organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

7-(Hy­droxy­meth­yl)-2-(1-hydr­­oxy-1-methyl­ethyl)-4-meth­­oxy-2,3-di­hydro-5H-furo[3,2-g]chromen-5-one methanol hemisolvate

aChemical Engineering and Pharmaceutics College, Henan University of Science and Technology, Luoyang 471003, People's Republic of China
*Correspondence e-mail: liudeng20022002@yahoo.com.cn

(Received 23 November 2007; accepted 27 November 2007; online 6 December 2007)

The title compound (cimifugin), C16H18O6·0.5CH3OH, was isolated from the rhizome of Actaea asiatica Hara. The asymmetric unit contains two independent mol­ecules and a solvent methanol mol­ecule. The five-numbered ring adopts an envelope conformation in each molecule. Intra- and inter­molecular O—H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For related literature, see: Kusano et al. (1998[Kusano, A., Takahira, M., Shibano, M., Miyase, T., Okuyama, T. & Kusano, G. (1998). Heterocycles, 48, 1003-1013.], 1999[Kusano, A., Takahira, M., Shibano, M., Miyase, T. & Kusano, G. (1999). Chem. Pharm. Bull. 47, 511-516.]); Wan (1990[Wan, D. R. (1990). J. Chin. Med. Mater. 13, 3-15.]).

[Scheme 1]

Experimental

Crystal data
  • C16H18O6·0.5CH4O

  • Mr = 322.33

  • Monoclinic, P 21

  • a = 9.4092 (14) Å

  • b = 13.4176 (19) Å

  • c = 12.6903 (18) Å

  • β = 91.600 (2)°

  • V = 1601.5 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 294 (2) K

  • 0.30 × 0.28 × 0.24 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1997[Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.956, Tmax = 0.976

  • 9210 measured reflections

  • 3408 independent reflections

  • 2556 reflections with I > 2σ(I)

  • Rint = 0.027

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.108

  • S = 1.03

  • 3408 reflections

  • 437 parameters

  • 12 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O12—H12⋯O9i 0.85 (3) 2.41 (4) 2.934 (3) 120 (4)
O12—H12⋯O11i 0.85 (3) 1.99 (3) 2.812 (3) 162 (5)
O6—H6⋯O13ii 0.85 (3) 1.80 (3) 2.618 (5) 159 (6)
O13—H13⋯O11 0.96 (3) 1.83 (4) 2.708 (4) 150 (6)
O7—H7⋯O6 0.87 (3) 1.92 (3) 2.779 (4) 169 (5)
O1—H1⋯O12 0.85 (3) 1.98 (3) 2.809 (4) 164 (5)
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+1]; (ii) x, y, z+1.

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97and SHELXL97. University of Göttingen, Germany.]); molecular graphics: SHELXTL (Bruker, 1997[Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Actaea asiatica Hara (Ranunculaceae) is widely distributed in the southwest and northwest of the People's Republic of China. As a Chinesa folk medicine, its rhizome is used to treat headache, sore throat, measles, pertussis, prolapse of uterus (Wan, 1990). Previous phytochemical investigations have reported in the isolation of cimiaceroside A and 26-deoxycimicifugoside from this plant (Kusano et al., 1998, 1999). To investigate the bioactive natural products from A. asiatica, chemical studies of the rhizome of the plant were undertaken by screening using immunopotent tests in vitro, we obtained a compund, viz. cimifugin, from the petroleum ether extract. The structure of cimifugin was elucidated by extensive spectroscopic analysis, including two-dimensional NMR spectroscopy, and established unequivocally by single-crystal X-ray diffraction analysis.

The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The asymmetric unit of (I) contains two independent molecules and a methanol of solvation. The molecule is composed of a fused five-numbered ring and two fused six-numbered viz. A(C1–C3/C11/O2), B(C3–C5/C9–C11) and C(C5–C9/O4). In the two molecules, two fused six-numbered (B and C) are almost planar with the r.m.s. deviations of 0.0129 (4) and 1.0103 (4) Å, respectively, while ring C does not deviate form the chromone plane. The O5—C6—C5 and C7—C6—C5 angles are 123.3 (4)° and 115.8 (3)°, respectively, which indicates that carbonyl C6 atom slightly deviates from the ideal value of 120°. The similar deviation is also observed for the C22 with the angles of O11—C22—C21 [124.4 (3)°] and C23—C22—C21 [115.2 (3)°].

The hydroxy groups are attached at atoms C12, C16, C28 and C32. The methoxy group located at atoms C4 and C20. The interactions of intermolecular and intramolecular hydrogen bonds are formed between the hydroxy and carbonyl groups, which stablize the crystal structure.

