2-Cyano­anilinium nitrate

Cui, L.-J.; Wen, X.-C.

doi:10.1107/S1600536808023313

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1620

doi:10.1107/S1600536808023313

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2-Cyanoanilinium nitrate

Li-Jing Cui ^a and Xiao-Chun Wen ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 16 July 2008; accepted 23 July 2008; online 31 July 2008)

In the title compound, C₇H₇N₂⁺·NO₃⁻, all atoms of the cation, with the exception of two H atoms of the NH₃ group, lie on a mirror plane, while the anion lies across this plane with the N and one O atom on the mirror plane. In the crystal structure, the organic cations and NO₃⁻ anions are linked by N—H⋯N and N—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (100).

Related literature

For the use of amino derivatives in coordination chemisty, see: Manzur et al. (2007 ); Ismayilov et al. (2007 ); Austria et al. (2007 ); Wen et al. (2008 ).

Experimental

Crystal data

C₇H₇N₂⁺·NO₃⁻
M_r = 181.16
Orthorhombic, P n m a
a = 16.373 (3) Å
b = 6.5627 (13) Å
c = 7.9948 (16) Å
V = 859.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 (2) K
0.25 × 0.25 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005 ) T_min = 0.927, T_max = 0.983
8381 measured reflections
1072 independent reflections
797 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.167
S = 1.12
1072 reflections
83 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 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 (3)	1.86 (3)	2.805 (2)	177 (2)
N1—H1A⋯N3ⁱ	0.95 (3)	2.56 (3)	3.4523 (13)	156 (2)
N1—H1A⋯O2ⁱ	0.95 (3)	2.61 (3)	3.2898 (7)	129 (2)
N1—H1B⋯O1ⁱⁱ	0.94 (5)	2.13 (4)	2.979 (3)	150 (1)
N1—H1B⋯O1ⁱⁱⁱ	0.94 (5)	2.13 (4)	2.979 (3)	150 (1)
N1—H1B⋯N3ⁱⁱ	0.94 (5)	2.49 (5)	3.427 (4)	180 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) $[x, -y+{\script{1\over 2}}, z-1]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808023313/ci2636sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023313/ci2636Isup2.hkl

checkCIF report

Comment top

In the past five years, we have focused on the chemistry of amine derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Manzur et al. 2007; Ismayilov et al. 2007; Austria et al. 2007; Wen 2008). We report here the crystal structure of the title compound, 2-cyanobenzenaminium nitrate.

In the title compound (Fig.1), N atom of the amine group is protonated. The nitrile group is essentially coplanar with the benzene ring. Bond lengths and angles lie within normal ranges.

In the crystal structure, the organic cation and NO₃^- anions are linked to form a two-dimensional network parallel to the (1 0 0) by N—H···N and N—H···O hydrogen bonds (Table 1, Fig.2).

Related literature top

For the use of amino derivatives in coordination chemisty, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007); Wen et al. (2008).

Experimental top

2-Cyanobenzenaminium nitrate (3 mmol) was dissolved in ethanol (20 ml). The solution was allowed to evaporate to obtain colourless block-shaped crystals of the title compound.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal packing of the title compound viewed along the c axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

2-Cyanoanilinium nitrate top

Crystal data top

C₇H₇N₂⁺·NO₃⁻	F(000) = 376
M_r = 181.16	D_x = 1.401 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1592 reflections
a = 16.373 (3) Å	θ = 2.5–27.4°
b = 6.5627 (13) Å	µ = 0.11 mm⁻¹
c = 7.9948 (16) Å	T = 298 K
V = 859.0 (3) Å³	Block, colourless
Z = 4	0.25 × 0.25 × 0.15 mm

Data collection top

Rigaku Mercury2 diffractometer	1072 independent reflections
Radiation source: fine-focus sealed tube	797 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −20→21
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005)	k = −8→8
T_min = 0.927, T_max = 0.983	l = −10→10
8381 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0725P)² + 0.211P] where P = (F_o² + 2F_c²)/3
1072 reflections	(Δ/σ)_max = 0.001
83 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₇H₇N₂⁺·NO₃⁻	V = 859.0 (3) Å³
M_r = 181.16	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 16.373 (3) Å	µ = 0.11 mm⁻¹
b = 6.5627 (13) Å	T = 298 K
c = 7.9948 (16) Å	0.25 × 0.25 × 0.15 mm

Data collection top

Rigaku Mercury2 diffractometer	1072 independent reflections
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005)	797 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.983	R_int = 0.041
8381 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.17 e Å⁻³
1072 reflections	Δρ_min = −0.18 e Å⁻³
83 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 > 2sigma(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
O1	0.76566 (11)	0.0885 (3)	0.9282 (2)	0.0793 (6)
O2	0.82708 (18)	0.2500	0.7321 (3)	0.0951 (9)
N3	0.78679 (15)	0.2500	0.8601 (3)	0.0603 (7)
N1	0.68710 (15)	0.2500	0.2370 (3)	0.0571 (7)
N2	0.6141 (4)	0.2500	0.6492 (5)	0.1409 (19)
C1	0.5859 (3)	0.2500	0.5202 (5)	0.0962 (14)
C2	0.5501 (2)	0.2500	0.3564 (4)	0.0714 (9)
C3	0.4664 (3)	0.2500	0.3345 (9)	0.1171 (18)
H3	0.4319	0.2500	0.4269	0.141*
C4	0.4342 (2)	0.2500	0.1752 (11)	0.125 (2)
H4	0.3779	0.2500	0.1609	0.150*
C5	0.4835 (3)	0.2500	0.0394 (7)	0.0980 (14)
H5	0.4609	0.2500	−0.0673	0.118*
C6	0.5668 (2)	0.2500	0.0584 (4)	0.0690 (9)
H6	0.6008	0.2500	−0.0347	0.083*
C7	0.59927 (17)	0.2500	0.2164 (3)	0.0516 (7)
H1A	0.7034 (16)	0.132 (5)	0.298 (3)	0.083 (8)*
H1B	0.714 (3)	0.2500	0.134 (6)	0.104 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0975 (13)	0.0642 (11)	0.0763 (11)	0.0153 (9)	0.0278 (9)	0.0156 (8)
O2	0.0991 (19)	0.097 (2)	0.0893 (17)	0.000	0.0552 (15)	0.000
N3	0.0525 (14)	0.0693 (17)	0.0592 (14)	0.000	0.0098 (12)	0.000
N1	0.0533 (15)	0.0752 (18)	0.0426 (13)	0.000	0.0006 (11)	0.000
N2	0.205 (5)	0.161 (4)	0.057 (2)	0.000	0.034 (3)	0.000
C1	0.126 (4)	0.105 (3)	0.057 (2)	0.000	0.039 (2)	0.000
C2	0.074 (2)	0.068 (2)	0.072 (2)	0.000	0.0283 (18)	0.000
C3	0.067 (3)	0.125 (4)	0.159 (5)	0.000	0.047 (3)	0.000
C4	0.045 (2)	0.113 (4)	0.219 (7)	0.000	−0.008 (3)	0.000
C5	0.072 (3)	0.085 (3)	0.137 (4)	0.000	−0.040 (3)	0.000
C6	0.064 (2)	0.074 (2)	0.069 (2)	0.000	−0.0116 (16)	0.000
C7	0.0504 (15)	0.0517 (15)	0.0527 (16)	0.000	0.0010 (12)	0.000

Geometric parameters (Å, º) top

O1—N3	1.241 (2)	C2—C7	1.378 (4)
O2—N3	1.218 (3)	C3—C4	1.378 (8)
N3—O1ⁱ	1.241 (2)	C3—H3	0.93
N1—C7	1.448 (4)	C4—C5	1.353 (8)
N1—H1A	0.95 (3)	C4—H4	0.93
N1—H1B	0.94 (5)	C5—C6	1.371 (5)
N2—C1	1.130 (6)	C5—H5	0.93
C1—C2	1.434 (6)	C6—C7	1.371 (4)
C2—C3	1.382 (6)	C6—H6	0.93

O2—N3—O1ⁱ	121.32 (12)	C5—C4—C3	120.9 (4)
O2—N3—O1	121.32 (12)	C5—C4—H4	119.5
O1ⁱ—N3—O1	117.4 (2)	C3—C4—H4	119.5
C7—N1—H1A	109.7 (16)	C4—C5—C6	120.2 (5)
C7—N1—H1B	112 (3)	C4—C5—H5	119.9
H1A—N1—H1B	109 (2)	C6—C5—H5	119.9
N2—C1—C2	179.9 (5)	C7—C6—C5	119.2 (4)
C3—C2—C7	118.5 (4)	C7—C6—H6	120.4
C3—C2—C1	121.4 (4)	C5—C6—H6	120.4
C7—C2—C1	120.2 (3)	C6—C7—C2	121.4 (3)
C2—C3—C4	119.7 (4)	C6—C7—N1	119.4 (3)
C2—C3—H3	120.1	C2—C7—N1	119.2 (3)
C4—C3—H3	120.1

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

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.95 (3)	1.86 (3)	2.805 (2)	177 (2)
N1—H1A···N3ⁱⁱ	0.95 (3)	2.56 (3)	3.4523 (13)	156 (2)
N1—H1A···O2ⁱⁱ	0.95 (3)	2.61 (3)	3.2898 (7)	129 (2)
N1—H1B···O1ⁱⁱⁱ	0.94 (5)	2.13 (4)	2.979 (3)	150 (1)
N1—H1B···O1^iv	0.94 (5)	2.13 (4)	2.979 (3)	150 (1)
N1—H1B···N3ⁱⁱⁱ	0.94 (5)	2.49 (5)	3.427 (4)	180 (3)

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·NO₃⁻
M_r	181.16
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	16.373 (3), 6.5627 (13), 7.9948 (16)
V (Å³)	859.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear, Rigaku, 2005)
T_min, T_max	0.927, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	8381, 1072, 797
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.167, 1.12
No. of reflections	1072
No. of parameters	83
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.95 (3)	1.86 (3)	2.805 (2)	177 (2)
N1—H1A···N3ⁱ	0.95 (3)	2.56 (3)	3.4523 (13)	156 (2)
N1—H1A···O2ⁱ	0.95 (3)	2.61 (3)	3.2898 (7)	129 (2)
N1—H1B···O1ⁱⁱ	0.94 (5)	2.13 (4)	2.979 (3)	150 (1)
N1—H1B···O1ⁱⁱⁱ	0.94 (5)	2.13 (4)	2.979 (3)	150 (1)
N1—H1B···N3ⁱⁱ	0.94 (5)	2.49 (5)	3.427 (4)	180 (3)

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

References

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