2-Cyano­anilinium perchlorate

Abstract

In the title compound, C₇H₇N₂ ⁺·ClO₄ ⁻, the cation is almost planar (r.m.s. deviation = 0.042 Å). In the crystal structure, the cations and anions are linked into a two-dimensional network parallel to (100) by N—H⋯O hydrogen bonds.

Related literature

For the crystal structure of 2-cyano­anilinium chloride, see: Oueslati et al. (2005 ▶). For Cl—O distances, see: Messai et al. (2009 ▶).

Experimental

Crystal data

• C₇H₇N₂ ⁺·ClO₄ ⁻

• M _r = 218.60

• Monoclinic,

• a = 11.089 (2) Å

• b = 7.4561 (15) Å

• c = 13.872 (5) Å

• β = 128.454 (18)°

• V = 898.2 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.42 mm⁻¹

• T = 298 K

• 0.40 × 0.05 × 0.05 mm

Data collection

• Rigaku Mercury2 diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.90, T _max = 1.00

• 9026 measured reflections

• 2070 independent reflections

• 1761 reflections with I > 2σ(I)

• R _int = 0.041

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.117

• S = 1.11

• 2070 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4i	0.89	2.14	2.936 (2)	148
N2—H2B⋯O4ii	0.89	2.24	3.007 (3)	144
N2—H2C⋯O1iii	0.89	1.98	2.842 (2)	161

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Aniline derivatives attracted more attention as phase transition dielectric materials for their applications in micro-electronics and memory storage. With the purpose of obtaining phase transition crystals of 2-aminobenzonitrile salts, its interaction with various acids has been studied and we have obtained a series of new materials with this organic molecule. In this paper, we describe the crystal structure of the title compound, 2-cyanoanilinium perchlorate.

The asymmetric unit is composed of a 2-cyanoanilinium cation and a perchlorate anion (Fig.1). The anion displays a typical tetrahedral geometry around Cl atom and the Cl—O distances compare well with previously reported values (Messai et al., 2009). The cation is almost planar (r.m.s. deviation 0.042 Å; maximum atomic deviation from coplanarity is 0.073 (2) Å by atom N1). The C—NH₃ [1.466 (2) Å] and C≡N [1.143 (3) Å] distances in the 2-cyanoanilinium cation are longer compared to the corresponding distances in the crystal structure of 2-cyanoanilinium chloride (1.457 (4) Å, 1.137 (4) Å; Oueslati et al., 2005).

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

Experimental

The commercial 2-aminobenzonitrile (3 mmol, 324 mg) was dissolved in a water-HClO₄ (50:1 v/v) solution. The solvent was slowly evaporated in air affording colourless crystals of the title compound suitable for X-ray analysis.

While the permittivity measurement shows that there is no phase transition within the temperature range (from 100 K to 400 K), and the permittivity is 7.8 at 1 MHz at room temperature.

Refinement

All H atoms were initially located in a difference Fourier map. They were then constrained to an ideal geometry, with C–H = 0.93 Å, N–H = 0.89 Å and U_iso(H) = 1.2U_eq(C) and 1.5U_eq(N). A rotating-group model was used for the -NH₃ group.

Figures

Fig. 1.

The asymmetric unit of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Fig. 2.

The crystal packing of the title compound, showing a two-dimensional network parallel to the (100). H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Crystal data

C7H7N2+·ClO4−	F(000) = 448
Mr = 218.60	Dx = 1.617 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1761 reflections
a = 11.089 (2) Å	θ = 3.3–27.5°
b = 7.4561 (15) Å	µ = 0.42 mm−1
c = 13.872 (5) Å	T = 298 K
β = 128.454 (18)°	Needle, colourless
V = 898.2 (4) Å3	0.40 × 0.05 × 0.05 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer	2070 independent reflections
Radiation source: fine-focus sealed tube	1761 reflections with I > 2σ(I)
graphite	Rint = 0.041
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.3°
CCD profile fitting scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.90, Tmax = 1.00	l = −18→18
9026 measured reflections

