supplementary materials


go2090 scheme

Acta Cryst. (2013). E69, o999-o1000    [ doi:10.1107/S1600536813014396 ]

2-Benzoyl-4-chlorophenyl benzoate

B. Begum A, M. Al-Ghorbani, S. Sharma, V. K. Gupta and S. A. Khanum

Abstract top

In the title compound, C20H13ClO3, the dihedral angles between the benzoate and the chlorobenzene and benzoyl rings are 68.82 (5) and 53.76 (6)°, respectively, while the dihedral angle between the benzoyl and benzoate rings is 81.17 (5)°. The eight atoms of the benzoyl residue are essentially planar with the exception of the O atom which lies 0.1860 (5) Å out of their mean plane (r.m.s. deviation = 0.97 Å). The nine atoms of benzoate residue are also essentially planar (r.m.s. deviation = 0.20 Å) with the ester O atom showing the greatest deviation [0.407 (12) Å] from their mean plane. In the crystal, molecules are connected into centrosymmetric dimers by pairs of C-H...O hydrogen bonds.

Comment top

The benzophenone nucleus is an important part of the therapeutically interesting drug candidate as inhibitors of HIV-1 reverse transcriptase RT, cancer (Revesz et al., 2004) and inflammatory (Khanum et al., 2004; Khanum et al., 2009; Khanum et al., 2010). Therefore, a number of benzophenone analogues were synthesized, and their chemistry has been extensively studied. The benzophenone moiety, a structural element often seen in compounds from natural sources, presents a variety of biological activities such as anti-inflammatory, antimalarial and anticancer and demonstrated to be a versatile pharmacophoric nucleus, largely used in medicinal chemistry programs (Belluti et al., 2011). The importance of these substances is basically due to the diverse biological and chemical properties that they possess. In view of the above importance and to understand the conformation of the benzophenone moiety, the crystal structure determination of the title compound, was carried out. Bond lengths and bond angles of the title molecule show a fair amount of agreement with some related molecules related structures (Sieroń et al., 2004; Naveen et al., 2006; Mahendra et al., 2005). All bond lengths and angles are within expected values (Allen et al., 1987). The title compound has three benzene rings which are linked by carbonyl and ester groups. The dihedral angles between the ring (C1–C6) and (C8–C13) is 68.82 (5)°, ring (C1–C6) and (C16–C21) is 53.76 (6)° and ring (C8–C13) makes a dihedral angle of 81.17 (5)° with ring (C16–C21). The conformation of attachment of the benzoyl and benzoate rings to the central benzene ring can be characterized by torsion angles C6—C1—C7—C8 and C1—C2—O14—C15 of -54.9 (2) and -58.4 (2)°, respectively. The double bonds C7O7 and C15O15 are confirmed by their respective distances of 1.214 (2) and 1.196 (2) Å. Packing view of the molecules in the unit cell viewed down the a axis is shown in Fig. 2. The molecules are linked by intermolecular C20—H20···O7 interactions through hydrogen bonding of the carbonyl (benzophenone moiety) and ester substituent. The interaction with a neighbouring molecule is related to the other by a centre of inversion and form hydrogen-bonded dimer unit. Each unit is independently stacked when viewed down the a axis Fig.3.

Related literature top

For related structures, see: Sieroń et al. (2004); Mahendra et al. (2005); Naveen et al. (2006). For the biological activity of the title compound, see: Belluti et al., (2011); Revesz et al., (2004); Khanum et al., (2004); Khanum et al., (2009); Khanum et al., (2010). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of (2-hydroxy-5-chlorophenyl) phenyl methanone (1, 1.99 g, 8.6 mmol) in 10% sodium hydroxide solution, benzoyl chloride (1.10 g, 8.6 mmol) was added with constant stirring. The reaction mixture was cooled to 0°C, made alkaline by adding 10% sodium solution and stirring was continued for about 1 h. The separated solid was extracted with ether (3 × 20 ml), the organic layer was washed with 10% sodium hydroxide solution (3 × 15 ml) and with distilled water (3 × 30 ml). The organic layer was dried over anhydrous sodium sulfate and ether was removed to afford crude product, which on recrystallization with alcohol gave white crystals of title compound. Yield: 71%, m.p. 365–367K.

Refinement top

All H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93 Å with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. ORTEP view of the molecule with the atom-labelling scheme. The thermal ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing arrangement of molecules viewed down the a axis.
2-Benzoyl-4-chlorophenyl benzoate top
Crystal data top
C20H13ClO3Z = 2
Mr = 336.75F(000) = 348
Triclinic, P1Dx = 1.397 Mg m3
Hall symbol: -P 1Melting point: 367 K
a = 9.1934 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.8641 (3) ÅCell parameters from 10537 reflections
c = 10.0778 (3) Åθ = 3.5–29.1°
α = 94.033 (2)°µ = 0.25 mm1
β = 114.207 (2)°T = 293 K
γ = 102.512 (2)°Block, white
V = 800.64 (4) Å30.30 × 0.20 × 0.20 mm
Data collection top
Oxford Xcalibur Sapphire3
diffractometer
3131 independent reflections
Radiation source: fine-focus sealed tube2631 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 16.1049 pixels mm-1θmax = 26.0°, θmin = 3.5°
ω scansh = 1111
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
k = 1212
Tmin = 0.871, Tmax = 1.000l = 1212
18813 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0283P)2 + 0.3095P]
where P = (Fo2 + 2Fc2)/3
3131 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C20H13ClO3γ = 102.512 (2)°
Mr = 336.75V = 800.64 (4) Å3
Triclinic, P1Z = 2
a = 9.1934 (2) ÅMo Kα radiation
b = 9.8641 (3) ŵ = 0.25 mm1
c = 10.0778 (3) ÅT = 293 K
α = 94.033 (2)°0.30 × 0.20 × 0.20 mm
β = 114.207 (2)°
Data collection top
Oxford Xcalibur Sapphire3
diffractometer
3131 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
2631 reflections with I > 2σ(I)
Tmin = 0.871, Tmax = 1.000Rint = 0.031
18813 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.084Δρmax = 0.20 e Å3
S = 1.03Δρmin = 0.21 e Å3
3131 reflectionsAbsolute structure: ?
217 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Elemental analysis for C20H13ClO3: IR (nujol): 1660 (CO), 1750 cm-1 (ester, CO); 1H NMR (CDCl3): δ 6.9–7.6 (m, 13H, Ar—H). Analysis, calculated for C20H13ClO3 (336.5): C 71.33, H 3.89, Cl 0.53; found: C 71.39, H 3.72, Cl 10.44%.

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
xyzUiso*/Ueq
Cl10.13053 (5)0.16990 (5)0.62243 (6)0.05937 (15)
O140.79582 (13)0.43743 (11)0.68298 (12)0.0453 (3)
O150.94425 (14)0.36025 (11)0.88776 (12)0.0459 (3)
C60.43806 (19)0.16383 (16)0.66293 (16)0.0384 (3)
H60.40440.06820.66440.046*
C20.64376 (18)0.36708 (16)0.67781 (16)0.0373 (3)
C10.59678 (18)0.22283 (15)0.67650 (16)0.0357 (3)
C50.33045 (18)0.24639 (17)0.64737 (17)0.0400 (4)
C70.70368 (18)0.12708 (15)0.67663 (17)0.0385 (3)
C150.94012 (18)0.43373 (15)0.79760 (16)0.0356 (3)
C161.08476 (18)0.53267 (15)0.79432 (17)0.0355 (3)
O70.75790 (16)0.12731 (13)0.58523 (15)0.0569 (3)
C80.73479 (18)0.03063 (15)0.78589 (17)0.0376 (3)
C30.5371 (2)0.44936 (16)0.66627 (18)0.0439 (4)
H30.57190.54590.66960.053*
C211.0687 (2)0.61313 (17)0.68447 (19)0.0466 (4)
H210.96460.60490.60850.056*
C40.3790 (2)0.38951 (17)0.64981 (18)0.0438 (4)
H40.30630.44470.64050.053*
C130.71872 (19)0.05701 (16)0.91536 (18)0.0422 (4)
H130.68000.13310.93210.051*
C171.24005 (19)0.54643 (16)0.90776 (18)0.0417 (4)
H171.25180.49250.98170.050*
C181.3775 (2)0.64032 (18)0.9110 (2)0.0496 (4)
H181.48160.65030.98770.060*
C90.7918 (2)0.08432 (17)0.7620 (2)0.0481 (4)
H90.80340.10320.67570.058*
C191.3604 (2)0.71918 (18)0.8006 (2)0.0527 (4)
H191.45310.78180.80260.063*
C201.2068 (2)0.70554 (19)0.6876 (2)0.0553 (5)
H201.19580.75860.61310.066*
C110.8161 (2)0.14242 (18)0.9953 (2)0.0539 (5)
H110.84410.20011.06590.065*
C120.7599 (2)0.02918 (18)1.0198 (2)0.0505 (4)
H120.74950.01051.10680.061*
C100.8310 (2)0.17028 (17)0.8670 (2)0.0551 (5)
H100.86780.24760.85040.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0354 (2)0.0713 (3)0.0687 (3)0.0086 (2)0.0220 (2)0.0177 (2)
O70.0698 (9)0.0553 (7)0.0646 (8)0.0210 (6)0.0445 (7)0.0177 (6)
O140.0337 (6)0.0453 (6)0.0512 (7)0.0043 (5)0.0140 (5)0.0220 (5)
O150.0434 (6)0.0429 (6)0.0474 (7)0.0067 (5)0.0168 (5)0.0174 (5)
C10.0348 (8)0.0362 (8)0.0338 (8)0.0081 (6)0.0132 (6)0.0089 (6)
C20.0327 (8)0.0382 (8)0.0366 (8)0.0055 (6)0.0121 (6)0.0121 (6)
C30.0429 (9)0.0341 (8)0.0464 (9)0.0090 (7)0.0115 (7)0.0107 (7)
C40.0402 (9)0.0443 (9)0.0437 (9)0.0166 (7)0.0127 (7)0.0078 (7)
C50.0310 (8)0.0484 (9)0.0360 (8)0.0073 (7)0.0119 (7)0.0074 (7)
C60.0385 (8)0.0349 (8)0.0375 (8)0.0054 (6)0.0143 (7)0.0078 (6)
C70.0348 (8)0.0343 (8)0.0429 (9)0.0039 (6)0.0167 (7)0.0043 (6)
C80.0308 (8)0.0310 (7)0.0463 (9)0.0058 (6)0.0137 (7)0.0054 (6)
C90.0436 (9)0.0396 (9)0.0581 (11)0.0116 (7)0.0202 (8)0.0032 (8)
C100.0467 (10)0.0340 (8)0.0779 (14)0.0161 (8)0.0182 (10)0.0093 (8)
C110.0463 (10)0.0418 (9)0.0638 (12)0.0107 (8)0.0134 (9)0.0201 (8)
C120.0515 (10)0.0476 (10)0.0500 (10)0.0127 (8)0.0192 (8)0.0150 (8)
C130.0427 (9)0.0345 (8)0.0487 (9)0.0116 (7)0.0183 (8)0.0082 (7)
C150.0375 (8)0.0307 (7)0.0375 (8)0.0091 (6)0.0152 (7)0.0067 (6)
C160.0353 (8)0.0313 (7)0.0387 (8)0.0071 (6)0.0162 (7)0.0049 (6)
C170.0409 (9)0.0409 (8)0.0403 (9)0.0103 (7)0.0153 (7)0.0066 (7)
C180.0338 (9)0.0498 (10)0.0534 (10)0.0048 (7)0.0124 (8)0.0009 (8)
C190.0426 (10)0.0439 (9)0.0683 (12)0.0011 (7)0.0281 (9)0.0052 (8)
C200.0533 (11)0.0502 (10)0.0635 (12)0.0068 (8)0.0280 (10)0.0241 (9)
C210.0389 (9)0.0460 (9)0.0497 (10)0.0065 (7)0.0156 (8)0.0169 (8)
Geometric parameters (Å, º) top
C1—C21.392 (2)C11—C121.375 (2)
C1—C61.394 (2)C11—H110.9300
C1—C71.503 (2)C12—C131.383 (2)
C2—C31.378 (2)C12—H120.9300
C2—O141.3977 (17)C13—H130.9300
C3—C41.381 (2)C15—O151.1952 (17)
C3—H30.9300C15—O141.3660 (18)
C4—C51.380 (2)C15—C161.483 (2)
C4—H40.9300C16—C211.385 (2)
C5—C61.381 (2)C16—C171.385 (2)
C5—Cl11.7333 (15)C17—C181.382 (2)
C6—H60.9300C17—H170.9300
C7—O71.2138 (19)C18—C191.378 (3)
C7—C81.485 (2)C18—H180.9300
C8—C131.385 (2)C19—C201.373 (3)
C8—C91.393 (2)C19—H190.9300
C9—C101.384 (2)C20—C211.381 (2)
C9—H90.9300C20—H200.9300
C10—C111.370 (3)C21—H210.9300
C10—H100.9300
C2—C1—C6117.95 (14)C10—C11—H11120.0
C2—C1—C7122.98 (13)C12—C11—H11120.0
C6—C1—C7118.88 (13)C11—C12—C13120.16 (17)
C3—C2—C1121.19 (14)C11—C12—H12119.9
C3—C2—O14115.25 (13)C13—C12—H12119.9
C1—C2—O14123.49 (14)C12—C13—C8120.34 (15)
C2—C3—C4120.46 (14)C12—C13—H13119.8
C2—C3—H3119.8C8—C13—H13119.8
C4—C3—H3119.8O15—C15—O14122.79 (13)
C5—C4—C3118.93 (15)O15—C15—C16126.12 (14)
C5—C4—H4120.5O14—C15—C16111.09 (12)
C3—C4—H4120.5C21—C16—C17119.55 (14)
C4—C5—C6120.98 (14)C21—C16—C15122.27 (14)
C4—C5—Cl1119.15 (12)C17—C16—C15118.16 (13)
C6—C5—Cl1119.87 (12)C18—C17—C16120.00 (15)
C5—C6—C1120.46 (14)C18—C17—H17120.0
C5—C6—H6119.8C16—C17—H17120.0
C1—C6—H6119.8C19—C18—C17120.01 (16)
O7—C7—C8121.80 (14)C19—C18—H18120.0
O7—C7—C1119.47 (14)C17—C18—H18120.0
C8—C7—C1118.69 (13)C20—C19—C18120.21 (15)
C13—C8—C9119.11 (15)C20—C19—H19119.9
C13—C8—C7121.70 (14)C18—C19—H19119.9
C9—C8—C7119.07 (15)C19—C20—C21120.11 (16)
C10—C9—C8119.83 (17)C19—C20—H20119.9
C10—C9—H9120.1C21—C20—H20119.9
C8—C9—H9120.1C20—C21—C16120.11 (15)
C11—C10—C9120.57 (16)C20—C21—H21119.9
C11—C10—H10119.7C16—C21—H21119.9
C9—C10—H10119.7C15—O14—C2119.99 (11)
C10—C11—C12119.99 (16)
C6—C1—C2—C30.1 (2)C8—C9—C10—C110.8 (3)
C7—C1—C2—C3175.00 (14)C9—C10—C11—C120.8 (3)
C6—C1—C2—O14176.52 (13)C10—C11—C12—C130.2 (3)
C7—C1—C2—O141.6 (2)C11—C12—C13—C80.4 (3)
C1—C2—C3—C41.4 (2)C9—C8—C13—C120.5 (2)
O14—C2—C3—C4175.44 (14)C7—C8—C13—C12175.37 (15)
C2—C3—C4—C51.0 (2)O15—C15—C16—C21179.39 (16)
C3—C4—C5—C60.8 (2)O14—C15—C16—C211.5 (2)
C3—C4—C5—Cl1178.51 (13)O15—C15—C16—C172.2 (2)
C4—C5—C6—C12.2 (2)O14—C15—C16—C17176.90 (13)
Cl1—C5—C6—C1177.15 (12)C21—C16—C17—C180.2 (2)
C2—C1—C6—C51.7 (2)C15—C16—C17—C18178.25 (14)
C7—C1—C6—C5173.43 (14)C16—C17—C18—C190.7 (3)
C2—C1—C7—O752.1 (2)C17—C18—C19—C200.4 (3)
C6—C1—C7—O7122.75 (17)C18—C19—C20—C210.3 (3)
C2—C1—C7—C8130.12 (15)C19—C20—C21—C160.8 (3)
C6—C1—C7—C855.02 (19)C17—C16—C21—C200.5 (3)
O7—C7—C8—C13160.10 (16)C15—C16—C21—C20178.90 (16)
C1—C7—C8—C1322.2 (2)O15—C15—O14—C28.1 (2)
O7—C7—C8—C915.7 (2)C16—C15—O14—C2171.02 (13)
C1—C7—C8—C9161.98 (14)C3—C2—O14—C15124.88 (15)
C13—C8—C9—C100.1 (2)C1—C2—O14—C1558.3 (2)
C7—C8—C9—C10176.07 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C20—H20···O7i0.932.503.394 (2)162
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C20—H20···O7i0.932.503.394 (2)162
Symmetry code: (i) x+2, y+1, z+1.
Acknowledgements top

RK acknowledges the Department of Science and Technology for the single-crystal X-ray diffractometer, sanctioned as a National Facility under Project No. SR/S2/CMP-47/2003. SAK gratefully acknowledges financial support provided by the UGC, New Delhi, under the Major Research Project Scheme.

references
References top

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