Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103019656/bm1540sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103019656/bm1540Isup2.hkl |
CCDC reference: 224675
The H atoms were initially placed in calculated positions and thereafter allowed to refine freely with individual isotropic displacement parameters.
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).
C13H9ClO2 | F(000) = 480 |
Mr = 232.65 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7838 reflections |
a = 15.3857 (3) Å | θ = 2.9–27.5° |
b = 5.8668 (1) Å | µ = 0.35 mm−1 |
c = 11.9540 (3) Å | T = 120 K |
β = 104.985 (2)° | Square prism, yellow |
V = 1042.33 (12) Å3 | 0.2 × 0.1 × 0.1 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 2133 reflections with I > 2σ(I) |
ϕ and ω scans to fill Ewald sphere | Rint = 0.069 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | θmax = 27.5°, θmin = 3.4° |
Tmin = 0.877, Tmax = 0.970 | h = −19→19 |
12435 measured reflections | k = −7→7 |
2375 independent reflections | l = −15→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All 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 = 1.03 | Δρmax = 0.31 e Å−3 |
2375 reflections | Δρmin = −0.29 e Å−3 |
182 parameters |
C13H9ClO2 | V = 1042.33 (12) Å3 |
Mr = 232.65 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.3857 (3) Å | µ = 0.35 mm−1 |
b = 5.8668 (1) Å | T = 120 K |
c = 11.9540 (3) Å | 0.2 × 0.1 × 0.1 mm |
β = 104.985 (2)° |
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 = 0.970 | Rint = 0.069 |
12435 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.092 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.31 e Å−3 |
2375 reflections | Δρmin = −0.29 e Å−3 |
182 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.07628 (2) | −0.27885 (6) | −0.00381 (3) | 0.02568 (13) | |
O1 | 0.20976 (7) | 0.51814 (17) | −0.20445 (8) | 0.0239 (2) | |
H1 | 0.2457 (16) | 0.600 (4) | −0.144 (2) | 0.052 (6)* | |
O2 | 0.30442 (7) | 0.61683 (16) | 0.00042 (8) | 0.0236 (2) | |
C1 | 0.21951 (8) | 0.2765 (2) | −0.03753 (11) | 0.0161 (3) | |
C2 | 0.18494 (8) | 0.3288 (2) | −0.15633 (11) | 0.0181 (3) | |
C3 | 0.12317 (9) | 0.1826 (2) | −0.22745 (11) | 0.0220 (3) | |
H3 | 0.1022 (12) | 0.220 (3) | −0.3090 (16) | 0.028 (4)* | |
C4 | 0.09129 (9) | −0.0060 (2) | −0.18135 (12) | 0.0227 (3) | |
H4 | 0.0483 (12) | −0.103 (3) | −0.2297 (14) | 0.026 (4)* | |
C5 | 0.12135 (9) | −0.0497 (2) | −0.06288 (11) | 0.0190 (3) | |
C6 | 0.18562 (8) | 0.0855 (2) | 0.00833 (11) | 0.0170 (3) | |
H6 | 0.2052 (12) | 0.052 (3) | 0.0887 (15) | 0.025 (4)* | |
C7 | 0.28690 (8) | 0.4282 (2) | 0.03586 (11) | 0.0172 (3) | |
C8 | 0.33624 (8) | 0.3589 (2) | 0.15577 (10) | 0.0162 (3) | |
C9 | 0.34364 (9) | 0.5177 (2) | 0.24486 (11) | 0.0190 (3) | |
H9 | 0.3132 (11) | 0.663 (3) | 0.2290 (14) | 0.023 (4)* | |
