Synthesis and spectroscopic characterization of the benzaldehyde Schiff base of S-allyldithiocarbazate and its copper(II) complex and the X-ray crystal structure of bis[S-allyl-β-N-benzylidenedithiocarbazato]copper(II)

Article abstract of DOI:10.1002/zaac.200700521

S-allyl-β-N-(benzylidene)dithiocarbazate (sabdtc, 1), prepared from hydrazine hydrate, carbon disulfide, allyl bromide and benzaldehyde, reacts with copper(II) nitrate in ethanol solution to form the complex Cu(sabdtc) ₂ (2). 1 function as a single negatively charged bidentate chelating ligand and coordinates via the azomethine nitrogen atom and thioenolate sulfur atom to the metal ion. 1 and 2 were characterized by elemental analyses, ¹H NMR, ¹³C NMR, UV/Vis, IR, and mass spectra. Spectroscopic evidences suggest a four-coordinate distorted square planar structure for 2. The molecular and crystal structure of 2 was determined by single crystal X-ray analysis. Crystallographic data for 2 at 291(2) K: space group C2/c, a = 20.340(3), b = 15.503(3), c = 7.659(1) A, β = 95.96(2)°, Z = 4, R₁ = 0.044 and wR2 = 0.0689.

Full text of DOI:10.1002/zaac.200700521

DOI: 10.1002/zaac.200700521
Synthesis and Spectroscopic Characterization of the Benzaldehyde Schiff Base
of S-Allyldithiocarbazate and its Copper(II) Complex and the X-ray Crystal
Structure of Bis[S-allyl-β-N-benzylidene)dithiocarbazato]Copper(II)
M. Yazdanbakhsha,*, M. M. Heravib, R. Takjooa and W. Frankc
a Mashhad/Iran, Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad
b Tehran/Iran, Department of Chemistry, Azzahra University
c Düsseldorf/Germany, Institut für Anorganische Chemie und Strukturchemie, Lehrstuhl II, Heinrich-Heine-Universität Düsseldorf
Received October 15th, 2007; accepted November 19th, 2007.
Abstract. S-allyl-β-N-(benzylidene)dithiocarbazate (sabdtc, 1), pre-
pared from hydrazine hydrate, carbon disulfide, allyl bromide and
benzaldehyde, reacts with copper(II) nitrate in ethanol solution to
form the complex Cu(sabdtc)2 (2). 1 function as a single negatively
charged bidentate chelating ligand and coordinates via the azo-
methine nitrogen atom and thioenolate sulfur atom to the metal
suggest a four-coordinate distorted square planar structure for 2.
The molecular and crystal structure of 2 was determined by single
crystal X-ray analysis. Crystallographic data for 2 at 291(2) K:
space group C2/c, a ϭ 20.340(3), b ϭ 15.503(3), c ϭ 7.659(1) A,
β ϭ 95.96(2)°, Z ϭ 4, R1 ϭ 0.044 and wR2 ϭ 0.0689.
˚
1
ion. 1 and 2 were characterized by elemental analyses, H NMR,
Keywords: Copper; S-allyldithiocarbazate; Crystal structures;
Bidentate NS Schiff base
13C NMR, UV/Vis, IR, and mass spectra. Spectroscopic evidences
1 Introduction
2 Experimental Section
2.1 Materials and physical measurements
Dithiocarbazates constitute an important class of mixed
hardϪsoft nitrogenϪsulfur donor ligands [1, 2]. There is
continuing interest in the coordination chemistry of hetero-
cyclic bidentate ligands containing the NS donor set [3].
Copper complexes of dithiocarbazates have been of interest
in numerous studies because of their chemical and biologi-
cal properties [4Ϫ7].
The dithiocarbazate Schiff base compounds RCHϭ
NNHC(S)SRЈ are known to coordinate via extended π-con-
jugation through ligand deprotonation [8] and give corre-
sponding copper(II) ion complexes that have attracted con-
siderable interest because of the occurrence of the CuN2S2
chromophore in blue copper proteins such as plastocyanin
[9].
