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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

(1R,4S,8R,9R,12S,13S,14R,16S,17R,19R)-17-[(Ethyl­sulfan­yl)meth­yl]-9,14-di­hy­droxy-7,7-di­methyl-2,18-dioxo-3,10-dioxa­penta­cyclo[14.2.1.01,13.04,12.08,12]nona­decan-19-yl acetate acetone solvate

aThe College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and bCollege of Animal Sciences, Zhejiang University, Hangzhou 310029, People's Republic of China
*Correspondence e-mail: shihao@126.com

(Received 27 November 2008; accepted 19 December 2008; online 24 December 2008)

The title compound, C24H32O8S·C3H6O, features three six-membered and two five-membered rings. The six-membered rings adopt chair, boat and slightly distorted boat conformations whereas one five-membered ring adopts an approximate envelope conformation and the other a twist conformation. Disorder was modelled for the ethyl­thio group with the ethyl-C atoms resolved over three positions with occupancies of 0.58 (4), 0.23 (4) and 0.19 (3). In the crystal, an O—H⋯O hydrogen bond links the molecules into chains.

Related literature

For puckering parameters, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]). For related literature, see: Yamaguchi et al. (1977[Yamaguchi, M., Taniguchi, M., Kubo, I. & Kubota, T. (1977). Agric. Biol. Chem. 41, 2475-2477.]); Chen et al. (1987[Chen, Y. Z., Wu, Z. W. & Cheng, P. Y. (1987). Chin. J. Org. Chem. 7, 21-28.]); He et al. (2007[He, S., Wu, B., Shi, H. & Sun, C. R. (2007). Chin. J. Struct. Chem., 26, 299-302.]); Shi et al. (2007[Shi, H., He, S., He, L. & Pan, Y. J. (2007). Chem. J. Chin. Univ. 28, 100-102.]).

[Scheme 1]

Experimental

Crystal data
  • C24H32O8S·C3H6O

  • Mr = 538.63

  • Orthorhombic, P 21 21 21

  • a = 10.6258 (12) Å

  • b = 11.4825 (18) Å

  • c = 22.265 (2) Å

  • V = 2716.6 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.17 mm−1

  • T = 298 (2) K

  • 0.53 × 0.32 × 0.28 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1999[Bruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.915, Tmax = 0.954

  • 11871 measured reflections

  • 4774 independent reflections

  • 3201 reflections with I > 2σ(I)

  • Rint = 0.041

Refinement
  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.112

  • S = 1.04

  • 4774 reflections

  • 373 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.23 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2053 Friedel pairs

  • Flack parameter: 0.00 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O5—H5⋯O8i 0.82 2.16 2.952 (4) 161
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 1999[Bruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Since the natural product diterpenoid Macrocalyxin J exhibits cytotoxicity against cultures of Hela cells (Shi et al., 2007), the title compound (1), a derivative, was synthesised for investigation. The molecule of (1) is composed of three six-membered and two five-membered rings, Fig. 1. The cyclohexane ring A (C4—C8/C12) adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q = 0.525 (4) Å, θ = 156.0 (4)° and ϕ = 275.2 (10)°. Ring B (O3/C2/C1/C13/C12/C4) exists in a distorted boat conformation (Q = 0.671 (3) Å, θ = 109.0 (3)° and ϕ = 94.9 (3)°) and ring C (C1/C13—C16/C19) adopts a boat conformation (Q = 0.851 (3) Å, θ = 79.9 (2) and ϕ = 296.0 (2)°). The five-membered ring D (C1/C18/C17/C16/C19) is twisted on C(16)/C(19), and five-membered ring E (O10/C9/C8/C12/C11) adopts an envelope conformation with C(12) displaced by 0.500 (5)Å from the mean plane of the remaining four atoms. The stereochemistry of the A/B ring juncture is trans, and at the B/C ring juncture, cis. With the C1, C19 and C16 atoms being located in both rings C and D, an α-configuration is adopted to avoid steric crowding; no evidence was found in this study for the synthesis of the β-configuration. The main difference between (1) and macrocalyxin J (He et al., 2007) is found in ring D. In the latter, the equivalent ring D is conjugated, i.e. is a α-methylenecyclopentanone ring. It has been reported that the α-methylenecyclopentanone group in the Rabdosia diterpenes is highly reactive toward sulfhydryl groups, essential to enzyme function (Yamaguchi et al., 1977). This observation is ascribed to the steric strain within the five-membered ring which increases the reactivity of the conjugated double bond (Chen et al., 1987). Compound (1) was characterised as an acetone solvate. In the crystal structure the constituent molecules are connected via hydrogen bonding, Table 1.

Related literature top

For puckering parameters, see: Cremer & Pople (1975). For related literature, see: Yamaguchi et al. (1977); Chen et al. (1987); He et al. (2007); Shi et al. (2007).

Experimental top

Compound (1) was obtained in a two-step syntheses, Scheme 1. In an ice-water bath, Jones reagent (0.2 ml ) was added to a solution of Macrocalyxin J (200 mg; isolated from Rabdosia macrocalyx) in acetone (20 ml). After stirring for 20 min, the solution was filtered and added to 15% NaHCO3 in water (120 ml). The mixture was extracted 3 times with diethyl ether (90 ml). After evaporation of the solvent, a white residue was isolated. Recrystallization from methanol gave 19-acetyloxy-10,13-dideoxy-5-hydroxy-10-oxo, (5β,19R)-enmain (175.6 mg) (2), see Scheme. Into an ethanol solution (50 ml) of (2) (150 mg) was added dropwise excess ethanethiol (0.5 ml). After stirring at room temperature for 3 h, the mixture was concentrated in vacuo to give an oily residue, which was washed with water (2.0 ml), then recrystallized from CH3COCH3 to afford (1) as colorless crystals (127.3 mg).

Refinement top

All H atoms were placed in geometrically calculated positions, and allowed to ride on their parent atoms with O-H = 0.82 Å and C-H = 0.96 - 0.98 Å, and with Uiso(H) = 1.2Ueq(C) for methylene- and methine-H, and 1.5Ueq for other H atoms. The ethyl-C atoms of the ethylthio group were found to be disordered over three positions (C25/C26, C25'/C26', and C25"/C26") with refined occupancies of 0.58 (4), 0.19 (3) and 0.23 (4).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (1) showing atomic numbering scheme and 30% probability displacement ellipsoids. The ethylthio group is disordered over three positions.
[Figure 2] Fig. 2. Reaction scheme.
(1R,4S,8R,9R,12S,13S,14R, 16S,17R,19R)-17-[(Ethylsulfanyl)methyl]-9,14-dihydroxy- 7,7-dimethyl-2,18-dioxo-3,10-dioxapentacyclo[14.2.1.01,13.04,12.08,12] nonadecan-19-yl acetate acetone solvate top
Crystal data top
C24H32O8S·C3H6OF(000) = 1152
Mr = 538.63Dx = 1.317 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3142 reflections
a = 10.6258 (12) Åθ = 2.6–24.5°
b = 11.4825 (18) ŵ = 0.17 mm1
c = 22.265 (2) ÅT = 298 K
V = 2716.6 (6) Å3Needle, colorless
Z = 40.53 × 0.32 × 0.28 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
4774 independent reflections
Radiation source: fine-focus sealed tube3201 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ϕ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1211
Tmin = 0.915, Tmax = 0.954k = 1313
11871 measured reflectionsl = 2326
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.112 w = 1/[σ2(Fo2) + (0.0474P)2 + 0.2952P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
4774 reflectionsΔρmax = 0.31 e Å3
373 parametersΔρmin = 0.23 e Å3
1 restraintAbsolute structure: Flack (1983), 2053 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (12)
Crystal data top
C24H32O8S·C3H6OV = 2716.6 (6) Å3
Mr = 538.63Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.6258 (12) ŵ = 0.17 mm1
b = 11.4825 (18) ÅT = 298 K
c = 22.265 (2) Å0.53 × 0.32 × 0.28 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
4774 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
3201 reflections with I > 2σ(I)
Tmin = 0.915, Tmax = 0.954Rint = 0.041
11871 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.31 e Å3
S = 1.04Δρmin = 0.23 e Å3
4774 reflectionsAbsolute structure: Flack (1983), 2053 Friedel pairs
373 parametersAbsolute structure parameter: 0.00 (12)
1 restraint
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*/UeqOcc. (<1)
S10.47821 (11)0.18342 (10)0.03744 (4)0.0714 (3)
O10.3800 (2)0.2350 (2)0.24301 (10)0.0512 (6)
O20.5729 (2)0.2605 (2)0.40864 (11)0.0619 (7)
O30.3052 (2)0.14753 (19)0.32251 (9)0.0452 (6)
O40.5666 (2)0.0665 (2)0.19581 (10)0.0529 (6)
O50.1792 (2)0.17561 (19)0.27787 (9)0.0503 (6)
H50.15520.23870.29080.075*
O60.2073 (2)0.10279 (18)0.15674 (9)0.0399 (5)
O70.0895 (2)0.1727 (2)0.23175 (10)0.0564 (7)
O80.8572 (3)0.1043 (3)0.15591 (13)0.0797 (9)
O100.5889 (2)0.0790 (2)0.37478 (10)0.0525 (6)
C10.3555 (3)0.0293 (3)0.23341 (13)0.0358 (7)
C20.3480 (3)0.1452 (3)0.26595 (14)0.0393 (8)
C40.2686 (3)0.0359 (3)0.34878 (14)0.0432 (9)
H40.19640.00480.32660.052*
C50.2298 (4)0.0579 (3)0.41315 (15)0.0564 (10)
H5A0.29610.09900.43430.068*
H5B0.15420.10510.41430.068*
C60.2057 (4)0.0590 (3)0.44251 (16)0.0594 (10)
H6A0.17040.04630.48210.071*
H6B0.14400.10130.41900.071*
C70.3247 (3)0.1332 (3)0.44839 (14)0.0491 (9)
C80.3832 (3)0.1511 (3)0.38431 (13)0.0425 (8)
H80.34290.21810.36500.051*
C90.5214 (3)0.1744 (3)0.39072 (14)0.0454 (8)
C110.5053 (3)0.0131 (3)0.35640 (14)0.0429 (8)
H11A0.49440.06920.38860.051*
H11B0.53860.05320.32150.051*
C120.3793 (3)0.0458 (3)0.34119 (13)0.0358 (7)
C130.3838 (3)0.0815 (2)0.27396 (13)0.0348 (7)
H130.47130.10300.26580.042*
C140.3048 (3)0.1865 (3)0.25581 (13)0.0413 (8)
H140.34240.25590.27410.050*
C150.3051 (3)0.2031 (3)0.18730 (13)0.0454 (8)
H15A0.23610.25420.17640.054*
H15B0.38280.24150.17580.054*
C160.2929 (3)0.0896 (3)0.15153 (14)0.0400 (8)
H160.23740.10100.11690.048*
C170.4186 (3)0.0347 (3)0.13140 (14)0.0415 (8)
H170.39840.02460.10120.050*
C180.4621 (3)0.0291 (3)0.18731 (13)0.0391 (8)
C190.2390 (3)0.0040 (3)0.19337 (13)0.0365 (8)
H190.16700.02440.21670.044*
C200.5225 (4)0.1088 (3)0.10578 (15)0.0566 (10)
H20A0.59480.05980.09760.068*
H20B0.54740.16600.13550.068*
C210.2897 (4)0.2544 (4)0.47245 (16)0.0684 (11)
H21A0.22830.28940.44650.103*
H21B0.36360.30250.47370.103*
H21C0.25540.24710.51220.103*
C220.4149 (4)0.0758 (3)0.49357 (14)0.0628 (11)
H22A0.37310.06680.53150.094*
H22B0.48790.12410.49860.094*
H22C0.44000.00080.47880.094*
C230.1289 (3)0.1822 (3)0.18166 (15)0.0426 (8)
C240.1034 (3)0.2786 (3)0.13884 (15)0.0548 (10)
H24A0.18090.31730.12920.082*
H24B0.06670.24760.10280.082*
H24C0.04630.33310.15690.082*
C250.624 (4)0.193 (4)0.0035 (14)0.077 (6)0.58 (4)
H25A0.62060.25730.03200.092*0.58 (4)
H25B0.69350.20660.02380.092*0.58 (4)
C260.640 (3)0.0763 (19)0.0366 (13)0.090 (5)0.58 (4)
H26A0.71550.07840.06030.134*0.58 (4)
H26B0.56890.06320.06240.134*0.58 (4)
H26C0.64580.01430.00780.134*0.58 (4)
C25'0.607 (6)0.117 (6)0.005 (2)0.077 (14)0.19 (3)
H25C0.68230.13300.01820.092*0.19 (3)
H25D0.59310.03330.00170.092*0.19 (3)
C26'0.641 (3)0.139 (5)0.069 (2)0.090 (15)0.19 (3)
H26D0.69000.07520.08390.134*0.19 (3)
H26E0.68830.20970.07170.134*0.19 (3)
H26F0.56510.14610.09240.134*0.19 (3)
C25"0.596 (10)0.185 (12)0.021 (4)0.09 (2)0.23 (4)
H25E0.55440.17600.05940.108*0.23 (4)
H25F0.63650.26100.02100.108*0.23 (4)
C26"0.700 (7)0.091 (4)0.016 (3)0.090 (13)0.23 (4)
H26G0.77700.12100.03300.134*0.23 (4)
H26H0.67470.02310.03820.134*0.23 (4)
H26I0.71310.07140.02510.134*0.23 (4)
C270.8435 (5)0.0177 (4)0.2396 (2)0.1042 (17)
H27A0.78130.07780.24360.156*
H27B0.92100.04320.25750.156*
H27C0.81480.05150.25960.156*
C280.8640 (4)0.0071 (4)0.1764 (2)0.0789 (13)
C290.8976 (5)0.0933 (5)0.1371 (3)0.121 (2)
H29A0.97810.12370.14890.181*
H29B0.83500.15310.14090.181*
H29C0.90150.06780.09600.181*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0911 (8)0.0713 (7)0.0519 (5)0.0094 (7)0.0110 (5)0.0107 (6)
O10.0627 (16)0.0337 (14)0.0572 (15)0.0065 (12)0.0024 (12)0.0024 (12)
O20.0736 (19)0.0572 (17)0.0549 (15)0.0222 (14)0.0119 (13)0.0024 (14)
O30.0572 (15)0.0353 (14)0.0430 (13)0.0039 (11)0.0002 (11)0.0028 (11)
O40.0424 (14)0.0578 (16)0.0584 (15)0.0122 (13)0.0034 (12)0.0013 (13)
O50.0514 (15)0.0399 (13)0.0596 (14)0.0139 (12)0.0073 (12)0.0035 (12)
O60.0414 (12)0.0389 (14)0.0394 (12)0.0081 (11)0.0005 (10)0.0031 (11)
O70.0626 (16)0.0597 (16)0.0468 (14)0.0095 (13)0.0118 (12)0.0023 (13)
O80.071 (2)0.070 (2)0.098 (2)0.0072 (17)0.0062 (16)0.0238 (19)
O100.0470 (14)0.0542 (16)0.0563 (14)0.0017 (13)0.0092 (11)0.0032 (13)
C10.0373 (18)0.0317 (18)0.0382 (17)0.0015 (15)0.0010 (14)0.0006 (15)
C20.041 (2)0.037 (2)0.0408 (19)0.0023 (16)0.0052 (15)0.0010 (16)
C40.047 (2)0.041 (2)0.0416 (18)0.0012 (17)0.0037 (15)0.0045 (17)
C50.063 (3)0.058 (3)0.048 (2)0.011 (2)0.0114 (18)0.004 (2)
C60.062 (2)0.071 (3)0.045 (2)0.003 (2)0.0146 (18)0.000 (2)
C70.057 (2)0.053 (2)0.0373 (17)0.0018 (19)0.0040 (16)0.0011 (17)
C80.050 (2)0.042 (2)0.0355 (16)0.0003 (17)0.0017 (15)0.0006 (15)
C90.052 (2)0.047 (2)0.0377 (18)0.007 (2)0.0063 (16)0.0049 (17)
C110.047 (2)0.0375 (19)0.0440 (18)0.0004 (17)0.0046 (16)0.0035 (16)
C120.0377 (18)0.0344 (18)0.0353 (16)0.0008 (15)0.0000 (14)0.0002 (14)
C130.0366 (18)0.0321 (17)0.0357 (16)0.0017 (15)0.0003 (14)0.0021 (14)
C140.047 (2)0.0361 (19)0.0408 (17)0.0009 (17)0.0030 (15)0.0000 (16)
C150.054 (2)0.036 (2)0.0459 (19)0.0022 (18)0.0027 (16)0.0038 (16)
C160.0428 (19)0.038 (2)0.0388 (17)0.0013 (17)0.0062 (15)0.0031 (16)
C170.043 (2)0.042 (2)0.0399 (17)0.0026 (17)0.0018 (15)0.0015 (16)
C180.041 (2)0.0352 (19)0.0410 (18)0.0019 (16)0.0004 (15)0.0038 (15)
C190.0365 (18)0.0330 (19)0.0400 (17)0.0008 (15)0.0032 (14)0.0010 (15)
C200.058 (2)0.056 (2)0.056 (2)0.008 (2)0.0032 (18)0.0025 (19)
C210.086 (3)0.069 (3)0.050 (2)0.012 (2)0.010 (2)0.005 (2)
C220.080 (3)0.071 (3)0.0380 (19)0.002 (2)0.0034 (18)0.0052 (19)
C230.0373 (19)0.042 (2)0.049 (2)0.0040 (18)0.0053 (16)0.0023 (18)
C240.060 (2)0.048 (2)0.056 (2)0.0148 (19)0.0020 (18)0.0074 (18)
C250.097 (16)0.071 (15)0.063 (13)0.018 (11)0.009 (9)0.001 (12)
C260.103 (12)0.084 (11)0.082 (13)0.006 (9)0.001 (10)0.016 (10)
C25'0.10 (4)0.07 (4)0.06 (3)0.02 (3)0.009 (19)0.00 (3)
C26'0.10 (2)0.08 (3)0.08 (3)0.01 (2)0.00 (2)0.02 (2)
C25"0.10 (4)0.08 (4)0.08 (5)0.01 (3)0.00 (3)0.02 (5)
C26"0.10 (3)0.08 (2)0.08 (2)0.01 (2)0.00 (2)0.016 (17)
C270.103 (4)0.092 (4)0.118 (4)0.001 (3)0.005 (3)0.050 (3)
C280.050 (3)0.065 (3)0.121 (4)0.005 (3)0.012 (3)0.015 (3)
C290.100 (4)0.090 (4)0.173 (6)0.013 (4)0.007 (4)0.007 (4)
Geometric parameters (Å, º) top
S1—C251.80 (4)C15—H15B0.9700
S1—C201.809 (4)C16—C191.534 (4)
S1—C25"1.81 (11)C16—C171.543 (4)
S1—C25'1.82 (5)C16—H160.9800
O1—C21.200 (4)C17—C201.506 (4)
O2—C91.198 (4)C17—C181.517 (4)
O3—C21.339 (4)C17—H170.9800
O3—C41.461 (4)C19—H190.9800
O4—C181.206 (4)C20—H20A0.9700
O5—C141.428 (4)C20—H20B0.9700
O5—H50.8200C21—H21A0.9600
O6—C231.354 (4)C21—H21B0.9600
O6—C191.437 (4)C21—H21C0.9600
O7—C231.196 (4)C22—H22A0.9600
O8—C281.208 (5)C22—H22B0.9600
O10—C91.357 (4)C22—H22C0.9600
O10—C111.441 (4)C23—C241.486 (4)
C1—C21.517 (4)C24—H24A0.9600
C1—C181.528 (4)C24—H24B0.9600
C1—C191.553 (4)C24—H24C0.9600
C1—C131.589 (4)C25—C261.54 (5)
C4—C51.512 (4)C25—H25A0.9700
C4—C121.515 (4)C25—H25B0.9700
C4—H40.9800C26—H26A0.9600
C5—C61.514 (5)C26—H26B0.9600
C5—H5A0.9700C26—H26C0.9600
C5—H5B0.9700C25'—C26'1.50 (9)
C6—C71.531 (5)C25'—H25C0.9700
C6—H6A0.9700C25'—H25D0.9700
C6—H6B0.9700C26'—H26D0.9600
C7—C211.537 (5)C26'—H26E0.9600
C7—C221.537 (5)C26'—H26F0.9600
C7—C81.569 (4)C25"—C26"1.54 (15)
C8—C91.500 (5)C25"—H25E0.9700
C8—C121.544 (4)C25"—H25F0.9700
C8—H80.9800C26"—H26G0.9600
C11—C121.538 (4)C26"—H26H0.9600
C11—H11A0.9700C26"—H26I0.9600
C11—H11B0.9700C27—C281.453 (6)
C12—C131.553 (4)C27—H27A0.9600
C13—C141.523 (4)C27—H27B0.9600
C13—H130.9800C27—H27C0.9600
C14—C151.537 (4)C28—C291.491 (7)
C14—H140.9800C29—H29A0.9600
C15—C161.533 (4)C29—H29B0.9600
C15—H15A0.9700C29—H29C0.9600
C25—S1—C20103.5 (12)C20—C17—H17107.1
C25—S1—C25"16 (3)C18—C17—H17107.1
C20—S1—C25"115 (4)C16—C17—H17107.1
C25—S1—C25'29 (2)O4—C18—C17125.6 (3)
C20—S1—C25'92 (2)O4—C18—C1125.2 (3)
C25"—S1—C25'28 (4)C17—C18—C1109.0 (3)
C2—O3—C4116.7 (2)O6—C19—C16107.2 (2)
C14—O5—H5109.5O6—C19—C1111.4 (2)
C23—O6—C19116.3 (2)C16—C19—C1100.5 (2)
C9—O10—C11109.9 (3)O6—C19—H19112.3
C2—C1—C18111.2 (3)C16—C19—H19112.3
C2—C1—C19113.3 (3)C1—C19—H19112.3
C18—C1—C19101.8 (2)C17—C20—S1113.3 (3)
C2—C1—C13116.2 (2)C17—C20—H20A108.9
C18—C1—C13103.9 (2)S1—C20—H20A108.9
C19—C1—C13109.1 (2)C17—C20—H20B108.9
O1—C2—O3118.6 (3)S1—C20—H20B108.9
O1—C2—C1122.4 (3)H20A—C20—H20B107.7
O3—C2—C1119.0 (3)C7—C21—H21A109.5
O3—C4—C5107.8 (3)C7—C21—H21B109.5
O3—C4—C12107.0 (2)H21A—C21—H21B109.5
C5—C4—C12114.9 (3)C7—C21—H21C109.5
O3—C4—H4109.0H21A—C21—H21C109.5
C5—C4—H4109.0H21B—C21—H21C109.5
C12—C4—H4109.0C7—C22—H22A109.5
C4—C5—C6107.9 (3)C7—C22—H22B109.5
C4—C5—H5A110.1H22A—C22—H22B109.5
C6—C5—H5A110.1C7—C22—H22C109.5
C4—C5—H5B110.1H22A—C22—H22C109.5
C6—C5—H5B110.1H22B—C22—H22C109.5
H5A—C5—H5B108.4O7—C23—O6122.4 (3)
C5—C6—C7113.0 (3)O7—C23—C24127.0 (3)
C5—C6—H6A109.0O6—C23—C24110.5 (3)
C7—C6—H6A109.0C23—C24—H24A109.5
C5—C6—H6B109.0C23—C24—H24B109.5
C7—C6—H6B109.0H24A—C24—H24B109.5
H6A—C6—H6B107.8C23—C24—H24C109.5
C6—C7—C21109.5 (3)H24A—C24—H24C109.5
C6—C7—C22109.4 (3)H24B—C24—H24C109.5
C21—C7—C22108.1 (3)C26—C25—S1106 (2)
C6—C7—C8108.8 (3)C26—C25—H25A110.4
C21—C7—C8107.1 (3)S1—C25—H25A110.4
C22—C7—C8113.9 (3)C26—C25—H25B110.4
C9—C8—C12103.0 (3)S1—C25—H25B110.4
C9—C8—C7108.9 (3)H25A—C25—H25B108.6
C12—C8—C7116.9 (3)C25—C26—H26A109.5
C9—C8—H8109.2C25—C26—H26B109.5
C12—C8—H8109.2H26A—C26—H26B109.5
C7—C8—H8109.2C25—C26—H26C109.5
O2—C9—O10120.8 (3)H26A—C26—H26C109.5
O2—C9—C8128.8 (3)H26B—C26—H26C109.5
O10—C9—C8110.4 (3)C26'—C25'—S1127 (6)
O10—C11—C12106.0 (2)C26'—C25'—H25C105.6
O10—C11—H11A110.5S1—C25'—H25C105.6
C12—C11—H11A110.5C26'—C25'—H25D105.6
O10—C11—H11B110.5S1—C25'—H25D105.6
C12—C11—H11B110.5H25C—C25'—H25D106.1
H11A—C11—H11B108.7C25'—C26'—H26D109.5
C4—C12—C11112.2 (3)C25'—C26'—H26E109.5
C4—C12—C8115.9 (3)H26D—C26'—H26E109.5
C11—C12—C8100.6 (2)C25'—C26'—H26F109.5
C4—C12—C13107.1 (2)H26D—C26'—H26F109.5
C11—C12—C13107.6 (2)H26E—C26'—H26F109.5
C8—C12—C13113.1 (2)C26"—C25"—S1116 (8)
C14—C13—C12116.6 (2)C26"—C25"—H25E108.3
C14—C13—C1112.3 (2)S1—C25"—H25E108.3
C12—C13—C1109.3 (2)C26"—C25"—H25F108.3
C14—C13—H13105.9S1—C25"—H25F108.3
C12—C13—H13105.9H25E—C25"—H25F107.4
C1—C13—H13105.9C25"—C26"—H26G109.5
O5—C14—C13110.8 (2)C25"—C26"—H26H109.5
O5—C14—C15110.8 (3)H26G—C26"—H26H109.5
C13—C14—C15111.1 (3)C25"—C26"—H26I109.5
O5—C14—H14108.0H26G—C26"—H26I109.5
C13—C14—H14108.0H26H—C26"—H26I109.5
C15—C14—H14108.0C28—C27—H27A109.5
C16—C15—C14114.2 (3)C28—C27—H27B109.5
C16—C15—H15A108.7H27A—C27—H27B109.5
C14—C15—H15A108.7C28—C27—H27C109.5
C16—C15—H15B108.7H27A—C27—H27C109.5
C14—C15—H15B108.7H27B—C27—H27C109.5
H15A—C15—H15B107.6O8—C28—C27122.6 (5)
C15—C16—C19108.2 (2)O8—C28—C29120.4 (5)
C15—C16—C17115.2 (3)C27—C28—C29117.0 (5)
C19—C16—C17102.3 (3)C28—C29—H29A109.5
C15—C16—H16110.3C28—C29—H29B109.5
C19—C16—H16110.3H29A—C29—H29B109.5
C17—C16—H16110.3C28—C29—H29C109.5
C20—C17—C18111.1 (3)H29A—C29—H29C109.5
C20—C17—C16120.9 (3)H29B—C29—H29C109.5
C18—C17—C16102.9 (2)
C4—O3—C2—O1179.3 (3)C2—C1—C13—C127.7 (4)
C4—O3—C2—C10.1 (4)C18—C1—C13—C12130.2 (3)
C18—C1—C2—O129.1 (4)C19—C1—C13—C12121.8 (3)
C19—C1—C2—O184.8 (4)C12—C13—C14—O549.6 (3)
C13—C1—C2—O1147.7 (3)C1—C13—C14—O577.6 (3)
C18—C1—C2—O3150.3 (3)C12—C13—C14—C15173.2 (3)
C19—C1—C2—O395.8 (3)C1—C13—C14—C1545.9 (4)
C13—C1—C2—O331.7 (4)O5—C14—C15—C1681.9 (3)
C2—O3—C4—C5177.2 (3)C13—C14—C15—C1641.6 (4)
C2—O3—C4—C1253.1 (3)C14—C15—C16—C1919.2 (4)
O3—C4—C5—C6173.9 (3)C14—C15—C16—C1794.5 (3)
C12—C4—C5—C654.7 (4)C15—C16—C17—C2043.5 (4)
C4—C5—C6—C765.9 (4)C19—C16—C17—C20160.6 (3)
C5—C6—C7—C21174.2 (3)C15—C16—C17—C1881.1 (3)
C5—C6—C7—C2267.5 (4)C19—C16—C17—C1836.0 (3)
C5—C6—C7—C857.4 (4)C20—C17—C18—O434.6 (4)
C6—C7—C8—C9155.1 (3)C16—C17—C18—O4165.3 (3)
C21—C7—C8—C986.6 (4)C20—C17—C18—C1140.5 (3)
C22—C7—C8—C932.8 (4)C16—C17—C18—C19.8 (3)
C6—C7—C8—C1239.0 (4)C2—C1—C18—O444.2 (4)
C21—C7—C8—C12157.2 (3)C19—C1—C18—O4165.2 (3)
C22—C7—C8—C1283.3 (4)C13—C1—C18—O481.5 (4)
C11—O10—C9—O2178.5 (3)C2—C1—C18—C17140.7 (3)
C11—O10—C9—C80.5 (3)C19—C1—C18—C1719.7 (3)
C12—C8—C9—O2162.4 (3)C13—C1—C18—C1793.7 (3)
C7—C8—C9—O272.9 (4)C23—O6—C19—C16163.2 (2)
C12—C8—C9—O1019.8 (3)C23—O6—C19—C187.8 (3)
C7—C8—C9—O10104.9 (3)C15—C16—C19—O6169.9 (2)
C9—O10—C11—C1219.4 (3)C17—C16—C19—O668.1 (3)
O3—C4—C12—C1143.7 (3)C15—C16—C19—C173.6 (3)
C5—C4—C12—C1176.0 (4)C17—C16—C19—C148.4 (3)
O3—C4—C12—C8158.5 (2)C2—C1—C19—O647.4 (3)
C5—C4—C12—C838.9 (4)C18—C1—C19—O672.0 (3)
O3—C4—C12—C1374.2 (3)C13—C1—C19—O6178.6 (2)
C5—C4—C12—C13166.2 (3)C2—C1—C19—C16160.8 (3)
O10—C11—C12—C4153.8 (2)C18—C1—C19—C1641.3 (3)
O10—C11—C12—C829.9 (3)C13—C1—C19—C1668.1 (3)
O10—C11—C12—C1388.6 (3)C18—C17—C20—S1178.0 (2)
C9—C8—C12—C4150.4 (3)C16—C17—C20—S161.4 (4)
C7—C8—C12—C431.1 (4)C25—S1—C20—C17149.1 (14)
C9—C8—C12—C1129.2 (3)C25"—S1—C20—C17138 (4)
C7—C8—C12—C1190.2 (3)C25'—S1—C20—C17122 (2)
C9—C8—C12—C1385.3 (3)C19—O6—C23—O71.4 (4)
C7—C8—C12—C13155.3 (3)C19—O6—C23—C24179.5 (2)
C4—C12—C13—C1487.3 (3)C20—S1—C25—C2684 (2)
C11—C12—C13—C14151.8 (3)C25"—S1—C25—C2657 (21)
C8—C12—C13—C1441.6 (4)C25'—S1—C25—C2614 (5)
C4—C12—C13—C141.3 (3)C25—S1—C25'—C26'63 (6)
C11—C12—C13—C179.6 (3)C20—S1—C25'—C26'177 (6)
C8—C12—C13—C1170.2 (2)C25"—S1—C25'—C26'29 (7)
C2—C1—C13—C14138.8 (3)C25—S1—C25"—C26"63 (19)
C18—C1—C13—C1498.8 (3)C20—S1—C25"—C26"20 (8)
C19—C1—C13—C149.2 (3)C25'—S1—C25"—C26"16 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O8i0.822.162.952 (4)161
Symmetry code: (i) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC24H32O8S·C3H6O
Mr538.63
Crystal system, space groupOrthorhombic, P212121
Temperature (K)298
a, b, c (Å)10.6258 (12), 11.4825 (18), 22.265 (2)
V3)2716.6 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.17
Crystal size (mm)0.53 × 0.32 × 0.28
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.915, 0.954
No. of measured, independent and
observed [I > 2σ(I)] reflections
11871, 4774, 3201
Rint0.041
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.112, 1.04
No. of reflections4774
No. of parameters373
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.23
Absolute structureFlack (1983), 2053 Friedel pairs
Absolute structure parameter0.00 (12)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O8i0.822.162.952 (4)161
Symmetry code: (i) x+1, y+1/2, z+1/2.
 

Acknowledgements

This research was supported by the Natural Science Found­ation of Zhejiang Province (grant No. Y205318) and the Open Foundation of Key Disciplines within Zhejiang Province.

References

First citationBruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChen, Y. Z., Wu, Z. W. & Cheng, P. Y. (1987). Chin. J. Org. Chem. 7, 21–28.  Google Scholar
First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHe, S., Wu, B., Shi, H. & Sun, C. R. (2007). Chin. J. Struct. Chem., 26, 299–302.  CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShi, H., He, S., He, L. & Pan, Y. J. (2007). Chem. J. Chin. Univ. 28, 100–102.  CAS Google Scholar
First citationYamaguchi, M., Taniguchi, M., Kubo, I. & Kubota, T. (1977). Agric. Biol. Chem. 41, 2475–2477.  CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds