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Isolation and crystal ctructure of sulfur from Capparis spinosa fruits

刺山柑果实中硫单质的分离与晶体结构



全 文 :广 西 植 物 Guihaia 32(2):257-260                  2012年3月 
DOI:10.3969/j.issn.1000-3142.2012.02.022
Isolation and crystal ctructure of sulfur
fromCapparis spinosafruits
LI Hai-Jun1,2,BAI Hong-Jin1,2*,ZHANG Ji-Wen3,WANG An-Yin1,2
(1.Key Laboratory of Protection and Utilization of Biological Resources in Tarim Basin,Xinjiang Prodution and
Construction Corps,Alar 843300,China;2.College of Life Sciences,Tarim University,Alar 843300,
China;3.College of Sciences,Northwest A &F University,Yangling 712100,China)
Abstract:The purpose of this paper studied single crystal structure of S8isolated firstly fromCapparis spinosa
fruits.The S8crystal structure was investigated by single-crystal X-ray crystalographic analysis crystalizes in
the monoclinic system,M=256.48.space group Fddd.Unit cel parameters a=10.456(7),b=12.908(9),
c=24.483(17),V=3305(4)3,Z=16,F(000)=2048.The final R1=0.0915,wR2=0.1820.
Key words:Capparis spinosal;element sulfur;single-crystal X-ray diffraction;crystal structure
CLC Number:R284.2;O723  Document Code:A  Article ID:1000-3142(2012)02-0257-04

刺山柑果实中硫单质的分离与晶体结构
李海军1,2,白红进1,2*,张继文3,王安银1,2
(1.新疆生产建设兵团塔里木盆地生物资源保护利用重点实验室,新疆 阿拉尔843300;2.塔里木大学
生命科学学院,新疆 阿拉尔843300;3.西北农林科技大学 理学院,陕西 杨凌712100)
摘 要:从刺山柑果实中首次分离纯化得到S8单质。经X-射线单晶衍射分析,确认该化合物为S8晶体,M=
256.48。晶体属斜方晶系,空间群Fddd。晶胞参数a=10.456(7),b=12.908(9),c=24.483(17),V=
3305(4)3,Z=16,F(000)=2048,R1=0.0915,wR2=0.1820。
关键词:刺山柑;硫单质;X-射线单晶衍射;晶体结构
  Capparis spinosa is a vine that belongs to
family Capparaceae,genus Capparis,mainly dis-
tributed in Xinjiang,Tibet and other places in Chi-
na,lives on extremely arid Gobi desert or arid ston-
y mountain(Liu et al.,2011).As the Uyghur folk
medicine,the root bark,leaf,fruit of C.spinosa
were widely used for treatment of gout,rheumatoid
arthritis(Chinese medicine dictionary,1977).
Chemical studies on C.spinosahave reported many
beneficial chemical compounds(Ao,et al.,2007).
Including volatile oil,mustard oil glycoside,alka-
loid,terpenes,flavonoids and other ingredients;mo-
reover,laboratory studies have shown that the ex-
tract of the plant has pharmacological effects such
as liver protection,antinflammatory,antiviral,an-
tioxidant,immune regulation,hypoglycemic,reduc-
① Received date:2012-01-05  Accepted date:2012-02-21
Foundation items:Supported by Policy Guiding Project of Science and Technology Bureau of Xinjiang Production and Construction Corps(2006YD29);Open
Project of Xinjiang Prodution and Constrction Key Laboratory of Protection and Utilization of Biological Resources in Tarim Basin(BR0609)
Biography:LI Hai-Jun(1984-),male,Datong of Shanxi Province,graduate student for a Master’s degree,research fields:Natural Product
Chemistry,(E-mail)lihaijun1030@163.com.
*Author for correspondence(E-mail:bhj67@163.com)
ing blood lipid and other biological activity(Chen,
et al.,2010;Li,et al.,2007;Nizar et al.,2010;
Yang,et al.,2008,2010;Gagdoli C,1999).This
paper reports the single-crystal structure of S8iso-
lated firstly from the fruit parts of C.spinosa,
which wil facilitate the study of this plant and lay
a foundation for its exploitation and utilization.
1 Experimental
1.1General experimental procedures
The melting point was performed on X-4mi-
cro melting point apparatus(uncorrected).The IR
spectra was recorded on a Fourier transform infra-
red spectrometer with KBr pelets.Single-crystal
structure of S8 was measured on an X-ray diffrac-
tion surface detector Bruker SMART CCDⅡ dif-
fractometer.
1.2Plant material
The fruit parts of C.spinosal were colected
from South Xinjiang in July 2008.It was identified
by Professor Li Zhi-Jun Colege of Plant Science,
Tarim University.
1.3Extraction and isolation
The air-dried and finely powdered fruit parts
of C.spinosa were extracted with petroleum ether
for three times at room temperature,every time for
48h,then filtrated.The filtrate was evaporated
under reduced pressure to gain crude petroleum e-
ther extraction.Firstly,the extraction was separa-
ted by silica gel column chromatography,further
purified by repeated silica gel column Chromatog-
raphy,finaly using crystalization to get a light
yelow compound.
1.4Preparation of the single crystal
The light yelow compound was recrystalized
in the mixture solution of petroleum ether and eth-
yl acetate,and the single crystal was obtained at
the constant temperature(20℃).
1.5Crystalographic data colection and structure de-
termination
  A yelow single crystal with dimensions 0.34mm
×0.27mm×0.19mm was put on a Bruker SMART
CCD Ⅱdiffractometer equipped with a graphite-
monochromatic Moka radiation(0.71073)by u-
singφ-ωscan mode.Out of the total 3 813reflec-
tions colected in the range of 2.64°to 25.09°.739
were unique(Rint=0.0338).An absorption correc-
tion by using SADABS software was applied.A-
tomic coordinates of atoms were dissolved with
SHELXS-97program firstly,and then atomic coor-
dinates and anisotropic thermal parameters of al
atoms were determined from difference Fourier
map.The crystal structure was solved by direct
methods using SHELXS-97program.Al atoms
were refined by ful-matrix least-squares tech-
niques on F2with SHELXTL-97.The final R indi-
ces(I>2σ(I))were R1=0.0915,wR2=0.1820.The
largest peak and hole on final difference Fourier
map were 1.298and-2.367e.-3,respectively.
2 Results and Analysis
The single crystal of S8was recrystalized un-
der the mixture solution of petroleum ether and
ethyl acetate at the constant temperature and isola-
ted from C.spinosa fruits for the first time.The
composition and configuration of S8have been in-
vestigated by single-crystal X-ray crystalographic
analysis crystalizes in the monoclinic system.The
crystal data and structure refinement are given in
Table 1.The atomic coordinates and equivalent iso-
tropic displacement parameters are given in Table
2.Bond lengths and bond angles are listed in Table
3.Anisotropic displacement parameters(2×103)
for title compound are listed in Table 4.Torsion
angles for title compound are listed in Table 5and
Figure 1shows the drawing of the molecule config-
uration and Figure 2shows the packing diagram of
the unit cel of compound.We obtained S8fromC.
spinosafruits through separation and purification,
but how it formed was stil not clear,maybe as the
report went the biochemical pathway leading to the
accumulation of elemental sulphur remained unex-
plained(Lognay,et al.,1993),maybe other reasons
need to be futher investigation.
852 广 西 植 物                  32卷
Table 1 Crystal data and structure refinement
for title compound
Item  Parameter
Empirical formula  S8
Formula weight  256.48
Temperature  296(2)K
Wavelength  0.71073
Crystal system,space group  Orthorhombic,Fddd
Unit cel dimensions  a=10.456(7),α=90deg
b=12.908(9),β=90deg
c=24.483(17),γ=90deg
Volume  3305(4)3
Z,Calculated density  16,2.062Mg/m3
Absorption coefficient  2.061mm-1
F(000) 2 048
Crystal size  0.34mm×0.27mm×0.
19mm
Theta range for data colection  2.64to 25.09deg
Limiting indices -5≤h≤12,-15≤k≤15,
-29≤l≤29
Reflections colected/unique  3813/739(Rint=0.0338)
Completeness to theta=25.09  100.0%
Absorption correction  None
Max.and Min.transmission  0.7017and 0.5400
Refinement method  Ful-matrix  least-squares
on F2
Data/restraints/parameters  739/0/37
Goodness-of-fit on F2  1.046
Final R indices[I>2σ(I)] R1=0.0915,wR2=0.1820
R indices(al data) R1=0.0939,wR2=0.1846
Largest diff.peak and hole  1.298and-2.367e.-3
Table 2 Atomic coordinates(×104)and equivalent
isotropic displacement parameters
(2×103)for title compound
Atom  x  y  z  Ueq
S(2) 341(1) 7803(1) 4238(1) 39(1)
S(3) -428(1) 7298(1) 4959(1) 37(1)
S(4) 1056(1) 7027(1) 5486(1) 37(1)
S(1) 359(1) 6578(1) 3705(1) 36(1)
 U(eq)is defined as one third of the trace of the orthogonalized Uij
tensor
Table 3 Bond lengths[]and angles
[°]for title compound
Bond lengths  Bond angles
S(2)-S(3) 2.0464(19)
S(3)-S(2)-S(1) 107.90(8)
S(2)-S(1) 2.049(2)
S(2)-S(3)-S(4) 107.45(9)
S(3)-S(4) 2.048(2)
S(4)#1-S(4)-S(3) 108.52(8)
S(4)-S(4)#1  2.046(3)
S(1)#1-S(1)-S(2) 109.15(8)
S(1)-S(1)#1  2.046(3)
  Symmetry transformations used to generate equivalent atoms:
#1-x+1/4,-y+5/4
Table 4 Anisotropic displacement parameters
(2×103)for title compound
U11 U22 U33 U23 U13 U12
S(2) 50(1) 30(1) 35(1) 9(1) -4(1) 1(1)
S(3) 36(1) 42(1) 34(1) -2(1) 5(1) 10(1)
S(4) 53(1) 32(1) 27(1) -8(1) -5(1) 3(1)
S(1) 27(1) 55(1) 27(1) -3(1) -6(1) -2(1)
 The anisotropic displacement factor exponent takes the form:-2
pi 2[h2 a*2 U11+...+2hk a*b* U12]
Table 5 Torsion angles[°]for title compound
S(1)-S(2)-S(3)-S(4) 100.75(8)
S(2)-S(3)-S(4)-S(4)#1 -98.84(9)
S(3)-S(2)-S(1)-S(1)#1 -97.98(9)
 Symmetry transformations used to generate equivalent atoms:#1
-x+1/4,-y+5/4
Fig.1 The molecular structure of the title compound
Fig.2Packing diagram of the unit cel of title compound
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062 广 西 植 物                  32卷