(E)-4-(β-d-Allopyran-os-yloxy)cinnamyl 4-bromo-phenyl ketone ethanol solvate.

The title compound, C(21)H(21)BrO(7)·C(2)H(6)O, was synthesized by the Claisen-Schimidt reaction of helicid (systematic name: 4-formyl-phenyl-β-d-allopyran-oside) with 4-bromo-aceto-phenone in ethanol. The pyran ring adopts a chair conformation. In the crystal structure, mol-ecules are linked into a three-dimensional network by inter-molecular O-H⋯O hydrogen bonds.

Related literature

For helicid and its biological activity, see: Chen et al. (1981 ▶); Sha & Mao (1987 ▶). For the synthesis and structure of related compound, see: Fan et al. (2007 ▶); Fu et al. (2009 ▶); Lv et al. (2009 ▶); Yang et al. (2009 ▶); Ye et al. (2009 ▶).

Experimental

Crystal data

C21H21BrO7·C2H6O

M = 511.36

Monoclinic,

a = 10.977 (2) Å

b = 7.6518 (15) Å

c = 13.259 (3) Å

β = 92.08 (3)°

V = 1113.0 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.89 mm−1

T = 113 K

0.20 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.703, T max = 0.805

9199 measured reflections

5171 independent reflections

3636 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.056

S = 0.75

5171 reflections

296 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.67 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), 2358 Friedel pairs

Flack parameter: 0.027 (6)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029687/rz2355sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029687/rz2355Isup2.hkl

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

C21H21BrO7·C2H6O	F(000) = 528
Mr = 511.36	Dx = 1.526 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3521 reflections
a = 10.977 (2) Å	θ = 1.5–27.9°
b = 7.6518 (15) Å	µ = 1.89 mm−1
c = 13.259 (3) Å	T = 113 K
β = 92.08 (3)°	Block, colourless
V = 1113.0 (4) Å3	0.20 × 0.16 × 0.12 mm
Z = 2

Rigaku Saturn CCD area-detector diffractometer	5171 independent reflections
Radiation source: rotating anode	3636 reflections with I > 2σ(I)
confocal	Rint = 0.039
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 1.5°
ω and φ scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −10→10
Tmin = 0.703, Tmax = 0.805	l = −13→17
9199 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056	(Δ/σ)max = 0.003
S = 0.75	Δρmax = 0.67 e Å−3
5171 reflections	Δρmin = −0.39 e Å−3
296 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
1 restraint	Extinction coefficient: 0.0242 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2358 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.027 (6)

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 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.

