3-Cyano­anilinium nitrate

Wang, B.

doi:10.1107/S1600536809034886

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2395

doi:10.1107/S1600536809034886

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3-Cyanoanilinium nitrate

Bo Wang ^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 18 August 2009; accepted 31 August 2009; online 9 September 2009)

In the cation of the title compound, C₇H₇N₂⁺·NO₃⁻, the nitrile group and the benzene ring are almost coplanar (r.m.s. deviation = 0.006 Å). In the crystal, the ions are connected by bifurcated N—H⋯(O,O) hydrogen bonds, forming a two-dimensional network parallel to (001).

Related literature

For the applications of metal-organic coordination compounds, see: Fu et al. (2007 ); Chen et al. (2001 ); Fu & Xiong (2008 ); Xiong et al. (1999 ); Xie et al. (2003 ); Zhao et al. (2004 ). For nitrile derivatives, see: Fu et al. (2008 ); Wang et al. 2002 .

Experimental

Crystal data

C₇H₇N₂⁺·NO₃⁻
M_r = 181.16
Orthorhombic, P b c a
a = 10.210 (2) Å
b = 10.812 (2) Å
c = 15.398 (3) Å
V = 1699.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.40 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.94, T_max = 1.00
15905 measured reflections
1871 independent reflections
1456 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.141
S = 1.14
1871 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.89	2.22	3.104 (2)	173
N2—H2A⋯O1ⁱ	0.89	2.44	3.107 (2)	133
N2—H2B⋯O2ⁱⁱ	0.89	2.06	2.859 (2)	150
N2—H2B⋯O3ⁱⁱ	0.89	2.25	3.049 (2)	149
N2—H2C⋯O2	0.89	1.85	2.738 (2)	172
N2—H2C⋯O1	0.89	2.56	3.090 (2)	119
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

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/S1600536809034886/ci2892sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034886/ci2892Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Fu et al., 2007; Chen et al., 2001; Fu & Xiong, 2008; Xie et al., 2003; Zhao et al., 2004; Xiong et al., 1999). Nitrile derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks (Wang et al. 2002; Fu et al., 2008). We report here the crystal structure of the title compound, 3-cyanoanilinium nitrate.

In the 3-cyanoanilinium cation (Fig.1), the nitrile group and the benzene ring are coplanar. The nitrile group C1≡N1 bond length of 1.102 (3) Å is within the normal range.

In the crystal structure, all the amine group H atoms are involved in N—H···O hydrogen bonds (Table 1) with O atoms of the NO₃^- anion. These hydrogen bonds link the ionic units into a two-dimensional network (Fig. 2) parallel to the (001) plane.

Related literature top

For the applications of metal-organic coordination compounds, see: Fu et al. (2007); Chen et al. (2001); Fu & Xiong (2008); Xiong et al. (1999); Xie et al. (2003); Zhao et al. (2004). For nitrile derivatives, see: Fu et al. (2008); Wang et al. 2002.

Experimental top

The commercial 3-aminobenzonitrile (3 mmol, 0.55 g) and HNO₃ (0.5 ml) were dissolved in ethanol (20 ml). Colourless block-shaped crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature.

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. The crystal packing of the title compound, viewed along the c axis, showing N—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

3-Cyanoanilinium nitrate top

Crystal data top

C₇H₇N₂⁺·NO₃⁻	F(000) = 752
M_r = 181.16	D_x = 1.416 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1456 reflections
a = 10.210 (2) Å	θ = 3.1–27.5°
b = 10.812 (2) Å	µ = 0.11 mm⁻¹
c = 15.398 (3) Å	T = 298 K
V = 1699.8 (6) Å³	Block, colourless
Z = 8	0.40 × 0.25 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	1871 independent reflections
Radiation source: fine-focus sealed tube	1456 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD profile fitting scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.94, T_max = 1.00	l = −19→19
15905 measured reflections

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.059P)² + 0.3685P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
1871 reflections	Δρ_max = 0.21 e Å⁻³
120 parameters	Δρ_min = −0.19 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: 0.021 (3)

Crystal data top

C₇H₇N₂⁺·NO₃⁻	V = 1699.8 (6) Å³
M_r = 181.16	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.210 (2) Å	µ = 0.11 mm⁻¹
b = 10.812 (2) Å	T = 298 K
c = 15.398 (3) Å	0.40 × 0.25 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	1871 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1456 reflections with I > 2σ(I)
T_min = 0.94, T_max = 1.00	R_int = 0.062
15905 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.14	Δρ_max = 0.21 e Å⁻³
1871 reflections	Δρ_min = −0.19 e Å⁻³
120 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
N1	0.06292 (19)	0.5067 (2)	0.39061 (13)	0.0724 (6)
N2	0.39497 (14)	0.44355 (16)	0.69503 (9)	0.0435 (4)
H2A	0.4110	0.5239	0.7016	0.065*
H2B	0.4620	0.4001	0.7158	0.065*
H2C	0.3224	0.4236	0.7238	0.065*
C1	0.1482 (2)	0.4737 (2)	0.42791 (13)	0.0526 (5)
C2	0.25733 (17)	0.43017 (19)	0.47337 (11)	0.0443 (5)
C3	0.27221 (17)	0.45958 (18)	0.56150 (11)	0.0420 (5)
H3	0.2108	0.5080	0.5904	0.050*
C4	0.37764 (16)	0.41559 (17)	0.60241 (11)	0.0382 (4)
C5	0.46585 (19)	0.34385 (19)	0.55934 (12)	0.0488 (5)
H5	0.5382	0.3131	0.5890	0.059*
C6	0.4502 (2)	0.3155 (2)	0.47200 (13)	0.0568 (6)
H6	0.5119	0.2669	0.4436	0.068*
C7	0.3461 (2)	0.3585 (2)	0.42905 (12)	0.0538 (5)
H7	0.3339	0.3403	0.3706	0.065*
O1	0.23542 (15)	0.20195 (16)	0.71257 (11)	0.0701 (5)
O2	0.16047 (13)	0.37804 (14)	0.76798 (10)	0.0594 (5)
O3	0.04000 (13)	0.21817 (14)	0.73494 (10)	0.0592 (5)
N3	0.14567 (15)	0.26571 (16)	0.73782 (10)	0.0449 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0625 (12)	0.1071 (17)	0.0476 (11)	0.0072 (12)	−0.0138 (9)	−0.0010 (11)
N2	0.0413 (8)	0.0563 (10)	0.0328 (8)	0.0053 (7)	−0.0013 (6)	−0.0047 (7)
C1	0.0517 (11)	0.0722 (14)	0.0339 (10)	−0.0038 (10)	−0.0043 (9)	−0.0017 (9)
C2	0.0432 (10)	0.0547 (12)	0.0351 (9)	−0.0056 (8)	−0.0034 (7)	0.0006 (8)
C3	0.0382 (9)	0.0536 (11)	0.0341 (9)	0.0008 (8)	0.0015 (7)	−0.0030 (8)
C4	0.0401 (9)	0.0440 (10)	0.0306 (9)	−0.0018 (8)	0.0004 (7)	−0.0021 (7)
C5	0.0473 (10)	0.0588 (12)	0.0403 (10)	0.0103 (9)	0.0008 (8)	−0.0038 (9)
C6	0.0572 (13)	0.0703 (14)	0.0429 (11)	0.0126 (11)	0.0061 (9)	−0.0134 (10)
C7	0.0612 (12)	0.0685 (14)	0.0318 (9)	−0.0020 (11)	0.0013 (9)	−0.0094 (9)
O1	0.0487 (9)	0.0727 (11)	0.0889 (12)	0.0073 (8)	0.0163 (8)	−0.0161 (9)
O2	0.0548 (9)	0.0635 (10)	0.0598 (9)	−0.0069 (7)	0.0087 (7)	−0.0173 (8)
O3	0.0395 (8)	0.0752 (10)	0.0628 (10)	−0.0077 (7)	−0.0046 (6)	−0.0065 (7)
N3	0.0440 (9)	0.0596 (11)	0.0310 (8)	−0.0007 (8)	−0.0012 (6)	0.0000 (7)

Geometric parameters (Å, º) top

N1—C1	1.102 (3)	C4—C5	1.361 (3)
N2—C4	1.469 (2)	C5—C6	1.389 (3)
N2—H2A	0.89	C5—H5	0.93
N2—H2B	0.89	C6—C7	1.335 (3)
N2—H2C	0.89	C6—H6	0.93
C1—C2	1.397 (3)	C7—H7	0.93
C2—C7	1.374 (3)	O1—N3	1.211 (2)
C2—C3	1.402 (3)	O2—N3	1.309 (2)
C3—C4	1.335 (2)	O3—N3	1.196 (2)
C3—H3	0.93

C4—N2—H2A	109.5	C3—C4—N2	118.82 (15)
C4—N2—H2B	109.5	C5—C4—N2	120.72 (16)
H2A—N2—H2B	109.5	C4—C5—C6	121.42 (18)
C4—N2—H2C	109.5	C4—C5—H5	119.3
H2A—N2—H2C	109.5	C6—C5—H5	119.3
H2B—N2—H2C	109.5	C7—C6—C5	119.66 (19)
N1—C1—C2	178.6 (2)	C7—C6—H6	120.2
C7—C2—C1	117.84 (17)	C5—C6—H6	120.2
C7—C2—C3	122.50 (17)	C6—C7—C2	118.37 (17)
C1—C2—C3	119.66 (17)	C6—C7—H7	120.8
C4—C3—C2	117.60 (17)	C2—C7—H7	120.8
C4—C3—H3	121.2	O3—N3—O1	115.22 (17)
C2—C3—H3	121.2	O3—N3—O2	121.07 (16)
C3—C4—C5	120.45 (17)	O1—N3—O2	123.69 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.89	2.22	3.104 (2)	173
N2—H2A···O1ⁱ	0.89	2.44	3.107 (2)	133
N2—H2B···O2ⁱⁱ	0.89	2.06	2.859 (2)	150
N2—H2B···O3ⁱⁱ	0.89	2.25	3.049 (2)	149
N2—H2C···O2	0.89	1.85	2.738 (2)	172
N2—H2C···O1	0.89	2.56	3.090 (2)	119

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·NO₃⁻
M_r	181.16
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	10.210 (2), 10.812 (2), 15.398 (3)
V (Å³)	1699.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.94, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	15905, 1871, 1456
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.141, 1.14
No. of reflections	1871
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

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
N2—H2A···O3ⁱ	0.89	2.22	3.104 (2)	173
N2—H2A···O1ⁱ	0.89	2.44	3.107 (2)	133
N2—H2B···O2ⁱⁱ	0.89	2.06	2.859 (2)	150
N2—H2B···O3ⁱⁱ	0.89	2.25	3.049 (2)	149
N2—H2C···O2	0.89	1.85	2.738 (2)	172
N2—H2C···O1	0.89	2.56	3.090 (2)	119

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

Acknowledgements

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

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