(2-Hy­droxy-4-meth­oxy­phen­yl)(2-hy­droxy­phen­yl)methanone

Richard Betz; Thomas Gerber; Eric Hosten; Henk Schalekamp

doi:10.1107/S1600536811030042

. 2011 Jul 30;67(Pt 8):o2180. doi: 10.1107/S1600536811030042

(2-Hydroxy-4-methoxyphenyl)(2-hydroxyphenyl)methanone

Richard Betz ^a,^*, Thomas Gerber ^a, Eric Hosten ^a, Henk Schalekamp ^a

PMCID: PMC3213614 PMID: 22091191

Abstract

The title compound, C₁₄H₁₂O₄, is an asymmetric substitution product of benzophenone. Both hydroxy groups are orientated towards the O atom of the keto group. Intramolecular as well as intermolecular O—H⋯O hydrogen bonds can be observed in the crystal structure, with the latter connecting the molecules into chains along the crystallographic b axis. C—H⋯O contacts [C⋯O = 3.3297 (18) Å] are also apparent. The closest centroid–centroid distance between two aromatic systems is 4.9186 (9) 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 the crystal structure of bis(2-hydroxyphenyl)methanone, see: Betz et al. (2011 ▶). For details on graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For a comparison of the thermodynamic stability of coordination compounds containing chelate ligands as opposed to monodentate ligands, see: Gade (1998 ▶).

Experimental

Crystal data

C₁₄H₁₂O₄
M _r = 244.24
Orthorhombic,
a = 4.8582 (2) Å
b = 14.0236 (5) Å
c = 16.8636 (5) Å
V = 1148.91 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.48 × 0.14 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
6314 measured reflections
1683 independent reflections
1484 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.083
S = 1.07
1683 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030042/lw2071sup1.cif

e-67-o2180-sup1.cif^{(16.1KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536811030042/lw2071Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030042/lw2071Isup3.hkl

e-67-o2180-Isup3.hkl^{(83KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811030042/lw2071Isup4.cml

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

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	2.6058 (17)	144
O3—H3⋯O1	0.84	1.91	2.6267 (17)	142
O3—H3⋯O4ⁱ	0.84	2.50	2.9306 (15)	113
C15—H15⋯O1ⁱⁱ	0.95	2.57	3.3297 (18)	137

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Mrs Angelika Obermeyer for helpful discussions.

supplementary crystallographic information

Comment

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) as is the crystal structure of bis(2-hydroxyphenyl)methanone (Betz et al., 2011).

The title compound is an asymmetric substitution product of benzophenone. Both aromatic moieties adopt a conformation in which its hydroxyl group is orientated towards the central oxygen atom. The least-squares planes defined by the respective carbon atoms of both aromatic rings intersect at an angle of 42.11 (6) °. Intracyclic C–C–C angles hardly deviate from the ideal value of 120 °. The methoxy group is nearly in plane with its resident aromatic system, the respective C–O–C–C torsional angle is found at 4.9 (2) ° (Fig. 1).

In the crystal structure, intra- as well as intermolecular hydrogen bonds are observed. While the intramolecular hydrogen bonds are apparent between the hydroxyl groups as donors and the double-bonded oxygen atom as acceptor, the intermolecular hydrogen bond stems from the hydroxyl group on the otherwise unsubstituted phenyl ring and has the etheric oxygen atom as acceptor (Fig. 2). The latter hydrogen bond thus shows bifurcation. In addition, a C–H···O contact whose range falls by more than 0.1 Å below the sum of van-der-Waals radii is present in the crystal structure. The latter one is supported by one of the CH groups in ortho-position to the methoxy substituent and has the keto group's oxygen atom as acceptor. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the hydrogen bonding system based on the hydroxyl groups on the unitary level is S(6)S(6)C(10) while the C–H···O contacts necessitate a C(6) descriptor on the same level. In total, the molecules are connected to undulated chains along the crystallographic b axis. The shortest intercentroid distance between two aromatic systems was measured to be at 4.9186 (9) Å and is apparent between the two different aromatic moieties.

The molecular 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.