Bis(2-hy­droxy­phen­yl)methanone

Betz, R.; Gerber, T.; Schalekamp, H.

doi:10.1107/S1600536811025438

organic compounds

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Volume 67| Part 8| August 2011| Page o1897

doi:10.1107/S1600536811025438

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Bis(2-hydroxyphenyl)methanone

Richard Betz,^a ^* Thomas Gerber ^a and Henk Schalekamp ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 23 June 2011; accepted 28 June 2011; online 2 July 2011)

In the title compound, C₁₃H₁₀O₃, a benzophenone derivative, the least-squares planes defined by the C atoms of the 2-hydroxyphenyl rings intersect at an angle of 45.49 (3)°. The substituents on the aromatic systems are both orientated towards the central O atom. Intra- as well as intermolecular O—H⋯O hydrogen bonds are observed, the latter giving rise to the formation of centrosymmetric dimers. The closest centroid–centroid distance between two π-systems is 3.7934 (7) Å.

Related literature

For the crystal structure of benzophenone, see: Lobanova (1968 ); Kutzke et al. (2000 ); Fleischer et al. (1968 ); Bernstein et al. (2002 ); Moncol & Coppens (2004 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ). Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of the resultant coordination compounds in relation to those exclusively applying comparable monodentate ligands, see: Gade (1998 ).

Experimental

Crystal data

C₁₃H₁₀O₃
M_r = 214.21
Monoclinic, P 2₁ /c
a = 7.7371 (2) Å
b = 12.2169 (4) Å
c = 11.3419 (3) Å
β = 110.610 (2)°
V = 1003.46 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
9306 measured reflections
2483 independent reflections
1939 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.05
2483 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.84	1.88	2.6061 (11)	144
O2—H2⋯O1ⁱ	0.84	2.44	2.9976 (12)	124
O3—H3⋯O1	0.84	1.95	2.6623 (11)	142
Symmetry code: (i) -x+2, -y, -z.

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025438/im2302sup1.cif

Supporting information file. DOI: 10.1107/S1600536811025438/im2302Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025438/im2302Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811025438/im2302Isup4.cml

checkCIF report

Comment top

Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of resultant coordination compounds in relation to coordination compounds exclusively applying comparable monodentate ligands (Gade, 1998). Combining two identical donor atoms in different states of hybridization seemed to be useful to us to accomodate a large variety of metal centers of variable Lewis acidity. To enable comparative studies in terms of bond lengths and angles in envisioned coordination compounds, we determined the molecular and crystal structure of the title compound. The crystal structure of benzophenone is apparent in the literature (Lobanova, 1968; Kutzke et al., 2000; Fleischer et al., 1968; Bernstein et al., 2002; Moncol & Coppens, 2004).

The title compound is a symmetrical substitution product of benzophenone bearing one hydroxyl group in ortho-position of each phenyl ring. Both aromatic moieties adopt a conformation in which the substituents are orientated towards the central oxygen atom. The least-squares planes defined by the respective carbon atoms of both ortho-hydroxyphenyl rings intersect at an angle of 45.49 (3) °. Intracyclic C–C–C angles hardly deviate from the ideal value of 120 °.

In the crystal structure, intra- as well as intermolecular hydrogen bonds are observed. In both cases, the sp²-hybridized oxygen atom acts as acceptor, but while one of the hydroxyl groups exclusively forms an intramolecular hydrogen bond, the other hydroxyl group forms a bifurcated hydrogen bond to the keto group's oxygen atom of a neighbouring molecule as well. In total, two molecules are connected to centrosymmetric dimers. The descriptor for the hydrogen bonding system in terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995) is DDR²₂(12) on the unitary level. The shortest intercentroid distance between two π-systems is 3.7934 (7) Å and is apparent between two different aromatic moieties.

The packing of the title compound in the crystal structure is shown in Figure 3.

Related literature top

For the crystal structure of benzophenone, see: Lobanova (1968); Kutzke et al. (2000); Fleischer et al. (1968); Bernstein et al. (2002); Moncol & Coppens (2004). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995). Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of the resultant coordination compounds in relation to those exclusively applying comparable monodentate ligands, see: Gade (1998).

Experimental top

The compound was obtained commercially (Aldrich). Crystals suitable for the X-ray diffraction study were taken directly from the provided product.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Intermolecular contacts, viewed along [-1 0 0]. Symmetry operator: ⁱ -x + 2, -y, -z.
	Fig. 3. Molecular packing of the title compound, viewed along [0 1 0] (anisotropic displacement ellipsoids drawn at 50% probability level).

Bis(2-hydroxyphenyl)methanone top

Crystal data top

C₁₃H₁₀O₃	F(000) = 448
M_r = 214.21	D_x = 1.418 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4455 reflections
a = 7.7371 (2) Å	θ = 2.5–28.3°
b = 12.2169 (4) Å	µ = 0.10 mm⁻¹
c = 11.3419 (3) Å	T = 200 K
β = 110.610 (2)°	Platelet, colourless
V = 1003.46 (5) Å³	0.24 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1939 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 28.3°, θ_min = 2.5°
ϕ and ω scans	h = −9→10
9306 measured reflections	k = −15→16
2483 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0563P)² + 0.1145P] where P = (F_o² + 2F_c²)/3
2483 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₁₀O₃	V = 1003.46 (5) Å³
M_r = 214.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7371 (2) Å	µ = 0.10 mm⁻¹
b = 12.2169 (4) Å	T = 200 K
c = 11.3419 (3) Å	0.24 × 0.20 × 0.18 mm
β = 110.610 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1939 reflections with I > 2σ(I)
9306 measured reflections	R_int = 0.033
2483 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.05	Δρ_max = 0.27 e Å⁻³
2483 reflections	Δρ_min = −0.19 e Å⁻³
147 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.97092 (13)	0.09617 (6)	0.08169 (7)	0.0405 (2)
O2	0.78137 (13)	0.09971 (7)	−0.15911 (8)	0.0407 (2)
H2	0.8528	0.0719	−0.0919	0.061*
O3	1.09865 (13)	0.09673 (6)	0.33247 (8)	0.0407 (2)
H3	1.0534	0.0664	0.2617	0.061*
C1	0.94988 (15)	0.19703 (8)	0.08687 (9)	0.0271 (2)
C11	0.80678 (14)	0.25299 (8)	−0.01695 (9)	0.0255 (2)
C12	0.73030 (15)	0.20048 (9)	−0.13533 (10)	0.0294 (2)
C13	0.59669 (16)	0.25366 (10)	−0.23411 (10)	0.0348 (3)
H13	0.5499	0.2199	−0.3146	0.042*
C14	0.53150 (16)	0.35473 (10)	−0.21639 (11)	0.0358 (3)
H14	0.4388	0.3896	−0.2844	0.043*
C15	0.60019 (16)	0.40645 (9)	−0.09954 (10)	0.0334 (3)
H15	0.5537	0.4759	−0.0876	0.040*
C16	0.73588 (15)	0.35604 (9)	−0.00167 (10)	0.0287 (2)
H16	0.7827	0.3915	0.0779	0.034*
C21	1.06958 (14)	0.25691 (8)	0.19946 (9)	0.0253 (2)
C22	1.13591 (15)	0.20282 (9)	0.31684 (9)	0.0283 (2)
C23	1.24280 (15)	0.25933 (10)	0.42392 (9)	0.0340 (3)
H23	1.2807	0.2242	0.5037	0.041*
C24	1.29406 (17)	0.36599 (10)	0.41490 (11)	0.0372 (3)
H24	1.3674	0.4039	0.4887	0.045*
C25	1.23981 (16)	0.41868 (9)	0.29931 (11)	0.0341 (3)
H25	1.2798	0.4913	0.2933	0.041*
C26	1.12737 (15)	0.36495 (8)	0.19308 (10)	0.0282 (2)
H26	1.0883	0.4017	0.1142	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0588 (6)	0.0236 (4)	0.0317 (4)	0.0033 (4)	0.0067 (4)	−0.0005 (3)
O2	0.0478 (5)	0.0359 (5)	0.0319 (4)	0.0011 (4)	0.0058 (4)	−0.0106 (3)
O3	0.0538 (6)	0.0312 (4)	0.0305 (4)	−0.0037 (4)	0.0068 (4)	0.0094 (3)
C1	0.0338 (6)	0.0232 (5)	0.0247 (5)	−0.0006 (4)	0.0107 (4)	0.0006 (4)
C11	0.0279 (5)	0.0258 (5)	0.0223 (5)	−0.0033 (4)	0.0081 (4)	0.0005 (4)
C12	0.0301 (5)	0.0315 (5)	0.0266 (5)	−0.0041 (4)	0.0101 (4)	−0.0028 (4)
C13	0.0319 (6)	0.0471 (7)	0.0217 (5)	−0.0048 (5)	0.0051 (4)	−0.0022 (5)
C14	0.0293 (6)	0.0478 (7)	0.0282 (5)	0.0025 (5)	0.0073 (5)	0.0099 (5)
C15	0.0340 (6)	0.0331 (6)	0.0341 (6)	0.0052 (5)	0.0131 (5)	0.0051 (5)
C16	0.0312 (5)	0.0296 (5)	0.0254 (5)	−0.0006 (4)	0.0099 (4)	0.0004 (4)
C21	0.0268 (5)	0.0258 (5)	0.0230 (5)	0.0023 (4)	0.0083 (4)	0.0012 (4)
C22	0.0290 (5)	0.0293 (5)	0.0264 (5)	0.0024 (4)	0.0097 (4)	0.0040 (4)
C23	0.0333 (6)	0.0448 (7)	0.0218 (5)	0.0014 (5)	0.0074 (5)	0.0038 (5)
C24	0.0355 (6)	0.0454 (7)	0.0279 (6)	−0.0065 (5)	0.0078 (5)	−0.0082 (5)
C25	0.0354 (6)	0.0313 (6)	0.0356 (6)	−0.0059 (5)	0.0125 (5)	−0.0042 (5)
C26	0.0304 (5)	0.0275 (5)	0.0269 (5)	0.0012 (4)	0.0101 (4)	0.0019 (4)

Geometric parameters (Å, º) top

O1—C1	1.2470 (12)	C15—C16	1.3760 (15)
O2—C12	1.3489 (13)	C15—H15	0.9500
O2—H2	0.8400	C16—H16	0.9500
O3—C22	1.3530 (13)	C21—C26	1.4035 (14)
O3—H3	0.8400	C21—C22	1.4112 (13)
C1—C11	1.4703 (14)	C22—C23	1.3886 (15)
C1—C21	1.4802 (14)	C23—C24	1.3763 (16)
C11—C16	1.4081 (15)	C23—H23	0.9500
C11—C12	1.4161 (14)	C24—C25	1.3864 (16)
C12—C13	1.3894 (15)	C24—H24	0.9500
C13—C14	1.3750 (17)	C25—C26	1.3790 (15)
C13—H13	0.9500	C25—H25	0.9500
C14—C15	1.3936 (16)	C26—H26	0.9500
C14—H14	0.9500

C12—O2—H2	109.5	C15—C16—H16	119.3
C22—O3—H3	109.5	C11—C16—H16	119.3
O1—C1—C11	119.72 (9)	C26—C21—C22	118.19 (9)
O1—C1—C21	118.46 (9)	C26—C21—C1	122.29 (9)
C11—C1—C21	121.81 (9)	C22—C21—C1	119.46 (9)
C16—C11—C12	118.09 (9)	O3—C22—C23	116.77 (9)
C16—C11—C1	122.23 (9)	O3—C22—C21	123.28 (9)
C12—C11—C1	119.62 (9)	C23—C22—C21	119.94 (10)
O2—C12—C13	116.92 (9)	C24—C23—C22	120.28 (10)
O2—C12—C11	123.30 (10)	C24—C23—H23	119.9
C13—C12—C11	119.78 (10)	C22—C23—H23	119.9
C14—C13—C12	120.60 (10)	C23—C24—C25	120.71 (10)
C14—C13—H13	119.7	C23—C24—H24	119.6
C12—C13—H13	119.7	C25—C24—H24	119.6
C13—C14—C15	120.62 (10)	C26—C25—C24	119.54 (10)
C13—C14—H14	119.7	C26—C25—H25	120.2
C15—C14—H14	119.7	C24—C25—H25	120.2
C16—C15—C14	119.44 (11)	C25—C26—C21	121.14 (10)
C16—C15—H15	120.3	C25—C26—H26	119.4
C14—C15—H15	120.3	C21—C26—H26	119.4
C15—C16—C11	121.37 (10)

O1—C1—C11—C16	159.44 (10)	O1—C1—C21—C26	146.95 (11)
C21—C1—C11—C16	−19.72 (15)	C11—C1—C21—C26	−33.88 (15)
O1—C1—C11—C12	−17.66 (15)	O1—C1—C21—C22	−30.02 (14)
C21—C1—C11—C12	163.18 (10)	C11—C1—C21—C22	149.15 (10)
C16—C11—C12—O2	−176.94 (9)	C26—C21—C22—O3	−175.80 (10)
C1—C11—C12—O2	0.28 (16)	C1—C21—C22—O3	1.29 (16)
C16—C11—C12—C13	3.58 (15)	C26—C21—C22—C23	5.22 (15)
C1—C11—C12—C13	−179.20 (9)	C1—C21—C22—C23	−177.68 (9)
O2—C12—C13—C14	177.36 (10)	O3—C22—C23—C24	176.91 (10)
C11—C12—C13—C14	−3.13 (17)	C21—C22—C23—C24	−4.05 (17)
C12—C13—C14—C15	0.97 (17)	C22—C23—C24—C25	0.12 (18)
C13—C14—C15—C16	0.68 (17)	C23—C24—C25—C26	2.53 (18)
C14—C15—C16—C11	−0.13 (17)	C24—C25—C26—C21	−1.22 (17)
C12—C11—C16—C15	−1.98 (15)	C22—C21—C26—C25	−2.61 (16)
C1—C11—C16—C15	−179.12 (10)	C1—C21—C26—C25	−179.62 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.84	1.88	2.6061 (11)	144
O2—H2···O1ⁱ	0.84	2.44	2.9976 (12)	124
O3—H3···O1	0.84	1.95	2.6623 (11)	142

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀O₃
M_r	214.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	7.7371 (2), 12.2169 (4), 11.3419 (3)
β (°)	110.610 (2)
V (Å³)	1003.46 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9306, 2483, 1939
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.05
No. of reflections	2483
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.19

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.84	1.88	2.6061 (11)	144
O2—H2···O1ⁱ	0.84	2.44	2.9976 (12)	124
O3—H3···O1	0.84	1.95	2.6623 (11)	142

Symmetry code: (i) −x+2, −y, −z.

Acknowledgements

The authors thank Mr Phindile Gaika for helpful discussions.

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