Related literature top

For related literature, see: Kusano et al. (1998, 1999); Wan (1990).

Experimental top

The rhizomes of Phlomis umbrosa turcz was collected in Jianshi county, Hubei province, China, January 2006. The plants were identified as Actaea asiatica Hara by Professor Ding-rong Wan, College of Life Science, South-Central University for Nationalities. A voucher specimen (No. D20050115) was deposited in the laboratory of Natural products, Tinjing Medical University. The rhizomes of Actaea asiatica Hara was dried at room temperature in the dark. The material (4.3 kg) was extracted three times with 95% ethanol under reflux. The 95% ethanol extract (500 g) was suspended in water, and then extracted with petroleum ether, ethyl acetate and n-butanol successively. The ethyl acetate layer (80 g) was absorbed on to silica gel (150 g) and chromatographed on a silica gel (1000 g) column eluted with petroleum ether–EtOAc with the increased polarity to give 25 fractions. Fraction 8 was further separated on Toyopear HW-40, pre. HPLC-ODS to afford 200 mg of cimifugin. 13C NMR (300 MHz, CD3OD, p.p.m.): 92.7, 28.8, 118.4, 167.1, 112.3, 179.7, 109.3, 168.7, 157.0, 94.5, 161.1, 72.3, 25.4, 25.5, 61.0, 61.2. Crystals suitable for X-ray structure analysis were obtained by slow evaporation from methanol at room temperature.

Refinement top

H atoms of the hydroxy group were located in a difference density map and the atomic coordinates allowed to refine freely. Other H atoms were positioned geometrically and refined as riding with C—H = 0.95–0.98 Å). For the CH and CH2 groups, Uiso(H) values are set equal to 1.2Ueq(carrier atom) and for the methyl groups they are set equal to 1.5Ueq(carrier atom). The absolute configuration could not be established because of the absence of significant anomalous effects. Friedel pairs were merged for the final cycles of refinement.

Structure description top

Actaea asiatica Hara (Ranunculaceae) is widely distributed in the southwest and northwest of the People's Republic of China. As a Chinesa folk medicine, its rhizome is used to treat headache, sore throat, measles, pertussis, prolapse of uterus (Wan, 1990). Previous phytochemical investigations have reported in the isolation of cimiaceroside A and 26-deoxycimicifugoside from this plant (Kusano et al., 1998, 1999). To investigate the bioactive natural products from A. asiatica, chemical studies of the rhizome of the plant were undertaken by screening using immunopotent tests in vitro, we obtained a compund, viz. cimifugin, from the petroleum ether extract. The structure of cimifugin was elucidated by extensive spectroscopic analysis, including two-dimensional NMR spectroscopy, and established unequivocally by single-crystal X-ray diffraction analysis.

The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The asymmetric unit of (I) contains two independent molecules and a methanol of solvation. The molecule is composed of a fused five-numbered ring and two fused six-numbered viz. A(C1–C3/C11/O2), B(C3–C5/C9–C11) and C(C5–C9/O4). In the two molecules, two fused six-numbered (B and C) are almost planar with the r.m.s. deviations of 0.0129 (4) and 1.0103 (4) Å, respectively, while ring C does not deviate form the chromone plane. The O5—C6—C5 and C7—C6—C5 angles are 123.3 (4)° and 115.8 (3)°, respectively, which indicates that carbonyl C6 atom slightly deviates from the ideal value of 120°. The similar deviation is also observed for the C22 with the angles of O11—C22—C21 [124.4 (3)°] and C23—C22—C21 [115.2 (3)°].

The hydroxy groups are attached at atoms C12, C16, C28 and C32. The methoxy group located at atoms C4 and C20. The interactions of intermolecular and intramolecular hydrogen bonds are formed between the hydroxy and carbonyl groups, which stablize the crystal structure.

For related literature, see: Kusano et al. (1998, 1999); Wan (1990).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms have been omitted for clarity.
7-(Hydroxymethyl)-2-(1-hydroxy-1-methylethyl)-4-methoxy-2,3-dihydro-5H- furo[3,2-g]chromen-5-one methanol hemisolvate top
Crystal data top
C16H18O6·0.5CH4OF(000) = 684
Mr = 322.33Dx = 1.337 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3898 reflections
a = 9.4092 (14) Åθ = 2.6–25.4°
b = 13.4176 (19) ŵ = 0.10 mm1
c = 12.6903 (18) ÅT = 294 K
β = 91.600 (2)°Plate, colourless
V = 1601.5 (4) Å30.30 × 0.28 × 0.24 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3408 independent reflections
Radiation source: fine-focus sealed tube2556 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
φ and ω scansθmax = 26.4°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1111
Tmin = 0.956, Tmax = 0.976k = 169
9210 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0592P)2 + 0.2147P]
where P = (Fo2 + 2Fc2)/3
3408 reflections(Δ/σ)max = 0.003
437 parametersΔρmax = 0.17 e Å3
12 restraintsΔρmin = 0.21 e Å3
Crystal data top
C16H18O6·0.5CH4OV = 1601.5 (4) Å3
Mr = 322.33Z = 4
Monoclinic, P21Mo Kα radiation
a = 9.4092 (14) ŵ = 0.10 mm1
b = 13.4176 (19) ÅT = 294 K
c = 12.6903 (18) Å0.30 × 0.28 × 0.24 mm
β = 91.600 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3408 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
2556 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.976Rint = 0.027
9210 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03912 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.17 e Å3
3408 reflectionsΔρmin = 0.21 e Å3
437 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.8781 (3)0.6603 (2)0.4785 (2)0.0674 (7)
H10.820 (5)0.621 (3)0.508 (4)0.101*
O20.9188 (3)0.65092 (18)0.70280 (17)0.0545 (6)
O30.7862 (3)0.97796 (18)0.7545 (2)0.0663 (7)
O40.6245 (3)0.71772 (16)0.98859 (17)0.0499 (6)
O50.6128 (4)1.0136 (2)0.9273 (3)0.1017 (12)
O60.4013 (3)0.7906 (2)1.1992 (2)0.0779 (9)
H60.475 (4)0.799 (5)1.239 (4)0.117*
O70.1990 (3)0.9270 (2)1.1264 (2)0.0634 (7)
H70.254 (5)0.878 (3)1.147 (4)0.095*
O80.1715 (3)0.7605 (2)0.98115 (17)0.0566 (6)
O90.3011 (3)0.93880 (18)0.67958 (17)0.0550 (6)
O100.4679 (2)0.60625 (15)0.73882 (16)0.0445 (5)
O110.4630 (3)0.84518 (19)0.54207 (17)0.0570 (6)
O120.6907 (3)0.5091 (2)0.53907 (19)0.0619 (7)
H120.642 (5)0.467 (3)0.502 (3)0.093*
C11.0036 (4)0.7143 (3)0.6349 (3)0.0518 (8)
H1A1.09940.72000.66680.062*
C20.9341 (4)0.8170 (3)0.6371 (3)0.0553 (9)
H2A1.00470.86940.64350.066*
H2B0.87520.82840.57430.066*
C30.8461 (4)0.8111 (3)0.7335 (3)0.0463 (8)
C40.7736 (4)0.8812 (2)0.7866 (3)0.0468 (8)
C50.6943 (3)0.8538 (2)0.8758 (3)0.0445 (7)
C60.6171 (4)0.9232 (3)0.9427 (3)0.0554 (9)
C70.5464 (4)0.8794 (3)1.0296 (3)0.0541 (9)
H7A0.49590.92041.07430.065*
C80.5506 (4)0.7821 (3)1.0485 (3)0.0505 (8)
C90.6955 (3)0.7524 (2)0.9032 (2)0.0430 (7)
C100.7682 (4)0.6792 (2)0.8496 (3)0.0460 (8)
H100.76620.61260.86960.055*
C110.8426 (4)0.7116 (2)0.7658 (2)0.0447 (8)
C121.0158 (4)0.6656 (3)0.5284 (3)0.0581 (9)
C131.0790 (6)0.5624 (4)0.5394 (4)0.0854 (14)
