3-Chloro-4-hydr­oxy-4′-methyl­benzophenone

Harrison, W.T.A.; Anilkumar, H.G.; Yathirajan, H.S.; Sadashivamurthy, B.; Basavaraju, Y.B.

doi:10.1107/S1600536805036780

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 12| December 2005| Pages o4146-o4148

https://doi.org/10.1107/S1600536805036780

3-Chloro-4-hydroxy-4′-methylbenzophenone

William T. A. Harrison,^a ^* H. G. Anilkumar,^b H. S. Yathirajan,^b B. Sadashivamurthy ^b and Y. B. Basavaraju ^b

^aDepartment of Chemistry, University of Aberdeen, Aberdeen AB24 3UE, Scotland, and ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 21 October 2005; accepted 9 November 2005; online 16 November 2005)

The title compound, C₁₄H₁₁ClO₂, possesses normal geometrical parameters. The two benzene rings are twisted by 54.70 (4)°, perhaps as a result of steric repulsion between H atoms. The crystal packing is consolidated by an O—H⋯O hydrogen bond, π–π stacking and C—H⋯O and C—H⋯π interactions, resulting in a two-dimensional network.

Comment

The title compound, (I) (Fig. 1), is an intermediate for the synthesis of podophyllotoxin and its derivatives which have pharmaceutical applications (Basavaraju & Devaraju, 2002 ). More generally, benzophenone derivatives have many applications in organic chemistry (Sieron et al., 2004 ; Khanum et al., 2005 ).

Compound (I) possesses normal geometrical parameters (Allen et al., 1995 ). The dihedral angle, δ, between the mean planes of the two benzene rings (atoms C1–C6 and C8–C13) is 54.70 (4)°. The C—C_c (c = carbonyl) C6—C7 [1.480 (2) Å] and C7—C8 [1.482 (2) Å] bond lengths are only slightly shorter than normal C—C single bonds, indicating negligible conjugation between the two aromatic ring systems. The rings may be twisted as a result of steric repulsion between the C5 and C9 H atoms (H5⋯H9 = 2.40 Å; van der Waals contact distance = 2.40 Å), although we note that H9 also participates in a C—H⋯O interaction (see below). Many other substituted benzophenones possess similar geometrical parameters for the equivalent distances and angles. For example, in 4-dimethylamino-4′-[bis(2-hydroxyethyl)amino]benzophenone (El Sayed et al., 2001 ), H⋯H = 2.38 Å, C—C_c = 1.460 (3) and 1.484 (3) Å, and δ = 47.4 (1)°, and in (3-chlorophenyl)(2-hydroxy-5-methylphenyl)methanone (Khanum et al., 2005) H⋯H = 2.52 Å, C—C_c = 1.468 (3) and 1.493 (3) Å, and δ = 57.37 (12)°.

As well as van der Waals forces, the crystal packing in (I) appears to be controlled by several different intermolecular interactions (Table 1). The most clearcut is an O—H⋯O hydrogen bond that links adjacent molecules of (I) in the b-axis direction. Fig. 2 shows that π–π stacking occurs between adjacent inversion-related C1–C6 benzene rings, with a centroid–centroid separation of 3.7642 (10) Å and an interplanar distance of 3.357 Å. Additionally, a PLATON (Spek, 2003 ) analysis of (I) identified probable C—H⋯O and C—H⋯π interactions (Table 1). Together, these interactions lead to a two-dimensional network that propagates in the ab plane. The packing is shown in Fig. 3.

Figure 1
The molecular structure of (I)

, with 50% probability displacement ellipsoids (arbitrary spheres for the H atoms).

Figure 2
Detail of (I)

showing how π–π stacking (pink line) and C—H⋯O (yellow lines) and C—H⋯π (green lines) weak intermolecular interactions help to establish the crystal packing. Symmetry codes as in Table 1

; additionally (iv) 1 − x, 1 − y, −z.

Figure 3
The packing for (I)

, with all H atoms except H1 omitted for clarity. The O—H⋯O hydrogen bond is indicated by a dashed line. The molecule containing O2* is generated by the symmetry code (x, 1 + y, z).

Experimental

A solution of o-chlorophenol (1 g, 0.0077 mol) in dry dichloromethane (10 ml) was treated with anhydrous aluminium chloride (1.037 g, 0.0077 mol). The reaction mixture was stirred continuously for 30 min and then cooled. To this, a solution of toluoyl chloride (1.203 g, 0.0077 mol) in methylene chloride (10 ml) was added dropwise and the mixture kept overnight. After 24 h, about 5 ml of concentrated HCl was added and the reaction mixture was stirred for another 24 h. Aqueous NaCl solution (10%) was added to break the emulsion and the lower organic layer was separated and washed with 10% brine. Excess dichloromethane was distilled off on a water bath. The concentrated solution was kept overnight, resulting in a pale-brown solid (yield: 89.2%; m.p. 352 K). Colourless single crystals of (I) were recrystallized from a 1:1 mixture of acetone and acetonitrile.

Crystal data

C₁₄H₁₁ClO₂
M_r = 246.68
Triclinic, $[P \overline 1]$
a = 7.1062 (3) Å
b = 8.5441 (5) Å
c = 9.8766 (6) Å
α = 86.124 (3)°
β = 83.804 (3)°
γ = 77.290 (3)°
V = 580.96 (5) Å³
Z = 2
D_x = 1.410 Mg m⁻³
Mo Kα radiation
Cell parameters from 2534 reflections
θ = 2.9–27.5°
μ = 0.31 mm⁻¹
T = 120 (2) K
Cut block, colourless
0.32 × 0.16 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan(SADABS; Bruker, 2003 )T_min = 0.906, T_max = 0.969
11199 measured reflections
2684 independent reflections
2037 reflections with I > 2σ(I)
R_int = 0.048
θ_max = 27.8°
h = −9 → 9
k = −11 → 11
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 1.05
2684 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0595P)² + 0.1677P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.78 (2)	1.93 (2)	2.6418 (17)	150 (2)
C9—H9⋯O1ⁱⁱ	0.95	2.48	3.375 (2)	157
C13—H13⋯Cg1ⁱⁱⁱ	0.95	2.59	3.3908 (17)	142
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+1, -z; (iii) -x+1, -y+2, -z. Cg1 is the centroid of the C1–C6 ring

The hydroxy H atom was located in a difference map and its position was freely refined with the constraint U_iso(H) = 1.2U_eq(O). Other H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier). The —CH₃ group was rotated to fit the electron density.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805036780/ac6218sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805036780/ac6218Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

3-Chloro-4-hydroxy-4'-methylbenzophenone top

Crystal data top

C₁₄H₁₁ClO₂	Z = 2
M_r = 246.68	F(000) = 256
Triclinic, P1	D_x = 1.410 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1062 (3) Å	Cell parameters from 2534 reflections
b = 8.5441 (5) Å	θ = 2.9–27.5°
c = 9.8766 (6) Å	µ = 0.31 mm⁻¹
α = 86.124 (3)°	T = 120 K
β = 83.804 (3)°	Cut block, colourless
γ = 77.290 (3)°	0.32 × 0.16 × 0.10 mm
V = 580.96 (5) Å³

Data collection top

Nonius KappaCCD diffractometer	2684 independent reflections
Radiation source: fine-focus sealed tube	2037 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 27.8°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
T_min = 0.906, T_max = 0.969	k = −11→11
11199 measured reflections	l = −12→12

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)] = 0.041	Hydrogen site location: difmap (O-H) and geom (others)
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0595P)² + 0.1677P] where P = (F_o² + 2F_c²)/3
2684 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

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
C1	0.8691 (2)	0.7775 (2)	−0.13871 (18)	0.0173 (4)
H2	0.9198	0.8558	−0.1953	0.021*
C2	0.8806 (2)	0.6279 (2)	−0.18629 (17)	0.0169 (4)
C3	0.8048 (2)	0.5108 (2)	−0.10592 (18)	0.0171 (4)
C4	0.7215 (2)	0.5473 (2)	0.02553 (18)	0.0179 (4)
H4	0.6712	0.4686	0.0820	0.021*
C5	0.7113 (2)	0.6977 (2)	0.07467 (18)	0.0176 (4)
H5	0.6550	0.7208	0.1647	0.021*
C6	0.7830 (2)	0.8149 (2)	−0.00730 (17)	0.0164 (4)
C7	0.7567 (2)	0.9819 (2)	0.03481 (18)	0.0175 (4)
C8	0.7257 (2)	1.0217 (2)	0.18041 (18)	0.0171 (4)
C9	0.8176 (3)	0.9232 (2)	0.28295 (18)	0.0188 (4)
H9	0.8970	0.8213	0.2621	0.023*
C10	0.7929 (3)	0.9743 (2)	0.41554 (19)	0.0213 (4)
H10	0.8573	0.9070	0.4845	0.026*
C11	0.6753 (3)	1.1224 (2)	0.44931 (19)	0.0225 (4)
C12	0.5813 (3)	1.2185 (2)	0.34659 (19)	0.0219 (4)
H12	0.4984	1.3189	0.3680	0.026*
C13	0.6067 (2)	1.1701 (2)	0.21448 (18)	0.0186 (4)
H13	0.5428	1.2382	0.1457	0.022*
C14	0.6528 (3)	1.1784 (3)	0.5928 (2)	0.0324 (5)
H14A	0.5353	1.2631	0.6058	0.049*
H14B	0.7659	1.2207	0.6083	0.049*
H14C	0.6426	1.0879	0.6576	0.049*
O1	0.81397 (19)	0.36984 (15)	−0.16234 (13)	0.0220 (3)
H1	0.780 (3)	0.308 (3)	−0.108 (2)	0.026*
O2	0.75791 (19)	1.09033 (14)	−0.05454 (13)	0.0235 (3)
Cl1	0.99046 (7)	0.58148 (5)	−0.34839 (5)	0.02638 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0197 (9)	0.0155 (8)	0.0175 (9)	−0.0062 (7)	−0.0020 (7)	0.0008 (7)
C2	0.0189 (9)	0.0175 (9)	0.0138 (9)	−0.0020 (7)	−0.0013 (7)	−0.0027 (7)
C3	0.0182 (8)	0.0122 (8)	0.0215 (9)	−0.0023 (7)	−0.0055 (7)	−0.0035 (7)
C4	0.0195 (9)	0.0163 (9)	0.0191 (9)	−0.0066 (7)	−0.0029 (7)	0.0017 (7)
C5	0.0188 (9)	0.0182 (9)	0.0157 (9)	−0.0037 (7)	−0.0015 (7)	−0.0012 (7)
C6	0.0176 (9)	0.0162 (8)	0.0156 (9)	−0.0029 (7)	−0.0034 (7)	−0.0020 (7)
C7	0.0174 (9)	0.0164 (9)	0.0196 (9)	−0.0051 (7)	−0.0010 (7)	−0.0025 (7)
C8	0.0188 (8)	0.0157 (8)	0.0188 (9)	−0.0078 (7)	−0.0015 (7)	−0.0027 (7)
C9	0.0202 (9)	0.0167 (9)	0.0203 (9)	−0.0053 (7)	−0.0008 (7)	−0.0033 (7)
C10	0.0236 (9)	0.0219 (9)	0.0203 (10)	−0.0077 (8)	−0.0047 (7)	−0.0002 (7)
C11	0.0224 (9)	0.0277 (10)	0.0203 (10)	−0.0114 (8)	0.0019 (7)	−0.0082 (8)
C12	0.0221 (9)	0.0171 (9)	0.0266 (10)	−0.0040 (8)	0.0006 (8)	−0.0079 (8)
C13	0.0189 (9)	0.0160 (8)	0.0217 (10)	−0.0045 (7)	−0.0029 (7)	−0.0023 (7)
C14	0.0344 (11)	0.0406 (12)	0.0239 (11)	−0.0101 (10)	0.0013 (9)	−0.0137 (9)
O1	0.0331 (8)	0.0122 (6)	0.0218 (7)	−0.0071 (6)	−0.0003 (6)	−0.0035 (5)
O2	0.0368 (8)	0.0146 (6)	0.0192 (7)	−0.0063 (6)	−0.0012 (6)	0.0000 (5)
Cl1	0.0371 (3)	0.0229 (3)	0.0189 (3)	−0.0084 (2)	0.00578 (19)	−0.00673 (18)

Geometric parameters (Å, º) top

C1—C2	1.374 (2)	C8—C13	1.400 (2)
C1—C6	1.400 (2)	C9—C10	1.389 (3)
C1—H2	0.9500	C9—H9	0.9500
C2—C3	1.400 (2)	C10—C11	1.393 (3)
C2—Cl1	1.7349 (17)	C10—H10	0.9500
C3—O1	1.346 (2)	C11—C12	1.394 (3)
C3—C4	1.393 (2)	C11—C14	1.507 (3)
C4—C5	1.388 (2)	C12—C13	1.377 (3)
C4—H4	0.9500	C12—H12	0.9500
C5—C6	1.395 (2)	C13—H13	0.9500
C5—H5	0.9500	C14—H14A	0.9800
C6—C7	1.480 (2)	C14—H14B	0.9800
C7—O2	1.236 (2)	C14—H14C	0.9800
C7—C8	1.482 (2)	O1—H1	0.78 (2)
C8—C9	1.395 (2)

C2—C1—C6	120.31 (16)	C13—C8—C7	117.82 (15)
C2—C1—H2	119.8	C10—C9—C8	119.97 (17)
C6—C1—H2	119.8	C10—C9—H9	120.0
C1—C2—C3	121.09 (16)	C8—C9—H9	120.0
C1—C2—Cl1	120.04 (14)	C9—C10—C11	121.24 (17)
C3—C2—Cl1	118.87 (13)	C9—C10—H10	119.4
O1—C3—C4	124.00 (16)	C11—C10—H10	119.4
O1—C3—C2	117.39 (16)	C10—C11—C12	118.31 (17)
C4—C3—C2	118.60 (15)	C10—C11—C14	120.88 (18)
C5—C4—C3	120.55 (16)	C12—C11—C14	120.80 (17)
C5—C4—H4	119.7	C13—C12—C11	120.97 (17)
C3—C4—H4	119.7	C13—C12—H12	119.5
C4—C5—C6	120.45 (16)	C11—C12—H12	119.5
C4—C5—H5	119.8	C12—C13—C8	120.71 (17)
C6—C5—H5	119.8	C12—C13—H13	119.6
C5—C6—C1	118.97 (15)	C8—C13—H13	119.6
C5—C6—C7	122.40 (16)	C11—C14—H14A	109.5
C1—C6—C7	118.42 (15)	C11—C14—H14B	109.5
O2—C7—C6	118.64 (15)	H14A—C14—H14B	109.5
O2—C7—C8	119.70 (15)	C11—C14—H14C	109.5
C6—C7—C8	121.65 (15)	H14A—C14—H14C	109.5
C9—C8—C13	118.79 (16)	H14B—C14—H14C	109.5
C9—C8—C7	123.28 (16)	C3—O1—H1	110.8 (17)

C6—C1—C2—C3	0.8 (3)	C1—C6—C7—C8	−160.64 (15)
C6—C1—C2—Cl1	−179.11 (12)	O2—C7—C8—C9	−144.16 (17)
C1—C2—C3—O1	177.04 (16)	C6—C7—C8—C9	37.0 (2)
Cl1—C2—C3—O1	−3.0 (2)	O2—C7—C8—C13	32.0 (2)
C1—C2—C3—C4	−1.7 (3)	C6—C7—C8—C13	−146.81 (16)
Cl1—C2—C3—C4	178.26 (13)	C13—C8—C9—C10	−1.1 (2)
O1—C3—C4—C5	−177.62 (16)	C7—C8—C9—C10	175.03 (16)
C2—C3—C4—C5	1.0 (3)	C8—C9—C10—C11	0.8 (3)
C3—C4—C5—C6	0.5 (3)	C9—C10—C11—C12	0.4 (3)
C4—C5—C6—C1	−1.4 (3)	C9—C10—C11—C14	−178.65 (17)
C4—C5—C6—C7	173.28 (16)	C10—C11—C12—C13	−1.3 (3)
C2—C1—C6—C5	0.7 (3)	C14—C11—C12—C13	177.77 (17)
C2—C1—C6—C7	−174.16 (15)	C11—C12—C13—C8	1.0 (3)
C5—C6—C7—O2	−154.18 (17)	C9—C8—C13—C12	0.3 (3)
C1—C6—C7—O2	20.5 (2)	C7—C8—C13—C12	−176.10 (15)
C5—C6—C7—C8	24.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.78 (2)	1.93 (2)	2.6418 (17)	150 (2)
C9—H9···O1ⁱⁱ	0.95	2.48	3.375 (2)	157
C13—H13···Cg1ⁱⁱⁱ	0.95	2.59	3.3908 (17)	142

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

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection.

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