All materials were purchased form Merck Chemical Company and
were used as received. All solvents were reagent grade and used
without further purification. C, H, N, S elemental analyses were
performed using a Thermo Finnigan Flash 1112EA elemental ana-
lyzer. The IR spectra were recorded using a Buck 500 Scientific
spectrometer in the range 4000-400 cmϪ1 and far-IR on a Thermo
Nicolet NEXUS 870 FT-IR in the range 700-200 cmϪ1 as KBr pel-
lets. The mass spectra were recorded on a Varian CH-7 instrument
at 70 eV.
1
The H and 13C NMR measurements were performed on a Bruker
BRX 500 AVANCE 500 MHz spectrometer. Samples were dis-
solved in DMSO-d6 with TMS as internal reference. Melting points
(m.p.) were determined by DSC technique.
The allyl group in the molecule structure has inclined for
many interesting chemical reactions and can be used as a
ligand [10Ϫ12]. Although, most previous studies on dithio-
carbazates were based on S-methyl and S-benzyl dithio-
carbazate chelating agents, Schiff base ligands derived from
S-allyldithiocarbazates have not received much attention.
Herein, we describe the synthesis, characterization and
crystal structure of bis[S-allyl-β-N-(benzylidene)dithiocar-
bazato]-copper(II) complex.
2.2 Preparation of S-allyl-β-N-
(benzylidene)dithiocarbazate (sabdtc, 1)
To a mixture of 5 ml (0.1 mol) hydrazine hydrate and 5.6 g
(0.1 mol) KOH in 30 ml of ethanol at 5 °C, was added a solution
of 6.1 ml (0.1 mol) of carbon disulfide and 8.6 ml (0.1 mol) of allyl
bromide with continuous string. To this mixture was added the
ethanolic solution (25 ml) of benzaldehyde (11.1 ml, 0.1 mol) and
heated. The yellow product was separated by filtration, washed
with water and dried in a vacuum. 1 was recrystallized from
ethanol. Yield 49.5 % (based on benzaldehyde); m.p. 137 °C.
C11H12N2S2 (236.36), Anal. calc.: C, 55.90; H, 5.12; N, 11.85; S,
27.13 for C H N S Found: C, 55.96; H, 5.00; N, 11.85; S, 28.26 %.
Mass spectrometry: m/z ϭ 236, 163, 118, 104, 90, 77, 41 and 28.
* Dr. Mohammad Yazdanbakhsh
Department of Chemistry, Faculty of Sciences
Ferdowsi University of Mashhad 91775-1436/Iran
Fax (ϩ)98-511-8796416
1H NMR (500 MHz, DMSO-d6, 25 °C): δ ϭ 3.90 (d, 2H; C2), 5.24 (dd, 2H;
C4), 5.87-5.96 (m, H; C3), 7.45 (dd, 3H; C7, C9, C11), 7.71 (dd, H; C8,
E-mail: myadzan@um.ac.ir
972
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Z. Anorg. Allg. Chem. 2008, 634, 972Ϫ976

Benzaldehyde Schiff Base of S-Allyldithiocarbazate and its Copper(II) Complex
C10), 8.24 (s, H; C5), 13.34 (s, H; NH). 13C NMR (500 MHz, DMSO-d6,
to 120 % of the equivalent isotropic displacement parameters of the
25 °C): δ ϭ 196.44 (C1), 146.56 (C5), 133.28 (C6), 133.16 (C9), 130.77 (C3),
128.95 (C7, C11), 127.42 (C8, C10), 118.45 (C4), 35.98 (C2).
parent carbon atom. Scattering factors, dispersion corrections and
absorption coefficients were taken from International Tables for
Crystallography (1992, Vol. C, Tables 6.114, 4.268 and 4.2.4.2).