H13A1.01470.52030.57650.128*
H13B1.16800.56620.57810.128*
H13C1.09430.53510.47070.128*
C141.1047 (5)0.7311 (4)0.4586 (3)0.0798 (13)
H14A1.11280.70030.39080.120*
H14B1.19760.73950.49040.120*
H14C1.05980.79500.45040.120*
C150.6701 (5)1.0182 (4)0.6989 (4)0.0815 (13)
H15A0.66730.99230.62840.122*
H15B0.67891.08940.69670.122*
H15C0.58411.00050.73330.122*
C160.4762 (5)0.7266 (3)1.1319 (3)0.0698 (11)
H16A0.41000.67981.09900.084*
H16B0.54530.68861.17340.084*
C170.0789 (4)0.8478 (3)0.9780 (3)0.0529 (8)
H170.01560.82720.95180.063*
C180.1425 (4)0.9172 (3)0.8981 (3)0.0535 (9)
H18A0.06910.94760.85360.064*
H18B0.19840.96920.93250.064*
C190.2351 (3)0.8488 (2)0.8353 (2)0.0414 (7)
C200.3053 (3)0.8572 (2)0.7426 (2)0.0409 (7)
C210.3860 (3)0.7750 (2)0.7045 (2)0.0373 (6)
C220.4621 (3)0.7746 (3)0.6053 (2)0.0420 (7)
C230.5373 (4)0.6851 (3)0.5837 (2)0.0459 (8)
H230.58690.68130.52140.055*
C240.5404 (3)0.6068 (2)0.6479 (2)0.0425 (7)
C250.3925 (3)0.6894 (2)0.7668 (2)0.0388 (7)
C260.3224 (4)0.6792 (3)0.8611 (2)0.0453 (8)
H260.32720.62120.90100.054*
C270.2462 (3)0.7599 (3)0.8910 (2)0.0452 (8)
C280.0656 (4)0.8878 (3)1.0900 (3)0.0597 (10)
C290.0371 (4)0.9744 (4)1.0879 (4)0.0836 (15)
H29A0.03741.00531.15610.125*
H29B0.13090.95081.06970.125*
H29C0.00831.02231.03640.125*
C300.0158 (6)0.8050 (4)1.1621 (3)0.0948 (17)
H30A0.08480.75231.16400.142*
H30B0.07380.77951.13580.142*
H30C0.00480.83091.23190.142*
C310.2736 (5)1.0340 (3)0.7232 (3)0.0749 (12)
H31A0.17291.04290.72920.112*
H31B0.31051.08480.67820.112*
H31C0.31881.03880.79180.112*
C320.6206 (4)0.5121 (3)0.6356 (3)0.0550 (9)
H32A0.69000.50560.69320.066*
H32B0.55540.45630.63920.066*
O130.5854 (4)0.7999 (3)0.3575 (2)0.0998 (12)
H130.569 (7)0.802 (6)0.432 (2)0.150*
C330.7073 (6)0.8399 (6)0.3440 (5)0.125 (2)
H33A0.73790.87370.40730.187*
H33B0.70040.88680.28700.187*
H33C0.77500.78910.32740.187*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0728 (18)0.077 (2)0.0523 (14)0.0222 (15)0.0001 (12)0.0111 (13)
O20.0746 (16)0.0410 (13)0.0481 (12)0.0016 (12)0.0068 (11)0.0057 (11)
O30.0728 (17)0.0358 (13)0.0905 (19)0.0054 (13)0.0057 (14)0.0072 (13)
O40.0659 (15)0.0334 (11)0.0506 (12)0.0051 (11)0.0029 (11)0.0036 (10)
O50.178 (4)0.0319 (15)0.098 (2)0.0235 (19)0.049 (2)0.0063 (15)
O60.105 (2)0.0615 (19)0.0684 (18)0.0135 (18)0.0215 (16)0.0086 (15)
O70.0598 (16)0.0650 (17)0.0650 (15)0.0035 (13)0.0056 (12)0.0216 (13)
O80.0731 (15)0.0553 (14)0.0425 (12)0.0063 (13)0.0191 (11)0.0037 (11)
O90.0782 (16)0.0441 (13)0.0431 (12)0.0104 (12)0.0091 (11)0.0063 (10)
O100.0612 (14)0.0357 (12)0.0371 (11)0.0021 (10)0.0088 (10)0.0013 (9)
O110.0722 (16)0.0570 (15)0.0426 (12)0.0135 (13)0.0156 (11)0.0146 (11)
O120.0786 (18)0.0524 (15)0.0559 (15)0.0120 (13)0.0216 (12)0.0181 (12)
C10.053 (2)0.049 (2)0.0533 (19)0.0027 (16)0.0018 (16)0.0045 (16)
C20.064 (2)0.048 (2)0.054 (2)0.0061 (18)0.0000 (17)0.0041 (16)
C30.0536 (19)0.0385 (17)0.0464 (17)0.0031 (15)0.0063 (15)0.0035 (14)
C40.0505 (18)0.0314 (17)0.0579 (19)0.0038 (14)0.0081 (16)0.0023 (14)
C50.0491 (18)0.0315 (16)0.0524 (18)0.0021 (14)0.0073 (15)0.0053 (14)
C60.074 (2)0.0324 (19)0.059 (2)0.0060 (17)0.0028 (18)0.0057 (16)
C70.065 (2)0.0394 (19)0.058 (2)0.0078 (16)0.0020 (17)0.0101 (16)
C80.063 (2)0.0402 (19)0.0480 (17)0.0059 (16)0.0013 (16)0.0070 (15)
C90.0505 (18)0.0342 (17)0.0438 (16)0.0018 (14)0.0078 (14)0.0030 (14)
C100.060 (2)0.0303 (15)0.0475 (17)0.0044 (15)0.0068 (15)0.0023 (14)
C110.055 (2)0.0351 (16)0.0434 (17)0.0049 (15)0.0076 (14)0.0068 (14)
C120.058 (2)0.060 (2)0.057 (2)0.0059 (19)0.0067 (17)0.0110 (18)
C130.103 (4)0.069 (3)0.085 (3)0.012 (3)0.021 (3)0.018 (3)
C140.071 (3)0.095 (4)0.073 (3)0.013 (3)0.016 (2)0.009 (3)
C150.087 (3)0.061 (3)0.097 (3)0.012 (2)0.018 (3)0.025 (2)
C160.108 (3)0.048 (2)0.054 (2)0.007 (2)0.016 (2)0.0045 (18)
C170.0483 (19)0.060 (2)0.0508 (18)0.0060 (17)0.0090 (15)0.0129 (17)
C180.058 (2)0.051 (2)0.0510 (19)0.0027 (17)0.0047 (16)0.0082 (16)
C190.0442 (17)0.0448 (18)0.0354 (15)0.0032 (14)0.0028 (13)0.0050 (14)
C200.0435 (17)0.0416 (17)0.0372 (15)0.0011 (14)0.0026 (13)0.0022 (13)
C210.0388 (15)0.0413 (17)0.0317 (13)0.0056 (13)0.0012 (11)0.0013 (13)
C220.0420 (17)0.0484 (19)0.0354 (15)0.0031 (15)0.0013 (13)0.0025 (14)
C230.0535 (19)0.0487 (19)0.0360 (15)0.0007 (16)0.0089 (14)0.0018 (14)
C240.0480 (18)0.0421 (17)0.0375 (16)0.0053 (15)0.0034 (13)0.0057 (14)
C250.0430 (17)0.0380 (17)0.0354 (15)0.0053 (14)0.0010 (13)0.0059 (13)
C260.060 (2)0.0402 (17)0.0364 (15)0.0103 (16)0.0064 (14)0.0016 (13)
C270.0515 (19)0.0509 (19)0.0335 (15)0.0111 (16)0.0074 (13)0.0092 (15)
C280.054 (2)0.077 (3)0.0486 (18)0.0041 (19)0.0108 (16)0.0169 (19)
C290.065 (2)0.108 (4)0.078 (3)0.016 (3)0.008 (2)0.040 (3)
C300.110 (4)0.120 (5)0.056 (2)0.026 (3)0.033 (2)0.009 (3)
C310.117 (4)0.049 (2)0.059 (2)0.004 (2)0.006 (2)0.0002 (19)
C320.078 (2)0.0362 (17)0.0510 (19)0.0038 (17)0.0131 (17)0.0068 (15)
O130.126 (3)0.113 (3)0.0614 (18)0.022 (2)0.0245 (19)0.0038 (19)
C330.081 (3)0.163 (6)0.130 (4)0.015 (4)0.012 (3)0.014 (5)
Geometric parameters (Å, º) top
O1—C121.428 (5)C14—H14A0.9600
O1—H10.85 (3)C14—H14B0.9600
O2—C111.359 (4)C14—H14C0.9600
O2—C11.464 (4)C15—H15A0.9600
O3—C41.367 (4)C15—H15B0.9600
O3—C151.393 (5)C15—H15C0.9600
O4—C81.356 (4)C16—H16A0.9700
O4—C91.370 (4)C16—H16B0.9700
O5—C61.229 (4)C17—C181.512 (5)
O6—C161.415 (5)C17—C281.527 (5)
O6—H60.85 (3)C17—H170.9800
O7—C281.426 (5)C18—C191.509 (4)
O7—H70.87 (3)C18—H18A0.9700
O8—C271.359 (4)C18—H18B0.9700
O8—C171.459 (5)C19—C201.369 (4)
O9—C201.356 (4)C19—C271.389 (5)
O9—C311.419 (5)C20—C211.431 (4)
O10—C241.356 (4)C21—C251.395 (4)
O10—C251.375 (4)C21—C221.465 (4)
O11—C221.242 (4)C22—C231.424 (5)
O12—C321.409 (4)C23—C241.330 (4)
O12—H120.85 (3)C23—H230.9300
C1—C121.508 (5)C24—C321.488 (5)
C1—C21.526 (5)C25—C261.388 (4)
C1—H1A0.9800C26—C271.358 (5)
C2—C31.498 (5)C26—H260.9300
C2—H2A0.9700C28—C291.511 (6)
C2—H2B0.9700C28—C301.522 (6)
C3—C41.354 (5)C29—H29A0.9600
C3—C111.397 (5)C29—H29B0.9600
C4—C51.421 (5)C29—H29C0.9600
C5—C91.403 (4)C30—H30A0.9600
C5—C61.467 (5)C30—H30B0.9600
C6—C71.430 (5)C30—H30C0.9600
C7—C81.328 (5)C31—H31A0.9600
C7—H7A0.9300C31—H31B0.9600
C8—C161.485 (5)C31—H31C0.9600
C9—C101.386 (4)C32—H32A0.9700
C10—C111.361 (5)C32—H32B0.9700
C10—H100.9300O13—C331.283 (7)
C12—C131.512 (6)O13—H130.96 (3)
C12—C141.515 (6)C33—H33A0.9600
C13—H13A0.9600C33—H33B0.9600
C13—H13B0.9600C33—H33C0.9600
C13—H13C0.9600
C12—O1—H1115 (4)H16A—C16—H16B107.9
C11—O2—C1107.7 (3)O8—C17—C18105.4 (3)
C4—O3—C15116.4 (3)O8—C17—C28108.7 (3)
C8—O4—C9119.7 (3)C18—C17—C28116.8 (3)
C16—O6—H691 (4)O8—C17—H17108.5
C28—O7—H7109 (4)C18—C17—H17108.5
C27—O8—C17107.7 (3)C28—C17—H17108.5
C20—O9—C31119.9 (3)C19—C18—C17103.0 (3)
C24—O10—C25119.4 (2)C19—C18—H18A111.2
C32—O12—H12104 (3)C17—C18—H18A111.2
O2—C1—C12109.4 (3)C19—C18—H18B111.2
O2—C1—C2105.8 (3)C17—C18—H18B111.2
C12—C1—C2116.8 (3)H18A—C18—H18B109.1
O2—C1—H1A108.2C20—C19—C27118.5 (3)
C12—C1—H1A108.2C20—C19—C18134.7 (3)
C2—C1—H1A108.2C27—C19—C18106.8 (3)
C3—C2—C1102.4 (3)O9—C20—C19124.5 (3)
C3—C2—H2A111.3O9—C20—C21115.4 (2)
C1—C2—H2A111.3C19—C20—C21120.0 (3)
C3—C2—H2B111.3C25—C21—C20117.2 (2)
C1—C2—H2B111.3C25—C21—C22118.0 (3)
H2A—C2—H2B109.2C20—C21—C22124.8 (3)
C4—C3—C11120.1 (3)O11—C22—C23120.4 (3)
C4—C3—C2131.9 (3)O11—C22—C21124.4 (3)
C11—C3—C2107.9 (3)C23—C22—C21115.2 (3)
C3—C4—O3117.6 (3)C24—C23—C22123.4 (3)
C3—C4—C5120.0 (3)C24—C23—H23118.3
O3—C4—C5122.4 (3)C22—C23—H23118.3
C9—C5—C4116.6 (3)C23—C24—O10121.6 (3)
C9—C5—C6118.2 (3)C23—C24—C32127.8 (3)
C4—C5—C6125.2 (3)O10—C24—C32110.7 (3)
O5—C6—C7120.9 (4)O10—C25—C26113.8 (3)
O5—C6—C5123.3 (4)O10—C25—C21122.4 (2)
C7—C6—C5115.8 (3)C26—C25—C21123.7 (3)
C8—C7—C6122.1 (3)C27—C26—C25115.5 (3)
C8—C7—H7A119.0C27—C26—H26122.3
C6—C7—H7A119.0C25—C26—H26122.3
C7—C8—O4122.6 (3)C26—C27—O8122.0 (3)
C7—C8—C16127.6 (3)C26—C27—C19125.1 (3)
O4—C8—C16109.8 (3)O8—C27—C19112.9 (3)
O4—C9—C10113.9 (3)O7—C28—C29106.2 (3)
O4—C9—C5121.7 (3)O7—C28—C30110.9 (3)
C10—C9—C5124.4 (3)C29—C28—C30111.4 (4)
C11—C10—C9115.4 (3)O7—C28—C17109.7 (3)
C11—C10—H10122.3C29—C28—C17108.8 (3)
C9—C10—H10122.3C30—C28—C17109.7 (3)
O2—C11—C10124.1 (3)C28—C29—H29A109.5
O2—C11—C3112.5 (3)C28—C29—H29B109.5
C10—C11—C3123.4 (3)H29A—C29—H29B109.5
O1—C12—C1109.1 (3)C28—C29—H29C109.5
O1—C12—C13110.2 (4)H29A—C29—H29C109.5
C1—C12—C13110.7 (3)H29B—C29—H29C109.5
O1—C12—C14106.2 (3)C28—C30—H30A109.5
C1—C12—C14109.2 (3)C28—C30—H30B109.5
C13—C12—C14111.3 (4)H30A—C30—H30B109.5
C12—C13—H13A109.5C28—C30—H30C109.5
C12—C13—H13B109.5H30A—C30—H30C109.5
H13A—C13—H13B109.5H30B—C30—H30C109.5
C12—C13—H13C109.5O9—C31—H31A109.5
H13A—C13—H13C109.5O9—C31—H31B109.5
H13B—C13—H13C109.5H31A—C31—H31B109.5
C12—C14—H14A109.5O9—C31—H31C109.5
C12—C14—H14B109.5H31A—C31—H31C109.5
H14A—C14—H14B109.5H31B—C31—H31C109.5
C12—C14—H14C109.5O12—C32—C24111.5 (3)
H14A—C14—H14C109.5O12—C32—H32A109.3
H14B—C14—H14C109.5C24—C32—H32A109.3
O3—C15—H15A109.5O12—C32—H32B109.3
O3—C15—H15B109.5C24—C32—H32B109.3
H15A—C15—H15B109.5H32A—C32—H32B108.0
O3—C15—H15C109.5C33—O13—H13107 (4)
H15A—C15—H15C109.5O13—C33—H33A109.5
H15B—C15—H15C109.5O13—C33—H33B109.5
O6—C16—C8112.2 (3)H33A—C33—H33B109.5
O6—C16—H16A109.2O13—C33—H33C109.5
C8—C16—H16A109.2H33A—C33—H33C109.5
O6—C16—H16B109.2H33B—C33—H33C109.5
C8—C16—H16B109.2
C15—O3—C4—C3105.4 (4)C7—C8—C16—O63.9 (6)
C15—O3—C4—C578.1 (4)O4—C8—C16—O6177.9 (3)
C31—O9—C20—C1926.1 (5)C27—O8—C17—C1819.7 (3)
C31—O9—C20—C21156.1 (3)C27—O8—C17—C28145.7 (3)
C11—O2—C1—C12145.4 (3)O8—C17—C18—C1919.3 (3)
C11—O2—C1—C218.8 (3)C28—C17—C18—C19140.1 (3)
O2—C1—C2—C318.2 (3)C17—C18—C19—C20168.0 (3)
C12—C1—C2—C3140.2 (3)C17—C18—C19—C2712.7 (3)
C1—C2—C3—C4170.2 (4)C27—C19—C20—O9178.6 (3)
C1—C2—C3—C1111.7 (4)C18—C19—C20—O92.2 (6)
C11—C3—C4—O3177.0 (3)C27—C19—C20—C210.9 (4)
C2—C3—C4—O35.1 (6)C18—C19—C20—C21179.9 (3)
C11—C3—C4—C50.3 (5)O9—C20—C21—C25179.7 (3)
C2—C3—C4—C5178.2 (3)C19—C20—C21—C251.9 (4)
C3—C4—C5—C90.6 (4)O9—C20—C21—C220.4 (4)
O3—C4—C5—C9177.0 (3)C19—C20—C21—C22178.3 (3)
C3—C4—C5—C6177.0 (3)C25—C21—C22—O11178.8 (3)
O3—C4—C5—C60.5 (5)C20—C21—C22—O111.4 (5)
C9—C5—C6—O5178.0 (4)C25—C21—C22—C230.7 (4)
C4—C5—C6—O50.5 (6)C20—C21—C22—C23179.1 (3)
C9—C5—C6—C71.5 (5)O11—C22—C23—C24179.9 (3)
C4—C5—C6—C7178.9 (3)C21—C22—C23—C240.3 (5)
O5—C6—C7—C8179.3 (4)C22—C23—C24—O101.6 (5)
C5—C6—C7—C80.1 (5)C22—C23—C24—C32176.9 (3)
C6—C7—C8—O41.5 (6)C25—O10—C24—C231.8 (4)
C6—C7—C8—C16176.4 (4)C25—O10—C24—C32176.9 (3)
C9—O4—C8—C71.7 (5)C24—O10—C25—C26179.6 (3)
C9—O4—C8—C16176.6 (3)C24—O10—C25—C210.7 (4)
C8—O4—C9—C10179.2 (3)C20—C21—C25—O10179.3 (3)
C8—O4—C9—C50.2 (4)C22—C21—C25—O100.5 (4)
C4—C5—C9—O4179.1 (3)C20—C21—C25—C261.9 (4)
C6—C5—C9—O41.4 (5)C22—C21—C25—C26178.3 (3)
C4—C5—C9—C100.2 (5)O10—C25—C26—C27179.7 (3)
C6—C5—C9—C10177.5 (3)C21—C25—C26—C270.8 (4)
O4—C9—C10—C11178.5 (3)C25—C26—C27—O8179.7 (3)
C5—C9—C10—C110.5 (5)C25—C26—C27—C190.3 (5)
C1—O2—C11—C10169.7 (3)C17—O8—C27—C26167.8 (3)
C1—O2—C11—C311.7 (4)C17—O8—C27—C1912.1 (3)
C9—C10—C11—O2179.1 (3)C20—C19—C27—C260.2 (5)
C9—C10—C11—C30.7 (5)C18—C19—C27—C26179.2 (3)
C4—C3—C11—O2178.9 (3)C20—C19—C27—O8179.7 (3)
C2—C3—C11—O20.5 (4)C18—C19—C27—O80.9 (4)
C4—C3—C11—C100.3 (5)O8—C17—C28—O767.5 (4)
C2—C3—C11—C10178.0 (3)C18—C17—C28—O751.5 (4)
O2—C1—C12—O164.8 (4)O8—C17—C28—C29176.7 (3)
C2—C1—C12—O155.4 (4)C18—C17—C28—C2964.3 (4)
O2—C1—C12—C1356.6 (4)O8—C17—C28—C3054.6 (4)
C2—C1—C12—C13176.8 (4)C18—C17—C28—C30173.6 (4)
O2—C1—C12—C14179.6 (3)C23—C24—C32—O124.5 (5)
C2—C1—C12—C1460.3 (4)O10—C24—C32—O12176.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O9i0.85 (3)2.41 (4)2.934 (3)120 (4)
O12—H12···O11i0.85 (3)1.99 (3)2.812 (3)162 (5)
O6—H6···O13ii0.85 (3)1.80 (3)2.618 (5)159 (6)
O13—H13···O110.96 (3)1.83 (4)2.708 (4)150 (6)
O7—H7···O60.87 (3)1.92 (3)2.779 (4)169 (5)
O1—H1···O120.85 (3)1.98 (3)2.809 (4)164 (5)
Symmetry codes: (i) x+1, y1/2, z+1; (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC16H18O6·0.5CH4O
Mr322.33
Crystal system, space groupMonoclinic, P21
Temperature (K)294
a, b, c (Å)9.4092 (14), 13.4176 (19), 12.6903 (18)
β (°) 91.600 (2)
V3)1601.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.28 × 0.24
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.956, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
9210, 3408, 2556
Rint0.027
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.108, 1.03
No. of reflections3408
No. of parameters437
No. of restraints12
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.21

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Selected torsion angles (º) top
C15—O3—C4—C3105.4 (4)C31—O9—C20—C1926.1 (5)
C15—O3—C4—C578.1 (4)C31—O9—C20—C21156.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O9i0.85 (3)2.41 (4)2.934 (3)120 (4)
O12—H12···O11i0.85 (3)1.99 (3)2.812 (3)162 (5)
O6—H6···O13ii0.85 (3)1.80 (3)2.618 (5)159 (6)
O13—H13···O110.96 (3)1.83 (4)2.708 (4)150 (6)
O7—H7···O60.87 (3)1.92 (3)2.779 (4)169 (5)
O1—H1···O120.85 (3)1.98 (3)2.809 (4)164 (5)
Symmetry codes: (i) x+1, y1/2, z+1; (ii) x, y, z+1.
 

Acknowledgements

This work was supported by the fund of the SRTP of Henan University of Science and Technology.

References

First citationBruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationKusano, A., Takahira, M., Shibano, M., Miyase, T. & Kusano, G. (1999). Chem. Pharm. Bull. 47, 511–516.  CrossRef CAS Google Scholar
First citationKusano, A., Takahira, M., Shibano, M., Miyase, T., Okuyama, T. & Kusano, G. (1998). Heterocycles, 48, 1003–1013.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationWan, D. R. (1990). J. Chin. Med. Mater. 13, 3–15.  Google Scholar

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