PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): m1569–m1570.
Published online 2008 November 20. doi:  10.1107/S1600536808037586
PMCID: PMC2959999

Hexaaqua­(5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate

Abstract

In the title compound, [Ca(C15H9O7S)(H2O)6](C15H9O7S)·3H2O, the Ca centre has a distorted deca­hedral geometry, coordinated by six O atoms from water mol­ecules and one sulfonate O atom. The crystal structure is stabilized by aromatic π–π inter­actions, with centroid–centroid distances of 3.765 (5) and 3.896 (5) Å between the phenyl ring and the benzene ring of the chromene unit of neighbouring mol­ecules. In addition, the stacked mol­ecules exhibit inter- and intra­molecular O—H(...)O hydrogen bonds, including the uncoordinated water mol­ecules.

Related literature

For biological activity, see: Chan et al. (2000 [triangle]); Hiroyuki et al. (1996 [triangle]); Jiang et al. (2001 [triangle]); Lee et al. (1999 [triangle]); Shin et al. (1999 [triangle]); Zanoli et al. (2000 [triangle]). For related structures, see: Cote & Shimizu (2003 [triangle]); Li & Zhang (2008 [triangle]); Morin et al. (2000 [triangle]); Pusz et al. (2001 [triangle]); Zhang et al. (2004 [triangle], 2006a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1569-scheme1.jpg

Experimental

Crystal data

  • [Ca(C15H9O7S)(H2O)6](C15H9O7S)·3H2O
  • M r = 868.79
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1569-efi1.jpg
  • a = 11.360 (2) Å
  • b = 12.390 (1) Å
  • c = 13.975 (2) Å
  • α = 95.136 (2)°
  • β = 102.167 (3)°
  • γ = 107.423 (2)°
  • V = 1809.9 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.38 mm−1
  • T = 296 (2) K
  • 0.36 × 0.23 × 0.14 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1999 [triangle]) T min = 0.874, T max = 0.947
  • 9179 measured reflections
  • 6299 independent reflections
  • 4416 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.167
  • S = 1.04
  • 6299 reflections
  • 558 parameters
  • 16 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: SMART (Bruker, 1999 [triangle]); cell refinement: SAINT-Plus (Bruker, 1999 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037586/lx2072sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037586/lx2072Isup2.hkl

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

Acknowledgments

Support from the Natural Science Foundation of Shaanxi Province (grant No. 2005B01) is gratefully acknowledged.

supplementary crystallographic information

Comment

Chrysin (5,7-dihydroxyflavone), a naturally wide distributed flavonoid, has many different biological activities such as anti-oxidant (Chan et al., 2000), anti-virus (Lee et al., 1999), anti-diabetogenic activity (Shin et al., 1999), anti-anxiolytic effect (Zanoli et al., 2000). Sulfonates belong to an important class of organic compounds, particularly flavonoidsulfonates have many different biological activities (Hiroyuki et al., 1996; Jiang et al., 2001). Previously, two chrysinsulfonate derivatives have been prepared. Zhang et al. (2004, 2006a, 2006b) have synthesized chrysin-6-sulfonate and its derivates, such as [Ba(C15H9O7S)2]n, [Zn(C15H8O7S)(DMSO)]2.H2O and [{Ca(C15H8O7S)(H2O)(DMSO)}3 {Ca(C15H8O7S)(DMSO)2}].4DMSO. Pusz et al. (2001) have reported chrysin-4'-sulfonate and its Ti4+, Mn2+ and Fe3+ complexes. On the other hand, the weak coordination nature of SO3- makes its coordination mode very flexible and sensitive to the chemical environment (Cote & Shimizu, 2003). Here we report the crystal structure of the title compound (Fig. 1).

As shown in Fig. 1, the Ca atom is seven-coordinated by the six O atoms from water molecules and the one sulfonate O atom. The Ca—O bond lengths are in agreement with the corresponding values in [Ca(C16H12O4)(H2O)6]. H2O (Morin et al., 2000). The flavone skeleton is essentially planar, the bond lengths and angles are similar to those reported for other flavonesulfonates, [Co(H2O)6](C16H11O7S)2.4H2O (Li & Zhang, 2008). The molecular packing (Fig. 2) is stabilized by two different aromatic π–π interactions within each stack of molecule; one between the phenyl ring (Cg1) and the benzene ring (Cg4ii) of the adjacent molecules {distance; 3.765 (5) Å}, and the other between the benzene ring (Cg2) and the phenyl ring (Cg3ii) of the neighbouring molecules {distance; 3.896 (5) Å} (Fig. 2; Cg1, Cg2, Cg3 and Cg4 are the centroids of the C1–C6 phenyl, the C10–C15 benzene, the C16–C21 phenyl and the C25–C30 benzene rings, respectively, symmetry code as in Fig. 2). Additionally, the crystal structure exhibits numerous inter- and intramolecular O—H···O hydrogen bonds (Fig. 1 & Hydrogen-bond geometry).

Experimental

5,7-Dihydroxyflavone (chrysin, 1.0 g, 3.9 mmol) was added slowly to concentrated sulfuric acid (6 ml) with stirring. The reaction was maintained at room temperature for 12 h. Then, it was poured into NaCl saturated aqueous solution (50 ml) and a yellow precipitate appeared. After 5 h, the precipitate was filtered and washed with NaCl saturated aqueous solution until the pH value of the filtrate was 7. It was dissolved in water (50 ml), and mixed with saturated CaCl2 solution (10 ml). (I) was obtained after 24 h. It was recrystallized from an ethanol-water (1:1 v/v) solution. Colorless sheet-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent for about 3 d at room temperature (yield 78%).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and O—H = 0.82 (phenolic) Å, Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O). H atoms of the water molecules were found in difference maps and positionally refined with constraints of Uiso(H) = 1.5Ueq(O). The reasonable position of H atoms in O22 were not obtained because of short inter distance with O19.

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. Hydrogen bonds are illustrated as dashed lines.
Fig. 2.
π–π interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) x - 1, y - 1, z; (ii) x + 1, y + 1, z.]

Crystal data

[Ca(C15H9O7S)(H2O)6](C15H9O7S)·3H2OZ = 2
Mr = 868.79F000 = 904
Triclinic, P1Dx = 1.594 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 11.360 (2) ÅCell parameters from 2128 reflections
b = 12.390 (1) Åθ = 2.5–23.9º
c = 13.975 (2) ŵ = 0.38 mm1
α = 95.136 (2)ºT = 296 (2) K
β = 102.167 (3)ºSheet, colourless
γ = 107.423 (2)º0.36 × 0.23 × 0.14 mm
V = 1809.9 (4) Å3

Data collection

Bruker SMART CCD area-detector diffractometer6299 independent reflections
Radiation source: fine-focus sealed tube4416 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
Detector resolution: 10.0 pixels mm-1θmax = 25.1º
T = 296(2) Kθmin = 1.5º
[var phi] and ω scansh = −9→13
Absorption correction: multi-scan(SADABS; Bruker, 1999)k = −14→14
Tmin = 0.874, Tmax = 0.947l = −16→16
9179 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.167  w = 1/[σ2(Fo2) + (0.0956P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
6299 reflectionsΔρmax = 0.40 e Å3
558 parametersΔρmin = −0.40 e Å3
16 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
Ca10.10081 (6)0.62071 (6)0.23114 (5)0.0393 (2)
S20.33030 (8)0.65555 (7)0.07174 (7)0.0427 (3)
O10.46932 (19)0.90038 (18)0.11438 (16)0.0358 (5)
O20.8501 (2)1.0701 (2)0.17925 (19)0.0492 (6)
O30.8907 (2)0.8768 (2)0.1856 (2)0.0551 (7)
H30.90730.94550.18330.083*
O40.5425 (3)0.5415 (2)0.1183 (3)0.0636 (8)
H40.46440.51670.10300.095*
O50.3082 (3)0.5319 (2)0.0591 (2)0.0645 (8)
O60.2916 (2)0.6914 (2)−0.02215 (19)0.0582 (7)
O70.2732 (2)0.6922 (2)0.14628 (19)0.0489 (6)
O80.3056 (3)0.6613 (3)0.3527 (2)0.0547 (7)
H8A0.289 (4)0.653 (4)0.4063 (18)0.080*
H8B0.332 (4)0.612 (3)0.331 (3)0.080*
O90.1102 (3)0.4520 (2)0.1496 (3)0.0698 (9)
H9A0.053 (3)0.390 (2)0.128 (3)0.080*
H9B0.170 (3)0.462 (4)0.124 (3)0.080*
O100.0505 (3)0.5170 (3)0.3609 (2)0.0716 (9)
H10A0.011 (4)0.4479 (12)0.345 (3)0.080*
H10B0.088 (4)0.534 (4)0.4197 (12)0.080*
O11−0.1277 (3)0.5121 (2)0.1799 (2)0.0533 (7)
H11B−0.169 (4)0.487 (4)0.1221 (13)0.080*
H11A−0.171 (4)0.473 (3)0.212 (3)0.080*
O120.0807 (3)0.7627 (2)0.3400 (2)0.0597 (8)
H12A0.039 (4)0.746 (4)0.381 (2)0.065 (15)*
H12B0.096 (4)0.8316 (11)0.343 (3)0.080*
O130.0262 (3)0.7350 (3)0.1202 (2)0.0633 (8)
H13B−0.009 (4)0.780 (3)0.137 (3)0.080*
H13A0.036 (5)0.742 (4)0.0644 (16)0.080*
C10.4349 (3)1.1836 (3)0.1122 (3)0.0416 (8)
H10.51831.23180.12190.050*
C20.3361 (4)1.2284 (3)0.0989 (3)0.0489 (9)
H20.35341.30680.09960.059*
C30.2126 (4)1.1585 (3)0.0846 (3)0.0528 (10)
H3A0.14661.18940.07510.063*
C40.1863 (4)1.0421 (3)0.0843 (3)0.0533 (10)
H4A0.10260.99490.07520.064*
C50.2837 (3)0.9957 (3)0.0974 (3)0.0438 (9)
H50.26540.91730.09730.053*
C60.4093 (3)1.0654 (3)0.1110 (2)0.0341 (7)
C70.5135 (3)1.0167 (3)0.1252 (2)0.0329 (7)
C80.6398 (3)1.0755 (3)0.1468 (3)0.0383 (8)
H80.66721.15500.15270.046*
C90.7315 (3)1.0169 (3)0.1605 (2)0.0373 (8)
C100.6825 (3)0.8946 (3)0.1508 (2)0.0364 (8)
C110.7630 (3)0.8262 (3)0.1641 (3)0.0408 (8)
C120.7130 (3)0.7104 (3)0.1546 (3)0.0485 (9)
H120.76710.66690.16550.058*
C130.5817 (3)0.6561 (3)0.1287 (3)0.0435 (8)
C140.4975 (3)0.7200 (3)0.1131 (3)0.0373 (8)
C150.5518 (3)0.8389 (3)0.1270 (2)0.0334 (7)
S1−0.31929 (8)0.40326 (7)0.37480 (7)0.0416 (2)
O14−0.4556 (2)0.16187 (18)0.37202 (17)0.0391 (6)
O15−0.8338 (2)−0.0055 (2)0.3292 (2)0.0579 (7)
O16−0.8755 (2)0.1864 (2)0.3212 (3)0.0693 (9)
H16−0.89200.11700.31960.104*
O17−0.5301 (3)0.5183 (2)0.3526 (3)0.0708 (9)
H17−0.45200.54270.36560.106*
O18−0.2978 (3)0.5258 (2)0.3808 (3)0.0689 (9)
O19−0.2916 (2)0.3558 (2)0.28751 (19)0.0521 (7)
O20−0.2531 (2)0.3747 (2)0.46429 (19)0.0556 (7)
C16−0.2675 (3)0.0700 (3)0.4116 (3)0.0474 (9)
H16A−0.24900.14910.41870.057*
C17−0.1700 (4)0.0242 (4)0.4252 (3)0.0601 (11)
H17A−0.08590.07250.44060.072*
C18−0.1959 (4)−0.0926 (4)0.4162 (3)0.0614 (11)
H18−0.1297−0.12320.42510.074*
C19−0.3201 (4)−0.1637 (3)0.3939 (3)0.0613 (11)
H19−0.3379−0.24250.38930.074*
C20−0.4183 (4)−0.1186 (3)0.3784 (3)0.0543 (10)
H20−0.5022−0.16750.36190.065*
C21−0.3936 (3)−0.0018 (3)0.3871 (2)0.0396 (8)
C22−0.4987 (3)0.0466 (3)0.3714 (2)0.0392 (8)
C23−0.6230 (4)−0.0108 (3)0.3576 (3)0.0460 (9)
H23−0.6490−0.08960.35700.055*
C24−0.7170 (3)0.0460 (3)0.3437 (3)0.0440 (9)
C25−0.6679 (3)0.1687 (3)0.3477 (3)0.0398 (8)
C26−0.7489 (3)0.2363 (3)0.3370 (3)0.0486 (9)
C27−0.6996 (3)0.3518 (3)0.3409 (3)0.0537 (10)
H27−0.75340.39580.33550.064*
C28−0.5694 (4)0.4046 (3)0.3529 (3)0.0491 (9)
C29−0.4845 (3)0.3408 (3)0.3635 (3)0.0378 (8)
C30−0.5383 (3)0.2232 (3)0.3608 (2)0.0371 (8)
O21−0.0582 (3)0.7003 (3)0.4724 (3)0.0810 (10)
H21B−0.126 (3)0.648 (3)0.448 (3)0.080*
H21A−0.022 (4)0.698 (4)0.5295 (16)0.080*
O22−0.0730 (3)0.2875 (2)0.3291 (2)0.0699 (8)
O230.0758 (3)0.7542 (2)−0.0680 (2)0.0539 (7)
H23B0.139 (3)0.734 (4)−0.063 (4)0.080*
H23A0.091 (4)0.809 (3)−0.098 (3)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ca10.0356 (4)0.0336 (4)0.0470 (4)0.0079 (3)0.0112 (3)0.0073 (3)
S20.0317 (5)0.0357 (5)0.0573 (6)0.0038 (4)0.0169 (4)0.0026 (4)
O10.0277 (12)0.0306 (12)0.0481 (14)0.0090 (10)0.0077 (10)0.0067 (10)
O20.0272 (13)0.0438 (14)0.0663 (17)0.0011 (11)0.0060 (12)0.0070 (12)
O30.0255 (13)0.0534 (16)0.083 (2)0.0134 (12)0.0080 (13)0.0070 (15)
O40.0544 (17)0.0368 (15)0.104 (2)0.0180 (13)0.0249 (18)0.0126 (15)
O50.0462 (16)0.0341 (14)0.112 (2)0.0042 (12)0.0365 (16)−0.0017 (15)
O60.0365 (15)0.0751 (19)0.0498 (16)0.0051 (14)0.0038 (12)0.0060 (14)
O70.0452 (15)0.0417 (14)0.0638 (17)0.0107 (12)0.0272 (13)0.0079 (12)
O80.0415 (15)0.0599 (18)0.0611 (18)0.0136 (13)0.0134 (14)0.0121 (15)
O90.056 (2)0.0396 (16)0.110 (3)0.0005 (14)0.0415 (18)−0.0045 (16)
O100.075 (2)0.0539 (18)0.0548 (18)−0.0136 (16)−0.0018 (16)0.0158 (16)
O110.0375 (15)0.0555 (17)0.0581 (18)0.0041 (13)0.0096 (13)0.0097 (14)
O120.077 (2)0.0357 (15)0.071 (2)0.0152 (15)0.0338 (17)0.0048 (15)
O130.069 (2)0.079 (2)0.071 (2)0.0456 (17)0.0370 (17)0.0371 (18)
C10.043 (2)0.038 (2)0.045 (2)0.0132 (16)0.0130 (16)0.0061 (16)
C20.058 (3)0.039 (2)0.058 (2)0.0242 (19)0.0158 (19)0.0144 (17)
C30.051 (2)0.058 (3)0.059 (2)0.031 (2)0.0124 (19)0.012 (2)
C40.032 (2)0.058 (3)0.067 (3)0.0143 (18)0.0086 (18)0.007 (2)
C50.034 (2)0.0360 (19)0.057 (2)0.0088 (16)0.0074 (17)0.0053 (16)
C60.0340 (18)0.0350 (18)0.0333 (17)0.0119 (15)0.0086 (14)0.0039 (14)
C70.0328 (18)0.0322 (17)0.0322 (17)0.0095 (14)0.0073 (14)0.0038 (13)
C80.0359 (19)0.0288 (17)0.048 (2)0.0078 (15)0.0110 (16)0.0069 (15)
C90.0287 (18)0.0381 (19)0.0389 (19)0.0031 (15)0.0067 (14)0.0057 (15)
C100.0298 (18)0.0387 (19)0.0399 (19)0.0103 (15)0.0076 (14)0.0084 (15)
C110.0295 (18)0.047 (2)0.046 (2)0.0126 (16)0.0089 (15)0.0082 (16)
C120.040 (2)0.047 (2)0.065 (3)0.0236 (18)0.0120 (18)0.0141 (19)
C130.043 (2)0.036 (2)0.056 (2)0.0152 (16)0.0180 (17)0.0113 (16)
C140.0336 (18)0.0337 (18)0.0451 (19)0.0093 (15)0.0133 (15)0.0074 (15)
C150.0246 (16)0.0385 (18)0.0394 (18)0.0108 (14)0.0113 (14)0.0084 (14)
S10.0318 (5)0.0354 (5)0.0513 (6)0.0048 (4)0.0067 (4)0.0057 (4)
O140.0316 (13)0.0314 (12)0.0528 (14)0.0078 (10)0.0110 (11)0.0072 (10)
O150.0353 (15)0.0471 (15)0.084 (2)−0.0010 (12)0.0207 (14)0.0092 (14)
O160.0327 (15)0.0594 (18)0.115 (3)0.0123 (13)0.0231 (16)0.0089 (19)
O170.0482 (17)0.0341 (15)0.133 (3)0.0165 (13)0.0234 (19)0.0167 (16)
O180.0450 (16)0.0344 (15)0.117 (3)0.0049 (13)0.0109 (16)0.0090 (15)
O190.0381 (14)0.0573 (16)0.0547 (16)0.0056 (12)0.0149 (12)0.0051 (13)
O200.0424 (15)0.0631 (17)0.0486 (15)0.0074 (13)−0.0013 (12)0.0090 (13)
C160.046 (2)0.0358 (19)0.056 (2)0.0113 (17)0.0063 (18)0.0089 (17)
C170.045 (2)0.053 (2)0.075 (3)0.018 (2)0.000 (2)0.007 (2)
C180.061 (3)0.060 (3)0.066 (3)0.034 (2)0.002 (2)0.007 (2)
C190.075 (3)0.039 (2)0.072 (3)0.023 (2)0.014 (2)0.014 (2)
C200.051 (2)0.045 (2)0.064 (3)0.0120 (19)0.015 (2)0.0100 (19)
C210.043 (2)0.0350 (19)0.0396 (19)0.0107 (16)0.0095 (16)0.0111 (15)
C220.042 (2)0.0309 (18)0.0414 (19)0.0065 (16)0.0105 (16)0.0062 (15)
C230.045 (2)0.0340 (19)0.055 (2)0.0047 (17)0.0159 (18)0.0086 (16)
C240.038 (2)0.040 (2)0.050 (2)0.0037 (17)0.0170 (17)0.0067 (16)
C250.0315 (19)0.0391 (19)0.046 (2)0.0062 (15)0.0127 (15)0.0041 (15)
C260.033 (2)0.049 (2)0.061 (2)0.0096 (17)0.0142 (17)0.0027 (18)
C270.036 (2)0.047 (2)0.082 (3)0.0186 (18)0.0180 (19)0.007 (2)
C280.042 (2)0.040 (2)0.066 (3)0.0147 (17)0.0131 (18)0.0093 (18)
C290.0322 (18)0.0332 (18)0.046 (2)0.0076 (15)0.0108 (15)0.0045 (15)
C300.0335 (18)0.0367 (19)0.0392 (19)0.0092 (15)0.0087 (15)0.0054 (15)
O210.065 (2)0.079 (2)0.077 (2)−0.0047 (18)0.0171 (19)0.003 (2)
O220.072 (2)0.0505 (17)0.087 (2)0.0173 (15)0.0254 (17)0.0091 (15)
O230.0456 (16)0.0439 (16)0.0679 (18)0.0051 (13)0.0177 (14)0.0126 (13)

Geometric parameters (Å, °)

Ca1—O122.317 (3)C9—C101.432 (5)
Ca1—O92.331 (3)C10—C151.389 (4)
Ca1—O102.383 (3)C10—C111.417 (5)
Ca1—O132.383 (3)C11—C121.359 (5)
Ca1—O112.453 (3)C12—C131.391 (5)
Ca1—O82.456 (3)C12—H120.9300
Ca1—O72.481 (3)C13—C141.409 (5)
Ca1—H8B2.74 (4)C14—C151.393 (4)
Ca1—H9B2.77 (4)S1—O191.441 (3)
S2—O71.445 (3)S1—O201.448 (3)
S2—O61.446 (3)S1—O181.456 (3)
S2—O51.464 (3)S1—C291.769 (3)
S2—C141.768 (3)O14—C221.363 (4)
O1—C71.359 (4)O14—C301.368 (4)
O1—C151.368 (4)O15—C241.251 (4)
O2—C91.267 (4)O16—C261.344 (4)
O3—C111.351 (4)O16—H160.8200
O3—H30.8200O17—C281.345 (4)
O4—C131.340 (4)O17—H170.8200
O4—H40.8200C16—C171.375 (5)
O8—H8A0.82 (3)C16—C211.392 (5)
O8—H8B0.82 (4)C16—H16A0.9300
O9—H9A0.83 (3)C17—C181.376 (6)
O9—H9B0.82 (3)C17—H17A0.9300
O10—H10A0.82 (3)C18—C191.372 (6)
O10—H10B0.82 (3)C18—H180.9300
O11—H11B0.82 (3)C19—C201.378 (6)
O11—H11A0.82 (4)C19—H190.9300
O12—H12A0.82 (4)C20—C211.377 (5)
O12—H12B0.81 (3)C20—H200.9300
O13—H13B0.82 (3)C21—C221.474 (5)
O13—H13A0.82 (3)C22—C231.340 (5)
C1—C21.381 (5)C23—C241.435 (5)
C1—C61.403 (4)C23—H230.9300
C1—H10.9300C24—C251.446 (5)
C2—C31.372 (5)C25—C301.387 (5)
C2—H20.9300C25—C261.413 (5)
C3—C41.381 (5)C26—C271.363 (5)
C3—H3A0.9300C27—C281.393 (5)
C4—C51.380 (5)C27—H270.9300
C4—H4A0.9300C28—C291.412 (5)
C5—C61.391 (5)C29—C301.395 (4)
C5—H50.9300O21—H21B0.82 (3)
C6—C71.468 (4)O21—H21A0.83 (4)
C7—C81.354 (4)O23—H23B0.82 (4)
C8—C91.429 (5)O23—H23A0.82 (4)
C8—H80.9300
O12—Ca1—O9166.74 (12)C8—C7—C6126.7 (3)
O12—Ca1—O1079.54 (12)O1—C7—C6111.8 (3)
O9—Ca1—O1087.19 (13)C7—C8—C9120.9 (3)
O12—Ca1—O1378.35 (12)C7—C8—H8119.6
O9—Ca1—O13113.01 (13)C9—C8—H8119.6
O10—Ca1—O13142.40 (12)O2—C9—C8121.9 (3)
O12—Ca1—O1195.00 (11)O2—C9—C10121.5 (3)
O9—Ca1—O1181.03 (11)C8—C9—C10116.5 (3)
O10—Ca1—O1172.82 (10)C15—C10—C11117.6 (3)
O13—Ca1—O1179.24 (11)C15—C10—C9120.0 (3)
O12—Ca1—O882.43 (11)C11—C10—C9122.4 (3)
O9—Ca1—O894.11 (11)O3—C11—C12119.7 (3)
O10—Ca1—O874.99 (11)O3—C11—C10119.6 (3)
O13—Ca1—O8130.90 (11)C12—C11—C10120.7 (3)
O11—Ca1—O8147.62 (10)C11—C12—C13120.7 (3)
O12—Ca1—O7113.40 (10)C11—C12—H12119.6
O9—Ca1—O777.30 (9)C13—C12—H12119.6
O10—Ca1—O7142.23 (12)O4—C13—C12115.9 (3)
O13—Ca1—O775.02 (10)O4—C13—C14123.2 (3)
O11—Ca1—O7136.16 (10)C12—C13—C14120.8 (3)
O8—Ca1—O772.10 (10)C15—C14—C13117.0 (3)
O12—Ca1—H8B99.3 (5)C15—C14—S2120.0 (2)
O9—Ca1—H8B77.3 (5)C13—C14—S2122.9 (3)
O10—Ca1—H8B76.7 (10)O1—C15—C10120.3 (3)
O13—Ca1—H8B136.9 (10)O1—C15—C14116.6 (3)
O11—Ca1—H8B143.1 (10)C10—C15—C14123.1 (3)
O8—Ca1—H8B17.0 (5)O19—S1—O20111.90 (16)
O7—Ca1—H8B66.5 (10)O19—S1—O18112.13 (18)
O12—Ca1—H9B169.3 (9)O20—S1—O18112.59 (17)
O9—Ca1—H9B15.9 (7)O19—S1—C29107.48 (15)
O10—Ca1—H9B98.9 (8)O20—S1—C29107.24 (16)
O13—Ca1—H9B108.1 (10)O18—S1—C29105.01 (16)
O11—Ca1—H9B94.7 (8)C22—O14—C30120.7 (3)
O8—Ca1—H9B86.9 (9)C26—O16—H16109.5
O7—Ca1—H9B61.6 (7)C28—O17—H17109.5
H8B—Ca1—H9B70.1 (11)C17—C16—C21120.1 (3)
O7—S2—O6112.63 (17)C17—C16—H16A120.0
O7—S2—O5112.18 (16)C21—C16—H16A120.0
O6—S2—O5111.20 (18)C16—C17—C18120.5 (4)
O7—S2—C14108.38 (16)C16—C17—H17A119.7
O6—S2—C14106.78 (16)C18—C17—H17A119.7
O5—S2—C14105.20 (16)C19—C18—C17119.6 (4)
C7—O1—C15120.8 (2)C19—C18—H18120.2
C11—O3—H3109.5C17—C18—H18120.2
C13—O4—H4109.5C18—C19—C20120.3 (4)
S2—O7—Ca1141.98 (14)C18—C19—H19119.9
Ca1—O8—H8A106 (3)C20—C19—H19119.9
Ca1—O8—H8B102 (3)C21—C20—C19120.6 (4)
H8A—O8—H8B114 (5)C21—C20—H20119.7
Ca1—O9—H9A129 (3)C19—C20—H20119.7
Ca1—O9—H9B114 (3)C20—C21—C16118.9 (3)
H9A—O9—H9B114 (5)C20—C21—C22120.7 (3)
Ca1—O10—H10A117 (3)C16—C21—C22120.4 (3)
Ca1—O10—H10B127 (3)C23—C22—O14121.4 (3)
H10A—O10—H10B112 (5)C23—C22—C21126.8 (3)
Ca1—O11—H11B125 (3)O14—C22—C21111.8 (3)
Ca1—O11—H11A128 (3)C22—C23—C24121.8 (3)
H11B—O11—H11A104 (5)C22—C23—H23119.1
Ca1—O12—H12A121 (3)C24—C23—H23119.1
Ca1—O12—H12B134 (4)O15—C24—C23123.3 (3)
H12A—O12—H12B105 (5)O15—C24—C25121.3 (3)
Ca1—O13—H13B122 (3)C23—C24—C25115.4 (3)
Ca1—O13—H13A129 (4)C30—C25—C26118.1 (3)
H13B—O13—H13A109 (5)C30—C25—C24120.1 (3)
C2—C1—C6119.9 (3)C26—C25—C24121.8 (3)
C2—C1—H1120.1O16—C26—C27119.8 (3)
C6—C1—H1120.1O16—C26—C25120.0 (3)
C3—C2—C1120.7 (3)C27—C26—C25120.3 (3)
C3—C2—H2119.6C26—C27—C28120.7 (3)
C1—C2—H2119.6C26—C27—H27119.6
C2—C3—C4119.9 (4)C28—C27—H27119.6
C2—C3—H3A120.0O17—C28—C27116.5 (3)
C4—C3—H3A120.0O17—C28—C29122.3 (3)
C5—C4—C3120.3 (4)C27—C28—C29121.2 (3)
C5—C4—H4A119.9C30—C29—C28116.4 (3)
C3—C4—H4A119.9C30—C29—S1120.7 (3)
C4—C5—C6120.4 (3)C28—C29—S1122.8 (3)
C4—C5—H5119.8O14—C30—C25120.5 (3)
C6—C5—H5119.8O14—C30—C29116.2 (3)
C5—C6—C1118.8 (3)C25—C30—C29123.3 (3)
C5—C6—C7120.7 (3)H21B—O21—H21A115 (5)
C1—C6—C7120.4 (3)H23B—O23—H23A103 (5)
C8—C7—O1121.4 (3)
O6—S2—O7—Ca1102.4 (3)C13—C14—C15—O1−178.3 (3)
O5—S2—O7—Ca1−23.9 (3)S2—C14—C15—O14.8 (4)
C14—S2—O7—Ca1−139.7 (2)C13—C14—C15—C102.8 (5)
O12—Ca1—O7—S2−176.2 (2)S2—C14—C15—C10−174.1 (3)
O9—Ca1—O7—S212.1 (3)C21—C16—C17—C18−0.9 (6)
O10—Ca1—O7—S280.2 (3)C16—C17—C18—C19−0.3 (7)
O13—Ca1—O7—S2−106.3 (3)C17—C18—C19—C201.5 (7)
O11—Ca1—O7—S2−50.2 (3)C18—C19—C20—C21−1.4 (7)
O8—Ca1—O7—S2110.7 (3)C19—C20—C21—C160.2 (6)
C6—C1—C2—C30.1 (5)C19—C20—C21—C22−179.4 (4)
C1—C2—C3—C40.6 (6)C17—C16—C21—C201.0 (6)
C2—C3—C4—C5−0.6 (6)C17—C16—C21—C22−179.4 (4)
C3—C4—C5—C6−0.1 (6)C30—O14—C22—C231.6 (5)
C4—C5—C6—C10.7 (5)C30—O14—C22—C21−178.6 (3)
C4—C5—C6—C7179.9 (3)C20—C21—C22—C236.8 (6)
C2—C1—C6—C5−0.8 (5)C16—C21—C22—C23−172.7 (4)
C2—C1—C6—C7−179.9 (3)C20—C21—C22—O14−173.0 (3)
C15—O1—C7—C81.3 (5)C16—C21—C22—O147.4 (5)
C15—O1—C7—C6−178.5 (3)O14—C22—C23—C24−0.6 (5)
C5—C6—C7—C8−174.4 (3)C21—C22—C23—C24179.6 (3)
C1—C6—C7—C84.7 (5)C22—C23—C24—O15179.0 (3)
C5—C6—C7—O15.4 (4)C22—C23—C24—C25−1.2 (5)
C1—C6—C7—O1−175.5 (3)O15—C24—C25—C30−178.0 (3)
O1—C7—C8—C9−1.0 (5)C23—C24—C25—C302.1 (5)
C6—C7—C8—C9178.8 (3)O15—C24—C25—C261.0 (6)
C7—C8—C9—O2178.9 (3)C23—C24—C25—C26−178.9 (3)
C7—C8—C9—C10−0.4 (5)C30—C25—C26—O16178.1 (3)
O2—C9—C10—C15−177.9 (3)C24—C25—C26—O16−1.0 (6)
C8—C9—C10—C151.3 (5)C30—C25—C26—C27−0.8 (6)
O2—C9—C10—C111.8 (5)C24—C25—C26—C27−179.9 (4)
C8—C9—C10—C11−178.9 (3)O16—C26—C27—C28−177.2 (4)
C15—C10—C11—O3178.8 (3)C25—C26—C27—C281.6 (6)
C9—C10—C11—O3−0.9 (5)C26—C27—C28—O17177.9 (4)
C15—C10—C11—C12−0.5 (5)C26—C27—C28—C29−1.4 (6)
C9—C10—C11—C12179.8 (3)O17—C28—C29—C30−178.9 (4)
O3—C11—C12—C13−177.4 (3)C27—C28—C29—C300.3 (6)
C10—C11—C12—C131.9 (6)O17—C28—C29—S1−1.4 (6)
C11—C12—C13—O4178.1 (4)C27—C28—C29—S1177.9 (3)
C11—C12—C13—C14−1.0 (6)O19—S1—C29—C3063.6 (3)
O4—C13—C14—C15179.7 (3)O20—S1—C29—C30−56.9 (3)
C12—C13—C14—C15−1.3 (5)O18—S1—C29—C30−176.8 (3)
O4—C13—C14—S2−3.5 (5)O19—S1—C29—C28−113.8 (3)
C12—C13—C14—S2175.5 (3)O20—S1—C29—C28125.7 (3)
O7—S2—C14—C15−63.6 (3)O18—S1—C29—C285.7 (4)
O6—S2—C14—C1558.0 (3)C22—O14—C30—C25−0.6 (5)
O5—S2—C14—C15176.3 (3)C22—O14—C30—C29179.4 (3)
O7—S2—C14—C13119.7 (3)C26—C25—C30—O14179.6 (3)
O6—S2—C14—C13−118.7 (3)C24—C25—C30—O14−1.2 (5)
O5—S2—C14—C13−0.5 (4)C26—C25—C30—C29−0.3 (5)
C7—O1—C15—C10−0.3 (4)C24—C25—C30—C29178.8 (3)
C7—O1—C15—C14−179.2 (3)C28—C29—C30—O14−179.4 (3)
C11—C10—C15—O1179.2 (3)S1—C29—C30—O143.0 (4)
C9—C10—C15—O1−1.0 (5)C28—C29—C30—C250.5 (5)
C11—C10—C15—C14−2.0 (5)S1—C29—C30—C25−177.1 (3)
C9—C10—C15—C14177.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O20.821.852.576 (4)148
O4—H4···O50.821.822.579 (4)153
O8—H8B···O17i0.82 (4)2.20 (3)2.934 (4)149 (4)
O8—H8A···O20ii0.82 (3)1.97 (3)2.790 (4)176 (5)
O9—H9B···O50.82 (4)1.99 (4)2.780 (4)163 (5)
O9—H9A···O23iii0.83 (3)1.92 (3)2.743 (4)175 (5)
O10—H10B···O20ii0.82 (3)2.13 (2)2.874 (4)151 (5)
O10—H10A···O220.82 (3)1.90 (3)2.715 (4)171 (5)
O11—H11B···O6iii0.82 (3)2.36 (3)3.024 (4)139 (4)
O11—H11A···O190.82 (4)2.19 (4)3.003 (4)175 (5)
O12—H12B···O15iv0.81 (3)1.98 (3)2.771 (4)165 (5)
O12—H12A···O210.82 (4)1.88 (4)2.695 (5)177 (4)
O13—H13B···O3v0.82 (4)2.05 (4)2.867 (4)174 (5)
O13—H13A···O230.82 (3)2.00 (3)2.819 (4)173 (5)
O16—H16···O150.821.832.567 (4)148
O17—H17···O180.821.802.556 (4)153
O21—H21B···O180.82 (3)2.05 (4)2.870 (4)176 (5)
O21—H21A···O22ii0.82 (3)2.01 (3)2.826 (5)173 (5)
O23—H23A···O2vi0.82 (4)2.00 (4)2.816 (4)171 (5)
O23—H23B···O60.82 (4)1.95 (4)2.755 (4)168 (5)
C12—H12···O11i0.932.553.462 (5)168
C20—H20···O8vii0.932.523.410 (5)161

Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) x+1, y+1, z; (v) x−1, y, z; (vi) −x+1, −y+2, −z; (vii) x−1, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2072).

References

  • Bruker (1999). SMART, SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chan, E. C. H., Patchareewan, P. & Owen, L. W. (2000). J. Cardiovasc. Pharmacol.35, 326–333. [PubMed]
  • Cote, A. P. & Shimizu, G. K. H. (2003). Coord. Chem. Rev.245, 49–64.
  • Hiroyuki, H., Isao, O., Sachiko, S. & Ayumi, F. (1996). J. Nat. Prod.59, 443–445.
  • Jiang, R. W., He, Z. D. & Chen, Y. M. (2001). Chem. Pharm. Bull.49, 1166–1169. [PubMed]
  • Lee, J. H., Kim, Y. S., Lee, C. K., Lee, H. K. & Han, S. S. (1999). Saengyak Hakhoechi, 30, 34–39.
  • Li, W.-W. & Zhang, Z.-T. (2008). Acta Cryst. C64, m176–m178. [PubMed]
  • Morin, G., Shang, M. & Smith, B. D. (2000). Acta Cryst. C56, 544–545. [PubMed]
  • Pusz, J., Nitka, B. & Wolowiec, S. (2001). Pol. J. Chem.75, 795–801.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shin, J. S., Kim, K. S., Kim, M. B., Jeong, J. H. & Kim, B. K. (1999). Bioorg. Med. Chem. Lett.9, 869–874. [PubMed]
  • Zanoli, P., Avallone, R. & Baraldi, M. (2000). Fitoterapia, 71, 117–123. [PubMed]
  • Zhang, Z. T., Guo, Y. N. & Liu, Q. G. (2004). Sci. China Ser. B, 34, 225–234.
  • Zhang, Z. T., Shi, J. & He, Y. (2006b). Acta Chim. Sin.64, 930–934.
  • Zhang, Z. T., Shi, J., He, Y. & Guo, Y. N. (2006a). Inorg. Chem. Commun.9, 579–581.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography