Experimental
Crystal data
C8H12N+·NO3− Mr = 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) Rint = 0.056 2 standard reflections frequency: 120 min intensity decay: 5%
|
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) ; (ii) . | |
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
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.
The nitrogen H atoms were located in a difference map and freely refined. The other H atoms were positioned geometrically(C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq (C) or 1.5 Ueq(methyl C).
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).
2,5-Dimethylanilinium nitrate
top Crystal data top C8H12N+·NO3− | F(000) = 392 |
Mr = 184.20 | Dx = 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 | Rint = 0.056 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 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(Fo2) + (0.0632P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max < 0.001 |
2365 reflections | Δρmax = 0.20 e Å−3 |
86 parameters | Δρmin = −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 |
Mr = 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 | Rint = 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 | Δρmax = 0.20 e Å−3 |
2365 reflections | Δρmin = −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 | Uiso*/Ueq | 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− |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.20, −0.21 |
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
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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).