4-(Cyano­meth­yl)anilinium chloride

Lin, J.

doi:10.1107/S1600536810018076

organic compounds

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Volume 66| Part 6| June 2010| Page o1403

https://doi.org/10.1107/S1600536810018076

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4-(Cyanomethyl)anilinium chloride

Jin-rui Lin ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: linjinrui23@163.com

(Received 12 May 2010; accepted 16 May 2010; online 22 May 2010)

The crystal structure of the title compound, C₈H₉N₂⁺·Cl⁻, is stabilized by N—H⋯Cl hydrogen bonds.

Related literature

For background to phase transition materials, see: Li et al. (2008 ); Zhang et al. (2009 ).

Experimental

Crystal data

C₈H₉N₂⁺·Cl⁻
M_r = 168.62
Monoclinic, P 2₁ /n
a = 5.4348 (12) Å
b = 8.5630 (18) Å
c = 18.000 (4) Å
β = 93.734 (16)°
V = 835.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 293 K
0.45 × 0.28 × 0.25 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.5, T_max = 0.5
8241 measured reflections
1890 independent reflections
1593 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.139
S = 1.18
1890 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl1	0.89	2.31	3.1638 (17)	162
N1—H1A⋯Cl1ⁱ	0.89	2.32	3.2061 (16)	177
N1—H1C⋯Cl1ⁱⁱ	0.89	2.29	3.1700 (17)	168
Symmetry codes: (i) x-1, y, z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810018076/jh2157sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018076/jh2157Isup2.hkl

checkCIF report

Comment top

Most non-hydrogen atoms of the 4-(cyanomethyl)anilinium were coplanar, with the mean deviation from plane of 0.0320 and N₂—C₈—C₇—C₄ torsion angle of 114 (37)°. The strong π-π packing interactions of benzene rings with Cg(1)···Cg(1) of 3.487 Å (Cg(1) is the centroid of benzene ring) stabilized the crystal structure. The N—H···Cl hydrogen bonding with the N···Cl distances from 3.1638 (17) Å to 3.2061 (17) Å link the molecules into infinite two-dimensional plane.

As a continuation of our study of phase transition materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Zhang et al., 2009 ),the dielectric constant of 4-(cyanomethyl)anilinium chloride compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 5.3 to 21.1), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range.

Related literature top

For our study of phase transition materials, see: Li et al. (2008); Zhang et al. (2009).

Experimental top

Single crystals (average size: 0.7×0.8×1.0 mm) of 4-(cyanomethyl)anilinium chloride were prepared by slowevaporation at room temperature of an ethanol solution of equal molar for 4 days.

Structure description top

For our study of phase transition materials, see: Li et al. (2008); Zhang 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: PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

4-(Cyanomethyl)anilinium chloride top

Crystal data top

C₈H₉N₂⁺·Cl⁻	F(000) = 352
M_r = 168.62	D_x = 1.340 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2330 reflections
a = 5.4348 (12) Å	θ = 3.2–27.6°
b = 8.5630 (18) Å	µ = 0.39 mm⁻¹
c = 18.000 (4) Å	T = 293 K
β = 93.734 (16)°	Prism, orange
V = 835.9 (3) Å³	0.45 × 0.28 × 0.25 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1890 independent reflections
Radiation source: fine-focus sealed tube	1593 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
CCD_Profile_fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.5, T_max = 0.5	l = −23→23
8241 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0842P)²] where P = (F_o² + 2F_c²)/3
1890 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₈H₉N₂⁺·Cl⁻	V = 835.9 (3) Å³
M_r = 168.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.4348 (12) Å	µ = 0.39 mm⁻¹
b = 8.5630 (18) Å	T = 293 K
c = 18.000 (4) Å	0.45 × 0.28 × 0.25 mm
β = 93.734 (16)°

Data collection top

Rigaku SCXmini diffractometer	1890 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1593 reflections with I > 2σ(I)
T_min = 0.5, T_max = 0.5	R_int = 0.036
8241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.18	Δρ_max = 0.50 e Å⁻³
1890 reflections	Δρ_min = −0.54 e Å⁻³
101 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
C1	0.4618 (3)	0.31846 (19)	0.11664 (9)	0.0300 (4)
C2	0.2846 (3)	0.3656 (2)	0.06362 (11)	0.0392 (4)
H2	0.1527	0.4266	0.0768	0.047*
C3	0.3045 (3)	0.3213 (2)	−0.00980 (11)	0.0399 (5)
H3	0.1846	0.3524	−0.0460	0.048*
C4	0.5017 (3)	0.2308 (2)	−0.02981 (9)	0.0318 (4)
C5	0.6768 (3)	0.1847 (2)	0.02470 (10)	0.0381 (4)
H5	0.8087	0.1233	0.0119	0.046*
C6	0.6587 (3)	0.2288 (2)	0.09839 (10)	0.0375 (4)
H6	0.7780	0.1981	0.1348	0.045*
C7	0.5134 (4)	0.1847 (3)	−0.11122 (11)	0.0424 (5)
H7A	0.3717	0.1201	−0.1257	0.051*
H7B	0.5031	0.2784	−0.1416	0.051*
C8	0.7369 (4)	0.1002 (2)	−0.12648 (10)	0.0380 (4)
N1	0.4471 (3)	0.36295 (19)	0.19498 (8)	0.0339 (4)
H1A	0.3056	0.4126	0.2005	0.051*
H1B	0.5727	0.4256	0.2087	0.051*
H1C	0.4541	0.2776	0.2233	0.051*
N2	0.9120 (4)	0.0349 (3)	−0.13867 (12)	0.0593 (6)
Cl1	0.94611 (8)	0.55382 (5)	0.21151 (3)	0.0395 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0310 (9)	0.0303 (8)	0.0290 (8)	−0.0016 (7)	0.0037 (7)	0.0014 (7)
C2	0.0324 (9)	0.0462 (11)	0.0391 (10)	0.0129 (8)	0.0023 (7)	−0.0008 (8)
C3	0.0344 (10)	0.0505 (11)	0.0339 (10)	0.0123 (8)	−0.0045 (7)	0.0023 (8)
C4	0.0309 (9)	0.0335 (9)	0.0310 (9)	0.0017 (7)	0.0011 (7)	0.0010 (7)
C5	0.0318 (9)	0.0460 (11)	0.0362 (10)	0.0116 (8)	0.0005 (7)	−0.0027 (8)
C6	0.0324 (9)	0.0471 (10)	0.0322 (9)	0.0095 (8)	−0.0030 (7)	0.0022 (8)
C7	0.0409 (11)	0.0528 (12)	0.0327 (10)	0.0119 (9)	−0.0024 (8)	−0.0024 (8)
C8	0.0395 (11)	0.0464 (10)	0.0279 (9)	0.0031 (9)	0.0011 (7)	0.0002 (8)
N1	0.0347 (8)	0.0367 (8)	0.0305 (8)	0.0031 (6)	0.0034 (6)	0.0007 (6)
N2	0.0484 (12)	0.0836 (15)	0.0463 (11)	0.0210 (10)	0.0059 (9)	−0.0014 (10)
Cl1	0.0360 (3)	0.0418 (3)	0.0404 (3)	0.00352 (17)	−0.0006 (2)	−0.00759 (18)

Geometric parameters (Å, º) top

C1—C2	1.372 (3)	C5—H5	0.9300
C1—C6	1.374 (2)	C6—H6	0.9300
C1—N1	1.468 (2)	C7—C8	1.455 (3)
C2—C3	1.386 (3)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C4	1.389 (2)	C8—N2	1.137 (3)
C3—H3	0.9300	N1—H1A	0.8900
C4—C5	1.380 (3)	N1—H1B	0.8900
C4—C7	1.523 (3)	N1—H1C	0.8900
C5—C6	1.389 (3)

C2—C1—C6	121.37 (16)	C1—C6—H6	120.5
C2—C1—N1	120.80 (16)	C5—C6—H6	120.5
C6—C1—N1	117.82 (16)	C8—C7—C4	113.47 (16)
C1—C2—C3	119.20 (16)	C8—C7—H7A	108.9
C1—C2—H2	120.4	C4—C7—H7A	108.9
C3—C2—H2	120.4	C8—C7—H7B	108.9
C2—C3—C4	120.63 (17)	C4—C7—H7B	108.9
C2—C3—H3	119.7	H7A—C7—H7B	107.7
C4—C3—H3	119.7	N2—C8—C7	179.6 (3)
C5—C4—C3	118.92 (16)	C1—N1—H1A	109.5
C5—C4—C7	122.68 (16)	C1—N1—H1B	109.5
C3—C4—C7	118.39 (16)	H1A—N1—H1B	109.5
C4—C5—C6	120.85 (17)	C1—N1—H1C	109.5
C4—C5—H5	119.6	H1A—N1—H1C	109.5
C6—C5—H5	119.6	H1B—N1—H1C	109.5
C1—C6—C5	119.02 (17)

C6—C1—C2—C3	0.2 (3)	C2—C1—C6—C5	−0.3 (3)
N1—C1—C2—C3	−179.95 (17)	N1—C1—C6—C5	179.84 (17)
C1—C2—C3—C4	−0.3 (3)	C4—C5—C6—C1	0.5 (3)
C2—C3—C4—C5	0.5 (3)	C5—C4—C7—C8	−5.2 (3)
C2—C3—C4—C7	179.66 (19)	C3—C4—C7—C8	175.67 (19)
C3—C4—C5—C6	−0.6 (3)	C4—C7—C8—N2	−114 (37)
C7—C4—C5—C6	−179.74 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl1	0.89	2.31	3.1638 (17)	162
N1—H1A···Cl1ⁱ	0.89	2.32	3.2061 (16)	177
N1—H1C···Cl1ⁱⁱ	0.89	2.29	3.1700 (17)	168

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₂⁺·Cl⁻
M_r	168.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.4348 (12), 8.5630 (18), 18.000 (4)
β (°)	93.734 (16)
V (Å³)	835.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.45 × 0.28 × 0.25

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.5, 0.5
No. of measured, independent and observed [I > 2σ(I)] reflections	8241, 1890, 1593
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.139, 1.18
No. of reflections	1890
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.54

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl1	0.89	2.31	3.1638 (17)	162.0
N1—H1A···Cl1ⁱ	0.89	2.32	3.2061 (16)	176.8
N1—H1C···Cl1ⁱⁱ	0.89	2.29	3.1700 (17)	168.1

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

Acknowledgements

The author is grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

References

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