2-Cyano­anilinium perchlorate

Cui, L.-J.; Chen, X.-Y.

doi:10.1107/S1600536810003077

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o467

https://doi.org/10.1107/S1600536810003077

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2-Cyanoanilinium perchlorate

Li-Jing Cui ^a ^* and Xin-Yuan Chen ^a

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

(Received 22 January 2010; accepted 25 January 2010; online 30 January 2010)

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, P 2₁ /c
a = 11.089 (2) Å
b = 7.4561 (15) Å
c = 13.872 (5) Å
β = 128.454 (18)°
V = 898.2 (4) Å³
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[F² > 2σ(F²)] = 0.044
wR(F²) = 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

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) -x+1, -y, -z+1; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x-1, y, z.

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: https://doi.org/10.1107/S1600536810003077/ci5023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810003077/ci5023Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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

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. 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.

2-Cyanoanilinium perchlorate top

Crystal data top

C₇H₇N₂⁺·ClO₄⁻	F(000) = 448
M_r = 218.60	D_x = 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 top

Rigaku Mercury2 diffractometer	2070 independent reflections
Radiation source: fine-focus sealed tube	1761 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD profile fitting scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.90, T_max = 1.00	l = −18→18
9026 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0456P)² + 0.522P] where P = (F_o² + 2F_c²)/3
2070 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₇H₇N₂⁺·ClO₄⁻	V = 898.2 (4) Å³
M_r = 218.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.089 (2) Å	µ = 0.42 mm⁻¹
b = 7.4561 (15) Å	T = 298 K
c = 13.872 (5) Å	0.40 × 0.05 × 0.05 mm
β = 128.454 (18)°

Data collection top

Rigaku Mercury2 diffractometer	2070 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1761 reflections with I > 2σ(I)
T_min = 0.90, T_max = 1.00	R_int = 0.041
9026 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.11	Δρ_max = 0.32 e Å⁻³
2070 reflections	Δρ_min = −0.30 e Å⁻³
128 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 > 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	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·ClO₄⁻
M_r	218.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.089 (2), 7.4561 (15), 13.872 (5)
β (°)	128.454 (18)
V (Å³)	898.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.40 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.90, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	9026, 2070, 1761
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.11
No. of reflections	2070
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.30

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···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.

Acknowledgements

This work was supported by the Innovative Dissertation Fund of Southeast University.

References

Messai, A., Direm, A., Benali-Cherif, N., Luneau, D. & Jeanneau, E. (2009). Acta Cryst. E65, o460. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oueslati, A., Kefi, R., Akriche, S. & Nasr, C. B. (2005). Z. Kristallogr. New Cryst. Struct. 220, 365–366. CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar