Self-assembly of N-1, 3-dithiolan-2-ylidene-N′-[1-furan-2-yl-meth-(E) -ylidene]-hydrazine via left-handed helical chains of S...O short contacts and C-H...N inter-molecular hydrogen-bonds

Article abstract of DOI:10.1007/s10870-008-9450-7

The title compound, N-1, 3-Dithiolan-2-ylidene-N′-[1-furan-2-yl-meth- (E)-ylidene]-hydrazine was synthesized via furfural with 2-hydrazono-1, 3-dithiolane and characterized by elemental analysis, ¹H NMR, ¹³C NMR, IR, UV-Vis and single crystal XRD. The crystal belongs to orthorhombic, space group F2₁2₁2₁ with unit cell parameters a = 6.4035(9) A, b = 11.8835(16) A, c = 12.3809(17) A, V = 942.1(2) A³, Z = 4, Dc = 1.497, Mr = 212.28, μ = 0.523 mm^-1, F(000) = 440, R₁ = 0.0243, and wR ₂ = 0.0602. The molecule is the anti-rotamer of the trans-isomer and every molecule forms zig-zag C(7) chains via C-H...N inter-molecular hydrogen-bond [H...N = 2.74 A, C...N = 3.354(3) A and C-H...N = 142°] running parallel to the [010] direction. At the same time many molecules self-assemble the left-handed spiral C(7) chains and inverse ones via the S...O short contacts [S...O = 3.1867(13) A] along a axis.

Full text of DOI:10.1007/s10870-008-9450-7

J Chem Crystallogr (2008) 38:867–871
DOI 10.1007/s10870-008-9450-7
COMMUNICATION
Self-Assembly of N-1, 3-Dithiolan-2-ylidene-N0-[1-furan-2-yl-
meth-(E)-ylidene]-hydrazine via Left-Handed Helical Chains
of SꢀꢀꢀO Short Contacts and C–HꢀꢀꢀN Inter-Molecular
Hydrogen-Bonds
Yong-Hong Liu Æ Zhi-Gang Li Æ Ling-Juan Yang Æ
Xiao-Lan Liu
Received: 18 October 2007 / Accepted: 10 July 2008 / Published online: 9 August 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The title compound, N-1, 3-Dithiolan-2-ylidene-
N0-[1-furan-2-yl-meth-(E)-ylidene]-hydrazine was synthe-
sized via furfural with 2-hydrazono-1, 3-dithiolane and
characterized by elemental analysis, 1H NMR, 13C NMR, IR,
UV–Vis and single crystal XRD. The crystal belongs to
orthorhombic, space group F212121 with unit cell parameters
Introduction
2-Hydrazono-1, 3-dithiolane and its derivatives are good
synthesis agents and biological activity compounds [1–5].
Many its Schiff’s bases, such as its pyruvoylhydrazone,
benzoylhydrazone and salicyloylhydrazone, have good
biological activities on Escherichia coli (1,047) and strep-
tococcus 1,123) and low toxicity [6]. Furthermore the
salicyloylhydrazone, as a good ligand, can coordinates with
lots of metal ions and some of its complexes have important
material properties [7, 8]. But its furfural-hydrazone was not
reported. Here as a ongoing research for new and better
biologically active agents and ligands [9–11], we report the
synthesis and supramolecular structure of the title compound
(I) (Fig. 1) which differs in several respects from those of 1,
2-bis(1,3-dithiolan- 2-ylidene)hydrazine (II) [12].
˚
3
˚
a = 6.4035(9) A, b = 11.8835(16) A, c = 12.3809(17) A,
˚
˚
V = 942.1(2) A , Z = 4, Dc = 1.497, Mr = 212.28, l =
0.523 mm-1, F(000) = 440, R1 = 0.0243, and wR2 =
0.0602. The molecule is the anti-rotamer of the trans-isomer
and every molecule forms zig-zag C(7) chains via C–HꢀꢀꢀN
˚
inter-molecular hydrogen-bond [HꢀꢀꢀN = 2.74 A, CꢀꢀꢀN =
˚
3.354(3) A and C–HꢀꢀꢀN = 142°] running parallel to the
[010] direction. At the same time many molecules self-
assemble the left-handed spiral C(7) chains and inverse ones
˚
via the SꢀꢀꢀO short contacts [SꢀꢀꢀO = 3.1867(13) A] along a
axis.
Keywords 2-Hydrazono-1, 3-dithiolane ꢀ Furfural ꢀ
Schiff’s base ꢀ Synthesis ꢀ Self-assembly ꢀ Crystal structure
Experimental
C, H and N elemental analyses were determined with a
Carlo-Erba 1106 elemental analyser. The IR spectrum was
recorded on a Brucker Tensor 27 spectrophotometer as KBr
pellets. Electronic spectrum was obtained using a Shima-
1
dzu UV-2550 spectrophotometer in CHCl3. The H NMR
and 13C NMR spectra were carried out on a Bruker Avance
600 NMR spectrometer using CDCl3 as solvent and TMS
as internal standard. Melting point was measured on a
Yanagimoto instrument and uncorrected.
Y.-H. Liu ꢀ X.-L. Liu (&)
College of Chemistry and Chemical Engineer, Yangzhou
University, Yangzhou 225002, People’s Republic of China
e-mail: xiaolanliu998@yahoo.com.cn
All chemicals were of reagent grade quality obtained
from commercial sources and used without further purifi-
cation. 1, 3-dithiolane were prepared by literature methods
(Scheme 1) [12].
Z.-G. Li
Tianshui Institute for Drug Control, Tianshui 741018,
People’s Republic of China
L.-J. Yang
College of Life and Chemistry, Tianshui Normal University,
Tianshui 741001, People’s Republic of China
Under Ar atmosphere two drops of acetyl acid were
added to a solution of ferrocene-carboxaldehyde (1.0 g,
123

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J Chem Crystallogr (2008) 38:867–871
X-ray Crystallography
X-ray data were collected on a Bruker SMART 1000
CCD diffractometer with graphite-monochromated Mo Ka
˚
radiation (k = 0.71073 A) at 294(2) K. Semi-empirical
absorption corrections were applied using the SADABS
program [14]. The structures were solved by direct meth-
ods and refined by full matrix least-squares methods based
on F2 with anisotropic thermal parameters for all nonhy-
drogen atoms. Hydrogen atoms were placed in their
calculated positions, assigned fixed isotropic thermal
parameters and allowed to ride on their respective parent
atoms. All computations were carried out using SHELXS-
97 and SHELXL-97 programs [15]. A PLATON view and
ORTEP-3 view were obtained with the WinGx Program
System [16]. A summary of the crystallographic data and
details of the structure refinements is listed in Table 1.
Fig. 1 The molecular structure with the atomic numbering scheme.
Displacement ellipsoids are drown at the 30% probability level
KOH
NH2NH2 + CS2 + BrCH2CH2Br
OCH
O
AcOH, EtOH
O
N
S
S
N
Results and Discussion
(I)
S
S
1
The H NMR, 13C NMR, IR, UV and elemental analysis
N
S
S
for the title compound were in good agreement with it.
Figure 1 shows ORTEP-3 drawing the molecular structure,
together with the numbering scheme used. Selected bond
lengths and bond angles are listed in Table 2.
N
(II)
Scheme 1 The synthetic process of compound I and the structure of
compound II
Compound (I) crystallizes in orthorhombic system and
space group P212121 with Z = 4, whereas (II) crystallizes
in monoclinic and P21/n with Z = 2 [11]. In (I) and (II) the
corresponding bond distances and angles are very similar.
The bond lengths S2–C6 and S1–C8 are not same in both
of them, indicating differences in the electronic environ-
ments of the two S atoms (Fig. 1, Table 1). While atoms
4.5 mmol) and 2-hydrazono-1, 3-dithiolane (0.6 g, 4.5
mmol) in 95% EtOH (20 mL). The reaction mixture was
stirred for 12 h at room temperature and boiled under
reflux for 4 h until a precipitate formed. After concentrated
to a fit volume, the mixture was set aside overnight in
refrigerator and dark red crystals were obtained. After
recrystallized in anhydrous ethanol, a yellowish needle
crystals obtained (0.9 g, yield 94.4%, m.p. 381–382 K).
Its crystal suitable for X-ray diffraction analysis was
grown from methylene dichloride at room temperature
over a period of several days. Analysis calculated for
C8H8N2OS2: C, 45.29; H, 3.71; N, 13.22%; found: C,
45.26; H, 3.80; N, 13.28.
1H NMR (600 MHz, CDCl3): d 8.20 (1H, s, N=CH);
7.59 (1H, s, 1-H of furan ring), 6.80 (1H, s, 3-H of furan
ring), 6.52 (s, 1H, 2-H of furan ring); 3.52 (s, 4H,
CH2CH2). 13C NMR (600 MHz, CDCl3, d, p.p.m.):
177.462 (Fur-C=N), 149.602 (CS2), 146.665 (4-C of furan
ring) 145.462 (1-C of furan ring), 115.507 (3-C of furan
ring), 112.111 (2-C of furan ring) 36.669, 35.413
(CH2CH2) [11]. IR (KBr, cm-1): 3150 (w, =C–H), 1612
(vs, C=N), 1,546 and 1,501 (s, C=C), 930 (s, N–N), 851 (s,
C–S). UV–Vis [kmax, nm (e 9 104), in CH2Cl2]: 280.0
(0.98) (B-band), 369.2 (1.29) (K-band) [13].
˚
C7 and C8 deviate by -0.442(6) and 0.226(7) A respec-
tively from the least-squares plane in (II), those are
˚
-0.27456(5) and 0.24401(5) A respectively in (I). It shows
that the rings conformation of 1, 3-dithiolane are also in
