2,5-Dimethyl­anilinium nitrate

Smirani, W.; Rzaigui, M.

doi:10.1107/S1600536809027718

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1917

doi:10.1107/S1600536809027718

Open

access

2,5-Dimethylanilinium nitrate

Wajda Smirani ^a ^* and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: wajda_sta@yahoo.fr

(Received 6 July 2009; accepted 14 July 2009; online 18 July 2009)

In the title salt, C₈H₁₂N⁺·NO₃⁻, all non-H atoms of the cation lie on mirror planes. The nitrate counteranion has m symmetry and acts as a hydrogen-bond acceptor of N—H⋯O hydrogen bonds, connecting the cations and anions into layers running parallel to the ab plane.

Related literature

Inorganic–organic hybrid materials display a great variety of structural topologies, see: Xiao et al. (2005 ). For comparative geometrical data in structures containing the same organic groups, see: Smirani & Rzaigui (2009 ); Souissi et al. (2009 ).

Experimental

Crystal data

C₈H₁₂N⁺·NO₃⁻
M_r = 184.20
Orthorhombic, P m c n
a = 6.762 (3) Å
b = 7.942 (3) Å
c = 17.137 (5) Å
V = 920.4 (6) Å³
Z = 4
Ag Kα radiation
μ = 0.06 mm⁻¹
T = 293 K
0.50 × 0.45 × 0.40 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
4249 measured reflections
2365 independent reflections
822 reflections with I > 2σ(I)
R_int = 0.056
2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.156
S = 0.92
2365 reflections
86 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.95 (2)	1.92 (3)	2.870 (2)	179 (3)
N1—H2A⋯O1ⁱⁱ	0.89 (3)	2.24 (3)	3.037 (3)	149.7 (8)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-1, z]$ .

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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027718/hg2534sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027718/hg2534Isup2.hkl

checkCIF report

Comment top

The combination of organic molecules and inorganic materials was the starting point for the developpement of new hybrid compounds with appropriate physical and chemical properties. These materials have a great interest due to their enormous variety of intriguing structural topologies (Xiao et al., 2005). In order to enrich the varieties in such kinds of hybrid materials and to investigate the influence of hydrogen bonds on the structural features, we report the crystal structure of 2,5 dimethylanilinium nitrate (I).

The title compound crystallizes in the space group Pcmn. Only the non-hydrogen atoms of the cation lie on the mirror planes. As shown in Fig. 1, the asymmetric unit of the crystal structure of this salt is built of half nitrate anion and half 2,5-dimethylanilinium cation. A projection of the structure along the a axis shows that the nitrate anions establish with the ammonium cations multiple hydrogen bonds, to form two inorganic layers at z = 1/4 and 3/4.

The examination of the organic cation shows that the values of the N—C, C—C distances and N—C—C, C—C—C angles range from 1.379 (4) to 1.516 (5) Å and 116. 2(3) to 122.4 (3)°, respectively. These values are similar to those obtained in other organic materials containing the same organic groups (Smirani and Rzaigui, 2009; Souissi et al. 2009).

Related literature top

Inorganic–organic hybrid materials display a great variety of structural topologies, see: Xiao et al. (2005). For comparative geometrical data in structures containing the same organic groups, see: Smirani & Rzaigui (2009); Souissi et al. (2009).

Experimental top

An ethanolic solution of 2,5-dimethylaniline (10 mmol, in 5 ml) was added drop wise to a magnetically stirred aqueous solution of nitric acid HNO₃ (1 M, 10 ml) in equimolar ratio. The so-obtained solution is then filtered to eliminate the white precipitated formed and then stirred for 1 h. After stirring, the reaction mixture was kept at room temperature until apparition of transparent single crystals of 2,5-dimethylanilinium nitrate.

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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP-3 (Farrugia,(1999)) view of (C₈H₁₂N)N0₃ with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
	Fig. 2. A view of the atomic arrangement of the title compound along the a axis.

2,5-Dimethylanilinium nitrate top

Crystal data top

C₈H₁₂N⁺·NO₃⁻	F(000) = 392
M_r = 184.20	D_x = 1.329 Mg m⁻³
Orthorhombic, Pmcn	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2n 2a	Cell parameters from 25 reflections
a = 6.762 (3) Å	θ = 9.0–10.5°
b = 7.942 (3) Å	µ = 0.06 mm⁻¹
c = 17.137 (5) Å	T = 293 K
V = 920.4 (6) Å³	Block, colorless
Z = 4	0.50 × 0.45 × 0.40 mm

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.056
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.2°
Graphite monochromator	h = −8→11
Non–profiled ω scans	k = 0→13
4249 measured reflections	l = 0→28
2365 independent reflections	2 standard reflections every 120 min
822 reflections with I > 2σ(I)	intensity decay: 5%

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) = 0.156	w = 1/[σ²(F_o²) + (0.0632P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
2365 reflections	Δρ_max = 0.20 e Å⁻³
86 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.166 (13)

Crystal data top

C₈H₁₂N⁺·NO₃⁻	V = 920.4 (6) Å³
M_r = 184.20	Z = 4
Orthorhombic, Pmcn	Ag Kα radiation, λ = 0.56085 Å
a = 6.762 (3) Å	µ = 0.06 mm⁻¹
b = 7.942 (3) Å	T = 293 K
c = 17.137 (5) Å	0.50 × 0.45 × 0.40 mm

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.056
4249 measured reflections	2 standard reflections every 120 min
2365 independent reflections	intensity decay: 5%
822 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 0.92	Δρ_max = 0.20 e Å⁻³
2365 reflections	Δρ_min = −0.21 e Å⁻³
86 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	Occ. (<1)
H1A	0.135 (3)	0.372 (3)	0.2106 (10)	0.086 (7)*
H2A	0.2500	0.209 (4)	0.2009 (14)	0.068 (8)*
C6	0.2500	0.4899 (2)	0.07043 (11)	0.0405 (5)
N1	0.2500	0.3185 (3)	0.18968 (10)	0.0427 (4)
C1	0.2500	0.3315 (2)	0.10432 (10)	0.0349 (4)
C2	0.2500	0.1853 (3)	0.06089 (12)	0.0432 (5)
H2	0.2500	0.0817	0.0862	0.052*
C5	0.2500	0.4935 (3)	−0.01074 (13)	0.0507 (6)
H5	0.2500	0.5971	−0.0361	0.061*
C3	0.2500	0.1907 (3)	−0.01996 (12)	0.0452 (5)
C4	0.2500	0.3481 (3)	−0.05467 (12)	0.0499 (6)
H4	0.2500	0.3559	−0.1088	0.060*
C7	0.2500	0.6490 (3)	0.11749 (13)	0.0550 (6)
H7A	0.3818	0.6722	0.1353	0.083*	0.50
H7B	0.1638	0.6361	0.1616	0.083*	0.50
H7C	0.2044	0.7406	0.0857	0.083*	0.50
C8	0.2500	0.0315 (3)	−0.06851 (15)	0.0685 (7)
H8A	0.1164	0.0016	−0.0814	0.103*	0.50
H8B	0.3098	−0.0582	−0.0393	0.103*	0.50
H8C	0.3238	0.0501	−0.1156	0.103*	0.50
N2	0.2500	0.9146 (2)	0.26822 (9)	0.0425 (4)
O1	0.09203 (15)	0.98204 (16)	0.24632 (7)	0.0604 (4)
O2	0.2500	0.7900 (2)	0.30947 (10)	0.0672 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.0373 (10)	0.0419 (11)	0.0424 (10)	0.000	0.000	0.0018 (9)
N1	0.0501 (10)	0.0419 (11)	0.0360 (9)	0.000	0.000	0.0017 (8)
C1	0.0330 (9)	0.0399 (10)	0.0318 (9)	0.000	0.000	0.0012 (8)
C2	0.0458 (11)	0.0363 (11)	0.0476 (11)	0.000	0.000	0.0020 (9)
C5	0.0620 (15)	0.0427 (11)	0.0474 (12)	0.000	0.000	0.0089 (10)
C3	0.0411 (11)	0.0505 (13)	0.0440 (11)	0.000	0.000	−0.0092 (10)
C4	0.0506 (12)	0.0630 (15)	0.0361 (10)	0.000	0.000	0.0019 (10)
C7	0.0642 (14)	0.0425 (12)	0.0584 (13)	0.000	0.000	−0.0034 (11)
C8	0.0796 (19)	0.0673 (16)	0.0586 (14)	0.000	0.000	−0.0229 (13)
N2	0.0476 (10)	0.0425 (10)	0.0374 (9)	0.000	0.000	−0.0025 (8)
O1	0.0435 (6)	0.0667 (9)	0.0708 (7)	0.0079 (5)	0.0007 (6)	0.0138 (6)
O2	0.0868 (13)	0.0550 (10)	0.0598 (10)	0.000	0.000	0.0189 (9)

Geometric parameters (Å, º) top

C6—C1	1.385 (3)	C3—C8	1.514 (3)
C6—C5	1.391 (3)	C4—H4	0.9300
C6—C7	1.499 (3)	C7—H7A	0.9600
N1—C1	1.467 (2)	C7—H7B	0.9600
N1—H1A	0.95 (2)	C7—H7C	0.9600
N1—H2A	0.89 (3)	C8—H8A	0.9600
C1—C2	1.379 (3)	C8—H8B	0.9600
C2—C3	1.386 (3)	C8—H8C	0.9600
C2—H2	0.9300	N2—O2	1.216 (2)
C5—C4	1.379 (3)	N2—O1	1.2525 (14)
C5—H5	0.9300	N2—O1ⁱ	1.2525 (14)
C3—C4	1.384 (3)

C1—C6—C5	115.98 (18)	C5—C4—C3	121.46 (19)
C1—C6—C7	122.67 (18)	C5—C4—H4	119.3
C5—C6—C7	121.35 (19)	C3—C4—H4	119.3
C1—N1—H1A	110.2 (11)	C6—C7—H7A	109.5
C1—N1—H2A	106.6 (16)	C6—C7—H7B	109.5
H1A—N1—H2A	110.6 (14)	H7A—C7—H7B	109.5
C2—C1—C6	122.56 (17)	C6—C7—H7C	109.5
C2—C1—N1	118.60 (18)	H7A—C7—H7C	109.5
C6—C1—N1	118.84 (17)	H7B—C7—H7C	109.5
C1—C2—C3	120.9 (2)	C3—C8—H8A	109.5
C1—C2—H2	119.6	C3—C8—H8B	109.5
C3—C2—H2	119.6	H8A—C8—H8B	109.5
C4—C5—C6	121.9 (2)	C3—C8—H8C	109.5
C4—C5—H5	119.1	H8A—C8—H8C	109.5
C6—C5—H5	119.1	H8B—C8—H8C	109.5
C4—C3—C2	117.2 (2)	O2—N2—O1	121.48 (9)
C4—C3—C8	121.2 (2)	O2—N2—O1ⁱ	121.48 (9)
C2—C3—C8	121.6 (2)	O1—N2—O1ⁱ	117.04 (17)

C5—C6—C1—C2	0.0	C7—C6—C5—C4	180.0
C7—C6—C1—C2	180.0	C1—C2—C3—C4	0.0
C5—C6—C1—N1	180.0	C1—C2—C3—C8	180.0
C7—C6—C1—N1	0.0	C6—C5—C4—C3	0.0
C6—C1—C2—C3	0.0	C2—C3—C4—C5	0.0
N1—C1—C2—C3	180.0	C8—C3—C4—C5	180.0
C1—C6—C5—C4	0.0

Symmetry code: (i) −x+1/2, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.95 (2)	1.92 (3)	2.870 (2)	179 (3)
N1—H2A···O1ⁱⁱⁱ	0.89 (3)	2.24 (3)	3.037 (3)	150 (1)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·NO₃⁻
M_r	184.20
Crystal system, space group	Orthorhombic, Pmcn
Temperature (K)	293
a, b, c (Å)	6.762 (3), 7.942 (3), 17.137 (5)
V (Å³)	920.4 (6)
Z	4
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.06
Crystal size (mm)	0.50 × 0.45 × 0.40

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4249, 2365, 822
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.156, 0.92
No. of reflections	2365
No. of parameters	86
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.95 (2)	1.92 (3)	2.870 (2)	179 (3)
N1—H2A···O1ⁱⁱ	0.89 (3)	2.24 (3)	3.037 (3)	149.7 (8)

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

References

Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smirani, W. & Rzaigui, M. (2009). Acta Cryst. E65, o83. Web of Science CSD CrossRef IUCr Journals Google Scholar
Souissi, S., Smirani, W. & Rzaigui, M. (2009). Acta Cryst. E65, m442. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xiao, D., An, H., Wang, E. & Xu, L. (2005). J. Mol. Struct. 738, 217–225. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1917

doi:10.1107/S1600536809027718

Open

access