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Molecules of the title compound, C13H9ClO2, contain an intramolecular O—H...O hydrogen bond, and the two aromatic rings are inclined at 57.02 (3)° with respect to one another. The crystal structure is supported by C—H...O, C—H...π and π–π interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103019656/bm1540sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103019656/bm1540Isup2.hkl
Contains datablock I

CCDC reference: 224675

Comment top

The title compound (I), also known as benzophenone-7, is a UV light absorber that has been found in cosmetics and personalcare products (Health Canada, 2002). Related molecules, e.g. benzophenones-1, −2, −3, −4, −6, −8 and −12 (Wang & Lee, 2003), are used as sunscreeen agents. The crystal structures of chlorinated benzophenones, such as 4-chloro-2-(3,4,5-trimethoxybenzoyl)phenol (Hseih et al., 2003) and pestalone (Cueto et al., 2001), have also been determined and their role as potential anticancer agents and antibiotics has been examined. \sch

In (I), the bond lengths and valence angles are normal and the molecular conformation can be characterized by the dihedral angle of 57.02 (3)° between the mean planes of the two aromatic rings. This compares with values of 56° for benzophenone (Fleischer et al., 1968) and 54.39 (8)° for 2-methylamino-5-chlorobenzophenone (Cox et al., 1997). Another indicator of conformation is the value of the C2—C1—C7—O2 [10.5 (2)°] and C9—C8—C7—O2 [46.4 (2)°] torsion angles. For benzophenones, these torsion angles normally take the same sign and are each reported to be 30° in energy-minimized benzophenone (Rappoport et al., 1990).

In (I), the carbonyl group at C7 and the hydroxy group at C2 are linked by an intramolecular hydrogen bond (Fig. 1 and Table 2). The resultant six-membered ring has a flattened twisted boat conformation, with 0S2 0.163 (Berces et al., 2001). Here, the O—H···O angle of 150 (2)° compares with the N—H···O angle of 133.1 (6)° for 2-methylamino-5-chlorobenzophenone (Cox et al., 1997).

The supramolecular structure of (I) contains a weak intermolecular C6—H6···O1i hydrogen bond [Table 2; symmetry code: (i) x, 1/2 − y, 1/2 + z]. The shortest Cl1···Cl1ii contact of 3.5159 (6) Å compares with the sum of the van der Waals radii of 3.50 Å (Bondi, 1964) [symmetry code: (ii) −x, −1 − y, −z]. Fig. 2 indicates the O—H···O, C—H···O, C—H···π and ππ interactions. Here, C12—H12 0.96 (2) Å, H12···Cg2 2.82 (2), C12—H12···Cg2 129 (1)° and C12···Cg2 3.505 (2) Å, where Cg2 is the centroid of the chlorohydroxy aromatic ring. The ππ interactions are between the phenyl ring and the chlorohydroxy aromatic ring, the latter being transposed by (x, 1/2 − y, z − 1/2]. Here, Cg1···Cg2 is 4.2140 (9) Å, the dihedral angle 10.5°, the interplanar distance 3.702 (1) Å and the offset 2.01 Å.

Crystal structures of related compounds include 2-(5'chloro-2'-hydroxybenzoyl) benzoic acid (Skrzat, 1980), 2-amino-5-chlorobenzophenone (Vasco-Mendez et al., 1996) and 4-amino-3-chlorobenzophenone (Lee et al., 1994).

Experimental top

The sample was purchased from Sigma and recrystallized from water.

Refinement top

The H atoms were initially placed in calculated positions and thereafter allowed to refine freely with individual isotropic displacement parameters.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The atomic arrangement and atom labelling for the molecule of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The intramolecular O—H···O interaction is shown as a broken line.
[Figure 2] Fig. 2. A partial packing diagram for (I), showing the O—H···O, C—H···O, C—H···π and ππ interactions as dotted lines. Ring centroids (Cg1 and Cg2) are indicated by an isolated dot where interactions are with other molecules.
(I) top
Crystal data top
C13H9ClO2F(000) = 480
Mr = 232.65Dx = 1.483 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7838 reflections
a = 15.3857 (3) Åθ = 2.9–27.5°
b = 5.8668 (1) ŵ = 0.35 mm1
c = 11.9540 (3) ÅT = 120 K
β = 104.985 (2)°Square prism, yellow
V = 1042.33 (12) Å30.2 × 0.1 × 0.1 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
2133 reflections with I > 2σ(I)
ϕ and ω scans to fill Ewald sphereRint = 0.069
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
θmax = 27.5°, θmin = 3.4°
Tmin = 0.877, Tmax = 0.970h = 1919
12435 measured reflectionsk = 77
2375 independent reflectionsl = 1515
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.046P)2 + 0.455P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.092(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.31 e Å3
2375 reflectionsΔρmin = 0.29 e Å3
182 parameters
Crystal data top
C13H9ClO2V = 1042.33 (12) Å3
Mr = 232.65Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.3857 (3) ŵ = 0.35 mm1
b = 5.8668 (1) ÅT = 120 K
c = 11.9540 (3) Å0.2 × 0.1 × 0.1 mm
β = 104.985 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
2375 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
2133 reflections with I > 2σ(I)
Tmin = 0.877, Tmax = 0.970Rint = 0.069
12435 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.092All H-atom parameters refined
S = 1.03Δρmax = 0.31 e Å3
2375 reflectionsΔρmin = 0.29 e Å3
182 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. All non-hydrogen atoms were refined in SHELXL97 with anisotropic thermal displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.07628 (2)0.27885 (6)0.00381 (3)0.02568 (13)
O10.20976 (7)0.51814 (17)0.20445 (8)0.0239 (2)
H10.2457 (16)0.600 (4)0.144 (2)0.052 (6)*
O20.30442 (7)0.61683 (16)0.00042 (8)0.0236 (2)
C10.21951 (8)0.2765 (2)0.03753 (11)0.0161 (3)
C20.18494 (8)0.3288 (2)0.15633 (11)0.0181 (3)
C30.12317 (9)0.1826 (2)0.22745 (11)0.0220 (3)
H30.1022 (12)0.220 (3)0.3090 (16)0.028 (4)*
C40.09129 (9)0.0060 (2)0.18135 (12)0.0227 (3)
H40.0483 (12)0.103 (3)0.2297 (14)0.026 (4)*
C50.12135 (9)0.0497 (2)0.06288 (11)0.0190 (3)
C60.18562 (8)0.0855 (2)0.00833 (11)0.0170 (3)
H60.2052 (12)0.052 (3)0.0887 (15)0.025 (4)*
C70.28690 (8)0.4282 (2)0.03586 (11)0.0172 (3)
C80.33624 (8)0.3589 (2)0.15577 (10)0.0162 (3)
C90.34364 (9)0.5177 (2)0.24486 (11)0.0190 (3)
H90.3132 (11)0.663 (3)0.2290 (14)0.023 (4)*
C100.39253 (9)0.4644 (2)0.35657 (11)0.0218 (3)
H100.3964 (13)0.570 (3)0.4179 (16)0.034 (5)*
C110.43665 (9)0.2563 (2)0.37857 (12)0.0227 (3)
H110.4692 (12)0.222 (3)0.4557 (16)0.031 (5)*
C120.43093 (9)0.0991 (2)0.29012 (12)0.0201 (3)
H120.4622 (11)0.043 (3)0.3046 (14)0.023 (4)*
C130.37934 (9)0.1480 (2)0.17865 (11)0.0179 (3)
H130.3734 (11)0.039 (3)0.1169 (14)0.022 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0232 (2)0.02238 (19)0.0298 (2)0.00617 (12)0.00394 (14)0.00163 (13)
O10.0282 (5)0.0255 (5)0.0174 (4)0.0016 (4)0.0050 (4)0.0046 (4)
O20.0288 (5)0.0186 (5)0.0224 (5)0.0040 (4)0.0048 (4)0.0022 (4)
C10.0160 (6)0.0171 (6)0.0153 (6)0.0024 (4)0.0041 (5)0.0008 (4)
C20.0173 (6)0.0212 (6)0.0166 (6)0.0037 (5)0.0057 (5)0.0016 (5)
C30.0189 (6)0.0309 (7)0.0145 (6)0.0024 (5)0.0015 (5)0.0007 (5)
C40.0169 (6)0.0281 (7)0.0205 (6)0.0015 (5)0.0001 (5)0.0049 (5)
C50.0172 (6)0.0180 (6)0.0216 (6)0.0005 (5)0.0046 (5)0.0004 (5)
C60.0160 (6)0.0181 (6)0.0163 (6)0.0034 (5)0.0029 (5)0.0013 (5)
C70.0178 (6)0.0165 (6)0.0184 (6)0.0010 (5)0.0066 (5)0.0005 (5)
C80.0153 (6)0.0166 (6)0.0166 (6)0.0031 (4)0.0042 (5)0.0012 (5)
C90.0194 (6)0.0169 (6)0.0212 (6)0.0026 (5)0.0062 (5)0.0030 (5)
C100.0244 (7)0.0240 (7)0.0172 (6)0.0067 (5)0.0055 (5)0.0053 (5)
C110.0207 (7)0.0287 (7)0.0165 (6)0.0063 (5)0.0007 (5)0.0020 (5)
C120.0172 (6)0.0193 (6)0.0224 (6)0.0009 (5)0.0027 (5)0.0028 (5)
C130.0174 (6)0.0181 (6)0.0183 (6)0.0016 (5)0.0047 (5)0.0025 (5)
Geometric parameters (Å, º) top
Cl1—C51.7435 (13)C6—H60.950 (17)
O1—C21.3506 (16)C7—C81.4946 (17)
O1—H10.93 (2)C8—C131.3970 (18)
O2—C71.2392 (16)C8—C91.3973 (18)
C1—C61.4057 (18)C9—C101.3883 (19)
C1—C21.4154 (17)C9—H90.968 (17)
C1—C71.4719 (18)C10—C111.388 (2)
C2—C31.3942 (19)C10—H100.948 (19)
C3—C41.381 (2)C11—C121.389 (2)
C3—H30.969 (18)C11—H110.950 (19)
C4—C51.3952 (19)C12—C131.3932 (18)
C4—H40.948 (18)C12—H120.957 (17)
C5—C61.3771 (18)C13—H130.963 (17)
C2—O1—H1105.5 (14)O2—C7—C8118.00 (11)
C6—C1—C2118.89 (12)C1—C7—C8120.79 (11)
C6—C1—C7121.66 (11)C13—C8—C9120.02 (12)
C2—C1—C7119.40 (12)C13—C8—C7121.77 (11)
O1—C2—C3118.00 (12)C9—C8—C7118.07 (11)
O1—C2—C1122.10 (12)C10—C9—C8120.00 (12)
C3—C2—C1119.90 (12)C10—C9—H9120.1 (10)
C4—C3—C2120.39 (12)C8—C9—H9119.9 (10)
C4—C3—H3121.5 (10)C9—C10—C11119.81 (12)
C2—C3—H3118.1 (10)C9—C10—H10120.5 (11)
C3—C4—C5119.57 (12)C11—C10—H10119.7 (11)
C3—C4—H4120.1 (10)C12—C11—C10120.55 (12)
C5—C4—H4120.3 (10)C12—C11—H11120.8 (11)
C6—C5—C4121.21 (12)C10—C11—H11118.6 (11)
C6—C5—Cl1119.40 (10)C11—C12—C13119.98 (12)
C4—C5—Cl1119.39 (10)C11—C12—H12120.8 (10)
C5—C6—C1119.84 (12)C13—C12—H12119.2 (10)
C5—C6—H6119.6 (10)C12—C13—C8119.60 (12)
C1—C6—H6120.5 (10)C12—C13—H13120.9 (10)
O2—C7—C1121.21 (12)C8—C13—H13119.5 (10)
C6—C1—C2—O1175.33 (11)C6—C1—C7—C813.19 (18)
C7—C1—C2—O12.02 (18)C2—C1—C7—C8169.53 (11)
C6—C1—C2—C34.63 (18)O2—C7—C8—C13129.39 (13)
C7—C1—C2—C3178.02 (12)C1—C7—C8—C1350.66 (17)
O1—C2—C3—C4176.02 (12)O2—C7—C8—C946.36 (16)
C1—C2—C3—C43.9 (2)C1—C7—C8—C9133.59 (13)
C2—C3—C4—C50.1 (2)C13—C8—C9—C101.12 (19)
C3—C4—C5—C63.2 (2)C7—C8—C9—C10176.95 (11)
C3—C4—C5—Cl1176.47 (10)C8—C9—C10—C112.32 (19)
C4—C5—C6—C12.43 (19)C9—C10—C11—C121.2 (2)
Cl1—C5—C6—C1177.22 (9)C10—C11—C12—C131.1 (2)
C2—C1—C6—C51.47 (18)C11—C12—C13—C82.29 (19)
C7—C1—C6—C5178.76 (11)C9—C8—C13—C121.18 (19)
C6—C1—C7—O2166.75 (12)C7—C8—C13—C12174.48 (11)
C2—C1—C7—O210.52 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.92 (2)1.73 (2)2.571 (1)150 (2)
C6—H6···O1i0.95 (2)2.49 (2)3.411 (2)164 (2)
Symmetry code: (i) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC13H9ClO2
Mr232.65
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)15.3857 (3), 5.8668 (1), 11.9540 (3)
β (°) 104.985 (2)
V3)1042.33 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.2 × 0.1 × 0.1
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995, 1997)
Tmin, Tmax0.877, 0.970
No. of measured, independent and
observed [I > 2σ(I)] reflections
12435, 2375, 2133
Rint0.069
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.092, 1.03
No. of reflections2375
No. of parameters182
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.31, 0.29

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), DENZO and COLLECT, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cl1—C51.7435 (13)O2—C71.2392 (16)
O1—C21.3506 (16)
O1—C2—C1122.10 (12)O2—C7—C8118.00 (11)
C7—C1—C2—O12.02 (18)O2—C7—C8—C13129.39 (13)
C6—C1—C7—O2166.75 (12)O2—C7—C8—C946.36 (16)
C2—C1—C7—O210.52 (18)C1—C7—C8—C9133.59 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.92 (2)1.73 (2)2.571 (1)150 (2)
C6—H6···O1i0.95 (2)2.49 (2)3.411 (2)164 (2)
Symmetry code: (i) x, y+1/2, z+1/2.
 

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