Refinement

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0456P)2 + 0.522P] where P = (Fo2 + 2Fc2)/3
2070 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.30 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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
N2	0.10356 (18)	0.1622 (2)	0.40630 (16)	0.0351 (4)
H2A	0.0666	0.0523	0.3784	0.053*
H2B	0.0743	0.2332	0.3435	0.053*
H2C	0.0675	0.2053	0.4438	0.053*
N1	0.2247 (3)	0.4407 (3)	0.2725 (2)	0.0647 (7)
C7	0.2722 (2)	0.1553 (3)	0.49390 (19)	0.0327 (4)
C1	0.2853 (3)	0.3504 (3)	0.3573 (2)	0.0472 (6)
C5	0.5007 (3)	0.0559 (4)	0.6835 (2)	0.0629 (8)
H5	0.5493	−0.0064	0.7572	0.075*
C2	0.3588 (2)	0.2429 (3)	0.4665 (2)	0.0386 (5)
C6	0.3415 (3)	0.0628 (3)	0.6013 (2)	0.0469 (6)
H6	0.2827	0.0054	0.6189	0.056*
C4	0.5883 (3)	0.1403 (4)	0.6574 (3)	0.0662 (8)
H4	0.6952	0.1343	0.7133	0.079*
C3	0.5183 (3)	0.2326 (4)	0.5496 (3)	0.0547 (7)
H3	0.5775	0.2886	0.5320	0.066*
Cl1	0.91401 (6)	0.33466 (7)	0.57188 (4)	0.03477 (17)
O4	0.8898 (2)	0.2197 (2)	0.64175 (15)	0.0471 (4)
O3	0.7769 (2)	0.4305 (3)	0.48297 (16)	0.0681 (6)
O2	1.0336 (2)	0.4577 (2)	0.65476 (18)	0.0610 (5)
O1	0.9559 (2)	0.2236 (3)	0.51274 (17)	0.0574 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N2	0.0340 (9)	0.0349 (9)	0.0403 (10)	−0.0018 (7)	0.0250 (8)	−0.0023 (7)
N1	0.0733 (16)	0.0653 (15)	0.0617 (14)	−0.0195 (13)	0.0451 (13)	−0.0017 (12)
C7	0.0326 (10)	0.0306 (10)	0.0365 (10)	−0.0049 (8)	0.0223 (9)	−0.0081 (8)
C1	0.0499 (13)	0.0460 (13)	0.0576 (15)	−0.0166 (11)	0.0393 (13)	−0.0111 (12)
C5	0.0518 (15)	0.0571 (16)	0.0415 (13)	0.0008 (13)	0.0101 (12)	−0.0004 (12)
C2	0.0391 (11)	0.0351 (11)	0.0491 (12)	−0.0064 (9)	0.0311 (10)	−0.0094 (9)
C6	0.0476 (13)	0.0474 (13)	0.0384 (12)	−0.0070 (11)	0.0232 (11)	−0.0029 (10)
C4	0.0314 (12)	0.0587 (16)	0.0718 (19)	−0.0030 (12)	0.0140 (13)	−0.0145 (15)
C3	0.0393 (13)	0.0495 (14)	0.0762 (18)	−0.0111 (11)	0.0364 (14)	−0.0166 (13)
Cl1	0.0407 (3)	0.0312 (3)	0.0334 (3)	0.0017 (2)	0.0235 (2)	−0.00068 (19)
O4	0.0561 (10)	0.0436 (9)	0.0532 (10)	−0.0028 (8)	0.0397 (9)	0.0023 (8)
O3	0.0669 (12)	0.0745 (14)	0.0424 (10)	0.0332 (11)	0.0238 (9)	0.0151 (9)
O2	0.0660 (12)	0.0423 (10)	0.0638 (11)	−0.0212 (9)	0.0349 (10)	−0.0126 (8)
O1	0.0724 (12)	0.0587 (11)	0.0635 (11)	0.0041 (9)	0.0534 (11)	−0.0085 (9)

Geometric parameters (Å, °)

N2—C7	1.466 (2)	C5—H5	0.93
N2—H2A	0.89	C2—C3	1.388 (3)
N2—H2B	0.89	C6—H6	0.93
N2—H2C	0.89	C4—C3	1.367 (4)
N1—C1	1.143 (3)	C4—H4	0.93
C7—C6	1.364 (3)	C3—H3	0.93
C7—C2	1.396 (3)	Cl1—O3	1.4181 (18)
C1—C2	1.437 (4)	Cl1—O2	1.4233 (18)
C5—C4	1.381 (4)	Cl1—O1	1.4315 (17)
C5—C6	1.385 (4)	Cl1—O4	1.4385 (17)
C7—N2—H2A	109.5	C7—C6—C5	118.8 (2)
C7—N2—H2B	109.5	C7—C6—H6	120.6
H2A—N2—H2B	109.5	C5—C6—H6	120.6
C7—N2—H2C	109.5	C3—C4—C5	120.2 (2)
H2A—N2—H2C	109.5	C3—C4—H4	119.9
H2B—N2—H2C	109.5	C5—C4—H4	119.9
C6—C7—C2	121.2 (2)	C4—C3—C2	120.0 (2)
C6—C7—N2	118.99 (19)	C4—C3—H3	120.0
C2—C7—N2	119.78 (19)	C2—C3—H3	120.0
N1—C1—C2	177.1 (3)	O3—Cl1—O2	109.53 (13)
C4—C5—C6	120.8 (3)	O3—Cl1—O1	110.35 (12)
C4—C5—H5	119.6	O2—Cl1—O1	111.38 (12)
C6—C5—H5	119.6	O3—Cl1—O4	109.75 (12)
C3—C2—C7	119.0 (2)	O2—Cl1—O4	108.07 (11)
C3—C2—C1	120.1 (2)	O1—Cl1—O4	107.72 (11)
C7—C2—C1	120.8 (2)
C6—C7—C2—C3	1.0 (3)	C4—C5—C6—C7	−0.3 (4)
N2—C7—C2—C3	−179.0 (2)	C6—C5—C4—C3	0.2 (4)
C6—C7—C2—C1	−175.6 (2)	C5—C4—C3—C2	0.5 (4)
N2—C7—C2—C1	4.4 (3)	C7—C2—C3—C4	−1.1 (4)
C2—C7—C6—C5	−0.3 (4)	C1—C2—C3—C4	175.5 (2)
N2—C7—C6—C5	179.7 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4i	0.89	2.14	2.936 (2)	148
N2—H2B···O4ii	0.89	2.24	3.007 (3)	144
N2—H2C···O1iii	0.89	1.98	2.842 (2)	161

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