C10 | 0.39253 (9) | 0.4644 (2) | 0.35657 (11) | 0.0218 (3) | |
H10 | 0.3964 (13) | 0.570 (3) | 0.4179 (16) | 0.034 (5)* | |
C11 | 0.43665 (9) | 0.2563 (2) | 0.37857 (12) | 0.0227 (3) | |
H11 | 0.4692 (12) | 0.222 (3) | 0.4557 (16) | 0.031 (5)* | |
C12 | 0.43093 (9) | 0.0991 (2) | 0.29012 (12) | 0.0201 (3) | |
H12 | 0.4622 (11) | −0.043 (3) | 0.3046 (14) | 0.023 (4)* | |
C13 | 0.37934 (9) | 0.1480 (2) | 0.17865 (11) | 0.0179 (3) | |
H13 | 0.3734 (11) | 0.039 (3) | 0.1169 (14) | 0.022 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0232 (2) | 0.02238 (19) | 0.0298 (2) | −0.00617 (12) | 0.00394 (14) | 0.00163 (13) |
O1 | 0.0282 (5) | 0.0255 (5) | 0.0174 (4) | −0.0016 (4) | 0.0050 (4) | 0.0046 (4) |
O2 | 0.0288 (5) | 0.0186 (5) | 0.0224 (5) | −0.0040 (4) | 0.0048 (4) | 0.0022 (4) |
C1 | 0.0160 (6) | 0.0171 (6) | 0.0153 (6) | 0.0024 (4) | 0.0041 (5) | −0.0008 (4) |
C2 | 0.0173 (6) | 0.0212 (6) | 0.0166 (6) | 0.0037 (5) | 0.0057 (5) | 0.0016 (5) |
C3 | 0.0189 (6) | 0.0309 (7) | 0.0145 (6) | 0.0024 (5) | 0.0015 (5) | −0.0007 (5) |
C4 | 0.0169 (6) | 0.0281 (7) | 0.0205 (6) | −0.0015 (5) | 0.0001 (5) | −0.0049 (5) |
C5 | 0.0172 (6) | 0.0180 (6) | 0.0216 (6) | 0.0005 (5) | 0.0046 (5) | −0.0004 (5) |
C6 | 0.0160 (6) | 0.0181 (6) | 0.0163 (6) | 0.0034 (5) | 0.0029 (5) | −0.0013 (5) |
C7 | 0.0178 (6) | 0.0165 (6) | 0.0184 (6) | 0.0010 (5) | 0.0066 (5) | −0.0005 (5) |
C8 | 0.0153 (6) | 0.0166 (6) | 0.0166 (6) | −0.0031 (4) | 0.0042 (5) | −0.0012 (5) |
C9 | 0.0194 (6) | 0.0169 (6) | 0.0212 (6) | −0.0026 (5) | 0.0062 (5) | −0.0030 (5) |
C10 | 0.0244 (7) | 0.0240 (7) | 0.0172 (6) | −0.0067 (5) | 0.0055 (5) | −0.0053 (5) |
C11 | 0.0207 (7) | 0.0287 (7) | 0.0165 (6) | −0.0063 (5) | 0.0007 (5) | 0.0020 (5) |
C12 | 0.0172 (6) | 0.0193 (6) | 0.0224 (6) | −0.0009 (5) | 0.0027 (5) | 0.0028 (5) |
C13 | 0.0174 (6) | 0.0181 (6) | 0.0183 (6) | −0.0016 (5) | 0.0047 (5) | −0.0025 (5) |
Cl1—C5 | 1.7435 (13) | C6—H6 | 0.950 (17) |
O1—C2 | 1.3506 (16) | C7—C8 | 1.4946 (17) |
O1—H1 | 0.93 (2) | C8—C13 | 1.3970 (18) |
O2—C7 | 1.2392 (16) | C8—C9 | 1.3973 (18) |
C1—C6 | 1.4057 (18) | C9—C10 | 1.3883 (19) |
C1—C2 | 1.4154 (17) | C9—H9 | 0.968 (17) |
C1—C7 | 1.4719 (18) | C10—C11 | 1.388 (2) |
C2—C3 | 1.3942 (19) | C10—H10 | 0.948 (19) |
C3—C4 | 1.381 (2) | C11—C12 | 1.389 (2) |
C3—H3 | 0.969 (18) | C11—H11 | 0.950 (19) |
C4—C5 | 1.3952 (19) | C12—C13 | 1.3932 (18) |
C4—H4 | 0.948 (18) | C12—H12 | 0.957 (17) |
C5—C6 | 1.3771 (18) | C13—H13 | 0.963 (17) |
C2—O1—H1 | 105.5 (14) | O2—C7—C8 | 118.00 (11) |
C6—C1—C2 | 118.89 (12) | C1—C7—C8 | 120.79 (11) |
C6—C1—C7 | 121.66 (11) | C13—C8—C9 | 120.02 (12) |
C2—C1—C7 | 119.40 (12) | C13—C8—C7 | 121.77 (11) |
O1—C2—C3 | 118.00 (12) | C9—C8—C7 | 118.07 (11) |
O1—C2—C1 | 122.10 (12) | C10—C9—C8 | 120.00 (12) |
C3—C2—C1 | 119.90 (12) | C10—C9—H9 | 120.1 (10) |
