Bis(2-Hydroxyphenyl)methanone

Abstract

In the title compound, C(13)H(10)O(3), a benzophenone derivative, the least-squares planes defined by the C atoms of the 2-hy-droxy-phenyl rings inter-sect 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 inter-molecular 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.

Full text

Bis(2-hydroxyphenyl)methanone
Richard Betz,* Thomas Gerber and Henk Schalekamp
Nelson 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
Key indicators: single-crystal X-ray study; T= 200 K; mean (C–C) = 0.002 A
˚;
Rfactor = 0.038; wR factor = 0.106; data-to-parameter ratio = 16.9.
In the title compound, C
13
H
10
O
3
, 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 -systems is
3.7934 (7) A
˚.
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 exclu-
sively applying comparable monodentate ligands, see: Gade
(1998).
Experimental
Crystal data
C
13
H
10
O
3
M
r
= 214.21
Monoclinic, P21=c
a= 7.7371 (2) A
˚
b= 12.2169 (4) A
˚
c= 11.3419 (3) A
˚
= 110.610 (2)
V= 1003.46 (5) A
˚
3
Z=4
Mo Kradiation
= 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>2(I)
R
int
= 0.033
Refinement
R[F
2
>2(F
2
)] = 0.038
wR(F
2
) = 0.106
S= 1.05
2483 reflections
147 parameters
H-atom parameters constrained

max
= 0.27 e A
˚
3

min
=0.19 e A
˚
3
Table 1
Hydrogen-bond geometry (A
˚,).
D—HAD—H HADAD—HA
O2—H2O1 0.84 1.88 2.6061 (11) 144
O2—H2O1
i
0.84 2.44 2.9976 (12) 124
O3—H3O1 0.84 1.95 2.6623 (11) 142
Symmetry code: (i) xþ2;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); soft-
ware used to prepare material for publication: SHELXL97 and
PLATON (Spek, 2009).
The authors thank Mr Phindile Gaika for helpful discus-
sions.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: IM2302).
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Bernstein, J., Ellern, A. & Henck, J.-O. (2002). Private communication (CCDC
118986, ref-code BPHNO11). CCDC, Cambridge, England.
Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsi-
n.USA.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Fleischer, E. B., Sung, N. & Hawkinson, S. (1968). J. Phys. Chem. 72, 4311–
4312.
Gade, L. H. (1998). Koordinationschemie, 1. Auflage, Weinheim: Wiley–VCH.
Kutzke, H., Klapper, H., Hammond, R. B. & Roberts, K. J. (2000). Acta Cryst.
B56, 486–496.
Lobanova, G. M. (1968). Kristallografiya,13, 984–986.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,
Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,
P. A. (2008). J. Appl. Cryst. 41, 466–470.
Moncol, J. & Coppens, P. (2004). Private communication (CCDC 245188, ref-
code BPHNO12). CCDC, Cambridge, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
organic compounds
Acta Cryst. (2011). E67, o1897 doi:10.1107/S1600536811025438 Betz et al. o1897
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

supplementary materials

supplementary materials
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Acta Cryst. (2011). E67, o1897 [ doi:10.1107/S1600536811025438 ]
Bis(2-hydroxyphenyl)methanone
R. Betz, T. Gerber and H. Schalekamp
Comment
Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of res-
ultant coordination compounds in relation to coordination compounds exclusively applying comparable monodentate lig-
ands (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.
Experimental
The compound was obtained commercially (Aldrich). Crystals suitable for the X-ray diffraction study were taken directly
from the provided product.
Refinement
Carbon-bound H atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding
model approximation, with U(H) set to 1.2Ueq(C). The hydrogen atoms of the hydroxyl groups were allowed to rotate with
a fixed angle around the O–C bonds to best fit the experimental electron density (HFIX 147 in the SHELX program suite
(Sheldrick, 2008).

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Figures
Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic dis-
placement 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 displace-
ment ellipsoids drawn at 50% probability level).
Bis(2-hydroxyphenyl)methanone
Crystal data
C13H10O3F(000) = 448
Mr = 214.21 Dx = 1.418 Mg m−3
Monoclinic, P21/cMo 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) Å30.24 × 0.20 × 0.18 mm

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Z = 4
Data collection
Bruker APEXII CCD
diffractometer 1939 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube Rint = 0.033
graphite θmax = 28.3°, θmin = 2.5°
φ and ω scans h = −9→10
9306 measured reflections k = −15→16
2483 independent reflections l = −15→15
Refinement
Refinement on F2Primary 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(Fo2) + (0.0563P)2 + 0.1145P]
where P = (Fo2 + 2Fc2)/3
2483 reflections (Δ/σ)max < 0.001
147 parameters Δρmax = 0.27 e Å−3
0 restraints Δρmin = −0.19 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
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)

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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)
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, °)
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)

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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, °)
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···O1i0.84 2.44 2.9976 (12) 124
O3—H3···O1 0.84 1.95 2.6623 (11) 142
Symmetry codes: (i) −x+2, −y, −z.

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Fig. 1

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Fig. 2

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Fig. 3