2-[(4-Chloro­anilino)meth­yl]phenol

Chen, L.-Z.

doi:10.1107/S1600536811029047

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2125

doi:10.1107/S1600536811029047

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2-[(4-Chloroanilino)methyl]phenol

Li-Zhuang Chen ^a ^*

^aSchool of Biology and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

(Received 13 July 2011; accepted 19 July 2011; online 23 July 2011)

In the title compound, C₁₃H₁₂ClNO, the dihedral angle between the two benzene ring planes is 68.71 (8)°. In the crystal, molecules are linked by pairs of O—H⋯N hydrogen bonds into inversion dimers, which are further linked by intermolecular N—H⋯O interactions into a chain running parallel to the a axis.

Related literature

For the synthesis of the title compound, see: Noda (1959 ). For related structures, see: Liu et al. (2007 ); Qu et al. (2007 ).

Experimental

Crystal data

C₁₃H₁₂ClNO
M_r = 233.69
Triclinic, $[P \overline 1]$
a = 5.5842 (11) Å
b = 7.9485 (16) Å
c = 13.023 (3) Å
α = 86.87 (3)°
β = 89.12 (3)°
γ = 88.65 (3)°
V = 577.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.895, T_max = 0.940
5968 measured reflections
2637 independent reflections
1383 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.186
S = 0.98
2637 reflections
153 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 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—H1B⋯O1ⁱ	0.86 (1)	2.20 (1)	3.038 (3)	165 (3)
O1—H1A⋯N1ⁱⁱ	0.85 (1)	1.93 (1)	2.777 (3)	171 (3)
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -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); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811029047/pv2430sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029047/pv2430Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811029047/pv2430Isup3.cml

checkCIF report

Comment top

In the title compound (Fig. 1), which was synthesized by the reduction of 2-((4-chlorophenylimino)methyl)phenol, the dihedral angle between the two benzene ring planes is 68.71 (8)°. In the crystal structure, the molecules are linked by intermolecular N—H···O, and O—H···N hydrogen bonds into a one-dimensional chain along the a-axis (Tab. 1 & Fig. 2).

The crystal structure of compounds closely related to the title molecule, eg., 2-[(4-chlorophenyl)aminomethyl]-6-methoxyphenol (Liu et al., 2007) and 2-(anilinomethyl)phenol (Qu et al., 2007) have been reported.

Related literature top

For the synthesis of the title compound, see: Noda (1959). For related structures, see: Liu et al. (2007); Qu et al. (2007).

Experimental top

The title compound was synthesized by the reaction of 2-((4-chlorophenylimino)- methyl)phenol (2.31 g, 10 mmol) with NaBH₄ (0.38 g, 10 mmol) in 50 ml methanol according to the reported method (Noda, 1959). Crystals were obtained from an ethanolic (95%) solution by slow evaporation 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with atomic labels. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The unit cell packing of the title compound viewed along the a-axis. Hydrogen bonds are drawn as dashed lines and the H-atoms not involved in hydrogen bonding have been excluded for clarity.

2-[(4-Chloroanilino)methyl]phenol top

Crystal data top

C₁₃H₁₂ClNO	Z = 2
M_r = 233.69	F(000) = 244
Triclinic, P1	D_x = 1.345 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5842 (11) Å	Cell parameters from 4578 reflections
b = 7.9485 (16) Å	θ = 3.1–27.5°
c = 13.023 (3) Å	µ = 0.31 mm⁻¹
α = 86.87 (3)°	T = 298 K
β = 89.12 (3)°	Prism, colorless
γ = 88.65 (3)°	0.40 × 0.30 × 0.20 mm
V = 577.0 (2) Å³

Data collection top

Rigaku SCXmini diffractometer	2637 independent reflections
Radiation source: fine-focus sealed tube	1383 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.895, T_max = 0.940	l = −16→16
5968 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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0821P)²] where P = (F_o² + 2F_c²)/3
2637 reflections	(Δ/σ)_max = 0.002
153 parameters	Δρ_max = 0.22 e Å⁻³
2 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₃H₁₂ClNO	γ = 88.65 (3)°
M_r = 233.69	V = 577.0 (2) Å³
Triclinic, P1	Z = 2
a = 5.5842 (11) Å	Mo Kα radiation
b = 7.9485 (16) Å	µ = 0.31 mm⁻¹
c = 13.023 (3) Å	T = 298 K
α = 86.87 (3)°	0.40 × 0.30 × 0.20 mm
β = 89.12 (3)°

Data collection top

Rigaku SCXmini diffractometer	2637 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1383 reflections with I > 2σ(I)
T_min = 0.895, T_max = 0.940	R_int = 0.061
5968 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	2 restraints
wR(F²) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.22 e Å⁻³
2637 reflections	Δρ_min = −0.26 e Å⁻³
153 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
Cl1	0.3943 (2)	0.26252 (15)	−0.02082 (7)	0.1029 (5)
O1	1.2068 (3)	0.3737 (2)	0.53931 (14)	0.0477 (5)
N1	0.6596 (4)	0.3048 (3)	0.41482 (17)	0.0427 (6)
C2	1.0518 (4)	0.2978 (3)	0.6089 (2)	0.0395 (6)
C1	0.8691 (4)	0.2033 (3)	0.5715 (2)	0.0431 (7)
C8	0.5997 (4)	0.2890 (3)	0.3104 (2)	0.0420 (6)
C3	1.0818 (5)	0.3070 (4)	0.7143 (2)	0.0504 (7)
H3	1.2079	0.3668	0.7391	0.061*
C7	0.8410 (5)	0.1848 (3)	0.4587 (2)	0.0500 (7)
H7A	0.9936	0.2038	0.4239	0.060*
H7B	0.7942	0.0707	0.4472	0.060*
C6	0.7158 (5)	0.1240 (4)	0.6421 (3)	0.0593 (8)
H6	0.5924	0.0604	0.6185	0.071*
C9	0.3944 (5)	0.3687 (4)	0.2737 (2)	0.0519 (7)
H9	0.2965	0.4278	0.3183	0.062*
C13	0.7429 (5)	0.2015 (4)	0.2433 (2)	0.0545 (8)
H13	0.8824	0.1469	0.2666	0.065*
C11	0.4753 (6)	0.2735 (4)	0.1065 (2)	0.0611 (8)
C10	0.3309 (6)	0.3627 (4)	0.1723 (2)	0.0621 (8)
H10	0.1924	0.4181	0.1485	0.074*
C4	0.9239 (5)	0.2272 (4)	0.7814 (2)	0.0589 (8)
H4	0.9426	0.2351	0.8519	0.071*
C12	0.6794 (6)	0.1947 (4)	0.1411 (2)	0.0642 (9)
H12	0.7768	0.1361	0.0960	0.077*
C5	0.7407 (6)	0.1367 (4)	0.7467 (2)	0.0633 (9)
H5	0.6338	0.0842	0.7928	0.076*
H1B	0.532 (3)	0.304 (4)	0.4527 (18)	0.058 (9)*
H1A	1.248 (6)	0.469 (2)	0.560 (2)	0.087 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1313 (10)	0.1297 (10)	0.0496 (6)	−0.0068 (7)	−0.0160 (6)	−0.0149 (6)
O1	0.0482 (11)	0.0441 (12)	0.0517 (12)	−0.0070 (9)	0.0071 (9)	−0.0107 (10)
N1	0.0390 (13)	0.0442 (13)	0.0453 (14)	0.0033 (10)	0.0031 (10)	−0.0089 (11)
C2	0.0350 (14)	0.0364 (14)	0.0471 (16)	0.0057 (11)	0.0012 (12)	−0.0044 (12)
C1	0.0388 (14)	0.0375 (15)	0.0533 (17)	0.0010 (12)	−0.0030 (12)	−0.0051 (13)
C8	0.0393 (14)	0.0427 (15)	0.0446 (16)	−0.0074 (12)	0.0031 (12)	−0.0067 (12)
C3	0.0465 (16)	0.0530 (18)	0.0521 (18)	0.0009 (13)	−0.0077 (13)	−0.0044 (14)
C7	0.0440 (15)	0.0448 (16)	0.0622 (19)	0.0038 (13)	−0.0050 (13)	−0.0137 (14)
C6	0.0494 (18)	0.0526 (18)	0.076 (2)	−0.0090 (14)	−0.0072 (16)	−0.0022 (16)
C9	0.0522 (17)	0.0562 (18)	0.0474 (17)	0.0053 (14)	0.0028 (13)	−0.0061 (14)
C13	0.0460 (16)	0.0617 (18)	0.0578 (19)	0.0016 (14)	0.0018 (14)	−0.0214 (15)
C11	0.069 (2)	0.068 (2)	0.0471 (18)	−0.0102 (18)	−0.0011 (15)	−0.0069 (16)
C10	0.0618 (19)	0.069 (2)	0.0547 (19)	0.0018 (16)	−0.0088 (15)	0.0042 (16)
C4	0.067 (2)	0.064 (2)	0.0448 (18)	0.0051 (17)	−0.0008 (15)	0.0032 (15)
C12	0.068 (2)	0.070 (2)	0.057 (2)	−0.0049 (17)	0.0073 (16)	−0.0234 (17)
C5	0.063 (2)	0.066 (2)	0.060 (2)	−0.0059 (17)	0.0085 (16)	0.0116 (17)

Geometric parameters (Å, º) top

Cl1—C11	1.733 (3)	C7—H7B	0.9700
O1—C2	1.370 (3)	C6—C5	1.381 (4)
O1—H1A	0.853 (10)	C6—H6	0.9300
N1—C8	1.418 (3)	C9—C10	1.376 (4)
N1—C7	1.475 (3)	C9—H9	0.9300
N1—H1B	0.858 (10)	C13—C12	1.387 (4)
C2—C1	1.391 (4)	C13—H13	0.9300
C2—C3	1.391 (3)	C11—C12	1.358 (4)
C1—C6	1.383 (4)	C11—C10	1.381 (4)
C1—C7	1.495 (4)	C10—H10	0.9300
C8—C9	1.376 (4)	C4—C5	1.361 (4)
C8—C13	1.381 (4)	C4—H4	0.9300
C3—C4	1.374 (4)	C12—H12	0.9300
C3—H3	0.9300	C5—H5	0.9300
C7—H7A	0.9700

C2—O1—H1A	110 (2)	C5—C6—H6	119.1
C8—N1—C7	117.0 (2)	C1—C6—H6	119.1
C8—N1—H1B	110.3 (19)	C8—C9—C10	121.4 (3)
C7—N1—H1B	110.4 (19)	C8—C9—H9	119.3
O1—C2—C1	118.1 (2)	C10—C9—H9	119.3
O1—C2—C3	121.4 (2)	C8—C13—C12	120.2 (3)
C1—C2—C3	120.4 (2)	C8—C13—H13	119.9
C6—C1—C2	117.9 (3)	C12—C13—H13	119.9
C6—C1—C7	120.8 (2)	C12—C11—C10	120.4 (3)
C2—C1—C7	121.3 (2)	C12—C11—Cl1	120.1 (3)
C9—C8—C13	118.6 (3)	C10—C11—Cl1	119.5 (3)
C9—C8—N1	118.7 (2)	C9—C10—C11	119.2 (3)
C13—C8—N1	122.7 (3)	C9—C10—H10	120.4
C4—C3—C2	119.5 (3)	C11—C10—H10	120.4
C4—C3—H3	120.2	C5—C4—C3	121.1 (3)
C2—C3—H3	120.2	C5—C4—H4	119.4
N1—C7—C1	111.6 (2)	C3—C4—H4	119.4
N1—C7—H7A	109.3	C11—C12—C13	120.2 (3)
C1—C7—H7A	109.3	C11—C12—H12	119.9
N1—C7—H7B	109.3	C13—C12—H12	119.9
C1—C7—H7B	109.3	C4—C5—C6	119.1 (3)
H7A—C7—H7B	108.0	C4—C5—H5	120.4
C5—C6—C1	121.8 (3)	C6—C5—H5	120.4

O1—C2—C1—C6	178.7 (2)	C13—C8—C9—C10	−0.1 (4)
C3—C2—C1—C6	1.9 (4)	N1—C8—C9—C10	177.9 (2)
O1—C2—C1—C7	−0.2 (4)	C9—C8—C13—C12	0.0 (4)
C3—C2—C1—C7	−177.0 (2)	N1—C8—C13—C12	−177.9 (2)
C7—N1—C8—C9	164.5 (2)	C8—C9—C10—C11	0.6 (5)
C7—N1—C8—C13	−17.7 (4)	C12—C11—C10—C9	−1.0 (5)
O1—C2—C3—C4	−179.2 (2)	Cl1—C11—C10—C9	179.0 (2)
C1—C2—C3—C4	−2.5 (4)	C2—C3—C4—C5	1.1 (4)
C8—N1—C7—C1	−174.1 (2)	C10—C11—C12—C13	0.8 (5)
C6—C1—C7—N1	83.6 (3)	Cl1—C11—C12—C13	−179.1 (2)
C2—C1—C7—N1	−97.5 (3)	C8—C13—C12—C11	−0.3 (5)
C2—C1—C6—C5	−0.1 (4)	C3—C4—C5—C6	0.7 (5)
C7—C1—C6—C5	178.8 (3)	C1—C6—C5—C4	−1.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.86 (1)	2.20 (1)	3.038 (3)	165 (3)
O1—H1A···N1ⁱⁱ	0.85 (1)	1.93 (1)	2.777 (3)	171 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂ClNO
M_r	233.69
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.5842 (11), 7.9485 (16), 13.023 (3)
α, β, γ (°)	86.87 (3), 89.12 (3), 88.65 (3)
V (Å³)	577.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.895, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	5968, 2637, 1383
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.186, 0.98
No. of reflections	2637
No. of parameters	153
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −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—H1B···O1ⁱ	0.858 (10)	2.201 (13)	3.038 (3)	165 (3)
O1—H1A···N1ⁱⁱ	0.853 (10)	1.932 (12)	2.777 (3)	171 (3)

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

Acknowledgements

This work was supported by a start-up grant from Jiangsu University of Science and Technology, China.

References

Liu, Y.-F., Xia, H.-T., Yang, S.-P. & Wang, D.-Q. (2007). Acta Cryst. E63, o3561. Web of Science CSD CrossRef IUCr Journals Google Scholar
Noda, M. (1959). J. Org. Chem. 24, 1209–1212. CrossRef CAS Web of Science Google Scholar
Qu, Y., Tian, L.-J. & Dong, J. (2007). Acta Cryst. E63, o4832. Web of Science CSD CrossRef IUCr Journals 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