2.3 Preparation of bis[S-allyl-β-N-
(benzylidene)dithiocarbazato]-copper(II) complex
(Cu(sabdtc)2, 2)
3 Results and Discussion
3.1 Spectroscopic characterization
Copper(II) nitrate trihydrate (0.242 g; 0.001 mol) in ethanol (10 ml)
was added to the ethanolic solution of 1 (0.473 g; 0.002 mol). The
mixture was heated and then left to stand overnight. The product
was filtered off, washed with ethanol, dried in a vacuum. Yield
68.97 % (based on 1); m.p. 125 °C. C22H22CuN4S4 (534.24), Anal.
Found: C, 49.46; H, 4.15; N, 10.49; S, 24.01; Cu, 11.51. Calc: C,
49.38; H, 4.04; N, 10.39; S, 24.88; Cu, 11.89 %. Mass spectrometry:
m/z ϭ 534, 236, 162, 104, 90, 77, 41 and 28.
In recent years, the interesting complexes of S-methyl and
S-benzyl dithiocarbazate have been prepared but S-allyldi-
thiocarbazate is a new series of this kind of compounds.
The S-allyl-β-N-(benzylidene)dithiocarbazate (sabdtc)
has the thioamide function -N(H)C(S) in order to be oc-
curred complexation. As be shown in Figure 1 the free
ligand must exhibit thiolϪthione tautomers.
2.4 Crystal structure determination of 2
Well shaped crystals of the compound investigated at 18 °C on an
STOE IPDS, using graphite monochromatized Mo-Kα radi-
˚
ation(λ ϭ 0.71073 A). Crystal data, as well as details of data collec-
tion and structure refinement are listed in Table 1. For all data LP
corrections were applied. The structure was solved by direct meth-
ods [13] and subsequent Fourier-syntheses. Approximate positions
of all hydrogen atoms with the exception of the ones within the
disordered part of the ligand were found via difference Fourier-
syntheses. Taking into account the disorder of the allyl group
(occupation 0.50(2):0.50(2)), has been refined by full-matrix least-
squares calculations on F2 [14] (applying appropriate distance and
displacement parameter restraints and constraints for the dis-
ordered region) converged (max. shift/esd: 0.000) to the final indi-
cators given in Table 1. Refined parameters include anisotropic dis-
placement parameters for all the non-hydrogen atoms. The H
atoms were treated as riding on their parent carbon atoms in ideal-
ised positions. Isotropic displacement parameters were kept equal
Figure 1 Tautomeric forms of thione and thiol of free ligand
(sabdtc, 1)
In the present of transition metal ions, the Schiff base
compound is converted into the thiol tautomeric form to
facilitate the formation of centric neutral bis-ligand metal
complexes [15]. The thiolo sulfur and azomethine nitrogen
like as the other kinds of these complexes coordinate to
metal atoms. However their IR spectra (Table 2) do not
show any band at ca. 2750 cmϪ1 that may be assigned to
ν(S-H), and it exhibits ν(N-H) at ca. 3104.9 cmϪ1 as a
medium band. According to the above mentioned data, one
may conclude that in solid state, the thione form must be
predominated. The ν(N-H) bond in free ligand disappear in
complex spectra that indicate deprotonation of ligand dur-
ing the complexation occur. In comparing the IR spectra of
starting ligand with synthesized complex, we find that the
vibrational band of ν(CϭN) has been red shifted from
1609.8 cmϪ1 to 1592.8 cmϪ1. The two bands at 676 and
673 cmϪ1 in Schiff base and CuII complex, respectively, has
been assigned to out of plain vibrations of mono substi-
tuted aromatic ring. The CϭC bond of allyl group has been
located at 1636.3-1631.6 cmϪ1. The IR spectrum in region
700-200 cmϪ1 show two bands at 352 and 478 cmϪ1 attri-
buted to S-Cu and N-Cu, respectively.
Table 1 Crystal data, and structure refinement for Cu(sabdtc)2
Empirical formula
Formula weight
Temperature
C22H22CuN4 S4
534.27
291(2) K
˚
Wavelength
0.71073 A
Crystal system
Space group
Unit cell dimensions
monoclinic
C2/c
a ϭ 20.340(3) A
b ϭ 15.503(3) A
˚
˚
Ͱ ϭ 90°
β ϭ 95.956(17)°
γ ϭ 90°
˚
c ϭ 7.6549(11) A
3
˚
Volume
2400.8(7) A
Z
4
Density (calculated)
Absorption coefficient
F(000)
1.478 g/cm3
1.275 mmϪ1
1100
Crystal size
0.10 ϫ 0.05 ϫ 0.03 mm
Theta range for data collection 2.01 to 26.06°
Index ranges
Ϫ25ՅhՅ25, Ϫ18ՅkՅ19, Ϫ9ՅlՅ9
13258
2369 [R(int) ϭ 0.0909]
Reflections collected
Independent reflections
Completeness to θ ϭ 26.06°
Absorption correction
Refinement method
99.5 %
none
The main parameters of 1H NMR and 13C NMR spectra
Full-matrix least-squares on F2
1
in DMSO are collected in Section 2.2. The H NMR of
Data / restraints / parameters 2369 / 61 / 164
free ligand 1 showed a peak at ca. 13.34 ppm attributed to
the resonance of NH proton, that disappear this peak in
deuteration, indicating that the ligand has lost a proton on
deuteration. The signal of the proton on CϭN double bond
Goodness-of-fit on F2
Final R indices [I>2σ(I)]
R indices (all data)
0.942
R1 ϭ 0.0442, wR2 ϭ 0.0689
R1 ϭ 0.1402, wR2 ϭ 0.0756
Ϫ3
˚
Largest diff. peak and hole
0.291 and Ϫ0.262 e.A
Z. Anorg. Allg. Chem. 2008, 972Ϫ976
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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973

M. Yazdanbakhsh, M. M. Heravi, R. Takjoo, W. Frank
Table 2 Main IR spectral vibrations (cmϪ1) and electronic spectral data
IR bands (cmϪ1 a
)
Electronic spectra (in CH2Cl2)
λmax (logε)
b
compound
NH
CϭC
CϭN
CϭS
N-N
M-N
M-S
sabdtc
3104.9
1636.3
1631.6
1609
1097
1025.4
1024.3
Ϫ
Ϫ
240(3.98), 334(4.56)
Cu(sabdtc)2
Ϫ
1592.8
Ϫ
478
352
252(4.70), 317(4.86), 366(4.84),439(3.71)
a) wavenumbers are in units cmϪ1 b) Units of λmax are in nm and logε (dm3 molϪ1cmϪ1) are given in parentheses.
appears at 8.24 ppm. The resonance peaks associated with
the aromatic groups are observed in the range
1
7.45Ϫ7.71 ppm. However, its H NMR spectrum does not
display any signal at approximately 4.00 ppm that is related
to the SϪH proton, indicating in DMSO solution it exists
as the thione tautomer [16]. The protons of SCH2, CH and
CH2 moieties display doublets, doublet of doublet and a
multiple at 3.90, 5.14 and 5.87-5.96 ppm, respectively.
The 13C NMR spectrum of 1 showed a signal at low field
196.44 ppm corresponding to the thioamide carbon is
found in DMSO at room temperature. In addition, the azo-
methine carbon signal of ligand appears at 146.56 ppm. The
SCH2, CH and CH2 carbon atoms in allyl group show
signals at 35.98, 130.77 and 118.45 ppm, respectively. The
signals of the carbon atoms on phenyl ring appear at 127.42
to 133.28 ppm.
Figure 2 ORTEP diagram of Cu(sabdtc)2 showing the atom label-
ling scheme; displacement ellipsoids are drawn at the 30 % probabi-
lity level; symmetry code: A Ϫx,Ϫy,Ϫz. Note the one to one dis-
order of the S-allyl groups.
The Schiff base mass spectra show parent ions
peaks at m/e 236 and the main fragmentation includes the
loss of phenyl with ion peak at m/e 77; the other peaks at
m/e 163, 118, 104, 90, 41 and 28 corresponds to
[PhCHϭNN(H)C(S)]ϩ, [PhCHϭNN(H)C]3ϩ, [PhCHϭN]ϩ,
[PhCH]2ϩ, allylϩ and N2, respectively. The molecular ion
for CuII complex is detected at m/e 534. The fragments
m/e 236, 162, 104, 90, 77, 41 and 28 attributed to
3.2 X-ray crystal structure of 2
Crystal data, as well as details of data collection and structure
refinement are compiled in Table 1. An ORTEP diagram of
the bis[S-allyl-β-N-(benzylidene)dithiocarbazato]copper(II)
molecule (2), with the atom numbering scheme is shown in
Figure 2 and the stacking of the molecules in the crystal is
illustrated in Figure 3. it should be pointed out that titled
complex crystallographically imposed inversion symmetry.
The Schiff base is coordinated to the CuII ion in its de-
protonated iminothiolate form. This form results in delocal-
ization of the negative charge caused by the deprotonation
of the NH proton as indicated by the intermediate C5-N1,
N1-N2, N2-C1 bands.
sabdtc, [PhCHϭNN(H)C(S)]ϩ, [PhCHϭN]ϩ, [PhCH]2ϩ
,
Ph, allylϩ, N2, respectively.
The electronic spectra in range of 200 to 380 nm in
CH2Cl2 solution are characteristic of L-L* absorption. The
absorption maxima at 252, 317 and 366 nm can be attri-
buted to intra-ligand transitions only. The πǞπ* band tran-
sition, of the ligand is observed at 366 nm that is red shifted
by ca. 30 nm metal complex. This bathochromic shift can
be attributed to overlap of the Cu-d-orbital with the
p-orbital of the donor atom, which causes an increase in
conjugation in the ligand and thus lowers the πǞπ* energy.
The absorption peak at 240 nm is assigned to phenyl ring
in ligand that shows a hypsochromic shift by ca. 14 nm in
the complex. The band appearing at 366 nm in the complex
bearing deprotonated ligand may have resulted from the
extended conjugation in the ligand forced by the chelated
metal ion [17]. The presence of chalcogen donor atoms in
the ligands brings about strong CT band at 439 nm in the
complex. The tail of CT band extend up to the visible
portion of the spectrum with this result that no dϪd bands
are generally observed in the electronic spectra of such com-
plex [18].
Two ligands coordinate to the CuII atom to form two
five-membered chelate rings Cu1-N1-N2-C1-S1. The coor-
dination of copper(II) is monomeric and distorted square-
˚
planar with two equivalent CuϪN (1.995(4) A) and CuϪS
˚
(2.254(1) A) bonds. The coordinated mercapto sulfur and
methine nitrogen atoms in the two ligands are in opposite
positions so that the complex has trans-configuration allyl
group moieties on the opposite side and thio S and imine
nitrogen atoms are cis to each other [19]. The bond dis-
˚
˚
tances C(1)-N(2), 1.290(5) A and C(1)-S(1), 1.692(5) A sug-
gest a CϭN double bond and C-S single bond [8]. One in-
tersting feature of our complex is the present of two equal
CϭN bonds (N2-C1, N1-C5). The copper(II)-donor atom
˚
˚
distances, namely Cu-S [2.254(1) A], Cu-N [1.995(4) A]
974
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© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 972Ϫ976

Benzaldehyde Schiff Base of S-Allyldithiocarbazate and its Copper(II) Complex
shorter and larger than the expected ideal value of 90°,
respectively. This distortion may be attributed to the restric-
ted bite angles which to be imposed by the planar bidentate
Schiff bases. For further information, the bond angles of
this complex have reported in table 3.
4 Conclusion
The reaction of copper nitrate with the bidentate Schiff
bases derived from S-allyldithiocarbazate and benzaldehyde
in ethanol produces a new crystalline green complex. The
X-ray crystal structure determination of Cu(sabdtc)2 shows
that it has a four NS coordinate distorted square planar
geometry.
Supplementary material. Crystallographic data for the structures re-
ported in this paper have been deposited with the Cambridge Crys-
tallographic Data Centre, CCDC no. 663339 for compound 2.
Copy of this information may be obtained free of charge from the
Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: ϩ44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk).
Figure 3 Stacking of the molecules along the c-axis of the unit
cell. Note the secondary Cu···S interactions between neighbouring
molecules. Symmetry codes: A Ϫx, Ϫy, Ϫz; B x, Ϫy, Ϫ0.5ϩz;
C Ϫx, y, Ϫ0.5Ϫz;
F x, Ϫy, Ϫ2.5ϩz; G Ϫx, y, Ϫ1.5Ϫz.
D x, Ϫy, Ϫ1.5ϩz;
E Ϫx, Ϫy, Ϫ1Ϫz;
Acknowledgement. We thank Ms E. Hammes for support during
the X-ray data collection.
˚
Table 3 Selected bond lengths/A and bond angles/° for Cu(sabdtc)2
References
Cu(1)-S(1)
Cu(1)-N(1)
S(1)-C(1)
2.254(1)
1.995(4)
1.692(5)
1.731(5)
1.799(1)
1.796(1)
1.397(5)
1.290(6)
1.290(5)
1.494(1)
1.304(1)
1.492(1)
1.306(1)
1.441(7)
1.342(6)
1.374(6)
1.367(7)
1.364(7)
1.331(6)
1.349(6)
S(1)-Cu(1)-N(1)
S(1)-Cu(1)-N(1)A
Cu(1)-S(1)-C(1)
C(1)-S(2)-C(21)
C(1)-S(2)-C(22)
Cu(1)-N(1)-N(2)
Cu(1)-N(1)-C(5)
N(2)-N(1)-C(5)
N(1)-N(2)-C(1)
S(1)-C(1)-S(2)
S(1)-C(1)-N(2)
S(2)-C(1)-N(2)
S(2)-C(21)-C(31)
S(2)-C(22)-C(32)
C(21)-C(31)-C(41)
C(22)-C(32)-C(42)
N(1)-C(5)-C(6)
C(5)-C(6)-C(7)
C(5)-C(6)-C(11)
C(7)-C(6)-C(11)
C(6)-C(7)-C(8)
C(7)-C(8)-C(9)
C(8)-C(9)-C(10)
C(9)-C(10)-C(11)
84.1(1)
95.9 (1)
95.2(2)
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S(2)-C(1)
102.8(8)
105.1(8)
119.6(3)
124.6(4)
115.6(4)
112.6(4)
114.6(3)
127.3(4)
118.1(4)
109.7(1)
109.3(1)
123(2)
S(2)-C(21)
S(2)-C(22)
N(1)-N(2)
N(1)-C(5)
N(2)-C(1)
C(21)-C(31)
C(31)-C(41)
C(22)-C(32)
C(32)-C(42)
C(5)-C(6)
C(6)-C(7)
C(6)-C(11)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
C(10)-C(11)
113(2)
132.2(5)
126.5(5)
116.3(5)
117.0(5)
121.1(5)
120.4(6)
118.8(6)
120.4(6)
Symmetry code: A Ϫx,Ϫy,Ϫz
could be compared well with other related published work
[8].
The dihedral angle between the phenyl ring and the five-
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The coordination environment of copper(II) atom may
be considered as distorted square planar. The S1-Cu-N1
and S1-Cu-N1A angles are 84.1(1)° and 95.9(1)°, which is
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© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
975

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