	x	y	z	Uiso*/Ueq
Br1	0.70240 (2)	0.31136 (4)	0.80385 (2)	0.02313 (10)
O1	0.15927 (15)	0.3593 (2)	−0.22799 (13)	0.0125 (5)
O2	0.08102 (18)	0.0860 (3)	−0.35522 (15)	0.0166 (5)
H2	0.0553	0.0678	−0.4147	0.025*
O3	−0.04022 (16)	0.4996 (3)	−0.44247 (14)	0.0162 (5)
H3	−0.0788	0.5823	−0.4169	0.024*
O4	0.05197 (19)	0.7491 (2)	−0.30705 (18)	0.0153 (5)
H4	0.0691	0.8554	−0.3136	0.023*
O5	0.32128 (15)	0.7681 (2)	−0.28189 (15)	0.0164 (5)
H5	0.2777	0.8430	−0.2541	0.025*
O6	0.32452 (16)	0.4805 (3)	−0.14705 (14)	0.0143 (5)
O7	0.23659 (17)	0.2120 (3)	0.45816 (14)	0.0192 (5)
C1	−0.0025 (3)	0.1941 (4)	−0.3055 (2)	0.0168 (8)
H1A	−0.0209	0.1412	−0.2396	0.020*
H1B	−0.0796	0.2006	−0.3464	0.020*
C2	0.0466 (2)	0.3767 (4)	−0.2884 (2)	0.0122 (7)
H2A	−0.0134	0.4455	−0.2496	0.015*
C3	0.0726 (3)	0.4741 (4)	−0.3866 (2)	0.0108 (7)
H3A	0.1279	0.4012	−0.4276	0.013*
C4	0.1343 (3)	0.6463 (4)	−0.3622 (2)	0.0142 (7)
H4A	0.1532	0.7077	−0.4264	0.017*
C5	0.2521 (2)	0.6144 (4)	−0.3006 (2)	0.0127 (7)
H5A	0.3033	0.5322	−0.3396	0.015*
C6	0.2173 (2)	0.5219 (4)	−0.2039 (2)	0.0126 (7)
H6	0.1627	0.5976	−0.1639	0.015*
C7	0.3110 (3)	0.4342 (4)	−0.0469 (2)	0.0135 (7)
C8	0.1998 (2)	0.4166 (4)	−0.0018 (2)	0.0145 (7)
H8	0.1258	0.4363	−0.0394	0.017*
C9	0.1983 (2)	0.3697 (4)	0.0992 (2)	0.0156 (7)
H9	0.1221	0.3584	0.1303	0.019*
C10	0.3045 (2)	0.3390 (4)	0.1562 (2)	0.0136 (7)
C11	0.4158 (2)	0.3544 (4)	0.1087 (2)	0.0190 (8)
H11	0.4899	0.3316	0.1457	0.023*
C12	0.4188 (2)	0.4030 (4)	0.0076 (2)	0.0178 (7)
H12	0.4947	0.4147	−0.0240	0.021*
C13	0.2936 (2)	0.2962 (5)	0.26334 (19)	0.0167 (7)
H13	0.2127	0.2824	0.2851	0.020*
C14	0.3805 (2)	0.2741 (4)	0.3339 (2)	0.0141 (7)
H14	0.4640	0.2796	0.3177	0.017*
C15	0.3446 (3)	0.2406 (4)	0.4391 (2)	0.0142 (7)
C16	0.4376 (2)	0.2468 (4)	0.5234 (2)	0.0116 (7)
C17	0.4006 (3)	0.2023 (4)	0.6211 (2)	0.0146 (7)
H17	0.3199	0.1618	0.6302	0.017*
C18	0.4800 (2)	0.2172 (4)	0.7029 (2)	0.0152 (7)
H18	0.4547	0.1872	0.7684	0.018*
C19	0.5973 (2)	0.2762 (4)	0.6893 (2)	0.0150 (8)
C20	0.6379 (2)	0.3148 (5)	0.59468 (18)	0.0139 (6)
H20	0.7194	0.3525	0.5864	0.017*
C21	0.5579 (2)	0.2977 (5)	0.51141 (18)	0.0137 (6)
H21	0.5857	0.3211	0.4457	0.016*
O8	0.7446 (2)	0.5264 (3)	0.15901 (15)	0.0236 (5)
H8A	0.7702	0.6293	0.1661	0.035*
C22	0.7527 (2)	0.4749 (4)	0.0559 (2)	0.0186 (7)
H22A	0.7139	0.5652	0.0120	0.022*
H22B	0.7076	0.3642	0.0448	0.022*
C23	0.8844 (2)	0.4500 (4)	0.0265 (2)	0.0283 (9)
H23A	0.9281	0.5612	0.0334	0.042*
H23B	0.8862	0.4100	−0.0437	0.042*
H23C	0.9237	0.3626	0.0708	0.042*

	U11	U22	U33	U12	U13	U23
Br1	0.02318 (17)	0.03083 (19)	0.01506 (14)	−0.0005 (2)	−0.00380 (11)	−0.0020 (2)
O1	0.0135 (10)	0.0100 (12)	0.0137 (10)	−0.0031 (9)	−0.0042 (8)	0.0028 (8)
O2	0.0266 (13)	0.0125 (13)	0.0105 (12)	0.0026 (11)	−0.0005 (10)	−0.0007 (10)
O3	0.0193 (12)	0.0162 (12)	0.0128 (12)	0.0055 (10)	−0.0041 (9)	−0.0025 (10)
O4	0.0169 (11)	0.0075 (11)	0.0216 (12)	0.0025 (9)	0.0040 (9)	−0.0012 (9)
O5	0.0157 (11)	0.0123 (14)	0.0214 (12)	−0.0043 (9)	0.0046 (9)	−0.0034 (9)
O6	0.0117 (11)	0.0202 (13)	0.0108 (11)	−0.0012 (9)	−0.0022 (9)	0.0021 (10)
O7	0.0108 (11)	0.0321 (14)	0.0148 (12)	−0.0053 (10)	0.0011 (9)	−0.0017 (10)
C1	0.020 (2)	0.0157 (18)	0.0144 (17)	0.0003 (15)	0.0014 (15)	0.0018 (15)
C2	0.0133 (17)	0.0116 (16)	0.0118 (16)	−0.0002 (13)	−0.0007 (13)	0.0000 (13)
C3	0.0106 (16)	0.0127 (17)	0.0091 (17)	0.0015 (14)	−0.0009 (13)	0.0010 (14)
C4	0.0166 (18)	0.0129 (17)	0.0135 (17)	0.0049 (14)	0.0071 (14)	0.0010 (14)
C5	0.0142 (16)	0.0104 (17)	0.0135 (16)	−0.0022 (13)	0.0021 (13)	−0.0012 (13)
C6	0.0142 (17)	0.0122 (16)	0.0113 (16)	0.0019 (14)	−0.0012 (13)	−0.0049 (14)
C7	0.0124 (16)	0.0186 (18)	0.0096 (16)	−0.0005 (14)	0.0014 (13)	−0.0024 (14)
C8	0.0102 (16)	0.0181 (18)	0.0148 (17)	0.0019 (14)	−0.0060 (13)	−0.0002 (14)
C9	0.0111 (15)	0.0218 (18)	0.0139 (16)	0.0004 (13)	0.0028 (12)	−0.0018 (13)
C10	0.0123 (14)	0.014 (2)	0.0145 (14)	−0.0020 (15)	−0.0004 (11)	−0.0002 (14)
C11	0.0130 (15)	0.029 (2)	0.0148 (15)	−0.0016 (14)	−0.0026 (12)	0.0016 (14)
C12	0.0090 (16)	0.0261 (19)	0.0185 (17)	−0.0015 (14)	0.0011 (13)	−0.0065 (14)
C13	0.0176 (15)	0.0177 (17)	0.0152 (14)	−0.0017 (19)	0.0037 (11)	−0.0018 (18)
C14	0.0130 (15)	0.014 (2)	0.0159 (15)	−0.0009 (14)	0.0032 (12)	0.0025 (14)
C15	0.0182 (17)	0.0133 (16)	0.0111 (16)	0.0031 (13)	−0.0010 (13)	−0.0029 (13)
C16	0.0161 (16)	0.0104 (15)	0.0084 (15)	0.0018 (13)	0.0003 (12)	−0.0021 (12)
C17	0.0119 (16)	0.0166 (18)	0.0155 (17)	0.0010 (13)	0.0045 (13)	0.0006 (14)
C18	0.0198 (18)	0.0188 (18)	0.0072 (15)	0.0014 (14)	0.0009 (13)	0.0029 (13)
C19	0.0176 (15)	0.013 (2)	0.0136 (14)	0.0049 (14)	−0.0041 (12)	−0.0014 (14)
C20	0.0106 (13)	0.0156 (14)	0.0156 (13)	−0.004 (2)	−0.0002 (10)	0.002 (2)
C21	0.0144 (14)	0.0167 (16)	0.0103 (13)	−0.0015 (19)	0.0045 (10)	0.0022 (18)
O8	0.0384 (14)	0.0154 (13)	0.0172 (13)	−0.0044 (11)	0.0052 (11)	−0.0017 (11)
C22	0.0192 (18)	0.0199 (19)	0.0164 (18)	0.0015 (15)	−0.0031 (14)	−0.0034 (15)
C23	0.0161 (18)	0.037 (2)	0.031 (2)	0.0019 (16)	−0.0027 (15)	−0.0014 (18)

Br1—C19	1.893 (3)	C9—C10	1.385 (3)
O1—C6	1.429 (3)	C9—H9	0.9500
O1—C2	1.456 (3)	C10—C11	1.400 (3)
O2—C1	1.415 (3)	C10—C13	1.468 (3)
O2—H2	0.8400	C11—C12	1.394 (4)
O3—C3	1.433 (3)	C11—H11	0.9500
O3—H3	0.8400	C12—H12	0.9500
O4—C4	1.421 (3)	C13—C14	1.323 (3)
O4—H4	0.8400	C13—H13	0.9500
O5—C5	1.417 (3)	C14—C15	1.485 (4)
O5—H5	0.8400	C14—H14	0.9500
O6—C7	1.387 (3)	C15—C16	1.487 (3)
O6—C6	1.411 (3)	C16—C21	1.391 (3)
O7—C15	1.241 (3)	C16—C17	1.413 (4)
C1—C2	1.511 (4)	C17—C18	1.371 (4)
C1—H1A	0.9900	C17—H17	0.9500
C1—H1B	0.9900	C18—C19	1.382 (3)
C2—C3	1.535 (4)	C18—H18	0.9500
C2—H2A	1.0000	C19—C20	1.378 (3)
C3—C4	1.511 (4)	C20—C21	1.392 (3)
C3—H3A	1.0000	C20—H20	0.9500
C4—C5	1.524 (4)	C21—H21	0.9500
C4—H4A	1.0000	O8—C22	1.429 (3)
C5—C6	1.526 (3)	O8—H8A	0.8400
C5—H5A	1.0000	C22—C23	1.523 (4)
C6—H6	1.0000	C22—H22A	0.9900
C7—C12	1.384 (4)	C22—H22B	0.9900
C7—C8	1.385 (4)	C23—H23A	0.9800
C8—C9	1.387 (4)	C23—H23B	0.9800
C8—H8	0.9500	C23—H23C	0.9800
C6—O1—C2	114.0 (2)	C8—C9—H9	119.0
C1—O2—H2	109.5	C9—C10—C11	118.2 (3)
C3—O3—H3	109.5	C9—C10—C13	118.0 (2)
C4—O4—H4	109.5	C11—C10—C13	123.8 (2)
C5—O5—H5	109.5	C12—C11—C10	120.4 (3)
C7—O6—C6	116.9 (2)	C12—C11—H11	119.8
O2—C1—C2	112.1 (2)	C10—C11—H11	119.8
O2—C1—H1A	109.2	C7—C12—C11	120.0 (3)
C2—C1—H1A	109.2	C7—C12—H12	120.0
O2—C1—H1B	109.2	C11—C12—H12	120.0
C2—C1—H1B	109.2	C14—C13—C10	129.2 (2)
H1A—C1—H1B	107.9	C14—C13—H13	115.4
O1—C2—C1	106.8 (2)	C10—C13—H13	115.4
O1—C2—C3	109.3 (2)	C13—C14—C15	118.5 (2)
C1—C2—C3	113.5 (3)	C13—C14—H14	120.8
O1—C2—H2A	109.0	C15—C14—H14	120.8
C1—C2—H2A	109.0	O7—C15—C14	120.6 (2)
C3—C2—H2A	109.0	O7—C15—C16	119.2 (3)
O3—C3—C4	111.4 (2)	C14—C15—C16	120.2 (2)
O3—C3—C2	108.7 (2)	C21—C16—C17	118.6 (2)
C4—C3—C2	109.8 (2)	C21—C16—C15	123.4 (2)
O3—C3—H3A	109.0	C17—C16—C15	118.0 (2)
C4—C3—H3A	109.0	C18—C17—C16	120.6 (3)
C2—C3—H3A	109.0	C18—C17—H17	119.7
O4—C4—C3	107.7 (2)	C16—C17—H17	119.7
O4—C4—C5	110.8 (2)	C17—C18—C19	119.5 (3)
C3—C4—C5	109.9 (2)	C17—C18—H18	120.2
O4—C4—H4A	109.5	C19—C18—H18	120.2
C3—C4—H4A	109.5	C20—C19—C18	121.5 (2)
C5—C4—H4A	109.5	C20—C19—Br1	119.5 (2)
O5—C5—C4	113.6 (2)	C18—C19—Br1	119.0 (2)
O5—C5—C6	112.8 (2)	C19—C20—C21	119.1 (2)
C4—C5—C6	106.9 (2)	C19—C20—H20	120.4
O5—C5—H5A	107.8	C21—C20—H20	120.4
C4—C5—H5A	107.8	C16—C21—C20	120.6 (2)
C6—C5—H5A	107.8	C16—C21—H21	119.7
O6—C6—O1	106.3 (2)	C20—C21—H21	119.7
