3-Cyano-N-(2-hydroxy­benz­yl)anilinium chloride

Dai, J.; Zheng, W.-N.

doi:10.1107/S1600536810003521

organic compounds

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Volume 66| Part 3| March 2010| Page o517

doi:10.1107/S1600536810003521

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3-Cyano-N-(2-hydroxybenzyl)anilinium chloride

Jing Dai ^a ^* and Wen-Ni Zheng ^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 18 January 2010; accepted 28 January 2010; online 3 February 2010)

In the cation of the title compound, C₁₄H₁₃N₂O⁺·Cl⁻, the two benzene rings are roughly parallel and are twisted slightly from each other by a dihedral angle of only 2.87 (1)°. In the crystal, weak intermolecular N—H⋯Cl and O—H⋯Cl hydrogen bonds link the cations and anions into chains extended along the b axis.

Related literature

For the crystal structures and properties of related compounds, see: Fu et al. (2007 , 2008 , 2009 ); Fu & Xiong (2008 ); Zhao et al. (2008 ); Loeb et al. (2005 ).

Experimental

Crystal data

C₁₄H₁₃N₂O⁺·Cl⁻
M_r = 260.71
Monoclinic, P 2₁ /n
a = 13.071 (3) Å
b = 7.9437 (16) Å
c = 13.141 (3) Å
β = 90.18 (3)°
V = 1364.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 K
0.4 × 0.35 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.881, T_max = 0.940
13632 measured reflections
3116 independent reflections
2264 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.127
S = 1.05
3116 reflections
163 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.90	2.29	3.1315 (17)	155
O1—H1⋯Cl1ⁱⁱ	0.85	2.24	3.0870 (18)	171
N1—H1B⋯Cl1	0.90	2.14	3.0376 (16)	173
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, 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: 10.1107/S1600536810003521/dn2531sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003521/dn2531Isup2.hkl

checkCIF report

Comment top

In the last few years, more and more people have focused on the chemistry of nitrile derivatives because of their wide range of applications in industry and coordination chemistry as ligands (Fu et al., 2007; Fu & Xiong 2008). For example, phthalonitriles have been used as starting materials for phthalocyanines, 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. Recently, we have reported a few benzonitrile compounds (Zhao et al., 2008; Fu et al., 2008; Fu et al., 2009). As an extension of our work on the structural characterization, we report here the crystal structure of the title compound, 3-cyano-N-(2-hydroxybenzyl)anilinium chloride.

In the title compound (Fig.1), the amino N atom is protonated. The phenyl rings are roughly parallel and only slightly twisted from each other by a dihedral angle of 2.87 (1) °. A larger twist angle of 20.7 (3)° is observed in the related N-(4-(Trifluoromethyl)benzyl)-4-methoxyanilinium trifluoromethanesulfonate compound (Loeb et al., 2005). The nitrile group bond length of 1.127 (2)Å is within the normal range.

The crystal packing is stabilized by N—H···Cl and O—H···Cl hydrogen bonds to form a one-dimensional chain parallel to the b axis. (Table 1, Fig. 2).

Related literature top

For the crystal structures and properties of related compounds, see: Fu et al. (2007, 2008, 2009); Fu & Xiong (2008); Zhao et al. (2008); Loeb et al. (2005).

Experimental top

The commercial 3-(2-hydroxybenzylamino)benzonitrile (3 mmol, 669 mg) was dissolved in water/HCl (50:1 v/v) solution. The solvent was slowly evaporated in air affording colourless block-shaped 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 9 at 1 MHz at room temperature.

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. 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, showing the one-dimensional hydrogen-bonded chain. H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

3-Cyano-N-(2-hydroxybenzyl)anilinium chloride top

Crystal data top

C₁₄H₁₃N₂O⁺·Cl⁻	F(000) = 544
M_r = 260.71	D_x = 1.269 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2264 reflections
a = 13.071 (3) Å	θ = 3.0–27.5°
b = 7.9437 (16) Å	µ = 0.27 mm⁻¹
c = 13.141 (3) Å	T = 298 K
β = 90.18 (3)°	Block, colourless
V = 1364.4 (5) Å³	0.4 × 0.35 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3116 independent reflections
Radiation source: fine-focus sealed tube	2264 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.881, T_max = 0.940	l = −17→17
13632 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0544P)² + 0.2789P] where P = (F_o² + 2F_c²)/3
3116 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.31 e Å⁻³
3 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₄H₁₃N₂O⁺·Cl⁻	V = 1364.4 (5) Å³
M_r = 260.71	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.071 (3) Å	µ = 0.27 mm⁻¹
b = 7.9437 (16) Å	T = 298 K
c = 13.141 (3) Å	0.4 × 0.35 × 0.2 mm
β = 90.18 (3)°

Data collection top

Rigaku Mercury2 diffractometer	3116 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2264 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.940	R_int = 0.048
13632 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	3 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
3116 reflections	Δρ_min = −0.26 e Å⁻³
163 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	0.64724 (11)	0.46075 (18)	0.35772 (11)	0.0389 (4)
H1A	0.6623	0.5479	0.3166	0.058*
H1B	0.6961	0.3821	0.3496	0.058*
O1	0.70213 (12)	0.84372 (19)	0.41720 (13)	0.0677 (5)
H1	0.7241	0.9398	0.3990	0.102*
C12	0.42880 (16)	0.1649 (2)	0.33106 (15)	0.0474 (5)
C13	0.52443 (14)	0.2279 (2)	0.35670 (14)	0.0420 (4)
H13	0.5712	0.1625	0.3927	0.050*
C8	0.54865 (14)	0.3902 (2)	0.32752 (14)	0.0389 (4)
C11	0.35950 (16)	0.2619 (3)	0.27743 (17)	0.0559 (5)
H11	0.2953	0.2190	0.2610	0.067*
C9	0.48044 (15)	0.4880 (2)	0.27398 (17)	0.0499 (5)
H9	0.4978	0.5972	0.2552	0.060*
C6	0.74965 (16)	0.5918 (3)	0.49665 (15)	0.0487 (5)
C1	0.77360 (16)	0.7568 (3)	0.47075 (16)	0.0494 (5)
C7	0.64809 (17)	0.5202 (3)	0.46654 (16)	0.0552 (6)
H7A	0.5957	0.6054	0.4753	0.066*
H7B	0.6318	0.4265	0.5109	0.066*
C2	0.86690 (18)	0.8245 (3)	0.50023 (18)	0.0611 (6)
H2	0.8834	0.9346	0.4828	0.073*
C10	0.38606 (16)	0.4227 (3)	0.24836 (19)	0.0603 (6)
H10	0.3400	0.4877	0.2112	0.072*
C14	0.40186 (18)	−0.0046 (3)	0.36042 (19)	0.0601 (6)
C3	0.93473 (19)	0.7289 (4)	0.55504 (19)	0.0690 (7)
H3	0.9973	0.7747	0.5745	0.083*
C5	0.81903 (19)	0.4986 (3)	0.55185 (17)	0.0613 (6)
H5	0.8032	0.3882	0.5693	0.074*
C4	0.9113 (2)	0.5654 (4)	0.58170 (18)	0.0702 (7)
H4	0.9573	0.5013	0.6194	0.084*
N2	0.3796 (2)	−0.1368 (3)	0.3823 (2)	0.0900 (8)
Cl1	0.79799 (4)	0.17211 (7)	0.33575 (4)	0.05632 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0389 (8)	0.0327 (8)	0.0452 (9)	−0.0017 (6)	0.0049 (6)	−0.0003 (7)
O1	0.0616 (10)	0.0608 (10)	0.0808 (12)	−0.0066 (8)	−0.0118 (8)	0.0039 (8)
C12	0.0514 (12)	0.0390 (10)	0.0519 (12)	−0.0115 (9)	0.0063 (9)	−0.0078 (9)
C13	0.0455 (11)	0.0337 (9)	0.0469 (11)	−0.0002 (8)	0.0006 (8)	0.0020 (8)
C8	0.0361 (10)	0.0360 (9)	0.0447 (10)	−0.0011 (8)	0.0059 (8)	−0.0030 (8)
C11	0.0419 (11)	0.0632 (14)	0.0625 (13)	−0.0077 (10)	−0.0020 (10)	−0.0044 (11)
C9	0.0440 (12)	0.0403 (11)	0.0654 (13)	0.0024 (9)	0.0048 (9)	0.0091 (9)
C6	0.0529 (12)	0.0520 (12)	0.0412 (10)	−0.0106 (10)	0.0068 (9)	−0.0092 (9)
C1	0.0490 (12)	0.0506 (12)	0.0487 (11)	−0.0075 (10)	−0.0008 (9)	−0.0096 (10)
C7	0.0590 (13)	0.0570 (13)	0.0497 (12)	−0.0183 (10)	0.0132 (10)	−0.0139 (10)
C2	0.0628 (15)	0.0572 (13)	0.0634 (14)	−0.0205 (11)	−0.0077 (11)	−0.0055 (11)
C10	0.0432 (12)	0.0614 (14)	0.0762 (16)	0.0049 (10)	−0.0043 (10)	0.0102 (12)
C14	0.0666 (15)	0.0466 (13)	0.0671 (14)	−0.0145 (11)	0.0020 (11)	−0.0045 (11)
C3	0.0585 (15)	0.0872 (18)	0.0613 (14)	−0.0176 (13)	−0.0128 (11)	−0.0104 (13)
C5	0.0781 (17)	0.0551 (13)	0.0507 (12)	−0.0046 (12)	0.0055 (11)	0.0002 (10)
C4	0.0719 (17)	0.0850 (18)	0.0537 (14)	0.0066 (14)	−0.0082 (12)	0.0000 (13)
N2	0.111 (2)	0.0551 (13)	0.1037 (19)	−0.0313 (13)	0.0078 (15)	0.0019 (12)
Cl1	0.0555 (3)	0.0508 (3)	0.0628 (3)	0.0132 (2)	0.0059 (2)	−0.0056 (2)

Geometric parameters (Å, º) top

N1—C8	1.459 (2)	C6—C5	1.376 (3)
N1—C7	1.506 (3)	C6—C1	1.390 (3)
N1—H1A	0.9000	C6—C7	1.496 (3)
N1—H1B	0.9000	C1—C2	1.387 (3)
O1—C1	1.356 (3)	C7—H7A	0.9700
O1—H1	0.8500	C7—H7B	0.9700
C12—C11	1.381 (3)	C2—C3	1.370 (3)
C12—C13	1.387 (3)	C2—H2	0.9300
C12—C14	1.445 (3)	C10—H10	0.9300
C13—C8	1.382 (3)	C14—N2	1.127 (3)
C13—H13	0.9300	C3—C4	1.380 (4)
C8—C9	1.375 (3)	C3—H3	0.9300
C11—C10	1.378 (3)	C5—C4	1.373 (3)
C11—H11	0.9300	C5—H5	0.9300
C9—C10	1.379 (3)	C4—H4	0.9300
C9—H9	0.9300

C8—N1—C7	112.49 (14)	O1—C1—C2	123.5 (2)
C8—N1—H1A	109.1	O1—C1—C6	116.84 (18)
C7—N1—H1A	109.1	C2—C1—C6	119.7 (2)
C8—N1—H1B	109.1	C6—C7—N1	111.97 (16)
C7—N1—H1B	109.1	C6—C7—H7A	109.2
H1A—N1—H1B	107.8	N1—C7—H7A	109.2
C1—O1—H1	111.7	C6—C7—H7B	109.2
C11—C12—C13	120.78 (18)	N1—C7—H7B	109.2
C11—C12—C14	119.76 (19)	H7A—C7—H7B	107.9
C13—C12—C14	119.5 (2)	C3—C2—C1	119.9 (2)
C8—C13—C12	118.45 (18)	C3—C2—H2	120.0
C8—C13—H13	120.8	C1—C2—H2	120.0
C12—C13—H13	120.8	C11—C10—C9	120.5 (2)
C9—C8—C13	121.38 (18)	C11—C10—H10	119.8
C9—C8—N1	119.52 (16)	C9—C10—H10	119.8
C13—C8—N1	119.06 (17)	N2—C14—C12	178.9 (3)
C10—C11—C12	119.56 (19)	C2—C3—C4	120.7 (2)
C10—C11—H11	120.2	C2—C3—H3	119.6
C12—C11—H11	120.2	C4—C3—H3	119.6
C8—C9—C10	119.37 (19)	C4—C5—C6	121.3 (2)
C8—C9—H9	120.3	C4—C5—H5	119.4
C10—C9—H9	120.3	C6—C5—H5	119.4
C5—C6—C1	119.2 (2)	C5—C4—C3	119.1 (2)
C5—C6—C7	121.2 (2)	C5—C4—H4	120.4
C1—C6—C7	119.6 (2)	C3—C4—H4	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.29	3.1315 (17)	155
O1—H1···Cl1ⁱⁱ	0.85	2.24	3.0870 (18)	171
N1—H1B···Cl1	0.90	2.14	3.0376 (16)	173

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₂O⁺·Cl⁻
M_r	260.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	13.071 (3), 7.9437 (16), 13.141 (3)
β (°)	90.18 (3)
V (Å³)	1364.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.4 × 0.35 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.881, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	13632, 3116, 2264
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.127, 1.05
No. of reflections	3116
No. of parameters	163
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.26

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
N1—H1A···Cl1ⁱ	0.90	2.29	3.1315 (17)	154.8
O1—H1···Cl1ⁱⁱ	0.85	2.24	3.0870 (18)	171.4
N1—H1B···Cl1	0.90	2.14	3.0376 (16)	172.8

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

Acknowledgements

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

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