2-Cyano­anilinium nitrate

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).

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.063
• wR factor = 0.167
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.43 Ang.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         N1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A    ..  O2      ..       2.61 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

C-bound H atoms were fixed geometrically (C-H = 0.93 Å) and treated as riding with U_iso(H) = 1.2U_eq(C). N-bound H atoms were located in a difference Fourier map and refined freely.

Computing details

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

	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

Crystal data

C7H7N2^+·NO3^−	F(000) = 376
Mr = 181.16	Dx = 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) Å^3	Block, colourless
Z = 4	0.25 × 0.25 × 0.15 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0725P)^2 + 0.211P] where P = (Fo^2 + 2Fc^2)/3
1072 reflections	(Δ/σ)max = 0.001
83 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

O1—N3	1.241 (2)	C2—C7	1.378 (4)
O2—N3	1.218 (3)	C3—C4	1.378 (8)
N3—O1^i	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—O1^i	121.32 (12)	C5—C4—C3	120.9 (4)
O2—N3—O1	121.32 (12)	C5—C4—H4	119.5
O1^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^ii	0.95 (3)	1.86 (3)	2.805 (2)	177 (2)
N1—H1A···N3^ii	0.95 (3)	2.56 (3)	3.4523 (13)	156 (2)
N1—H1A···O2^ii	0.95 (3)	2.61 (3)	3.2898 (7)	129 (2)
N1—H1B···O1^iii	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···N3^iii	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.