2-(2-Methyl-benzo-yl)benzoic acid: catemeric hydrogen bonding in a γ-keto acid.

The crystal structure of the title compound, C15H12O3, displays catemeric aggregation involving O-H⋯O hydrogen bonds progressing from the carboxyl group of one mol-ecule to the ketone O atom of another glide-related neighbor. The mol-ecule is twisted, with the toluene 80.61 (3)° out of plane with respect to the phenyl group of the benzoic acid. The acid group makes a dihedral angle of 13.79 (14)° with the attached phenyl ring. The mol-ecules are achiral, but the space group glide planes create alternating conformational chirality in the chain units. The four hydrogen-bonding chains progress along [001] in an A-A-B-B pattern (right-to-left versus left-to-right), and are related to each other by the center of symmetry at (0.5, 0.5, 0.5) in the chosen cell. There is one close contact (2.54 Å) between a phenyl H atom and the acid carbonyl from a symmetry-related mol-ecule.

Related literature

For a discussion of highly ordered carboxyl bond distances and angles, see: Borthwick (1980 ▶). For close contact information, see: Steiner (1997 ▶). For related structures, see: Abell et al. (1991 ▶); Barcon et al. (1998 ▶, 2002 ▶); Degen & Bolte (1999 ▶); Hickmott et al. (1985 ▶); Kashyap et al. (1995 ▶); Song et al. (2008 ▶); Thompson et al. (1998 ▶); Watson et al. (1990 ▶). For preparation of the title compound, see: Newman & McCleary (1941 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C15H12O3

M = 240.25

Orthorhombic,

a = 10.7450 (2) Å

b = 10.1737 (2) Å

c = 21.6588 (4) Å

V = 2367.66 (8) Å3

Z = 8

Cu Kα radiation

μ = 0.77 mm−1

T = 100 K

0.45 × 0.26 × 0.20 mm

Data collection

Bruker SMART CCD APEXII area-detector diffractometer

Absorption correction: numerical (SADABS; Sheldrick, 2008a ▶) T min = 0.724, T max = 0.862

20799 measured reflections

2143 independent reflections

2075 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.076

S = 1.07

2143 reflections

169 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813025099/bg2513sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025099/bg2513Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813025099/bg2513Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H12O3	F(000) = 1008
Mr = 240.25	Dx = 1.348 Mg m−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9881 reflections
a = 10.7450 (2) Å	θ = 4.1–69.4°
b = 10.1737 (2) Å	µ = 0.77 mm−1
c = 21.6588 (4) Å	T = 100 K
V = 2367.66 (8) Å3	Block, colourless
Z = 8	0.45 × 0.26 × 0.20 mm

Bruker SMART CCD APEXII area-detector diffractometer	2143 independent reflections
Radiation source: fine-focus sealed tube	2075 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 69.7°, θmin = 4.1°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −12→12
Tmin = 0.724, Tmax = 0.862	k = −12→11
20799 measured reflections	l = −26→25

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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0323P)2 + 0.9262P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2143 reflections	Δρmax = 0.24 e Å−3
169 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00145 (14)

Experimental. 'crystal mounted on a Cryoloop using Paratone-N'

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.

	x	y	z	Uiso*/Ueq
O1	0.94221 (8)	0.35848 (8)	0.62029 (4)	0.0310 (2)
O2	0.77379 (7)	0.10436 (8)	0.62358 (3)	0.0265 (2)
O3	0.71268 (8)	−0.03026 (8)	0.69973 (4)	0.0296 (2)
H3A	0.6595 (17)	−0.0633 (17)	0.6695 (8)	0.059 (5)*
C1	0.86743 (10)	0.12547 (10)	0.72243 (5)	0.0192 (2)
C2	0.96175 (10)	0.20965 (10)	0.70233 (5)	0.0194 (2)
C3	1.04111 (10)	0.26693 (11)	0.74557 (5)	0.0247 (3)
H3	1.1060	0.3236	0.7322	0.030*
C4	1.02588 (11)	0.24164 (12)	0.80801 (5)	0.0285 (3)
H4	1.0800	0.2815	0.8372	0.034*
C5	0.93210 (11)	0.15848 (12)	0.82799 (5)	0.0282 (3)
H5	0.9218	0.1413	0.8708	0.034*
C6	0.85359 (11)	0.10055 (11)	0.78538 (5)	0.0239 (3)
H6	0.7896	0.0432	0.7991	0.029*
C7	0.78069 (10)	0.06640 (10)	0.67642 (5)	0.0205 (2)
C8	0.97910 (10)	0.24909 (10)	0.63557 (5)	0.0209 (2)
C9	1.04899 (9)	0.16186 (10)	0.59332 (5)	0.0197 (2)
C10	1.07236 (10)	0.19649 (11)	0.53104 (5)	0.0220 (2)
C11	1.14050 (10)	0.10824 (12)	0.49536 (5)	0.0272 (3)
H11	1.1585	0.1303	0.4537	0.033*
C12	1.18287 (11)	−0.01046 (12)	0.51844 (5)	0.0282 (3)
H12	1.2278	−0.0689	0.4925	0.034*
C13	1.15975 (11)	−0.04392 (11)	0.57930 (5)	0.0257 (3)
H13	1.1892	−0.1249	0.5955	0.031*
C14	1.09334 (10)	0.04195 (10)	0.61622 (5)	0.0217 (2)
H14	1.0775	0.0191	0.6580	0.026*
C15	1.02565 (11)	0.32089 (12)	0.50152 (5)	0.0286 (3)
H15A	1.0573	0.3267	0.4592	0.043*
H15B	1.0548	0.3968	0.5253	0.043*
H15C	0.9345	0.3201	0.5009	0.043*

	U11	U22	U33	U12	U13	U23
O1	0.0390 (5)	0.0237 (4)	0.0303 (4)	0.0084 (4)	0.0099 (4)	0.0048 (3)
O2	0.0248 (4)	0.0380 (5)	0.0166 (4)	−0.0045 (3)	0.0004 (3)	−0.0019 (3)
O3	0.0312 (5)	0.0272 (4)	0.0303 (4)	−0.0101 (3)	−0.0078 (4)	0.0056 (3)
C1	0.0196 (5)	0.0190 (5)	0.0191 (5)	0.0039 (4)	0.0003 (4)	−0.0028 (4)
C2	0.0198 (5)	0.0174 (5)	0.0210 (5)	0.0046 (4)	0.0006 (4)	−0.0035 (4)
C3	0.0224 (5)	0.0204 (5)	0.0312 (6)	0.0011 (4)	−0.0030 (5)	−0.0047 (5)
C4	0.0319 (6)	0.0269 (6)	0.0268 (6)	0.0063 (5)	−0.0105 (5)	−0.0098 (5)
C5	0.0365 (7)	0.0308 (6)	0.0172 (5)	0.0085 (5)	−0.0024 (5)	−0.0038 (5)
C6	0.0260 (6)	0.0251 (6)	0.0206 (5)	0.0037 (5)	0.0029 (4)	−0.0004 (4)
C7	0.0195 (5)	0.0208 (5)	0.0211 (5)	0.0020 (4)	0.0023 (4)	−0.0030 (4)
C8	0.0177 (5)	0.0207 (5)	0.0243 (6)	−0.0020 (4)	0.0003 (4)	0.0001 (4)
C9	0.0154 (5)	0.0227 (5)	0.0210 (5)	−0.0029 (4)	−0.0008 (4)	−0.0026 (4)
C10	0.0164 (5)	0.0292 (6)	0.0204 (5)	−0.0038 (4)	−0.0026 (4)	−0.0013 (4)
C11	0.0223 (6)	0.0423 (7)	0.0169 (5)	−0.0007 (5)	−0.0008 (4)	−0.0042 (5)
C12	0.0209 (6)	0.0385 (6)	0.0254 (6)	0.0049 (5)	−0.0011 (5)	−0.0120 (5)
C13	0.0229 (6)	0.0260 (6)	0.0281 (6)	0.0042 (4)	−0.0031 (5)	−0.0050 (5)
C14	0.0204 (5)	0.0242 (5)	0.0205 (5)	−0.0012 (4)	−0.0007 (4)	−0.0021 (4)
C15	0.0271 (6)	0.0366 (6)	0.0222 (5)	0.0002 (5)	−0.0001 (5)	0.0053 (5)

O1—C8	1.2269 (13)	C8—C9	1.4796 (15)
O2—C7	1.2102 (13)	C9—C14	1.4004 (15)
O3—C7	1.3251 (13)	C9—C10	1.4165 (15)
O3—H3A	0.932 (18)	C10—C11	1.3926 (16)
C1—C6	1.3948 (15)	C10—C15	1.5041 (16)
C1—C2	1.3965 (15)	C11—C12	1.3840 (18)
C1—C7	1.4909 (15)	C11—H11	0.9500
C2—C3	1.3942 (15)	C12—C13	1.3838 (17)
C2—C8	1.5120 (15)	C12—H12	0.9500
C3—C4	1.3863 (17)	C13—C14	1.3828 (15)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.3851 (18)	C14—H14	0.9500
C4—H4	0.9500	C15—H15A	0.9800
C5—C6	1.3823 (16)	C15—H15B	0.9800
C5—H5	0.9500	C15—H15C	0.9800
C6—H6	0.9500
H12···O2i	2.54
C7—O3—H3A	109.8 (11)	C14—C9—C10	119.58 (10)
C6—C1—C2	119.57 (10)	C14—C9—C8	118.43 (9)
C6—C1—C7	120.89 (10)	C10—C9—C8	121.99 (10)
C2—C1—C7	119.51 (9)	C11—C10—C9	117.47 (10)
C3—C2—C1	119.40 (10)	C11—C10—C15	118.82 (10)
C3—C2—C8	117.13 (10)	C9—C10—C15	123.70 (10)
C1—C2—C8	123.38 (9)	C12—C11—C10	122.35 (10)
C4—C3—C2	120.37 (11)	C12—C11—H11	118.8
C4—C3—H3	119.8	C10—C11—H11	118.8
C2—C3—H3	119.8	C13—C12—C11	119.98 (11)
C5—C4—C3	120.26 (11)	C13—C12—H12	120.0
C5—C4—H4	119.9	C11—C12—H12	120.0
C3—C4—H4	119.9	C14—C13—C12	119.21 (11)
C6—C5—C4	119.73 (11)	C14—C13—H13	120.4
C6—C5—H5	120.1	C12—C13—H13	120.4
C4—C5—H5	120.1	C13—C14—C9	121.41 (10)
C5—C6—C1	120.66 (11)	C13—C14—H14	119.3
C5—C6—H6	119.7	C9—C14—H14	119.3
C1—C6—H6	119.7	C10—C15—H15A	109.5
O2—C7—O3	124.28 (10)	C10—C15—H15B	109.5
O2—C7—C1	122.80 (10)	H15A—C15—H15B	109.5
O3—C7—C1	112.91 (9)	C10—C15—H15C	109.5
O1—C8—C9	122.77 (10)	H15A—C15—H15C	109.5
O1—C8—C2	117.31 (9)	H15B—C15—H15C	109.5
C9—C8—C2	119.67 (9)
C6—C1—C2—C3	0.35 (15)	C3—C2—C8—C9	99.68 (11)
C7—C1—C2—C3	178.67 (9)	C1—C2—C8—C9	−83.75 (13)
C6—C1—C2—C8	−176.14 (10)	O1—C8—C9—C14	176.35 (10)
C7—C1—C2—C8	2.17 (15)	C2—C8—C9—C14	2.36 (14)
C1—C2—C3—C4	−0.62 (16)	O1—C8—C9—C10	−3.38 (16)
C8—C2—C3—C4	176.09 (10)	C2—C8—C9—C10	−177.37 (9)
C2—C3—C4—C5	0.43 (17)	C14—C9—C10—C11	−0.57 (15)
C3—C4—C5—C6	0.04 (17)	C8—C9—C10—C11	179.15 (10)
C4—C5—C6—C1	−0.31 (17)	C14—C9—C10—C15	178.13 (10)
C2—C1—C6—C5	0.11 (16)	C8—C9—C10—C15	−2.14 (16)
C7—C1—C6—C5	−178.18 (10)	C9—C10—C11—C12	1.15 (16)
C6—C1—C7—O2	165.34 (10)	C15—C10—C11—C12	−177.62 (11)
C2—C1—C7—O2	−12.94 (15)	C10—C11—C12—C13	−1.14 (18)
C6—C1—C7—O3	−14.30 (14)	C11—C12—C13—C14	0.51 (17)
C2—C1—C7—O3	167.41 (9)	C12—C13—C14—C9	0.05 (17)
C3—C2—C8—O1	−74.63 (13)	C10—C9—C14—C13	0.00 (16)
C1—C2—C8—O1	101.94 (12)	C8—C9—C14—C13	−179.74 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1ii	0.932 (18)	1.714 (18)	2.6477 (11)	172.3 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1ii	0.932 (18)	1.714 (18)	2.6477 (11)	172.3 (16)

Symmetry code: (ii) .