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 0.86	w = 1/[σ²(F_o²) + (0.0586P)²] where P = (F_o² + 2F_c²)/3
4541 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₈H₁₂N⁺·NO₃⁻	V = 1872.5 (6) Å³
M_r = 184.20	Z = 8
Orthorhombic, Pbca	Ag Kα radiation, λ = 0.56083 Å
a = 10.889 (2) Å	µ = 0.06 mm⁻¹
b = 10.110 (2) Å	T = 293 K
c = 17.010 (3) Å	0.4 × 0.3 × 0.2 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.056
8719 measured reflections	2 standard reflections every 120 min
4541 independent reflections	intensity decay: 2%
1933 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 0.86	Δρ_max = 0.13 e Å⁻³
4541 reflections	Δρ_min = −0.15 e Å⁻³
121 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.10288 (17)	0.74955 (19)	0.26311 (10)	0.0625 (5)
O2	0.01325 (15)	0.68356 (15)	0.24486 (9)	0.0858 (6)
O3	0.18890 (15)	0.69932 (14)	0.30086 (10)	0.0812 (5)
O1	0.11018 (16)	0.86708 (16)	0.24375 (10)	0.0992 (6)
C2	0.22220 (17)	0.44029 (17)	0.46097 (12)	0.0523 (5)
C1	0.12753 (19)	0.39756 (18)	0.41282 (12)	0.0517 (5)
N2	0.13609 (14)	0.42040 (15)	0.32795 (10)	0.0613 (5)
H2A	0.1490	0.5060	0.3189	0.092*
H2B	0.0663	0.3956	0.3050	0.092*
H2C	0.1981	0.3735	0.3084	0.092*
C3	0.2094 (2)	0.4186 (2)	0.54217 (13)	0.0629 (6)
C6	0.0239 (2)	0.33705 (19)	0.44060 (15)	0.0668 (6)
H6	−0.0381	0.3111	0.4063	0.080*
C7	0.33189 (17)	0.5102 (2)	0.42887 (14)	0.0669 (6)
H7A	0.3361	0.4968	0.3731	0.100*
H7B	0.4048	0.4756	0.4531	0.100*
H7C	0.3254	0.6030	0.4398	0.100*
C4	0.1061 (2)	0.3555 (2)	0.56938 (15)	0.0788 (7)
H4	0.0986	0.3394	0.6230	0.095*
C5	0.0131 (2)	0.3153 (2)	0.51969 (16)	0.0792 (8)
H5	−0.0564	0.2738	0.5398	0.095*
C8	0.3045 (2)	0.4673 (3)	0.59902 (15)	0.0933 (8)
H8A	0.3094	0.5619	0.5962	0.140*
H8B	0.3828	0.4297	0.5859	0.140*
H8C	0.2821	0.4413	0.6514	0.140*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0656 (11)	0.0694 (12)	0.0525 (10)	0.0014 (12)	0.0011 (10)	0.0037 (10)
O2	0.0669 (10)	0.1033 (14)	0.0872 (12)	−0.0192 (10)	−0.0084 (9)	0.0135 (9)
O3	0.0770 (10)	0.0763 (11)	0.0902 (12)	0.0059 (9)	−0.0291 (10)	0.0099 (9)
O1	0.1262 (15)	0.0573 (9)	0.1142 (14)	−0.0031 (11)	−0.0345 (13)	0.0181 (10)
C2	0.0550 (13)	0.0402 (11)	0.0615 (13)	0.0111 (10)	−0.0002 (10)	0.0052 (10)
C1	0.0564 (12)	0.0385 (10)	0.0601 (13)	0.0065 (10)	0.0027 (11)	0.0020 (9)
N2	0.0620 (11)	0.0539 (10)	0.0681 (12)	0.0002 (9)	−0.0070 (9)	−0.0017 (9)
C3	0.0766 (16)	0.0531 (13)	0.0590 (14)	0.0207 (12)	0.0058 (12)	0.0057 (11)
C6	0.0624 (14)	0.0465 (12)	0.0915 (17)	−0.0005 (12)	0.0080 (13)	−0.0024 (12)
C7	0.0590 (13)	0.0721 (14)	0.0696 (14)	−0.0010 (12)	−0.0089 (11)	0.0076 (12)
C4	0.104 (2)	0.0593 (15)	0.0731 (16)	0.0218 (15)	0.0272 (17)	0.0126 (13)
C5	0.0821 (18)	0.0518 (15)	0.104 (2)	0.0026 (13)	0.0325 (16)	0.0089 (14)
C8	0.111 (2)	0.103 (2)	0.0656 (15)	0.0249 (18)	−0.0158 (15)	−0.0014 (14)

Geometric parameters (Å, º) top

N1—O2	1.222 (2)	C3—C8	1.500 (3)
N1—O1	1.236 (2)	C6—C5	1.368 (3)
N1—O3	1.244 (2)	C6—H6	0.9300
C2—C1	1.386 (3)	C7—H7A	0.9600
C2—C3	1.406 (3)	C7—H7B	0.9600
C2—C7	1.491 (3)	C7—H7C	0.9600
C1—C6	1.368 (3)	C4—C5	1.381 (3)
C1—N2	1.465 (2)	C4—H4	0.9300
N2—H2A	0.8900	C5—H5	0.9300
N2—H2B	0.8900	C8—H8A	0.9600
N2—H2C	0.8900	C8—H8B	0.9600
C3—C4	1.373 (3)	C8—H8C	0.9600

O2—N1—O1	120.6 (2)	C5—C6—H6	120.6
O2—N1—O3	120.63 (19)	C2—C7—H7A	109.5
O1—N1—O3	118.80 (19)	C2—C7—H7B	109.5
C1—C2—C3	117.3 (2)	H7A—C7—H7B	109.5
C1—C2—C7	121.81 (19)	C2—C7—H7C	109.5
C3—C2—C7	120.9 (2)	H7A—C7—H7C	109.5
C6—C1—C2	123.3 (2)	H7B—C7—H7C	109.5
C6—C1—N2	117.6 (2)	C3—C4—C5	122.1 (2)
C2—C1—N2	119.08 (18)	C3—C4—H4	118.9
C1—N2—H2A	109.5	C5—C4—H4	118.9
C1—N2—H2B	109.5	C6—C5—C4	119.4 (2)
H2A—N2—H2B	109.5	C6—C5—H5	120.3
C1—N2—H2C	109.5	C4—C5—H5	120.3
H2A—N2—H2C	109.5	C3—C8—H8A	109.5
H2B—N2—H2C	109.5	C3—C8—H8B	109.5
C4—C3—C2	119.0 (2)	H8A—C8—H8B	109.5
C4—C3—C8	120.0 (2)	C3—C8—H8C	109.5
C2—C3—C8	120.9 (2)	H8A—C8—H8C	109.5
C1—C6—C5	118.9 (2)	H8B—C8—H8C	109.5
C1—C6—H6	120.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.89	2.03	2.915 (2)	177
N2—H2A···O2	0.89	2.64	3.296 (2)	131
N2—H2B···O1ⁱ	0.89	2.11	2.995 (2)	171
N2—H2B···O2ⁱ	0.89	2.46	3.148 (2)	134
N2—H2C···O3ⁱⁱ	0.89	2.15	2.973 (2)	153
N2—H2C···O1ⁱⁱ	0.89	2.36	3.158 (2)	149
C4—H4···O2ⁱⁱⁱ	0.93	2.57	3.439 (3)	156
C7—H7A···O1ⁱⁱ	0.96	2.63	3.522 (3)	155

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.89	2.03	2.915 (2)	176.5
N2—H2A···O2	0.89	2.64	3.296 (2)	130.8
N2—H2B···O1ⁱ	0.89	2.11	2.995 (2)	170.7
N2—H2B···O2ⁱ	0.89	2.46	3.148 (2)	134.2
N2—H2C···O3ⁱⁱ	0.89	2.15	2.973 (2)	153.1
N2—H2C···O1ⁱⁱ	0.89	2.36	3.158 (2)	149.4
C4—H4···O2ⁱⁱⁱ	0.93	2.57	3.439 (3)	156.4
C7—H7A···O1ⁱⁱ	0.96	2.63	3.522 (3)	155.4

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

Acknowledgements

This work was supported by the Tunisian Ministry of HEScR.

References

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