organic papers
Acta Cryst.(2004). E60, o1135±o1136 DOI: 10.1107/S1600536804013261 Zhifang Yuet al. C15H14O3
o1135
Acta Crystallographica Section EStructure Reports
Online
ISSN 1600-5368
3-Hydroxy-3-(3-hydroxyphenyl)-1-phenyl-propan-1-one
Zhifang Yu,* Jianwei Sun, Bing Zhao, Xiuyan Gu and Zhongzhen Tian
Department of Chemistry, Tianjin University, Tianjin 300072, People's Repulic of China
Correspondence e-mail: zhifang@public.tpt.tj.cn
Key indicators Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.004 AÊ Disorder in main residue
Rfactor = 0.048
wRfactor = 0.145
Data-to-parameter ratio = 12.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C15H14O3, was synthesized by a
Reformatsky reaction in an aqueous medium. The two aromatic rings are approximately orthogonal. Intermolecular OÐH O hydrogen bonds are formed between the carbonyl and hydroxyl groups. The hydroxyl group in the central chain is disordered over two sites.
Comment
We have researched the Reformatsky reaction (Bieberet al., 1997) of -haloketones in an aqueous medium (Chanet al., 1994; Shen et al., 1997). A new compound has been syn-thesized by the reaction of 2-bromoacetophenone with 3-hydroxybenzaldehyde in the presence of zinc in an aqueous system (Yuet al., 2003).
The molecular structure of the title compound, (I), is illustrated in Fig. 1. The two aromatic rings are approximately orthogonal, forming a dihedral angle of 80.7 (1). The angle
C6ÐC7ÐC8 is 119.1 (2), indicating that atom C7 is sp2
-hybridized. The torsion angle C6ÐC7ÐC8ÐC9 is
ÿ165.5 (2), indicating these atoms are almost coplanar.
Experimental
3-Hydroxybenzaldehyde (3 mmol) and 2-bromoacetophenone (4.5 mmol) were added to a mixture of zinc (12 mmol), ammonium chloride (1.5 g), a trace amount of iodine, cetyltrimethylammonium bromide (0.005 g) and tetrahydrofuran (1 ml) in a saturated solution of calcium chloride (12 ml). The mixture was stirred at room temperature for 8 h and extracted with diethyl ether, evaporated and separated by ¯ash chromatography (ethyl acetate±petroleum ether). A yellow powder was obtained (yield 53%) and single crystals (m.p. 377±378 K) suitable for crystallographic analysis were obtained by slow evaporation of an ethyl acetate±petroleum ether solution. Spectroscopic analyses, IR [KBr, (cmÿ1)]: 3333, 1676; 1H NMR
(CDCl3):7.95±6.93 (m, 9H), 5.28 (t, 1H), 3.35 (d, 2H), 2.02(s, 1H).
Elemental analysis, required for C15H14O3: C 74.38, H 5.79%; found:
C 74.35, H 5.74%. Crystal data C15H14O3 Mr= 242.26
Monoclinic, P21=c a= 14.251 (5) AÊ
b= 9.984 (3) AÊ
c= 8.994 (3) AÊ
= 105.305 (5)
V= 1234.3 (7) AÊ3 Z= 4
Dx= 1.304 Mg mÿ3
MoKradiation Cell parameters from 877
re¯ections
= 3.2±23.4
= 0.09 mmÿ1 T= 293 (2) K Block, colourless 0.340.220.16 mm
Data collection
Bruker SMART CCD area-detector diffractometer
'and!scans
Absorption correction: none 6168 measured re¯ections 2173 independent re¯ections
1313 re¯ections withI> 2(I)
Rint= 0.035 max= 25.0 h=ÿ16!11
k=ÿ11!11
l=ÿ9!10 Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.048 wR(F2) = 0.145 S= 0.99 2173 re¯ections 176 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0648P)2
+ 0.3761P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.24 e AÊÿ3
min=ÿ0.20 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,). O1ÐC7 1.216 (3)
O3ÐC14 1.374 (3) C9ÐO2C7ÐC8 1.477 (3)1.506 (4)
O2ÐC9ÐC10 108.9 (2)
O1ÐC7ÐC8 120.6 (2) C15ÐC14ÐC13 120.4 (2) C6ÐC7ÐC8ÐC9 ÿ165.5 (2)
O2ÐC9ÐC8ÐC7 63.0 (3) O3ÐC14ÐC15ÐC10 179.9 (2)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O2ÐH2 O1i 0.82 2.15 2.960 (3) 171
O3ÐH3 O2i 0.82 2.03 2.818 (3) 161 Symmetry code: (i)x;3
2ÿy;zÿ12.
