Methyl 2-(4-hy­droxy­benzo­yl)benzoate

Siddegowda, M.S.; Jasinski, J.P.; Golen, J.A.; Yathirajan, H.S.; Swamy, M.T.

doi:10.1107/S1600536811026651

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1994

doi:10.1107/S1600536811026651

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Methyl 2-(4-hydroxybenzoyl)benzoate

M. S. Siddegowda,^a Jerry P. Jasinski,^b ^* James A. Golen,^b H. S. Yathirajan ^a and M. T. Swamy ^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 ^cDepartment of Chemistry, Sambhram Institute of Technology, Bengaluru, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 4 July 2011; accepted 4 July 2011; online 9 July 2011)

In the title compound, C₁₅H₁₂O₄, the dihedral angle between the benzene rings is 64.0 (6)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming C(8) chains propagating in [10 $[\overline{1}]$ ] and the packing is reinforced by weak C—H⋯O interactions.

Related literature

For background to benzophenone derivatives, see: Sieroń et al. (2004). For related structures, see: Cox et al. (2008 ); Jasinski et al. (2009 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₂O₄
M_r = 256.25
Monoclinic, P 2₁ /n
a = 8.9017 (12) Å
b = 13.9940 (17) Å
c = 10.0473 (12) Å
β = 94.687 (12)°
V = 1247.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.38 × 0.32 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.963, T_max = 0.977
11331 measured reflections
3231 independent reflections
2722 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.117
S = 1.02
3231 reflections
177 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O3ⁱ	0.85 (1)	1.88 (2)	2.7310 (14)	173 (2)
C12—H12A⋯O2ⁱ	0.95	2.50	3.4333 (15)	167
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811026651/hb5942sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026651/hb5942Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026651/hb5942Isup3.cml

checkCIF report

Comment top

The title compound is a starting material for the synthesis of pitofenone, which is an antispasmodic. More generally, benzophenone derivatives have many applications in organic chemistry (Sieroń et al., 2004). The crystal structures of some substituted benzophenones (Cox et al., 2008) and 2-amino-5-nitrophenyl 2-chlorophenyl ketone (Jasinski et al., 2009) have been reported. In view of the importance of the title compound, this paper reports the crystal structure of (I), C₁₅H₁₂O₄.

In the title compound, C₁₅H₁₂O₄, the dihedral angle between the mean planes of the two benzene rings is 64.0 (6)° (Fig. 1). Bond distances are in normal ranges (Allen et al., 1987). Crystal packing is stabilized by O—H···O hydrogen bonds and weak C—H···O intermolecular interactions (Table 1, Fig. 2).

Related literature top

For background to benzophenone derivatives, see: Sieroń et al. (2004). For related structures, see: Cox et al. (2008); Jasinski et al. (2009). For reference bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was obtained as a gift sample from R. L. Fine Chem, Bengaluru, india. Colourless blocks were grown from methanol solution (430-433 K).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound showing 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed down the c axis. Dashed lines represent O—H···O hydrogen bonds.

Methyl 2-(4-hydroxybenzoyl)benzoate top

Crystal data top

C₁₅H₁₂O₄	F(000) = 536
M_r = 256.25	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4807 reflections
a = 8.9017 (12) Å	θ = 3.3–32.3°
b = 13.9940 (17) Å	µ = 0.10 mm⁻¹
c = 10.0473 (12) Å	T = 173 K
β = 94.687 (12)°	Block, colorless
V = 1247.4 (3) Å³	0.38 × 0.32 × 0.24 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	3231 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2722 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 16.1500 pixels mm^-1	θ_max = 28.7°, θ_min = 3.3°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −18→18
T_min = 0.963, T_max = 0.977	l = −12→13
11331 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0567P)² + 0.3281P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3231 reflections	Δρ_max = 0.25 e Å⁻³
177 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.059 (4)

Crystal data top

C₁₅H₁₂O₄	V = 1247.4 (3) Å³
M_r = 256.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9017 (12) Å	µ = 0.10 mm⁻¹
b = 13.9940 (17) Å	T = 173 K
c = 10.0473 (12) Å	0.38 × 0.32 × 0.24 mm
β = 94.687 (12)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	3231 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	2722 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.977	R_int = 0.020
11331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.25 e Å⁻³
3231 reflections	Δρ_min = −0.18 e Å⁻³
177 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.

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
O1	0.67772 (14)	0.53971 (7)	1.02990 (9)	0.0554 (3)
O2	0.65842 (11)	0.66691 (6)	0.89536 (10)	0.0444 (2)
O3	0.46662 (10)	0.59366 (8)	0.66899 (10)	0.0467 (3)
O4	0.67624 (12)	0.86689 (8)	0.21951 (11)	0.0538 (3)
H4O	0.7691 (17)	0.8749 (14)	0.2078 (19)	0.065*
C1	0.6277 (3)	0.59825 (13)	1.13629 (15)	0.0679 (5)
H1A	0.6325	0.5611	1.2192	0.102*
H1B	0.5236	0.6189	1.1131	0.102*
H1C	0.6930	0.6545	1.1487	0.102*
C2	0.68941 (13)	0.58440 (9)	0.91453 (12)	0.0353 (3)
C3	0.75070 (13)	0.52066 (8)	0.81331 (12)	0.0339 (3)
C4	0.85127 (16)	0.44807 (10)	0.85257 (14)	0.0452 (3)
H4A	0.8748	0.4357	0.9449	0.054*
C5	0.91727 (18)	0.39370 (11)	0.75845 (17)	0.0531 (4)
H5A	0.9850	0.3437	0.7862	0.064*
C6	0.88503 (17)	0.41180 (10)	0.62450 (16)	0.0494 (3)
H6A	0.9308	0.3745	0.5599	0.059*
C7	0.78597 (15)	0.48435 (9)	0.58380 (13)	0.0404 (3)
H7A	0.7654	0.4972	0.4913	0.048*
C8	0.71643 (12)	0.53855 (8)	0.67704 (11)	0.0322 (2)
C9	0.59158 (13)	0.60509 (8)	0.62820 (11)	0.0326 (2)
C10	0.61847 (12)	0.67596 (8)	0.52514 (11)	0.0308 (2)
C11	0.76378 (12)	0.70441 (8)	0.49875 (12)	0.0331 (3)
H11A	0.8483	0.6784	0.5502	0.040*
C12	0.78631 (13)	0.76950 (9)	0.39946 (12)	0.0353 (3)
H12A	0.8855	0.7890	0.3835	0.042*
C13	0.66243 (14)	0.80656 (9)	0.32274 (12)	0.0359 (3)
C14	0.51685 (13)	0.78068 (9)	0.34968 (13)	0.0384 (3)
H14A	0.4325	0.8073	0.2987	0.046*
C15	0.49546 (13)	0.71679 (9)	0.44985 (12)	0.0352 (3)
H15A	0.3959	0.7000	0.4684	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0885 (8)	0.0476 (6)	0.0317 (5)	0.0005 (5)	0.0142 (5)	0.0028 (4)
O2	0.0508 (5)	0.0381 (5)	0.0459 (5)	0.0019 (4)	0.0124 (4)	0.0004 (4)
O3	0.0334 (5)	0.0645 (6)	0.0436 (5)	0.0006 (4)	0.0112 (4)	0.0083 (4)
O4	0.0446 (5)	0.0645 (7)	0.0533 (6)	0.0042 (5)	0.0097 (5)	0.0255 (5)
C1	0.1059 (15)	0.0657 (10)	0.0344 (7)	−0.0035 (10)	0.0198 (8)	−0.0063 (7)
C2	0.0359 (6)	0.0384 (6)	0.0315 (6)	−0.0050 (5)	0.0029 (4)	0.0014 (4)
C3	0.0351 (6)	0.0321 (5)	0.0349 (6)	−0.0029 (4)	0.0046 (4)	0.0023 (4)
C4	0.0487 (7)	0.0425 (7)	0.0443 (7)	0.0041 (5)	0.0037 (6)	0.0103 (5)
C5	0.0536 (8)	0.0420 (7)	0.0647 (9)	0.0140 (6)	0.0101 (7)	0.0088 (6)
C6	0.0512 (8)	0.0415 (7)	0.0572 (9)	0.0084 (6)	0.0144 (6)	−0.0060 (6)
C7	0.0430 (7)	0.0410 (6)	0.0379 (6)	0.0008 (5)	0.0081 (5)	−0.0042 (5)
C8	0.0318 (5)	0.0317 (5)	0.0337 (6)	−0.0026 (4)	0.0054 (4)	0.0004 (4)
C9	0.0308 (5)	0.0383 (6)	0.0289 (5)	−0.0003 (4)	0.0041 (4)	−0.0033 (4)
C10	0.0287 (5)	0.0350 (6)	0.0289 (5)	0.0018 (4)	0.0036 (4)	−0.0028 (4)
C11	0.0274 (5)	0.0398 (6)	0.0317 (5)	0.0021 (4)	0.0005 (4)	−0.0015 (4)
C12	0.0286 (5)	0.0408 (6)	0.0368 (6)	−0.0018 (4)	0.0056 (4)	−0.0004 (5)
C13	0.0376 (6)	0.0374 (6)	0.0335 (6)	0.0036 (5)	0.0066 (5)	0.0019 (5)
C14	0.0305 (5)	0.0470 (7)	0.0375 (6)	0.0081 (5)	0.0015 (4)	0.0045 (5)
C15	0.0257 (5)	0.0438 (6)	0.0365 (6)	0.0019 (4)	0.0043 (4)	−0.0001 (5)

Geometric parameters (Å, º) top

O1—C2	1.3286 (15)	C6—C7	1.3844 (19)
O1—C1	1.4458 (18)	C6—H6A	0.9500
O2—C2	1.1991 (15)	C7—C8	1.3895 (17)
O3—C9	1.2270 (14)	C7—H7A	0.9500
O4—C13	1.3508 (15)	C8—C9	1.5013 (16)
O4—H4O	0.852 (14)	C9—C10	1.4675 (16)
C1—H1A	0.9800	C10—C11	1.3993 (15)
C1—H1B	0.9800	C10—C15	1.4009 (16)
C1—H1C	0.9800	C11—C12	1.3777 (17)
C2—C3	1.4894 (17)	C11—H11A	0.9500
C3—C4	1.3896 (18)	C12—C13	1.3930 (17)
C3—C8	1.4007 (16)	C12—H12A	0.9500
C4—C5	1.382 (2)	C13—C14	1.3932 (17)
C4—H4A	0.9500	C14—C15	1.3711 (17)
C5—C6	1.377 (2)	C14—H14A	0.9500
C5—H5A	0.9500	C15—H15A	0.9500

C2—O1—C1	115.42 (12)	C8—C7—H7A	119.7
C13—O4—H4O	109.8 (13)	C7—C8—C3	119.21 (11)
O1—C1—H1A	109.5	C7—C8—C9	118.48 (10)
O1—C1—H1B	109.5	C3—C8—C9	121.78 (10)
H1A—C1—H1B	109.5	O3—C9—C10	121.90 (11)
O1—C1—H1C	109.5	O3—C9—C8	118.49 (11)
H1A—C1—H1C	109.5	C10—C9—C8	119.39 (10)
H1B—C1—H1C	109.5	C11—C10—C15	118.39 (10)
O2—C2—O1	124.05 (12)	C11—C10—C9	122.18 (10)
O2—C2—C3	124.01 (11)	C15—C10—C9	119.43 (10)
O1—C2—C3	111.90 (10)	C12—C11—C10	121.12 (10)
C4—C3—C8	119.47 (11)	C12—C11—H11A	119.4
C4—C3—C2	120.49 (11)	C10—C11—H11A	119.4
C8—C3—C2	119.85 (10)	C11—C12—C13	119.43 (11)
C5—C4—C3	120.55 (13)	C11—C12—H12A	120.3
C5—C4—H4A	119.7	C13—C12—H12A	120.3
C3—C4—H4A	119.7	O4—C13—C12	122.68 (11)
C6—C5—C4	120.09 (13)	O4—C13—C14	117.13 (11)
C6—C5—H5A	120.0	C12—C13—C14	120.18 (11)
C4—C5—H5A	120.0	C15—C14—C13	119.95 (11)
C5—C6—C7	120.04 (13)	C15—C14—H14A	120.0
C5—C6—H6A	120.0	C13—C14—H14A	120.0
C7—C6—H6A	120.0	C14—C15—C10	120.87 (10)
C6—C7—C8	120.61 (12)	C14—C15—H15A	119.6
C6—C7—H7A	119.7	C10—C15—H15A	119.6

C1—O1—C2—O2	−1.6 (2)	C3—C8—C9—O3	−51.01 (16)
C1—O1—C2—C3	176.40 (13)	C7—C8—C9—C10	−54.18 (15)
O2—C2—C3—C4	147.15 (13)	C3—C8—C9—C10	134.26 (12)
O1—C2—C3—C4	−30.85 (16)	O3—C9—C10—C11	165.69 (12)
O2—C2—C3—C8	−27.74 (18)	C8—C9—C10—C11	−19.76 (16)
O1—C2—C3—C8	154.27 (11)	O3—C9—C10—C15	−14.46 (17)
C8—C3—C4—C5	0.0 (2)	C8—C9—C10—C15	160.09 (11)
C2—C3—C4—C5	−174.93 (12)	C15—C10—C11—C12	−1.31 (17)
C3—C4—C5—C6	0.7 (2)	C9—C10—C11—C12	178.54 (11)
C4—C5—C6—C7	−0.2 (2)	C10—C11—C12—C13	−0.95 (18)
C5—C6—C7—C8	−1.0 (2)	C11—C12—C13—O4	−176.60 (12)
C6—C7—C8—C3	1.68 (19)	C11—C12—C13—C14	2.41 (18)
C6—C7—C8—C9	−170.10 (12)	O4—C13—C14—C15	177.49 (12)
C4—C3—C8—C7	−1.16 (17)	C12—C13—C14—C15	−1.58 (19)
C2—C3—C8—C7	173.77 (11)	C13—C14—C15—C10	−0.74 (19)
C4—C3—C8—C9	170.33 (11)	C11—C10—C15—C14	2.16 (17)
C2—C3—C8—C9	−14.73 (16)	C9—C10—C15—C14	−177.69 (11)
C7—C8—C9—O3	120.55 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3ⁱ	0.85 (1)	1.88 (2)	2.7310 (14)	173 (2)
C12—H12A···O2ⁱ	0.95	2.50	3.4333 (15)	167

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₄
M_r	256.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	8.9017 (12), 13.9940 (17), 10.0473 (12)
β (°)	94.687 (12)
V (Å³)	1247.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.32 × 0.24

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.963, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	11331, 3231, 2722
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.117, 1.02
No. of reflections	3231
No. of parameters	177
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.18

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3ⁱ	0.852 (14)	1.883 (15)	2.7310 (14)	172.8 (19)
C12—H12A···O2ⁱ	0.95	2.50	3.4333 (15)	167

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

Acknowledgements

MSS thanks the University of Mysore for the research facilities and HSY thanks R. L. Fine Chem, Bengaluru, India, for a gift sample of the title compound. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

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