Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 206 parameters

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organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 1-(2-Hydroxy-3,4-dimethoxyphenyl)-2- (4-methoxyphenyl)ethanone Zhu-Ping Xiao* and He-Ying Xiao College of

com Received 19 October 2008; accepted 6 November 2008 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = 0.005 Å; R factor = 0.071; wr factor = 0.215; data-to-parameter ratio = 12.9. In the title compound, C 17 H 18 O 5, the pyrogallol group is almost coplanar with the mean plane of the attached carbonyl group [dihedral angle of 1.

1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN (2-Hydroxy-3,4-dimethoxyphenyl)-2- (4-methoxyphenyl)ethanone Zhu-Ping Xiao* and He-Ying Xiao College of Chemistry & Chemical Engineering, Jishou University, Jishou , People s Republic of China Correspondence xiaozhuping2005@163.com Received 19 October 2008; accepted 6 November 2008 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = Å; R factor = 0.071; wr factor = 0.215; data-to-parameter ratio = In the title compound, C 17 H 18 O 5, the pyrogallol group is almost coplanar with the mean plane of the attached carbonyl group [dihedral angle of 1.95 (13) ] and makes a dihedral angle of (10) with the other benzene ring. Of the three methoxy groups, only one is significantly twisted relative to its attached benzene ring [C O C C torsion angles of 4.0 (5), 3.9 (6) and (4) ]. Intramolecular O HO and C HO hydrogen bonds help to establish the conformation, and the packing is consolidated by C HO interactions and stacking interactions [centroid centroid separation = (2) Å]. Related literature For background on the properties of deoxybenzoins, see: Kiuchi et al. (1990); Li et al. (2008); Niwa et al. (1999); Papoutsi et al. (2007); Parmar et al. (1996); Sanduja et al. (1985); Xiao et al. (2008); Xiao, Fang et al. (2007); Xiao, Shi et al. (2007). Experimental Crystal data C 17 H 18 O 5 M r = Monoclinic, P2 1 =c a = (3) Å b = (3) Å c = (15) Å = (3) V = (5) Å 3 Z =4 Mo K radiation = 0.10 mm 1 T = 293 (2) K mm Data collection Enraf Nonius CAD-4 diffractometer Absorption correction: scan (North et al., 1968) T min = 0.971, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 206 parameters Table 1 Hydrogen-bond geometry (Å, ) measured reflections 2667 independent reflections 1543 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.28 e Å 3 min = 0.35 e Å 3 D HA D H HA DA D HA O2 H18O (4) 1.78 (4) (4) 148 (4) C15 H15AO (5) 115 C11 H11O3 i (4) 138 C17 H17BO4 ii (6) 133 Symmetry codes: (i) x þ 1; y þ 1 2 ; z þ 3 2 ; (ii) x þ 1; y þ 3 2 ; z 1 2. Data collection: CAD-4 Software (Enraf Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. The work was financed by a grant (No. JDKYZZ0801) from Jishou University for talent introduction, China. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2823). References Enraf Nonius (1989). CAD-4 Software. Enraf Nonius, Delft, The Netherlands. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Kiuchi, F., Chen, X. & Tsuda, Y. (1990). Heterocycles, 31, Li, H.-Q., Xue, J.-Y., Shi, L., Gui, S.-Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. 43, Niwa, K., Hashimoto, M., Morishita, S., Yokoyama, Y., Mori, H. & Tamaya, T. (1999). J. Cancer Res. 90, North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, Papoutsi, Z., Kassi, E., Fokialakis, N., Mitakou, S., Lambrinidis, G., Mikros, E. & Moutsatsou, P. (2007). Steroids, 72, Parmar, V. S., Bisht, K. S., Jain, R., Singh, S., Sharma, S. K., Gupta, S., Malhotra, S., Tyagi, O. D., Vardhan, A. & Pati, H. N. (1996). Indian J. Chem. Sect. B, 35, Sanduja, R., Weinheimer, A. J. & Alam, M. (1985). J. Chem. Res. Synop. pp Sheldrick, G. M. (2008). Acta Cryst. A64, Xiao, Z.-P., Fang, R.-Q., Shi, L., Ding, H., Xu, C. & Zhu, H.-L. (2007). Can. J. Chem. 85, Xiao, Z.-P., Li, H.-Q., Xue, J.-Y., Shi, L. & Zhu, H.-L. (2008). Synth. Commun. 38, Xiao, Z.-P., Shi, D.-H., Li, H.-Q., Zhang, L.-N., Xu, C. & Zhu, H.-L. (2007). Bioorg. Med. Chem. 15, o2324 Xiao and Xiao doi: /s

2 supporting information [doi: /s ] 1-(2-Hydroxy-3,4-dimethoxyphenyl)-2-(4-methoxyphenyl)ethanone Zhu-Ping Xiao and He-Ying Xiao S1. Comment Deoxybenzoins are intermediates in the synthesis of isoflavones (Xiao et al., 2008; Xiao, Fang et al., 2007) and found in several plants, such as Glycyrrhiza sp., Trifolium subterraneum and Ononis spinosa, and marine sources (Kiuchi et al., 1990; Niwa et al., 1999; Sanduja et al., 1985). Many of the deoxybenzoins have shown quite significant estrogen receptor modulatory, urease inhibitory, antimicrobial and antiviral properties (Papoutsi et al., 2007; Xiao, Shi et al., 2007; Parmar et al., 1996; Li et al., 2008). Consequently, we have synthesized a series of deoxybenzoins for bioactivity screen. The bond lengths and angles of the title compound, (I), are unexceptional. The carbonyl group is almost coplanar with the pyrogallol fragment with a dihedral angle of 1.95 (13). The C16 O4 C4 C5 torsion angle [4.0 (5) ] indicates that the methoxy group is coplanar with the attached phenyl ring (pyrogallol fragment), the same as the methoxy group (O5, C17) attached to the p-methoxyphenyl moiety. However, the C15 O3 C3 C4 torsion angle indicates that the methoxy group is twisted at (4) with respect to the pyrogallol ring. The molecule of (I) is stabilized by intramolecular O H O and C H O hydrogen bonds (Table 1). The sixmembered pseudo-ring closed by the former bond is almost planar with mean deviation of 0.010Å and coplanar with the fused C1 C6 benzene ring (Fig. 1). The packing is stabilized by intermolecular C H O hydrogen bonds as well as weak π-π interactions with a centroid-to-centroid distance of (2)Å. S2. Experimental 4-Methoxyphenacetyl chloride was prepared by treating 4-methoxyphenacetic acid with thionyl chloride at room temperature for 24 h. The solvent was removed in vacuo. To a mixture of pyrogallol trimethoxyl ether (2 g, 11.9 mmol) and 4-methoxyphenacetyl chloride (2.3 g, 12.2 mmol) in dried carbon disulfide (4 ml) was added anhydrous aluminium chloride (2.8 g) with stirring at room temperature overnight. Then the mixture was heated under reflux for 0.5 h. After removal of the solvent by decantation, the residue was poured into ice-cold diluted hydrochloric acid. The precipitate was suction filtered and crystallized from methanol to furnish light yellow blocks of (I). S3. Refinement The H atom bonded to O2 was located in a difference Fourier map and freely refined. All other H atoms were placed in geometrically idealized positions (C H = Å) and refined as riding with U iso = 1.2U eq (C) or 1.5U eq (methyl C). sup-1

3 Figure 1 The molecular structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level. 1-(2-Hydroxy-3,4-dimethoxyphenyl)-2-(4-methoxyphenyl)ethanone Crystal data C 17 H 18 O 5 M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (3) Å b = (3) Å c = (15) Å β = (3) V = (5) Å 3 Z = 4 Data collection Enraf Nonius CAD-4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω/2θ scans Absorption correction: ψ scan (North et al., 1968) T min = 0.971, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 206 parameters 0 restraints Primary atom site location: structure-invariant direct methods F(000) = 640 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 1217 reflections θ = µ = 0.10 mm 1 T = 293 K Block, light-yellow mm 2893 measured reflections 2667 independent reflections 1543 reflections with I > 2σ(I) R int = θ max = 25.0, θ min = 1.4 h = k = 16 0 l = 0 8 Secondary atom site location: difference Fourier map Hydrogen site location: difmap and geom H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.1231P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.28 e Å 3 Δρ min = 0.35 e Å 3 sup-2

4 Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq C (2) (2) (5) (8) C (2) (2) (4) (8) C (2) (2) (4) (8) C (2) (2) (4) (9) C (2) (2) (4) (8) H * C (2) (2) (5) (9) H * C (2) (2) (5) (9) C (3) (3) (5) (10) H * C (3) (3) (5) (11) H * C (2) (3) (6) (10) C (3) (3) (5) (9) H * C (3) (2) (5) (9) H * C (2) (3) (5) (10) H13A * H13B * C (2) (2) (4) (9) C (3) (3) (6) (12) H15A * H15B * H15C * C (3) (3) (6) (12) H16A * H16B * H16C * C (4) (4) (9) (2) H17A * H17B * H17C * O (18) (18) (4) (8) sup-3

5 O (2) (17) (4) (7) O (18) (17) (3) (7) O (17) (18) (4) (7) O (19) (2) (5) (10) H (3) (3) (6) (14)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (19) (19) (19) (16) (15) (15) C (2) (18) (18) (15) (15) (14) C (2) (19) (19) (16) (15) (15) C (2) (2) (19) (16) (15) (16) C (2) (19) (2) (15) (16) (15) C (2) (19) (2) (16) (17) (16) C (2) (18) (2) (16) (16) (16) C (2) (2) (2) (19) (18) (18) C (2) (2) (3) (19) (19) (2) C (2) (2) (3) (17) (19) (19) C (2) (2) (2) (18) (18) (17) C (2) (19) (2) (17) (17) (16) C (2) (2) (2) (18) (18) (19) C (2) (2) (19) (16) (15) (16) C (3) (2) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (4) (6) (3) (4) (4) O (16) (15) (19) (12) (13) (13) O (17) (14) (18) (12) (14) (12) O (17) (14) (17) (12) (12) (12) O (15) (15) (18) (12) (12) (13) O (18) (2) (3) (16) (16) (19) Geometric parameters (Å, º) C1 C (5) C11 C (5) C1 C (5) C11 H C1 C (5) C12 H C2 O (4) C13 C (5) C2 C (5) C13 H13A C3 O (4) C13 H13B C3 C (5) C14 O (4) C4 O (4) C15 O (5) C4 C (5) C15 H15A C5 C (5) C15 H15B C5 H C15 H15C C6 H C16 O (5) C7 C (5) C16 H16A C7 C (5) C16 H16B sup-4

6 C7 C (5) C16 H16C C8 C (5) C17 O (5) C8 H C17 H17A C9 C (5) C17 H17B C9 H C17 H17C C10 O (4) O2 H (4) C10 C (5) C6 C1 C (3) C7 C12 H C6 C1 C (3) C11 C12 H C2 C1 C (3) C7 C13 C (3) O2 C2 C (3) C7 C13 H13A O2 C2 C (3) C14 C13 H13A C3 C2 C (3) C7 C13 H13B O3 C3 C (3) C14 C13 H13B O3 C3 C (3) H13A C13 H13B C2 C3 C (3) O1 C14 C (3) O4 C4 C (3) O1 C14 C (3) O4 C4 C (3) C1 C14 C (3) C3 C4 C (3) O3 C15 H15A C6 C5 C (3) O3 C15 H15B C6 C5 H H15A C15 H15B C4 C5 H O3 C15 H15C C5 C6 C (3) H15A C15 H15C C5 C6 H H15B C15 H15C C1 C6 H O4 C16 H16A C12 C7 C (3) O4 C16 H16B C12 C7 C (3) H16A C16 H16B C8 C7 C (3) O4 C16 H16C C9 C8 C (3) H16A C16 H16C C9 C8 H H16B C16 H16C C7 C8 H O5 C17 H17A C8 C9 C (4) O5 C17 H17B C8 C9 H H17A C17 H17B C10 C9 H O5 C17 H17C O5 C10 C (3) H17A C17 H17C O5 C10 C (3) H17B C17 H17C C9 C10 C (3) C2 O2 H (3) C10 C11 C (3) C3 O3 C (3) C10 C11 H C4 O4 C (3) C12 C11 H C10 O5 C (3) C7 C12 C (3) C6 C1 C2 O (3) C8 C9 C10 C (6) C14 C1 C2 O2 1.3 (5) O5 C10 C11 C (4) C6 C1 C2 C3 1.1 (5) C9 C10 C11 C (6) C14 C1 C2 C (3) C8 C7 C12 C (5) O2 C2 C3 O3 5.9 (5) C13 C7 C12 C (3) sup-5

7 C1 C2 C3 O (3) C10 C11 C12 C7 0.0 (6) O2 C2 C3 C (3) C12 C7 C13 C (4) C1 C2 C3 C4 2.0 (5) C8 C7 C13 C (5) O3 C3 C4 O4 6.4 (4) C6 C1 C14 O (3) C2 C3 C4 O (3) C2 C1 C14 O1 1.2 (5) O3 C3 C4 C (3) C6 C1 C14 C (5) C2 C3 C4 C5 1.7 (5) C2 C1 C14 C (3) O4 C4 C5 C (3) C7 C13 C14 O1 6.7 (5) C3 C4 C5 C6 0.5 (5) C7 C13 C14 C (3) C4 C5 C6 C1 0.3 (5) C2 C3 O3 C (4) C2 C1 C6 C5 0.0 (5) C4 C3 O3 C (4) C14 C1 C6 C (3) C3 C4 O4 C (3) C12 C7 C8 C9 1.1 (6) C5 C4 O4 C (5) C13 C7 C8 C (4) C9 C10 O5 C (4) C7 C8 C9 C (6) C11 C10 O5 C (6) C8 C9 C10 O (4) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O2 H18 O (4) 1.78 (4) (4) 148 (4) C15 H15A O (5) 115 C11 H11 O3 i (4) 138 C17 H17B O4 ii (6) 133 Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y+3/2, z 1/2. sup-6

Experimental. Crystal data. C 12 H 12 BrNO 4 S 2 M r = Monoclinic, P2 1 =c a = (17) Å b = (2) Å c = (3) Å = 99.

Experimental. Crystal data. C 12 H 12 BrNO 4 S 2 M r = Monoclinic, P2 1 =c a = (17) Å b = (2) Å c = (3) Å = 99. organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Ethyl 3-bromo-4-cyano-5-[(2-ethoxy-2- oxoethyl)sulfanyl]thiophene-2-carboxylate Xiuping Li,* Xiaochuan Jia and