half-chair forms, but the 1, 3-dithiolane ring is more
co-plane after jointed by fural, because the atoms of S1,
C6, S2, N2, N1, C5, C4, C3, C2, C1 and O1 form a large
p-conjugation system (for the atom deviations of them
for the plane are -0.0929(16), -0.005(5), -0.0446(15),
0.054(5), 0.142(4), -0.012(5), 0.027(5), 0.068(6), 0.012
˚
(7), -0.076(7) and -0.072(5) A respectively). That is also
˚
indicates by that the bond length of 1.439(2) A for C4–C5,
˚
˚
1.410(2) A for N1–N2, 1.7571(18) A for S1–C6 and
˚
1.7520(18) A for S2–C6 for (I) are shorter than the single
2
2
2
˚
˚
band values of 1.46 A for Csp –Csp , 1.45 A for Nsp –
Nsp2 [17], 1.819 (2) A for S1–C8 and 1.809(2) A for
S2–C7, respectively (Table 1). The length of Cgf (centre
of furan ring) to Cgd (center of 1, 3-dithiolane ring) is
˚
˚
˚
6.728(3) A in the same molecular. The structure of
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J Chem Crystallogr (2008) 38:867–871
869
Table 1 Summary of crystallographic results
Empirical formula
C8H8N2OS2
CCDC deposition
Color/shape
620306
Light yellow/transparent block
212.28
Formula weight
Crystal size, mm
Crystal system
Space group
0.24 9 0.16 9 0.14
Orthorhombic
P212121
Unit cell dimensions
˚
a (A)
6.4035 (9)
11.8835 (16)
12.3809 (17)
942.1(2)
4
˚
b (A)
˚
c (A)
3
V (A )
˚
Z
Density (calculated, mg/m3)
1.497
F(000)
440
˚
Radiation
Mo Ka (k = 0.71073 A)
Temperature
l(Mo-Ka) (mm-1
294 (2) K
)
0.532
Scan mode
U and x
h Range for data collection (°)
Limiting indices
2.38 * 26.46
-6 B h B 8,
-11 B k B 14,
-15 B l B 15
5,315
Reflections collected
Independent reflections/reflections with I [ 2r(I)
Diffractometer
1,926/1,787
Bruker SMART 1000 CCD
Mult-scan SADABS
0.940643/0.903605
Full-matrix least-squares on F2
1,787/0/118
Absorption correction
Transmission factor, TMax/Tmin
Refinement method
Data/restraints/parameters
R(int)
0.0234
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
R indices (all data)
1.089
R1 = 0.0243, wR2 = 0.0579
R1 = 0.0283, wR2 = 0.0602
0.02 (7)
Flack parameter
Friedel pairs
783
-3
˚
Largest diff. peak and hole, (e A
Weights
)
0.171 and -0.134
1/[r2(Fo2) + (0.0279 9 P)2 + 0.1272 9 P], where P = [Fo2 + 2F2c]/3
(I) can be assigned to E-isomer, which is most stable respectively. The SꢀꢀꢀO distance is certainly short then the
˚
sum of the vand der Waals radii (3.32 A) given by Bondi
configuration.
The most striking difference between (I) and (II) lies in
their supramolecular aggregations. In (I), there are C(7)
chains [18], which formed by short contacts of SꢀꢀꢀO and
the seven atoms are in order of S1, C6, N2, N1, C5, C4 and
O1 in every molecular inside, involving molecules with
[19], but these are consistent with the results of a database
˚
analysis [20] (SꢀꢀꢀO distance of 3.19 A and OꢀꢀꢀS–C angle
of 163.0°). Many molecules form a C(7) left-handed helical
spiral chain by one 21 screw axis along (x, , 0). The
torsion of the O1#ꢀꢀꢀS1 to O1ꢀꢀꢀS1* in the spiral ring is
11.2(3)° and the length of Cgf to Cgf (or Cgd to Cgd)
˚
SꢀꢀꢀO distance of 3.1867(13) A along a axis (Fig. 2), such
˚
as S1 and O1 at (x, y, z) to O1 at (-‘ + x, ‘ - y, -z) and
S2 at (‘ + x, ‘ - y, -z), respectively. C6–S1ꢀꢀꢀO1 angle
between the two adjacent molecular layers is 6.404(2) A,
˚
which is shorter than 6.728(3) A, the length of Cgf to Cgd
and S1ꢀꢀꢀO1–C4 angle are 164.7(2) and 152.9(3)°, in the molecule itself (Table 3).
123

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J Chem Crystallogr (2008) 38:867–871
˚
˚
Table 2 Slected bond lengths and bond angles (A and °)
Table 3 Hydrogen-bond geometry (A, °)
Bond lengths
D–HꢀꢀꢀA
D–H
0.93
3
HꢀꢀꢀA
2.74
DꢀꢀꢀA
3.354(3)
D-HꢀꢀꢀA
124
C1–H1aꢀꢀꢀN2
S1–C6
1.7571(18)
1.819(2)
N1–N2
1.410(2)
1.282(2)
a
Symmetry code: (i) - x, 1 - y, ‘ + z
S1–C8
N2–C6
2
S2–C6
1.7520(18)
1.809(2)
C1–C2
1.331(3)
S2–C7
C2–C3
1.410(3)
in order of O1, C5, C4, N1, N2, C6 and S1 in every
molecular inside, just in the opposite direction to the cen-
tral spiral chains. Every molecule, which is made up of the
five spiral chains, gives rise to zig-zag chains via C(7) of
C–HꢀꢀꢀN inter-molecular hydrogen-bonds running parallel
to the (0, 1, 0) plane. Atom C1 at (32 - x, 1 - y,  + z)
and C1 at (x, y, 1 + z) act as hydrogen-bond donors, via
atom H1 at (32 - x, 1 - y, ‘ + z) and H1 at (x, y, 1 + z),
respectively, to N2 at (x, y, z) and N2 at (32 - x, 1 - y,
O1–C1
1.356(2)
C3–C4
1.352(3)
O1–C4
1.368(2)
C4–C5
1.439(2)
N1–C5
1.271(2)
C7–C8
1.508(3)
C6–S1–C8
C6–S2–C7
S2–C6–N2
S1–C6–N2
C3–C4–C5
O1–C4–C5
C1–O1–C4
C2–C3–C4
S1–C6–S2
95.86(21)
95.18(21)
119.31(21)
125.42(17)
133.10(15)
117.77(15)
106.36(20)
107.10(12)
115.26(17)
S2–C7–C8
S1–C8–C7
N2–N1–C5
N1–N2–C6
N1–C5–C4
C3–C4–O1
O1–C1–C2
C1–C2–C3
108.74(16)
109.18(16)
113.31(18)
110.72(19)
122.04(13)
121.20(15)
111.11(14)
106.29(10)
˚
‘ + z) with the same HꢀꢀꢀN distances of 2.74 A and
˚
C1ꢀꢀꢀN2 distance of 3.354(3) A and C–HꢀꢀꢀN angle of 142°.
The torsions of the H1&ꢀꢀꢀN2$ to H1$ꢀꢀꢀN2, O1#ꢀꢀꢀS1 to
N2ꢀꢀꢀH1$ and S1*ꢀꢀꢀO1 to N2ꢀꢀꢀH1$ are -126, -59 and
126°, respectively.
Supplementary Material
CCDC-620306 for the title compound contains the sup-
plementary crystallographic data for this paper. These data
can be obtained free of charge via www.ccdc.cam.
ac.uk /data\_request/cif, by e-mail data\_request@ ccdc.
cam.ac.uk, or by contacting The Cambridge Crystallo-
graphic Data Center, 12 Union Road, Cambridge, CB21EZ,
UK; fax: +44(0)1223-336033.
Acknowledgment This work was supported financially by Tianshui
Normal College (No. 2002-02) and Yangzhou University (No.
2006XJJ03).
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Fig. 2 A stereoview of part of compound (I), showing the formation
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Along c axis and around the helical spiral chains there
are four inverse C(7) left-handed helical spiral chains
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screw and two is up and two is down. The seven atoms are
123

J Chem Crystallogr (2008) 38:867–871
871
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