4-Cyano­anilinium perchlorate

Dai, J.

doi:10.1107/S1600536808030687

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o2025

doi:10.1107/S1600536808030687

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4-Cyanoanilinium perchlorate

Jing Dai ^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 13 September 2008; accepted 23 September 2008; online 27 September 2008)

The title compound, C₇H₇N₂⁺·ClO₄⁻, comprises discrete ions which are interconnected by N—H⋯O hydrogen bonds, leading to a neutral one-dimensional network along the [100] direction.

Related literature

For the chemistry of nitrile derivatives, see: Xiong et al. (2002 ); Jin et al. (1994 ); Brewis et al. (2003 ); Fu et al. (2008 ); Duncia et al. (1991 ); Fu & Zhao (2007 ); Dai & Fu (2008 ); Smith et al. (2000 ).

Experimental

Crystal data

C₇H₇N₂⁺·ClO₄⁻
M_r = 218.60
Triclinic, $[P \overline 1]$
a = 4.9905 (10) Å
b = 6.9465 (14) Å
c = 13.998 (3) Å
α = 94.87 (3)°
β = 95.68 (3)°
γ = 103.99 (3)°
V = 465.57 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 298 (2) K
0.25 × 0.15 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.941, T_max = 1.000 (expected range = 0.886–0.942)
4861 measured reflections
2126 independent reflections
1851 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 1.05
2126 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	2.04	2.881 (2)	158
N1—H1B⋯O3ⁱⁱ	0.89	1.98	2.855 (2)	166
N1—H1C⋯O4ⁱⁱⁱ	0.89	2.04	2.871 (2)	156
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -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) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030687/bx2181sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030687/bx2181Isup2.hkl

checkCIF report

Comment top

Nitrile derivatives have found wide range of applications in industry and coordination chemistry as ligands. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (Brewis et al., 2003). And nitrile compounds are the precursor of tetrazole complexes (Duncia et al., 1991; Xiong et al., 2002; Fu et al., 2008). Recently, a series of benzonitrile compounds have been reported (Fu & Zhao, 2007; Dai & Fu, 2008; Smith et al., 2000). As an extension of these work on the structural characterization, we report here the crystal structure of the title compound p-cyanoanilinium perchloride. The crystal data show that in the title compound, the N1 atom of the amine group is protonated. The nitrile group and the benzene ring are essentially coplanar. The C1≡N2 bond length of 1.135 (3) Å is within the normal range (Fig. 1).The crystal packing is stablized by cation–anion N—H···O hydrogen bonds, building an infinite one-dimensional chain parallel to the a axis. (Table 1, Fig. 2).

Related literature top

For the chemistry of nitrile derivatives, see: Xiong et al. (2002); Jin et al. (1994); Brewis et al. (2003); Fu et al. (2008); Duncia et al. (1991); Fu & Zhao (2007); Dai & Fu (2008); Smith et al. (2000).

Experimental top

p-cyanoaniline (3 mmol, 354 mg) was dissolved in the solution of distilled water (10 ml) and perchloride acid (0.5 ml), and evaporated in the air affording colorless block crystals of this compound suitable for X-ray analysis were obtained.

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) and PLATON (Spek, 2003); 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 were drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

4-Cyanoanilinium perchlorate top

Crystal data top

C₇H₇N₂⁺·ClO₄⁻	Z = 2
M_r = 218.60	F(000) = 224
Triclinic, P1	D_x = 1.559 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9905 (10) Å	Cell parameters from 1806 reflections
b = 6.9465 (14) Å	θ = 3.0–27.5°
c = 13.998 (3) Å	µ = 0.40 mm⁻¹
α = 94.87 (3)°	T = 298 K
β = 95.68 (3)°	Block, colourless
γ = 103.99 (3)°	0.25 × 0.15 × 0.15 mm
V = 465.57 (17) Å³

Data collection top

Rigaku Mercury2 diffractometer	2126 independent reflections
Radiation source: fine-focus sealed tube	1851 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.941, T_max = 1.000	l = −18→18
4861 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0483P)² + 0.1253P] where P = (F_o² + 2F_c²)/3
2126 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₇H₇N₂⁺·ClO₄⁻	γ = 103.99 (3)°
M_r = 218.60	V = 465.57 (17) Å³
Triclinic, P1	Z = 2
a = 4.9905 (10) Å	Mo Kα radiation
b = 6.9465 (14) Å	µ = 0.40 mm⁻¹
c = 13.998 (3) Å	T = 298 K
α = 94.87 (3)°	0.25 × 0.15 × 0.15 mm
β = 95.68 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2126 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1851 reflections with I > 2σ(I)
T_min = 0.941, T_max = 1.000	R_int = 0.023
4861 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
2126 reflections	Δρ_min = −0.34 e Å⁻³
128 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
N1	0.6157 (3)	0.2508 (2)	0.12597 (11)	0.0399 (4)
H1A	0.4771	0.2405	0.0791	0.048*
H1B	0.6876	0.1460	0.1180	0.048*
H1C	0.7468	0.3623	0.1238	0.048*
N2	0.0727 (7)	0.2647 (4)	0.5503 (2)	0.1058 (10)
C1	0.1672 (6)	0.2642 (4)	0.47983 (19)	0.0743 (8)
C2	0.2877 (5)	0.2620 (3)	0.38998 (16)	0.0549 (5)
C3	0.2722 (5)	0.4100 (3)	0.33016 (17)	0.0557 (5)
H3	0.1860	0.5101	0.3478	0.067*
C4	0.3859 (4)	0.4064 (3)	0.24466 (15)	0.0458 (4)
H4	0.3789	0.5049	0.2041	0.055*
C5	0.5097 (3)	0.2566 (3)	0.21961 (13)	0.0362 (4)
C6	0.5293 (4)	0.1094 (3)	0.27829 (14)	0.0464 (5)
H6	0.6169	0.0104	0.2604	0.056*
C7	0.4158 (5)	0.1127 (4)	0.36408 (16)	0.0574 (6)
H7	0.4252	0.0145	0.4046	0.069*
Cl1	−0.00044 (8)	0.22266 (6)	0.91125 (3)	0.03315 (14)
O1	−0.2849 (3)	0.1812 (2)	0.92711 (11)	0.0552 (4)
O2	0.1712 (3)	0.3237 (2)	0.99794 (12)	0.0598 (4)
O3	0.0665 (3)	0.0398 (2)	0.88369 (13)	0.0593 (4)
O4	0.0420 (4)	0.3478 (2)	0.83610 (12)	0.0668 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0442 (8)	0.0392 (8)	0.0403 (9)	0.0162 (7)	0.0100 (6)	0.0048 (6)
N2	0.141 (3)	0.0996 (19)	0.0746 (17)	0.0122 (17)	0.0625 (17)	−0.0038 (14)
C1	0.0839 (18)	0.0741 (17)	0.0597 (16)	0.0059 (14)	0.0296 (13)	−0.0047 (13)
C2	0.0545 (12)	0.0599 (13)	0.0450 (12)	0.0039 (10)	0.0167 (9)	−0.0053 (10)
C3	0.0560 (13)	0.0514 (12)	0.0617 (14)	0.0159 (10)	0.0210 (10)	−0.0056 (10)
C4	0.0485 (11)	0.0424 (10)	0.0506 (12)	0.0168 (8)	0.0126 (9)	0.0046 (8)
C5	0.0328 (8)	0.0375 (9)	0.0366 (9)	0.0068 (7)	0.0046 (7)	0.0004 (7)
C6	0.0547 (11)	0.0455 (10)	0.0441 (11)	0.0205 (9)	0.0097 (9)	0.0072 (8)
C7	0.0714 (15)	0.0609 (13)	0.0425 (12)	0.0163 (11)	0.0126 (10)	0.0140 (10)
Cl1	0.0306 (2)	0.0284 (2)	0.0426 (3)	0.00948 (15)	0.00733 (15)	0.00697 (15)
O1	0.0333 (7)	0.0667 (9)	0.0627 (10)	0.0079 (6)	0.0146 (6)	−0.0046 (7)
O2	0.0531 (9)	0.0534 (9)	0.0661 (10)	0.0147 (7)	−0.0150 (7)	−0.0090 (7)
O3	0.0595 (9)	0.0396 (7)	0.0839 (12)	0.0271 (7)	0.0058 (8)	−0.0036 (7)
O4	0.0880 (12)	0.0539 (9)	0.0623 (11)	0.0127 (8)	0.0217 (9)	0.0293 (8)

