3-(4-Biphenyl-1-yl)-3-hydr­oxy-1-phenyl­prop-2-en-1-one

Chunyang Zheng; Dunjia Wang; Ling Fan

doi:10.1107/S1600536808042566

. 2008 Dec 20;65(Pt 1):o160–o161. doi: 10.1107/S1600536808042566

3-(4-Biphenyl-1-yl)-3-hydroxy-1-phenylprop-2-en-1-one

Chunyang Zheng ^a,^*, Dunjia Wang ^b, Ling Fan ^b

PMCID: PMC2968073 PMID: 21581618

Abstract

In the title compound, C₂₁H₁₆O₂, the six crystallographically independent molecules (Z′ = 6) all exist in the enolized form. Strong intramolecular hydrogen bonds are observed: one approximate H-atom-centered O⋯H⋯O hydrogen bond, two tautomeric forms O—H⋯O (three molecules) and O⋯H—O (two molecules). Only one weak intermolecular C—H⋯O hydrogen bond between two neighboring molecules is observed in the crystal structure. In addition, eight very weak non-conventional intermolecular C—H⋯π hydrogen-bonding contacts between molecules are observed.

Related literature

For proton transfer in solid 1-phenylbutane-1,3-dione and related 1,3-diones, see: Vila et al. (1991 ▶). For the crystal structures of eight intramolecular hydrogen-bonded 1,3-diaryl-1,3-propanedione enols, see: Bertolasi et al. (1991 ▶). For a discussion of the covalent versus the electrostatic nature of the strong hydrogen bond, see: Gilli et al. (2004 ▶). For electron transfer reactions of aromatic α,β-epoxy ketones, see: Hasegawa et al. (1997 ▶). For 1,3-diketones used as ligands, see: Jang et al. (2006 ▶). For weak hydrogen bonds, see: Desiraju & Steiner (2001 ▶).

Experimental

Crystal data

C₂₁H₁₆O₂
M _r = 300.34
Triclinic,
a = 10.6087 (13) Å
b = 17.814 (2) Å
c = 26.394 (3) Å
α = 72.170 (2)°
β = 86.069 (2)°
γ = 89.450 (2)°
V = 4736.8 (10) Å³
Z = 12
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.980, T _max = 0.989
55512 measured reflections
16514 independent reflections
9991 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.078
wR(F ²) = 0.154
S = 1.07
16514 reflections
1255 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; 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 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808042566/si2145sup1.cif

e-65-0o160-sup1.cif^{(61.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042566/si2145Isup2.hkl

e-65-0o160-Isup2.hkl^{(807.1KB, hkl)}

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
O1—H1A⋯O2	1.20 (5)	1.33 (5)	2.480 (4)	156 (4)
O3—H3A⋯O4	1.21 (4)	1.33 (4)	2.479 (4)	156 (3)
O5—H5A⋯O6	1.33 (5)	1.22 (5)	2.474 (4)	152 (4)
O7—H7A⋯O8	1.28 (5)	1.26 (5)	2.465 (4)	152 (4)
O9—H9A⋯O10	1.20 (5)	1.34 (5)	2.473 (4)	154 (3)
O11—H11A⋯O12	1.33 (5)	1.25 (5)	2.494 (4)	152 (4)
C122—H122⋯O10ⁱ	0.93	2.58	3.429 (5)	152
C19—H19⋯Cg10ⁱⁱ	0.93	2.93	3.739 (5)	147
C23—H23⋯Cg17ⁱⁱⁱ	0.93	2.90	3.714 (4)	146
C32—H32⋯Cg17^iv	0.93	2.94	3.749 (4)	147
C39—H39⋯Cg3ⁱ	0.93	2.82	3.674 (5)	152
C48—H48⋯Cg11^v	0.93	2.79	3.618 (4)	149
C69—H69⋯Cg8ⁱ	0.93	2.95	3.820 (4)	155
C93—H93⋯Cg2^vi	0.93	3.00	3.692 (3)	133
C107—H107⋯Cg14ⁱ	0.93	2.83	3.670 (4)	151

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg2 is the centroid of atoms C7–C12, Cg3 of atoms C16–C21, Cg8 of atoms C49–C54, Cg10 of atoms C64–C69, Cg11 of atoms C70–C75, Cg14 of atoms C91–C96 and Cg17 of atoms C112–C117.

Acknowledgments

The authors are grateful to Hubei Normal University for financial support.

supplementary crystallographic information

Comment

Both in solution and in the solid state, considerable attention has been focused on the structures of 1,3-diketones due to their enolic tautomeric forms and their ability to form strong intermolecular or intramolecular hydrogen bonds (Vila et al., 1991; Bertolasi et al., 1991; Gilli et al., 2004). These compounds posses sometimes unique chemical properties, which make them extremely attractive as intermediates in syntheses (Hasegawa et al., 1997). They are also used widely in the chemistry of metallocomplexes (Jang et al., 2006).

The crystal structure of the title compound (Fig. 1), has six independent molecules which all exist in the enol form, stabilized by intramolecular hydrogen bonds. The O—H distances of enol six ring and dihedral angles in six independent molecules are different. In molecule 4, the intramolecular O···H···O hydrogen bond can be described as approximately proton-centered, and the others as dynamic or static mixtures (Gilli et al., 2004) of two tautomeric O—H···O and O···H—O forms. Molecules 1, 2, 5 belong to O—H···O, and molecules 3 and 6 to the O···H—H tautomer (Table 1). In addition, there is only one weak intermolecular hydrogen bond between molecules 5 and 6, and other pairs of molecules do not show any C—H···O contacts, but probably C—H···π interactions (Table 1). Details of such non-conventional π contacts are reviewed by Desiraju & Steiner (2001). The following Cgs in Table 1 are the centroids of the π acceptor ring systems: Cg2 = C7 - C12, Cg3 = C16 - C21, Cg8 = C49 - C54, Cg10 = C64 - C69, Cg11 = C70 - C75, Cg14 = C91 - C96, Cg17 = C112 - C117. The central benzene ring in molecule 1 (C7 - C12) makes dihedral angles of 28.04 (8) and 9.01 (7) ° with the benzene rings C1 - C6 and C16 - C21, respectively; in the other five molecules, the corresponding angles are 18.49 (3) and 5.74 (2) °, 30.57 (5) and 12.48 (4) °, 26.58 (4) and 29.54 (3) °, 25.09 (5) and 28.07 (3) °, 27.68 (2) and 13.52 (4) °, respectively.

Experimental

1-(4-bilphenyl)ethanone (7.84 g, 0.04 mol), ethyl benzoate (6.02 g, 0.04 mol), NaNH₂ (1.95 g, 0.05 mol) and dry ether (100 ml) were placed into round bottom flask. The mixture was stirred 6 h at room temperature under a blanket of nitrogen, acidified with dilute hydrochloric acid, and stirring was continued until all solids dissolved. The ether layer was separated and washed with saturated NaHCO₃ solution, dried over anhydrous Na₂SO₄ and was removed by evaporation. The residual solid was recrystallized from ethanol solution to give the title compound (yield 4.60 g, 38.3%, m.p. 383 K). Crystals suitable for X-ray diffraction were grown by slow evaporation of the CHCl₃—EtOH (1:4) solutions at room temperature.