C4—C3—C2 | 120.39 (12) | C8—C9—H9 | 119.9 (10) |
C4—C3—H3 | 121.5 (10) | C9—C10—C11 | 119.81 (12) |
C2—C3—H3 | 118.1 (10) | C9—C10—H10 | 120.5 (11) |
C3—C4—C5 | 119.57 (12) | C11—C10—H10 | 119.7 (11) |
C3—C4—H4 | 120.1 (10) | C12—C11—C10 | 120.55 (12) |
C5—C4—H4 | 120.3 (10) | C12—C11—H11 | 120.8 (11) |
C6—C5—C4 | 121.21 (12) | C10—C11—H11 | 118.6 (11) |
C6—C5—Cl1 | 119.40 (10) | C11—C12—C13 | 119.98 (12) |
C4—C5—Cl1 | 119.39 (10) | C11—C12—H12 | 120.8 (10) |
C5—C6—C1 | 119.84 (12) | C13—C12—H12 | 119.2 (10) |
C5—C6—H6 | 119.6 (10) | C12—C13—C8 | 119.60 (12) |
C1—C6—H6 | 120.5 (10) | C12—C13—H13 | 120.9 (10) |
O2—C7—C1 | 121.21 (12) | C8—C13—H13 | 119.5 (10) |
C6—C1—C2—O1 | 175.33 (11) | C6—C1—C7—C8 | 13.19 (18) |
C7—C1—C2—O1 | −2.02 (18) | C2—C1—C7—C8 | −169.53 (11) |
C6—C1—C2—C3 | −4.63 (18) | O2—C7—C8—C13 | −129.39 (13) |
C7—C1—C2—C3 | 178.02 (12) | C1—C7—C8—C13 | 50.66 (17) |
O1—C2—C3—C4 | −176.02 (12) | O2—C7—C8—C9 | 46.36 (16) |
C1—C2—C3—C4 | 3.9 (2) | C1—C7—C8—C9 | −133.59 (13) |
C2—C3—C4—C5 | −0.1 (2) | C13—C8—C9—C10 | −1.12 (19) |
C3—C4—C5—C6 | −3.2 (2) | C7—C8—C9—C10 | −176.95 (11) |
C3—C4—C5—Cl1 | 176.47 (10) | C8—C9—C10—C11 | 2.32 (19) |
C4—C5—C6—C1 | 2.43 (19) | C9—C10—C11—C12 | −1.2 (2) |
Cl1—C5—C6—C1 | −177.22 (9) | C10—C11—C12—C13 | −1.1 (2) |
C2—C1—C6—C5 | 1.47 (18) | C11—C12—C13—C8 | 2.29 (19) |
C7—C1—C6—C5 | 178.76 (11) | C9—C8—C13—C12 | −1.18 (19) |
C6—C1—C7—O2 | −166.75 (12) | C7—C8—C13—C12 | 174.48 (11) |
C2—C1—C7—O2 | 10.52 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.92 (2) | 1.73 (2) | 2.571 (1) | 150 (2) |
C6—H6···O1i | 0.95 (2) | 2.49 (2) | 3.411 (2) | 164 (2) |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H9ClO2 |
Mr | 232.65 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 15.3857 (3), 5.8668 (1), 11.9540 (3) |
β (°) | 104.985 (2) |
V (Å3) | 1042.33 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.2 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.877, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12435, 2375, 2133 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.092, 1.03 |
No. of reflections | 2375 |
No. of parameters | 182 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
Cl1—C5 | 1.7435 (13) | O2—C7 | 1.2392 (16) |
O1—C2 | 1.3506 (16) | ||
O1—C2—C1 | 122.10 (12) | O2—C7—C8 | 118.00 (11) |
C7—C1—C2—O1 | −2.02 (18) | O2—C7—C8—C13 | −129.39 (13) |
C6—C1—C7—O2 | −166.75 (12) | O2—C7—C8—C9 | 46.36 (16) |
C2—C1—C7—O2 | 10.52 (18) | C1—C7—C8—C9 | −133.59 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.92 (2) | 1.73 (2) | 2.571 (1) | 150 (2) |
C6—H6···O1i | 0.95 (2) | 2.49 (2) | 3.411 (2) | 164 (2) |
Symmetry code: (i) x, −y+1/2, z+1/2. |
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 π–π 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 π–π 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).