Geometric parameters (Å, º) top

N1—C5	1.462 (2)	C4—C5	1.371 (3)
N1—H1A	0.8900	C4—H4	0.9300
N1—H1B	0.8900	C5—C6	1.380 (3)
N1—H1C	0.8900	C6—C7	1.378 (3)
N2—C1	1.135 (3)	C6—H6	0.9300
C1—C2	1.447 (3)	C7—H7	0.9300
C2—C7	1.385 (3)	Cl1—O4	1.4202 (15)
C2—C3	1.392 (3)	Cl1—O3	1.4215 (14)
C3—C4	1.375 (3)	Cl1—O1	1.4222 (14)
C3—H3	0.9300	Cl1—O2	1.4346 (16)

C5—N1—H1A	109.5	C4—C5—C6	122.22 (18)
C5—N1—H1B	109.5	C4—C5—N1	118.25 (16)
H1A—N1—H1B	109.5	C6—C5—N1	119.50 (16)
C5—N1—H1C	109.5	C7—C6—C5	118.39 (19)
H1A—N1—H1C	109.5	C7—C6—H6	120.8
H1B—N1—H1C	109.5	C5—C6—H6	120.8
N2—C1—C2	179.6 (3)	C6—C7—C2	120.1 (2)
C7—C2—C3	120.66 (19)	C6—C7—H7	120.0
C7—C2—C1	119.9 (2)	C2—C7—H7	120.0
C3—C2—C1	119.4 (2)	O4—Cl1—O3	109.51 (11)
C4—C3—C2	119.1 (2)	O4—Cl1—O1	109.25 (11)
C4—C3—H3	120.4	O3—Cl1—O1	108.89 (10)
C2—C3—H3	120.4	O4—Cl1—O2	109.01 (11)
C5—C4—C3	119.54 (19)	O3—Cl1—O2	110.69 (10)
C5—C4—H4	120.2	O1—Cl1—O2	109.47 (10)
C3—C4—H4	120.2

C7—C2—C3—C4	0.0 (3)	C4—C5—C6—C7	1.1 (3)
C1—C2—C3—C4	−179.7 (2)	N1—C5—C6—C7	−176.89 (19)
C2—C3—C4—C5	0.6 (3)	C5—C6—C7—C2	−0.4 (3)
C3—C4—C5—C6	−1.2 (3)	C3—C2—C7—C6	−0.1 (4)
C3—C4—C5—N1	176.83 (18)	C1—C2—C7—C6	179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	2.04	2.881 (2)	158
N1—H1B···O3ⁱⁱ	0.89	1.98	2.855 (2)	166
N1—H1C···O4ⁱⁱⁱ	0.89	2.04	2.871 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·ClO₄⁻
M_r	218.60
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.9905 (10), 6.9465 (14), 13.998 (3)
α, β, γ (°)	94.87 (3), 95.68 (3), 103.99 (3)
V (Å³)	465.57 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.25 × 0.15 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.941, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4861, 2126, 1851
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.05
No. of reflections	2126
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.34

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	2.04	2.881 (2)	157.8
N1—H1B···O3ⁱⁱ	0.89	1.98	2.855 (2)	165.7
N1—H1C···O4ⁱⁱⁱ	0.89	2.04	2.871 (2)	155.8

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

Acknowledgements

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

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