2-[(2-Chloro­phen­yl)(hy­droxy)meth­yl]phenol

Prakasha, G.; Jasinski, J.P.; Brown, J.S.; Yathirajan, H.S.; Ravishankara, D.K.

doi:10.1107/S1600536813018667

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1240

doi:10.1107/S1600536813018667

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2-[(2-Chlorophenyl)(hydroxy)methyl]phenol

G. Prakasha,^a Jerry P. Jasinski,^b ^* Jared S. Brown,^b H. S. Yathirajan ^a and D. K. Ravishankara ^c

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^cSri Mahadeshwara Government First Grade College, (Affiliated to University of Mysore), Kollegal 571 440, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 4 July 2013; accepted 5 July 2013; online 13 July 2013)

In the title compound, C₁₃H₁₁ClO₂, the dihedral angle between the mean planes of the 2-chlorophenyl and phenol rings is 87.4 (9)°. The methyl hydroxy group lies nearly perpendicular to the plane of its attached benzene ring [O—C—C—C torsion angle = 84.3 (3)°]. The two hydroxy groups lie on the same side of the molecule and are in a slightly twisted gauche conformation [O—C—C—O torsion angle = 77.1 (8)°] to each other. In the crystal, O—H⋯O hydrogen bonds between nearby methylhydroxy groups form dimers in alternating pairs aligned diagonally along the b axis. A view along the c axis reveals a hexameric aggregate mediated by a ring of six O—H⋯O hydrogen bonds generating an R₆⁶(12) motif loop.

Related literature

For general background to the use of benzhydrols, see: Ohkuma et al. (2000 ). For the use of the title compound in the perfume and pharmaceutical industries, see: Meguro et al. (1985 ). For related diphenylmethanol structures, see: Betz et al. (2011 ); Ferguson et al. (1995 ); Siddaraju et al. (2010 ).

Experimental

Crystal data

C₁₃H₁₁ClO₂
M_r = 234.67
Trigonal, $[R \overline 3]$
a = 23.4627 (8) Å
c = 11.3722 (4) Å
V = 5421.6 (4) Å³
Z = 18
Cu Kα radiation
μ = 2.66 mm⁻¹
T = 173 K
0.46 × 0.38 × 0.24 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ) T_min = 0.517, T_max = 1.000
11532 measured reflections
2364 independent reflections
2055 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.213
S = 1.07
2364 reflections
151 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.84	1.84	2.656 (2)	163
Symmetry code: (i) $[y+{\script{1\over 3}}, -x+y+{\script{2\over 3}}, -z+{\script{5\over 3}}]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813018667/sj5343sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018667/sj5343Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813018667/sj5343Isup3.cml

checkCIF report

Comment top

Optically active diarylmethanols are crucial structural elements in many physiologically or/and biologically active molecules such as in the antihistamines (R)-orphenadrine and (S)-neobenodine. Benzhydrols are widely used as intermediates for the synthesis of pharmaceuticals (Ohkuma et al., 2000), including drugs such as diphenhydramine, orphenadrine, diphenidol and phenyltoloxamine. The crystal structures and hydrogen bonding in some diphenylmethanols have been reported (Ferguson et al., 1995). The title compound, 2-[(2-chlorophenyl) hydroxymethyl]phenol, (I), is a derivative of diphenylmethanol and it is used in the perfume and pharmaceutical industries (Meguro et al., 1985). Recently, the crystal structure of (2-methylphenyl) (phenyl)methanol (Siddaraju et al., 2010) and 2-(2-benzylphenyl) propan-2-ol (Betz et al., 2011) were reported. In view of the importance of diarylmethanols, this paper reports the crystal structure of the title compound, C₁₃H₁₁O₂Cl, (I).

In (I), the dihedral angle between the mean planes of the 2-chlorophenyl and phenol rings is 87.4 (9)° (Fig. 1). The methyl hydroxy group lies nearly perpendicular to the plane of its attached benzene ring [O1/C1/C2/C3 torsion angle = 84.3 (3)°]. The two hydroxy groups lie on the same side of the molecule and are in a slightly twisted gauche conformation [O1/C1/C3/O2 angle = 77.1 (8)°] to each other. In the crystal O—H···O hydrogen bonds between nearby methylhydroxy groups form dimers in alternating pairs aligned diagonally along the b axis and conribute to packing stability (Fig. 2). A view along the c axis reveals a hexameric aggregate mediated by a ring of six O—H···O hydrogen bonds generating an R⁶₆(12) motif loop (Fig. 3).

Related literature top

For general background to the use of benzhydrols, see: Ohkuma et al. (2000). For the use of the title compound in the perfume and pharmaceutical industries, see: Meguro et al. (1985). For related diphenylmethanol structures, see: Betz et al. (2011); Ferguson et al. (1995); Siddaraju et al. (2010).

Experimental top

The title compound was obtained as a gift sample from R. L. Fine Chem, Bengaluru, India. X-ray quality crystals were obtained from benzene solution by slow evaporation. (m.p.: 368–373 K).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Dashed lines indicate O1—H1···O1 hydrogen bonds between nearby methylhydroxy groups which form dimers in alternating pairs algned diagonally along the b axis. H atoms not involved in hydrogen bonding have been deleted for clarity.
	Fig. 3. Packing of the molecules along c axis displaying a hexameric aggregate mediated by a ring of six O—H···O hydrogen bonds generating an R⁶₆(12) motif loop.

2-[(2-Chlorophenyl)(hydroxy)methyl]phenol top

Crystal data top

C₁₃H₁₁ClO₂	D_x = 1.294 Mg m⁻³
M_r = 234.67	Cu Kα radiation, λ = 1.5418 Å
Trigonal, R3	Cell parameters from 3836 reflections
a = 23.4627 (8) Å	θ = 3.8–72.3°
c = 11.3722 (4) Å	µ = 2.66 mm⁻¹
V = 5421.6 (4) Å³	T = 173 K
Z = 18	Irregular, colourless
F(000) = 2196	0.46 × 0.38 × 0.24 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	2364 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2055 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 16.0416 pixels mm^-1	θ_max = 72.5°, θ_min = 3.8°
ω scans	h = −28→25
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −22→28
T_min = 0.517, T_max = 1.000	l = −12→13
11532 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.065	w = 1/[σ²(F_o²) + (0.1357P)² + 8.799P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.213	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.40 e Å⁻³
2364 reflections	Δρ_min = −0.62 e Å⁻³
151 parameters	Extinction correction: SHELXL2012 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00038 (12)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₃H₁₁ClO₂	Z = 18
M_r = 234.67	Cu Kα radiation
Trigonal, R3	µ = 2.66 mm⁻¹
a = 23.4627 (8) Å	T = 173 K
c = 11.3722 (4) Å	0.46 × 0.38 × 0.24 mm
V = 5421.6 (4) Å³

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	2364 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	2055 reflections with I > 2σ(I)
T_min = 0.517, T_max = 1.000	R_int = 0.047
11532 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.213	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.40 e Å⁻³
2364 reflections	Δρ_min = −0.62 e Å⁻³
151 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.66585 (5)	0.59567 (4)	0.59620 (10)	0.0780 (4)
O1	0.64040 (8)	0.41759 (8)	0.77861 (16)	0.0393 (5)
H1	0.6760	0.4335	0.8159	0.059*
O2	0.56637 (10)	0.49236 (11)	0.91391 (16)	0.0436 (5)
H2	0.590 (2)	0.532 (2)	0.888 (4)	0.068 (12)*
C1	0.63717 (10)	0.46886 (11)	0.71725 (19)	0.0295 (5)
H1A	0.6573	0.5090	0.7683	0.035*
C2	0.56447 (11)	0.44658 (11)	0.7019 (2)	0.0310 (5)
C3	0.53051 (12)	0.45681 (12)	0.7923 (2)	0.0370 (6)
C4	0.46358 (14)	0.43543 (14)	0.7772 (3)	0.0480 (7)
H4	0.4400	0.4422	0.8384	0.058*
C5	0.43171 (13)	0.40498 (16)	0.6757 (3)	0.0541 (8)
H5	0.3865	0.3918	0.6661	0.065*
C6	0.46467 (14)	0.39338 (17)	0.5873 (3)	0.0558 (8)
H6	0.4421	0.3711	0.5177	0.067*
C7	0.53144 (13)	0.41460 (14)	0.6004 (2)	0.0446 (7)
H7	0.5544	0.4070	0.5392	0.054*
C8	0.67533 (10)	0.48591 (12)	0.6030 (2)	0.0329 (5)
C9	0.69119 (12)	0.54381 (13)	0.5431 (2)	0.0437 (7)
C10	0.73000 (15)	0.5615 (2)	0.4418 (3)	0.0679 (11)
H10	0.7409	0.6013	0.4021	0.081*
C11	0.75243 (16)	0.5216 (3)	0.3997 (3)	0.0783 (14)
H11	0.7792	0.5339	0.3312	0.094*
C12	0.73624 (15)	0.4639 (2)	0.4566 (3)	0.0695 (12)
H12	0.7513	0.4360	0.4264	0.083*
C13	0.69824 (13)	0.44599 (15)	0.5574 (2)	0.0458 (7)
H13	0.6876	0.4060	0.5961	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0763 (7)	0.0518 (5)	0.1047 (9)	0.0312 (4)	−0.0183 (5)	0.0120 (4)
O1	0.0278 (8)	0.0368 (9)	0.0499 (11)	0.0137 (7)	−0.0014 (7)	0.0132 (7)
O2	0.0534 (11)	0.0509 (12)	0.0340 (9)	0.0318 (10)	0.0080 (8)	−0.0075 (8)
C1	0.0277 (11)	0.0279 (10)	0.0316 (11)	0.0130 (8)	−0.0020 (8)	−0.0008 (8)
C2	0.0282 (11)	0.0317 (11)	0.0341 (11)	0.0158 (9)	0.0014 (8)	0.0026 (9)
C3	0.0403 (13)	0.0361 (12)	0.0416 (13)	0.0243 (10)	0.0078 (10)	0.0066 (10)
C4	0.0406 (14)	0.0513 (16)	0.0607 (17)	0.0294 (12)	0.0158 (12)	0.0136 (13)
C5	0.0283 (12)	0.0592 (18)	0.073 (2)	0.0208 (12)	0.0050 (12)	0.0138 (15)
C6	0.0332 (14)	0.0679 (19)	0.0545 (17)	0.0164 (13)	−0.0109 (12)	−0.0024 (14)
C7	0.0318 (12)	0.0575 (16)	0.0386 (13)	0.0179 (11)	−0.0008 (10)	−0.0053 (11)
C8	0.0229 (10)	0.0350 (12)	0.0339 (12)	0.0093 (9)	−0.0032 (8)	−0.0030 (9)
C9	0.0319 (12)	0.0434 (14)	0.0393 (13)	0.0065 (10)	−0.0076 (10)	0.0084 (10)
C10	0.0386 (15)	0.083 (2)	0.0433 (16)	0.0008 (16)	−0.0057 (13)	0.0225 (16)
C11	0.0346 (15)	0.135 (4)	0.0338 (15)	0.0182 (19)	0.0038 (12)	0.0009 (19)
C12	0.0385 (15)	0.118 (3)	0.0506 (18)	0.0378 (18)	−0.0045 (13)	−0.032 (2)
C13	0.0336 (12)	0.0563 (16)	0.0476 (14)	0.0226 (12)	−0.0031 (10)	−0.0144 (12)

Geometric parameters (Å, º) top

Cl1—C9	1.710 (3)	C5—C6	1.376 (5)
O1—H1	0.8400	C6—H6	0.9500
O1—C1	1.425 (3)	C6—C7	1.394 (4)
O2—H2	0.87 (5)	C7—H7	0.9500
O2—C3	1.617 (3)	C8—C9	1.394 (4)
C1—H1A	1.0000	C8—C13	1.392 (4)
C1—C2	1.524 (3)	C9—C10	1.396 (4)
C1—C8	1.514 (3)	C10—H10	0.9500
C2—C3	1.393 (3)	C10—C11	1.369 (6)
C2—C7	1.383 (4)	C11—H11	0.9500
C3—C4	1.400 (4)	C11—C12	1.372 (7)
C4—H4	0.9500	C12—H12	0.9500
C4—C5	1.367 (5)	C12—C13	1.382 (4)
C5—H5	0.9500	C13—H13	0.9500

C1—O1—H1	109.5	C7—C6—H6	120.2
C3—O2—H2	99 (3)	C2—C7—C6	120.5 (3)
O1—C1—H1A	108.1	C2—C7—H7	119.7
O1—C1—C2	106.83 (17)	C6—C7—H7	119.7
O1—C1—C8	111.67 (19)	C9—C8—C1	120.8 (2)
C2—C1—H1A	108.1	C13—C8—C1	121.2 (2)
C8—C1—H1A	108.1	C13—C8—C9	118.0 (2)
C8—C1—C2	113.87 (18)	C8—C9—Cl1	120.2 (2)
C3—C2—C1	119.7 (2)	C8—C9—C10	120.6 (3)
C7—C2—C1	120.6 (2)	C10—C9—Cl1	119.2 (3)
C7—C2—C3	119.7 (2)	C9—C10—H10	119.9
C2—C3—O2	121.7 (2)	C11—C10—C9	120.1 (3)
C2—C3—C4	118.9 (2)	C11—C10—H10	119.9
C4—C3—O2	119.4 (2)	C10—C11—H11	120.1
C3—C4—H4	119.6	C10—C11—C12	119.9 (3)
C5—C4—C3	120.9 (3)	C12—C11—H11	120.1
C5—C4—H4	119.6	C11—C12—H12	119.7
C4—C5—H5	119.8	C11—C12—C13	120.6 (4)
C4—C5—C6	120.4 (2)	C13—C12—H12	119.7
C6—C5—H5	119.8	C8—C13—H13	119.6
C5—C6—H6	120.2	C12—C13—C8	120.7 (3)
C5—C6—C7	119.6 (3)	C12—C13—H13	119.6

Cl1—C9—C10—C11	178.1 (2)	C3—C2—C7—C6	0.9 (4)
O1—C1—C2—C3	84.3 (3)	C3—C4—C5—C6	1.6 (5)
O1—C1—C2—C7	−93.8 (3)	C4—C5—C6—C7	−1.8 (5)
O1—C1—C8—C9	−165.2 (2)	C5—C6—C7—C2	0.6 (5)
O1—C1—C8—C13	11.7 (3)	C7—C2—C3—O2	178.5 (2)
O2—C3—C4—C5	−179.8 (2)	C7—C2—C3—C4	−1.2 (4)
C1—C2—C3—O2	0.4 (3)	C8—C1—C2—C3	−151.9 (2)
C1—C2—C3—C4	−179.3 (2)	C8—C1—C2—C7	29.9 (3)
C1—C2—C7—C6	179.0 (3)	C8—C9—C10—C11	0.6 (4)
C1—C8—C9—Cl1	−1.7 (3)	C9—C8—C13—C12	0.8 (4)
C1—C8—C9—C10	175.8 (2)	C9—C10—C11—C12	0.6 (5)
C1—C8—C13—C12	−176.3 (2)	C10—C11—C12—C13	−1.0 (5)
C2—C1—C8—C9	73.7 (3)	C11—C12—C13—C8	0.3 (4)
C2—C1—C8—C13	−109.4 (2)	C13—C8—C9—Cl1	−178.72 (19)
C2—C3—C4—C5	0.0 (4)	C13—C8—C9—C10	−1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84	1.84	2.656 (2)	163

Symmetry code: (i) y+1/3, −x+y+2/3, −z+5/3.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁ClO₂
M_r	234.67
Crystal system, space group	Trigonal, R3
Temperature (K)	173
a, c (Å)	23.4627 (8), 11.3722 (4)
V (Å³)	5421.6 (4)
Z	18
Radiation type	Cu Kα
µ (mm⁻¹)	2.66
Crystal size (mm)	0.46 × 0.38 × 0.24

Data collection
Diffractometer	Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)
T_min, T_max	0.517, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11532, 2364, 2055
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.213, 1.07
No. of reflections	2364
No. of parameters	151
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.62

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2012 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84	1.84	2.656 (2)	162.7

Symmetry code: (i) y+1/3, −x+y+2/3, −z+5/3.

Acknowledgements

GP thanks the UOM for research facilities to complete MSc dissertation work. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

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