O6—C6—C5	108.9 (2)	C22—O8—H8A	109.5
O1—C6—C5	109.8 (2)	O8—C22—C23	111.9 (2)
O6—C6—H6	110.6	O8—C22—H22A	109.2
O1—C6—H6	110.6	C23—C22—H22A	109.2
C5—C6—H6	110.6	O8—C22—H22B	109.2
C12—C7—C8	120.5 (3)	C23—C22—H22B	109.2
C12—C7—O6	115.1 (2)	H22A—C22—H22B	107.9
C8—C7—O6	124.4 (3)	C22—C23—H23A	109.5
C7—C8—C9	118.9 (3)	C22—C23—H23B	109.5
C7—C8—H8	120.5	H23A—C23—H23B	109.5
C9—C8—H8	120.5	C22—C23—H23C	109.5
C10—C9—C8	122.1 (3)	H23A—C23—H23C	109.5
C10—C9—H9	119.0	H23B—C23—H23C	109.5
C6—O1—C2—C1	−179.3 (2)	C7—C8—C9—C10	−0.4 (5)
C6—O1—C2—C3	57.5 (3)	C8—C9—C10—C11	−0.7 (5)
O2—C1—C2—O1	−59.0 (3)	C8—C9—C10—C13	177.9 (3)
O2—C1—C2—C3	61.6 (3)	C9—C10—C11—C12	1.3 (5)
O1—C2—C3—O3	−176.5 (2)	C13—C10—C11—C12	−177.2 (3)
C1—C2—C3—O3	64.4 (3)	C8—C7—C12—C11	−0.3 (4)
O1—C2—C3—C4	−54.5 (3)	O6—C7—C12—C11	−179.5 (3)
C1—C2—C3—C4	−173.6 (2)	C10—C11—C12—C7	−0.8 (5)
O3—C3—C4—O4	57.7 (3)	C9—C10—C13—C14	−174.7 (4)
C2—C3—C4—O4	−62.7 (3)	C11—C10—C13—C14	3.8 (6)
O3—C3—C4—C5	178.6 (2)	C10—C13—C14—C15	176.7 (3)
C2—C3—C4—C5	58.1 (3)	C13—C14—C15—O7	9.0 (4)
O4—C4—C5—O5	−66.2 (3)	C13—C14—C15—C16	−169.0 (3)
C3—C4—C5—O5	174.9 (2)	O7—C15—C16—C21	−172.2 (3)
O4—C4—C5—C6	58.8 (3)	C14—C15—C16—C21	5.7 (4)
C3—C4—C5—C6	−60.1 (3)	O7—C15—C16—C17	6.2 (4)
C7—O6—C6—O1	−76.7 (3)	C14—C15—C16—C17	−175.8 (3)
C7—O6—C6—C5	165.1 (2)	C21—C16—C17—C18	3.1 (4)
C2—O1—C6—O6	−179.19 (19)	C15—C16—C17—C18	−175.5 (3)
C2—O1—C6—C5	−61.5 (3)	C16—C17—C18—C19	0.0 (4)
O5—C5—C6—O6	−57.9 (3)	C17—C18—C19—C20	−2.3 (5)
C4—C5—C6—O6	176.6 (2)	C17—C18—C19—Br1	175.7 (2)
O5—C5—C6—O1	−173.9 (2)	C18—C19—C20—C21	1.5 (5)
C4—C5—C6—O1	60.6 (3)	Br1—C19—C20—C21	−176.5 (3)
C6—O6—C7—C12	−176.9 (3)	C17—C16—C21—C20	−3.9 (5)
C6—O6—C7—C8	3.9 (4)	C15—C16—C21—C20	174.6 (3)
C12—C7—C8—C9	0.9 (4)	C19—C20—C21—C16	1.6 (6)
O6—C7—C8—C9	−179.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3i	0.84	1.97	2.783 (3)	164
O3—H3···O7ii	0.84	2.05	2.702 (3)	134
O3—H3···O4	0.84	2.38	2.786 (3)	110
O4—H4···O2iii	0.84	1.85	2.677 (3)	166
O5—H5···O8iv	0.84	1.91	2.678 (3)	152
O8—H8A···O1iv	0.84	2.08	2.893 (3)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3i	0.84	1.97	2.783 (3)	164
O3—H3⋯O7ii	0.84	2.05	2.702 (3)	134
O3—H3⋯O4	0.84	2.38	2.786 (3)	110
O4—H4⋯O2iii	0.84	1.85	2.677 (3)	166
O5—H5⋯O8iv	0.84	1.91	2.678 (3)	152
O8—H8A⋯O1iv	0.84	2.08	2.893 (3)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .