Synthesis, characterization and crystal structure of 4,5- Bis(Cyclohexanecarbonylthio)-1,3-dithiolane-2-thione crystal

Article abstract of DOI:10.1007/s10870-010-9685-y

A new crystal of 4,5-bis(cyclohexanecarbonylthio)- 1,3-dithiolane-2-thione has been prepared at room temperature and characterized by elemental analysis, UV- Vis-NIR absorption spectrum and X-ray single crystal determination. The complex crystallized in t

Full text of DOI:10.1007/s10870-010-9685-y

J Chem Crystallogr (2010) 40:501–504
DOI 10.1007/s10870-010-9685-y
ORIGINAL PAPER
Synthesis, Characterization and Crystal Structure
of 4,5-Bis(Cyclohexanecarbonylthio)-1,3-dithiolane-2-thione
Crystal
•
Yan Ling Wang Mei Li Jun Yao Ye Fei Wang
•
•
•
•
Jing Jing Zheng Li Ma
Received: 9 November 2009 / Accepted: 6 January 2010 / Published online: 13 February 2010
Ó Springer Science+Business Media, LLC 2010
Abstract A new crystal of 4,5-bis(cyclohexanecarbon-
ylthio)-1,3-dithiolane-2-thione has been prepared at room
temperature and characterized by elemental analysis, UV–
Vis–NIR absorption spectrum and X-ray single crystal
determination. The complex crystallized in triclinic space
conjugated structure [2]. In order to obtain materials with
high optical and/or electric properties and investigate their
structure–property relationship, various groups are bonded
to sulfur in the 4- and 5-positions. Being a ligand with
potential sulfur donors, 2-thioxo-1,3-dithiole-4,5-dithiolate
(dmit) are generally used as important building blocks for
organic, organometallic and coordination complex electri-
cal conductors and superconductors [3]. Recently, these
complexes have been reported as possessing nonlinear
optical properties [4, 5]. Therefore, as a part of these
studies, the synthesis, characterization and crystal structure
of 4,5-bis(cyclohexanecarbonylthio)-1,3-dithiolane-2-thi-
one crystal, as a precursor of TTF and BEDT-TTF deriv-
atives, will be reported in this article for the first time.
˚
group P-1 with unit cell dimensions a = 5.37370(10) A,
˚
˚
b = 12.8618(2) A, c = 15.2481(2) A, a = 74.8530(10)°,
3
˚
b = 80.6000(10)°, c = 85.9550(10)°, V = 1003.18(3) A ,
. The X-ray structure
Z = 2, Dx = 1.3861(1) g cm-3
determination revealed that the crystal is centered-sym-
metrical and the molecules form dimers with a long
intermolecular SÁÁÁS interaction in the crystal.
Keywords X-ray crystallography Á
2-thioxo-1,3-dithiole-4,5-dithiolate(dmit) Á Ligand
Experimental
Introduction
Synthesis of 4,5-bis(cyclohexanecarbonylthio)-1,3-
dithiolane-2-thione
TTF (tetrathiafulvalene), BEDT-TTF [bis(ethylenedithio)-
tetrathiafulvalene] derivatives and their charge-transfer
salts have attracted much interest because of their high
electronic conductivity or superconductivity[1]. Moreover,
these compounds have received some attention in third-
order nonlinearity optical field due to their relatively large
All the starting materials were reagent grade (C98.0%) and
used as purchased, and the growth processes were carried out
in acetone solutions. The title compound was prepared by the
reaction of (Bu4N)2[Zn(dmit)2] (dmit is the 2-thioxo-1,3-
dithiole-4,5-dithiolate dianion, C3S52-) and cyclohexane-
carboxylic acid chloride in acetone. Cyclohexanecarboxylic
acid chloride (8.80 g, 60 mmol) was added dropwisely into a
solution of (Bu4N)2[Zn(dmit)2] (14.12 g, 15 mmol) in ace-
tone (100 ml). The mixture was stirred vigorously for 2 h at
room temperature. The resulting orange precipitate was
isolated by filtration and washed with water and MeOH,
affording microcrystals of the title compound. These
microcrystals were used for element analysis. Large orange-
yellow organic crystals, suitable for the X-ray structure
Y. L. Wang (&) Á J. Yao Á Y. F. Wang Á J. J. Zheng Á L. Ma
School of Petroleum Engineering, China University
of Petroleum (East China), 266555 Qingdao,
People’s Republic of China
e-mail: wangyl_hdpu@hotmail.com
M. Li
Material Science and Engineering of Shandong Institute of Light
Industry, 250353 Jinan, People’s Republic of China
123

502
J Chem Crystallogr (2010) 40:501–504
UV–Vis–NIR Spectrum
determination, were obtained by recrystallization in acetone
by slow evaporation at room temperature. Yield: 86%.
The linear absorption spectrum of acetone solution of 4,5-
bis(cyclohexanecarbonylthio)-1,3-dithiolane-2-thione was
recorded using a UV–Vis–NIR scanning spectrophotome-
ter (Hitachi U-4100, Japan) with the wavelength region
330–2000 nm at room temperature using acetone solvent
as reference.
Structural Determination
X-ray diffraction data were collected using a Bruker APEX2
CCD area-detector diffractometer with graphite-monochro-
˚
mated Mo - Ka radiation (k = 0.71073 A) at 293(2) K. A
crystal with dimensions 0.49 mm 9 0.19 mm 9 0.11 mm
was used. Absorption correction was not used. The structure
was solved by the direct method and refined on F2 by full-
matrix least-squares methods using the SHELXTL-97. The
graphical tool used was SHELXTL (Bruker, 1997). Crystal
data and experimental details are listed in Table 1.
Results and Discussion
The results of the elemental analyses are summarized in
Table 2. The measured data are identical with the theo-
retical value, which indicates that the chemical composi-
tion of the crystals should be correct.
Elemental Analyses
Figure 1 is the molecular scheme of the as-prepared
organic compound. Figure 2 gives a perspective view of
the complex with the atomic labeling system. Selected
bond distances and angles for the complex are shown in
Table 3. The doubly-bonded atom S1 lies in the five-
membered dithiole ring plane. The C1–S1 distance [1.636
Elemental analyses were carried out using a Pekin Elmer
2400 instrument.
Table 1 Crystal data and refinement parameters of the compound
˚
(2) A] is slightly longer than a typical C=S double bond.
Empirical formula
Radiation k
C17H22O2S5
˚
Mo - Ka(0.71073A)
418.65
The C–S bond lengths in the five-membered ring are
shorter than a typical C–S single bond [range 1.726(2)–
Molecular weight
Temperature (K)
Description
˚
˚
1.738(2) A]. The C=C bond length [1.341(3) A] in the five-
membered ring corresponds to a normal double bond. This
shows the high degree of conjugation of five-membered
ring moiety in the dmit compound. The introduction of
electron acceptor group, the carbonyl group, results in a
slight decrease in C2–S2 and C3–S3 distance [1.737(2) and
293 (2)
Prism
Color
Orange-yellow
0.49 9 0.19 9 0.11
Triclinic
Crystal size (mm)
Crystal system
Crystal group
h limit (8)
P - 1
˚
1.738(2) A, respectively], which is different from other
2.41–27.25
5.37370 (10)
12.8618 (2)
15.2481 (2)
74.8530 (10)
80.6000 (10)
85.9550 (10)
1003.18 (3)
2
˚
a (A)
˚
b (A)
Table 2 Elemental analyses of the compound crystal
˚
c (A)
Element
Composition (%)
Theoretical
a (8)
b (8)
c (8)
Measured
C
H
S
48.77
5.31
48.65
5.18
3
˚
V (A )
Z
38.29
38.33
Dcal. (mgÁm-3
)
1.3861
Absorption coefficient (mm-1
)
0.585
Absorption correction Tmin and Tmax. 0.7629 and 0.9374
No. of observed data, I [ 2r(I) 5777
Final R indices [I [ 2r(I)](R, wR) 0.0420/0.1042
O
R indices (all data) (R, wR)
F (0 0 0)
0.0531/0.1127
440
S
S
S
S
Range/indices (h, k, l)
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
-6,6;-15,16;-19,19
Full-matrix least-squares on F2
4575/0/217
S
O
1.031
w = [s2(Fo)2 ? (0.0497P)2 ? 0.5396P]-1, where P = (Fo2 ? 2Fc2)/3
Fig. 1 The molecular scheme of the compound
123

J Chem Crystallogr (2010) 40:501–504
503
Fig. 2 The molecular structure of compound, showing 50% proba-
bility displacement ellipsoids, H atoms have been omitted for clarity;
numbering according to Table 3
˚
Table 3 Selected bond distances (A) and angles (°) for the
compound
C1–S1
1.636(2)
1.726(2)
1.726(2)
1.341(3)
1.737(2)
1.751(2)
3.5242(10)
97.70(10)
97.70(10)
C3–S3
C3–S5
C4–S4
C11–S5
C4–O2
C11–O1
1.738(2)
1.751(2)
1.797(2)
1.806(2)
1.183(3)
1.193(3)
Fig. 3 Crystal packing of the compound, viewing along the a-axis
C1–S2
C1–S3
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
C2–C3
C2–S2
C2–S4
S4–S4i
C1–S2–C2
C1–S3–C3
C2–S4–C4
100.80(10)
101.26(10)
C3–S5–C11
symmetry code: (i) 1-x, -y, 1-z
analogous compounds substituted by alkyl groups [6–8]
and consistent with those similar compounds [9, 10]. The
two six-membered rings have a dihedral angle of
45.21(15)°, and the dmit ring forms dihedral angles of
78.66(12)° and 33.50(13)° with cyclohexane rings,
respectively.
200 400 600 800 1000 1200 1400 1600 1800 2000 2200
Wavelength/nm
Fig. 4 UV–Vis–NIR absorption spectrum of the acetone solution of
the compound (1 9 10-3 mol L-1) using acetone solvent as refer-
ence at room temperature
Figure 3 shows the crystal packing of the compound,
viewing along the a-axis. The packing styles basically
belong to the structural motif with the following features.
There are weak intermolecular contacts for S4ÁÁÁS4i [sym-
metry code: (i) 1-x, -y, 1-z] with a distance of
Conclusions
The elemental analysis and UV–Vis–NIR spectrum studies
have provided the basic structural and physical character-
istics of the prepared single crystal. The structure of the
crystal is centered-symmetrical and the intermolecular
contacts of SÁÁÁS make the molecules form discrete pairs in
the packing.
˚
3.5242(10) A, slightly shorter than that of the sum of van
der Waals radii of two sulfur atoms. Thereby the molecules
form dimers in a side-to-side manner with the long inter-
molecular SÁÁÁS interactions in the crystal packing. As seen
from Fig. 3, these molecules are (in a face-to-face manner)
arranged to form columns or stacks along the a-axis.
The title compound exhibits strong absorption at
386 nm in 10-3 mol L-1 acetone solutions as shown in
Fig. 4, which is assigned to local excitation of the dmit
ring.
Acknowledgments The authors acknowledge the financial support
of the High Technology Development Project of China (grant No.
2007AA090701-4), National Key Science and Technology Project of
China (grant Nos. 2008ZX05024-02-005, 2008ZX05002-005), the
Postdoctoral Science Foundation of China (grant No. 20090451347),
123

504
J Chem Crystallogr (2010) 40:501–504
National Outstanding Youth Foundation of China (grant No.
50925414) and Outstanding Research Award Fund for Young Sci-
entist of Shandong Province (grant No. BS2009CL019).
4. Wang SF, Huang WT, Zhang TQ, Yang H, Gong QH, Okuma Y,
Horikiri M, Miura YF (1999) Appl Phys Lett 75:1845–1847
5. Zhai J, Huang CH, Wei TX, Gan LB, Cao H (1999) Polyhedron
18:1513–1518
6. Low JN, Chohan ZH, Howie RA, Wardell JL (1999) Acta
Crystallogr C 55:0124–0126
7. Simonsen O, Varma KS, Clark A, Underhill AE (1990) Acta
Crystallogr C 46:804–806
References
1. Willams JM, Ferraro JR, Thorn RJ, Carlson KD, Geiser U, Wang
HH, Kini AM, Whangbo M-H (1992) Organic superconductors.
Prentice Hall, New Jersey
8. Yu WT, Fang Q, Lei H (1995) Acta Crystallogr C 51:2606–2609
9. Wang YL, Yu WT, Xu D, Wang XQ, Zhang GH (2005) Acta
Crystallogr E61:o971–o973
2. Huggard PG, Blau W (1987) Appl Phys Lett 51:2183–2185
3. Pullen AE, Olk RM (1999) Coord Chem Rev 188:211–262
10. Wang Y-L, Yu W-T, Xu D, Wang X-Q, Zhang G-H, Feng L
(2005) Acta Crystallogr E61:o1432–o1433
123