All H atoms were located in a difference Fourier map and were re®ned as riding [OÐH = 0.82 AÊ and CÐH = 0.93±0.98 AÊ;Uiso= 1.0
(disordered atoms) or 1.5Ueq(O) and 1.2Ueq(C)]. The torsion angles
about the CÐO bond of the hydroxyl groups were re®ned. The hydroxyl group attached to atom C9 is disordered over two sites [occupancies 0.72 (4) and 0.28 (4)].
Data collection:SMART(Bruker, 1997); cell re®nement:SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication:SHELXTL.
The authors thank the State Key Laboratory of Elemento-Organic Chemistry, Nankai University. This research was supported by the Visiting Scholar Foundation of the Key Laboratory of Tianjin University. The work was also supported by the `985' Project of Tianjin University.
References
Bieber, L. W., Malvestiti, I. & Storch, E. C. (1997).J. Org. Chem.62, 9061± 9064.
Bruker (1997).SMART, SAINTandSHELXTL.Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Chan, T. H., Li, C. J. & Lee, M. C. (1994).Can. J. Chem.72, 1181±1192. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
GoÈttingen, Germany.
Shen, Z., Zhang, J. Q., Zou, H. X. & Yan, M. M. (1997).Tetrahedron Lett.38, 2733±2736.
Yu, Z. F., Zhao, B.,Tian, Z. Z. & Gu. X. Y. (2003).Acta Cryst.E59, o2020± o2021.
Figure 1
supporting information
sup-1 Acta Cryst. (2004). E60, o1135–o1136
supporting information
Acta Cryst. (2004). E60, o1135–o1136 [https://doi.org/10.1107/S1600536804013261]
3-Hydroxy-3-(3-hydroxyphenyl)-1-phenylpropan-1-one
Zhifang Yu, Jianwei Sun, Bing Zhao, Xiuyan Gu and Zhongzhen Tian
3-Hydroxy-3-(3-hydroxyphenyl)-1-phenylpropan-1-one
Crystal data
C15H14O3
Mr = 242.26
Monoclinic, P21/c
Hall symbol: -P 2ybc a = 14.251 (5) Å b = 9.984 (3) Å c = 8.994 (3) Å β = 105.305 (5)° V = 1234.3 (7) Å3
Z = 4
F(000) = 512 Dx = 1.304 Mg m−3
Melting point: 377 K
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 877 reflections θ = 3.2–23.4°
µ = 0.09 mm−1
T = 293 K Plate, colourless 0.34 × 0.22 × 0.16 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
6168 measured reflections 2173 independent reflections
1313 reflections with I > 2σ(I) Rint = 0.035
θmax = 25.0°, θmin = 1.5°
h = −16→11 k = −11→11 l = −9→10
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.048
wR(F2) = 0.145
S = 0.99 2173 reflections 176 parameters 3 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0648P)2 + 0.3761P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.24 e Å−3
Δρmin = −0.20 e Å−3
Special details
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq Occ. (<1)
O1 0.86038 (15) 0.7149 (3) 0.9155 (2) 0.0939 (8)
O3 0.58108 (17) 0.5451 (2) 0.1076 (2) 0.0828 (7)
H3 0.6113 0.6151 0.1079 0.124*
C9 0.72482 (18) 0.6158 (2) 0.6580 (3) 0.0554 (7)
H9 0.6989 0.6080 0.7472 0.066* 0.726 (5)
H9′ 0.7186 0.7116 0.6342 0.066* 0.274 (5)
O2 0.72238 (18) 0.7572 (2) 0.6085 (3) 0.0592 (9) 0.726 (5)
H2 0.7549 0.7658 0.5463 0.089* 0.726 (5)
O2′ 0.6959 (5) 0.5813 (9) 0.8092 (7) 0.078 (3) 0.274 (5)
H2′ 0.6367 0.5864 0.7935 0.117* 0.274 (5)
C1 1.0625 (2) 0.7175 (3) 0.9674 (3) 0.0674 (8)
H1 1.0353 0.7780 1.0227 0.081*
C2 1.1623 (2) 0.7117 (3) 0.9931 (4) 0.0799 (9)
H2A 1.2017 0.7695 1.0638 0.096*
C3 1.2029 (2) 0.6219 (3) 0.9156 (4) 0.0815 (9)
H3A 1.2702 0.6179 0.9337 0.098*
C4 1.1451 (2) 0.5370 (3) 0.8106 (4) 0.0774 (9)
H4 1.1734 0.4753 0.7581 0.093*
C5 1.0452 (2) 0.5425 (3) 0.7822 (3) 0.0638 (7)
H5 1.0064 0.4845 0.7108 0.077*
C6 1.00237 (19) 0.6341 (2) 0.8600 (3) 0.0525 (6)
C7 0.8949 (2) 0.6454 (3) 0.8323 (3) 0.0573 (7)
C8 0.82974 (18) 0.5707 (3) 0.6989 (3) 0.0563 (7)
H8A 0.8323 0.4760 0.7238 0.068*
H8B 0.8548 0.5817 0.6093 0.068*
C10 0.66330 (17) 0.5331 (2) 0.5268 (3) 0.0489 (6)
C11 0.62129 (19) 0.4143 (3) 0.5545 (3) 0.0597 (7)
H11 0.6302 0.3841 0.6551 0.072*
C12 0.5662 (2) 0.3407 (3) 0.4334 (3) 0.0664 (8)
H12 0.5382 0.2608 0.4533 0.080*
C13 0.55157 (19) 0.3827 (3) 0.2840 (3) 0.0599 (7)
H13 0.5138 0.3326 0.2029 0.072*
C14 0.5942 (2) 0.5011 (3) 0.2564 (3) 0.0584 (7)
C15 0.64949 (19) 0.5753 (3) 0.3771 (3) 0.0571 (7)
H15 0.6778 0.6549 0.3572 0.069*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2004). E60, o1135–o1136
O3 0.1096 (18) 0.0795 (15) 0.0551 (11) −0.0062 (13) 0.0143 (11) 0.0117 (10)
C9 0.0584 (17) 0.0526 (15) 0.0588 (16) 0.0020 (13) 0.0218 (13) −0.0034 (12)
O2 0.0698 (18) 0.0453 (15) 0.0684 (18) 0.0015 (12) 0.0284 (13) −0.0039 (12)
O2′ 0.067 (5) 0.110 (6) 0.063 (5) 0.007 (5) 0.028 (4) −0.003 (4)
C1 0.076 (2) 0.0650 (18) 0.0590 (16) 0.0021 (15) 0.0132 (14) −0.0048 (14)
C2 0.073 (2) 0.081 (2) 0.079 (2) −0.0080 (18) 0.0079 (17) −0.0038 (17)
C3 0.065 (2) 0.082 (2) 0.096 (2) 0.0025 (18) 0.0179 (18) 0.010 (2)
C4 0.073 (2) 0.0694 (19) 0.092 (2) 0.0155 (17) 0.0250 (17) 0.0014 (17)
C5 0.0639 (19) 0.0587 (17) 0.0669 (17) 0.0049 (14) 0.0138 (14) −0.0047 (14)
C6 0.0621 (17) 0.0498 (14) 0.0446 (14) 0.0038 (13) 0.0126 (12) 0.0056 (11)
C7 0.0678 (19) 0.0574 (16) 0.0472 (14) 0.0097 (14) 0.0163 (13) 0.0002 (12)
C8 0.0608 (17) 0.0523 (15) 0.0571 (15) 0.0031 (13) 0.0179 (12) −0.0029 (12)
C10 0.0465 (14) 0.0491 (14) 0.0544 (15) 0.0056 (12) 0.0190 (11) −0.0008 (12) C11 0.0659 (17) 0.0591 (16) 0.0569 (16) −0.0055 (14) 0.0213 (13) 0.0097 (13)
C12 0.0693 (19) 0.0561 (16) 0.076 (2) −0.0139 (14) 0.0224 (15) 0.0038 (15)
C13 0.0575 (17) 0.0604 (17) 0.0600 (17) 0.0008 (14) 0.0125 (13) −0.0084 (13) C14 0.0644 (17) 0.0599 (17) 0.0535 (16) 0.0143 (14) 0.0204 (13) 0.0079 (13) C15 0.0670 (18) 0.0473 (14) 0.0615 (17) 0.0002 (13) 0.0251 (14) 0.0046 (12)
Geometric parameters (Å, º)
O1—C7 1.216 (3) C3—H3A 0.9300
O3—C14 1.374 (3) C4—C5 1.380 (4)
O3—H3 0.8200 C4—H4 0.9300
C9—O2 1.477 (3) C5—C6 1.387 (3)
C9—O2′ 1.559 (6) C5—H5 0.9300
C9—C8 1.511 (4) C6—C7 1.490 (4)
C9—C10 1.516 (3) C7—C8 1.506 (4)
C9—H9 0.9708 C8—H8A 0.9700
C9—H9′ 0.9788 C8—H8B 0.9700
O2—H9′ 0.5193 C10—C15 1.374 (3)
O2—H2 0.8200 C10—C11 1.380 (3)
O2′—H9 0.6292 C11—C12 1.375 (4)
O2′—H2′ 0.8200 C11—H11 0.9300
C1—C2 1.380 (4) C12—C13 1.370 (4)
C1—C6 1.386 (4) C12—H12 0.9300
C1—H1 0.9300 C13—C14 1.381 (4)
C2—C3 1.356 (4) C13—H13 0.9300
C2—H2A 0.9300 C14—C15 1.377 (4)
C3—C4 1.371 (4) C15—H15 0.9300
C14—O3—H3 109.5 C4—C5—C6 120.2 (3)
O2—C9—O2′ 118.9 (4) C4—C5—H5 119.9
O2—C9—C8 107.5 (2) C6—C5—H5 119.9
O2′—C9—C8 101.2 (3) C5—C6—C1 118.3 (3)
O2—C9—C10 108.9 (2) C5—C6—C7 122.4 (2)
O2′—C9—C10 109.1 (3) C1—C6—C7 119.4 (2)
O2—C9—H9 110.0 O1—C7—C8 120.6 (2)
O2′—C9—H9 10.4 C6—C7—C8 119.1 (2)
C8—C9—H9 110.1 C7—C8—C9 114.1 (2)
C10—C9—H9 109.3 C7—C8—H8A 108.7
O2—C9—H9′ 7.0 C9—C8—H8A 108.7
O2′—C9—H9′ 112.2 C7—C8—H8B 108.7
C8—C9—H9′ 111.8 C9—C8—H8B 108.7
C10—C9—H9′ 111.2 H8A—C8—H8B 107.6
H9—C9—H9′ 103.1 C15—C10—C11 118.9 (2)
C9—O2—H9′ 13.2 C15—C10—C9 119.9 (2)
C9—O2—H2 109.5 C11—C10—C9 121.1 (2)
H9′—O2—H2 122.6 C12—C11—C10 120.0 (2)
C9—O2′—H9 16.1 C12—C11—H11 120.0
C9—O2′—H2′ 109.5 C10—C11—H11 120.0
C2—C1—C6 120.8 (3) C13—C12—C11 121.3 (3)
C2—C1—H1 119.6 C13—C12—H12 119.3
C6—C1—H1 119.6 C11—C12—H12 119.3
C3—C2—C1 120.2 (3) C12—C13—C14 118.6 (3)
C3—C2—H2A 119.9 C12—C13—H13 120.7
C1—C2—H2A 119.9 C14—C13—H13 120.7
C2—C3—C4 120.2 (3) O3—C14—C15 119.9 (2)
C2—C3—H3A 119.9 O3—C14—C13 119.7 (2)
C4—C3—H3A 119.9 C15—C14—C13 120.4 (2)
C3—C4—C5 120.4 (3) C10—C15—C14 120.7 (2)
C3—C4—H4 119.8 C10—C15—H15 119.6
C5—C4—H4 119.8 C14—C15—H15 119.6
C6—C1—C2—C3 −1.4 (5) O2—C9—C10—C15 26.2 (3)
C1—C2—C3—C4 0.4 (5) O2′—C9—C10—C15 157.4 (4)
C2—C3—C4—C5 0.3 (5) C8—C9—C10—C15 −92.0 (3)
C3—C4—C5—C6 0.0 (4) O2—C9—C10—C11 −154.5 (2)
C4—C5—C6—C1 −1.0 (4) O2′—C9—C10—C11 −23.3 (4)
C4—C5—C6—C7 179.2 (2) C8—C9—C10—C11 87.3 (3)
C2—C1—C6—C5 1.7 (4) C15—C10—C11—C12 −0.4 (4)
C2—C1—C6—C7 −178.5 (3) C9—C10—C11—C12 −179.7 (2)
C5—C6—C7—O1 170.9 (3) C10—C11—C12—C13 −0.1 (4)
C1—C6—C7—O1 −8.8 (4) C11—C12—C13—C14 0.5 (4)
C5—C6—C7—C8 −9.8 (4) C12—C13—C14—O3 179.7 (2)
C1—C6—C7—C8 170.5 (2) C12—C13—C14—C15 −0.4 (4)
O1—C7—C8—C9 13.8 (4) C11—C10—C15—C14 0.4 (4)
C6—C7—C8—C9 −165.5 (2) C9—C10—C15—C14 179.7 (2)
O2—C9—C8—C7 63.0 (3) O3—C14—C15—C10 179.9 (2)
O2′—C9—C8—C7 −62.4 (4) C13—C14—C15—C10 0.0 (4)
supporting information
sup-5 Acta Cryst. (2004). E60, o1135–o1136
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O2—H2···O1i 0.82 2.15 2.960 (3) 171
O3—H3···O2i 0.82 2.03 2.818 (3) 161
