Synthesis and crystal structure of [chlorobis(triphenylphospino)(p-chlorobenzaldehyde thiosemicarbazone)] copper(I) complex

Article abstract of DOI:10.1007/s12039-015-1030-8

Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H¹L) and triphenylphosphine in 1: 1: 2 molar ratio yielded complexes of stoichiometry, [CuX(η ¹-S- H ¹L)(Ph₃P)₂] (X = I, 1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR, ¹H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) ?, b = 13.027(5) ?, c = 16.269(5) ?, α= 100.054(5), β= 99.228(5) and γ= 97.234(5). This complex has distorted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of complex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemicarbazone, [Cu₂Cl₂(μ ₂-S-Hbtsc)₂(Ph₃P)₂] 2H₂O. The intermolecular H-bonding, Cl ?HC _ph, 2.733 ? and π interactions, {CH_ph?π, 2.796; 2.776 ?} in this complex led to the formation of 1D chain. Two such 1D chains were cross-linked via, Cl ?HC _ph, 2.896 ? H-bonding to form a 2D network. [Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-015-1030-8

c
J. Chem. Sci. ꢀ Indian Academy of Sciences.
DOI 10.1007/s12039-015-1030-8
Synthesis and crystal structure of [chlorobis(triphenylphospino)
(p-chlorobenzaldehyde thiosemicarbazone)] copper(I) complex
ASHIQ KHANa, POONAM SHARMAa, RAJNIKANTb, VIVEK K GUPTAb, NARESH PADHAb
and REKHA SHARMAa,∗
aDepartment of Chemistry, Lovely Professional University, Phagwara, Punjab, India
bPost Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180006, India
e-mail: rekha.14537@lpu.co.in
MS received 9 June 2015; revised 13 December 2015; accepted 14 December 2015
Abstract. Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H1L) and triph-
enylphosphine in 1 : 1 : 2 molar ratio yielded complexes of stoichiometry, [CuX(η1-S- H1L)(Ph3P)2] (X = I,
1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR,
1H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found
to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) Å, b =
13.027(5) Å, c = 16.269(5) Å, α = 100.054(5)◦, β = 99.228(5)◦ and γ = 97.234(5)◦. This complex has dis-
torted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of
thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of com-
plex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemi-
carbazone, [Cu2Cl2(μ2-S-Hbtsc)2(Ph3P)2]·2H2O. The intermolecular H-bonding, Cl· · · HCph, 2.733 Å and π
interactions, {CHph · · · π, 2.796; 2.776 Å} in this complex led to the formation of 1D chain. Two such 1D
chains were cross-linked via, Cl· · · HCph, 2.896 Å H-bonding to form a 2D network.
Keywords. p-chlorobenzaldehyde thiosemicarbazone; tetrahedral monomer; copper(I) halides; X-ray crys-
tallography; hydrogen bonding; triphenylphosphine.
1. Introduction
of type D or E depending upon the halogen atom
attached.19,28,29 Phenyl ring at N1 atom of thiosemicar-
bazone resulted into formation of either three coordi-
nated monomer (B) or sulfur bridged dimer (F), where
no triphenylphosphine molecule coordinated.28,29 Ace-
tylthiophene-2-carbaldehyde thiosemicarbazone formed
monomer with coordination number three of type C
with copper(I) bromide and chloride.30 A unique type
of hetero-bridging (G) was observed in the complex
of copper(I) iodide with acetophenone thiosemicar-
bazone.31 It was observed in literature that solvent also
played an important role in altering the bonding modes.
For example, benzaldehyde thiosemicarbazone formed
tetrahedral monomer in acetonitrile, whereas a halogen-
bridged dimer was obtained from similar reaction in
acetonitrile-chloroform mixture.32 Similar reaction with
copper(I) bromide in acetonitrile formed bromo-
bridged dimer, while the use of acetonitrile-chloroform
mixture as solvent changed the bridging mode from
halogen-bridging to sulfur bridging.32
Thiosemicarbazones (R1R2C2=N3-N2H-C1(=S)N1HR3)
are important N, S-donor ligands as they exhibit vari-
able bonding modes, structural diversity,1–7 analytical
applications8–13 and biological activities (antibacterial,
antifungal, antitumor, antiamoebic, antimalarial, antivi-
ral, radioprotective, trypanocidal and anti-inflammatory
activities).14–18 Copper(I), being a soft acid, binds
strongly with soft bases like sulfur, phosphorus and
selenium.19–24 Coordination chemistry of copper(I)
halides with thiosemicarbazones had proved to be very
interesting as the substituents on C2 or N1 atoms of
thiosemicarbazones, halogen atoms and solvent sys-
tem played important role in generating complexes of
variable geometries, nuclearities and bonding modes
(Chart 1).24–32
When C2 carbon of thiosemicarbazone was substi-
tuted with pyridine, two phenyl rings or isatin ring at C2
carbon, only tetrahedral monomers of type A were
obtained,19–25 whereas with thiophene, furan and pyr-
role ring at C2 carbon, it formed only dimers, either
In continuation to this work, in this paper, reaction of
p-cholorobenzaldehye thiosemicarbazone (H1L, I) with
copper(I) halides in the presence of triphenylphosphine
as co-ligand has been investigated. The synthesized
∗For correspondence

Ashiq Khan et al.
2.1b [CuBr(η1 − S − H1L)(Ph3P2)] 2: Yield:
X
X
X
75%; M.p. 178-180◦C. Elemental analysis for
C44H38N3P2SClCuBr, Found (%): C, 59.91; H, 4.29;
N, 4.74; S, 3.62. Calcd. (%): C, 59.93; H, 4.31; N,
4.76; S, 3.63.Main IR peaks (KBr, cm−1), υ(N–H),
3476s,3362s,3285m; υ(–NH–), 3134m; υ(C–HPh),
3051s; δ(NH2) + υ(C=N) + υ(C–C), 1582s, 1541s;
υ(C=S) 820m (thioamide moiety),υ(P–CPh),1094s. 1H
NMR (CDCl3, δ ppm,): 10.41s (1H, N2H), 8.14s (1H,
C2H), 7.68-6.97m (34H, C4,5.7.8H+Ph3P).
Cu
(A)
Cu
(C)
Cu
(B)
S
P
S
P
S
S
P
X
P
S
P
S
S
P
X
P
S
Cu
(E)
Cu
(D)
Cu
Cu
Cu
X
X
S
S
S
X
2.1c [CuCl(η1 − S − H1L)(Ph3P2)] 3: Yield: 78%;
M.p. 181-183oC. Elemental analysis for C44H38N3P2
SCl2Cu, Found (%): C, 63.07; H, 4.52; N, 5.00; S, 3.84.
Calcd. (%): C, 63.04; H, 4.54; N, 5.01; S, 3.82.Main
IR peaks (KBr, cm−1), υ(N–H), 3449s,3362s,3285m;
υ(–NH–), 3160m; υ(C–HPh), 3050s; δ(NH2) +υ(C=N)
+υ(C–C), 1591s, 1545s; υ(C=S) 818s (thioamide
Cu
Cu
Cu
I
I
X
S
S
(G)
(F)
Chart 1. Types of bonding modes and nuclearity obtained
for copper(I) halide complexes of thiosemicarbazones.
1
moiety),υ(P–CPh),1092s. H NMR (CDCl3, δ ppm,):
10.35s (1H, N2H), 8.16s (1H, C2H), 7.65-6.98m (34H,
complexes were characterized using elemental analysis,
IR, H NMR and single crystal X-ray crystallography
(complex 3).
1
C4,5.7.8H+Ph3P).
2.2 Chemicals and physical measurements
Cl
Potassium chloride, potassium bromide, potassium
iodide, triphenylphosphine, p-chloro-benzaldehyde, thio-
semicarbazide and triphenylphosphine were procured
from Loba Pvt. Ltd, Copper(I) iodide, bromide and
chloride were prepared by the reduction of CuSO4·
5H2O using SO2 in the presence of KI, KBr or KCl
in water.33 p-chlorobenzaldehydethiosemicarbazone
was prepared by refluxing p-chlorobenzaldehyde and
thiosemicarbazides in methanol for 4-5 h. C, H and
N analyses were obtained with a Thermoelectron
FLASHEA1112 CHNS analyzer. Infrared spectra were
recorded from KBr pellets in the range 4000-200 cm−1
on a SHIMADZU FTIR 8400S spectrophotometer.
Melting points were determined with an electrically
heated Gallenkamp apparatus. 1H NMR were recorded
on an AV500 FT spectrometer operating at a frequency
of 500 MHz using CDCl3as solvent with TMS as the
internal standard. X-ray Diffraction(XRD) patterns
of the powder were recorded on PANalytical X-ray
powder diffractrometer (Model X’pert3 powder) with
CuKα radiation (λ =1.5406 Å) with scan speed 0.066
degree per second in the 2θ range 5-40 for 1, 5-80
degrees for 2 and 5-50 degrees for 3.
3
N
S
2
2
1
C
C
NH
1
H
NH2
(H1L, I)
2. Experimental
2.1 Synthesis
2.1a [CuI(η1 − S − H1L)(Ph3P2)] 1: To a solution
of CuI (0.050 g, 0.26 mmol) in 15 mL of acetonitrile
was added solid H1L (0.056 g, 0.26 mmol) and the reac-
tion mixture was stirred for 3-4 h. To this was added
solid Ph3P (0.137 g, 0.52mmol) and stirred for 10-20
min. The yellow coloured clear solution thus obtained
was filtered and kept for crystallization at room tem-
perature. Yield: 80%; M.p. 190-192◦C. Elemental anal-
ysis for C44H38N3P2SClCuI, Found (%): C, 56.87; H,
4.06; N, 4.51; S, 3.46. Calcd. (%): C, 56.89; H, 4.09;
N, 4.52; S, 3.45. Main IR peaks (KBr, cm−1), υ(N–
H), 3474s,3358m,3229; υ(–NH–), 3129m; υ(C–HPh),
3050s; δ(NH2) +υ(C=N) +υ(C–C), 1632s, 1539s;
υ(C=S) 829m (thioamide moiety), υ(P–CPh),1094s. 1H
NMR (CDCl3, δ ppm,): 10.23s (1H, N2H), 8.20s (1H,
C2H), 7.67-6.93m (34H, C4,5.7.8H+Ph3P).
2.3 X-ray data collection, structure solution
and refinement
X-ray intensity data of 29686 reflections (of which 6397
Complexes 2 and 3 were prepared by similar method. unique) were collected on X’calibur CCD equipped

X-ray Structure of new copper(I)-thiosemicarbazone complex
Table 1. Crystallographic data of complex 3.
Empirical Formula
C44H38Cl2CuN3P2S
Formula Weight
Temperature (K)
Wavelength (Å)
Crystal system
Crystal size (mm)
Space group
837.21
293(2)
0.71073
Triclinic
0.3 x 0.2 x 0.2
P-1
2
Z, calculated
Density (g cm−3
)
1.339
0.817
Absorption coefficient (mm−1
)
a (Å)
b (Å)
c (Å)
α (◦)
10.207(5)
13.027(5)
16.269(5)
100.054(5)
99.228(5)
97.234(5)
2075.9(14)
864
β (◦)
γ (◦)
V(A3)
F(000)
Theta range for data collection (◦)
Limiting indices
3.48-26.00
−12 ≥ h ≥ 12, −16 ≥ k ≥ 16, −20 ≥ l ≥ 20
Reflections
29686
Collected/unique
Completeness to theta
Data/restraints
8127
3.48-26.00
8127/0/423
1.031
Goodness-of- fit on F2
Final R indices
R1 = 0.0378 wR2 = 0.0866
[I> 2σ(I)]
6397
R indices (all data)
ꢀρmax, ꢀρmin (e Å−3
R1 = 0.0543 wR2 = 0.0969
0.326, −0.343
)
X
Cl
Cu
S
+
CuX
S
R
2PPh3
N
Ph3P
PPh3
C
NH
C
CH3CN
H
NH2
X = I 1, Br 2, Cl 3
S
R
Scheme 1. Reaction scheme for synthesis of complexes 1-3.
Table 2. Selected bond length (Å) and bond angles (◦) for complex 3.
Bond Lengths
Cu(1) – S(1)
Cu(1) – Cl(1)
Cu(1) – P(1)
Cu(1) – P(2)
2.4534(9)
2.3350(13)
2.3024(10)
2.2832(8)
S(1) – C(12)
C(12) – N(7)
C(12) – N(8)
1.697(3)
1.320(3)
1.327(3)
Bond Angles
P(1) - Cu(1) - P(1)
P(2) – Cu(1) – Cl(1)
P(1) – Cu(1) – Cl(1)
P(2) – Cu(1) – S(1)
P(1) – Cu(1) – S(1)
123.54(3)
110.93(3)
102.32(3)
102.50(3)
109.90(3)
Cl(1) – Cu(1) – S(1)
N(7) – C(12) – N(8)
S(1) – C(12) – N(7)
Cu(1) – S(1) – C(12)
106.84(3)
117.5(2)
123.8(2)
114.23(9)

Ashiq Khan et al.
Figure 1. Molecular structure of complex 3.
with graphite monochromated MoKα radiation (λ = (1), Br (2), Cl (3) (scheme 1). Geometry around
0.71073 Å). The crystal used for data collection was copper center was found to be distorted tetrahedral
of dimensions 0.3 x 0.2 x 0.2 mm. The cell dimen- in complex 3. This monomer was in contrast
sions were determined by least-squares fit of angu- to the previous results with benzaldehydethiosemi-
lar settings of 10580 reflections in the θ range 3.48 carbazone, where sulfur bridged dimer [Cu2(μ2-S-
to 29.08◦. The intensities were measured by ω scan Hbtsc)2(Ph3P)2Cl2]·2H2O was formed with copper(I)
mode for θ ranges 3.48 to 24.99◦. 1798 reflections were chloride.19 It was already proved by theoretical studies
treated as observed (I >2σ(I)). Data were corrected for that tetrahedral monomer and halogen-bridged dimers
Lorentz, polarization and absorption factors. The struc- were thermodynamically more stable than S-bridged
ture was solved by direct methods using SHELXS97.34 dimers. The S-bridged dimers could be stabilized by H-
All non-hydrogen atoms of the molecule were located bonding between hydrogen atom of solvent molecule
in the best E-map. Full-matrix least-squares refinement and halogen atom.19 Since there is no solvent molecule
was carried out using SHELXL97.35 The final refine- entrapped in the lattice of complex 3, formation of tetra-
ment cycles converged to an R = 0.0320 and wR hedral molecule is thermodynamically more favored.
(F2) = 0.0835 for the observed data. Residual elec- The CHN analysis of complexes 1-3 indicates that the
tron densities ranged from −0.167 to 0.175 eÅ−3. The molecular formula for all the three complexes are sim-
crystallographic data are summarized in table 1.
ilar. The PXRD pattern. The peaks in PXRD pattern of
3. Results and Discussion
Reaction of p-chlorobenzaldehydethiosemicarbazone
(H1L) with copper(I) halides (I, Br, Cl) and triph-
enylphosphine in 1 : 1 : 1 (L : M : PPh3) molar
ratio formed insoluble compounds of stoichiometry,
{CuX(H1L)(Ph3P)}. An effort was made to solubi-
lize it, but no crystalline product was obtained. To
solubilize these compounds, one extra mole of triph-
enylphosphine was added, which yielded complexes
of stoichiometry, [CuX(η1-S-H1L)(Ph3P)2] (X = I
Figure 2. Interaction between two molecules of complex 3.

X-ray Structure of new copper(I)-thiosemicarbazone complex
Figure 3. Intermolecular iteractions leading to the formation of 1D chain in 3.
these complexes appeared at different angles implying phosphorus atoms from two triphenylphosphine ligands
that the lattice structure of these complexes may be dif- occupied tetrahedral sites around the copper center. The
ferent due to the presence of different anions or solvent Cu−S bond length in complex 3, 2.4534(9) Å is close
molecules (See Supplementary Information).
to the other copper(I) halide-thiosemicarbazone com-
The ν(N-H) band due to (-NH2) and (-NH-) groups plexes reported in literature.19,20,25–27 The Cu−Cl bond
appeared in ranges, 3476-3285 cm−1 and 3160-3129 length, 2.3350(13) Å is less than the sum of ionic radii
cm−1, respectively. Presence of these bands suggested of Cu and Cl (Cu+, Cl−, 2.58 Å).36 The Cu-P bond
that thiosemicarbazone coordinated as neutral ligand in lengths, {2.3024(10), 2.2832(8) Å 3} are close to lit-
these complexes. Low energy shift of ν(C=S) in com- erature value.19,20,25–27 The C-S bond length, 1.697(3)
plexes 1-3 (829 (1), 820 (2), 818(3) cm−1) vis-à-vis Å in 3 is close to free ligand (1.687(3) Å),37 but much
free ligand (854 cm−1) supported binding of ligand via shorter than that, {1.772(4)Å} in [PyPhHg(btsc)] (btsc
thione sulfur. The appearance of characteristic ν(P-CPh) = anionic form of benzaldehyde thiosemicarbazone),38
in range 1092-1094 cm−1 in complexes 1-3 indicated which indicates that ligand is coordinated to copper
coordination of Ph3P to metal center.
center in thione form. Two S−Cu−P bond angles
are different, {S−Cu−P(1), 109.90(3)◦; S−Cu−P(2),
102.50(3)◦}. The S−Cu−Cl and P−Cu−P bond angles
are 106.84(3)◦ and 123.54(3)◦ respectively. The vari-
3.1 Structure of complex 3
The crystallographic data and important bond param- ation in these angles in 3 from 109.5◦ reveals distor-
eters (bond lengths and bond angles) of complex 3 tion from regular tetrahedral geometry. Coordination
are given in tables 1 and 2, respectively. The molecu- of two bulky triphenylphosphine molecules to copper,
lar structure along with numbering scheme is given in creates maximum distortion in P−Cu−P bond angle,
figure 1. Complex 3 crystallized in triclinic crystal 123.54◦. The Cu-S-C bond angle, 114.23(9)◦ is much
system with space group P-1.
larger than that in [2-PyPhHg(btsc)], {99.09(12)◦},
In complex 3, thione sulfur of p-chloroben- where thiosemicarbazone ligand forms a chelate
zaldehydethiosemicarbazone, chloride ion and two ring.38
Figure 4. Inter molecular H-bonding within two 1D layer to form 2D layer isn complex 3.

Ashiq Khan et al.
Copies of this information can be obtained free of
3.2 Supramolecular Architecture of complex 3
charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: 44-1223-336-033;
email: deposit@ccdc.cam.ac.uk; or http://www.ccdc.
cam.ac.uk). Cif file of complex 3 and PXRD patterns of
complexes 1-3 are given in Supplementary Information,
available at www.ias.ac.in/chemsci.
Intermolecular H-bonding and different π-interactions
in complex 3 has resulted in the formation of 2D sheet.
The stepwise formation of supramolecular architecture
of this complex can be explained as: two molecules of
complex 3 are interconnected via H-bonding between
chloride ion and phenyl hydrogen of triphenylphos-
phine, Cl· · · HCph, 2.733 Å. These molecules also show
strong π interaction, {CHph · · · π, 2.796; 2.776 Å} to
form dimeric unit. The distance between phenyl hydro-
gen of p-cholorobenzaldehyde ring and centroid of
phenyl ring of triphenylphosphine is 2.550 Å (figure 2).
The same interactions are repeated to form 1D layer
(figure 3).
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4. Conclusions
Reactions of copper(I) halides with p-chlorobenzalde-
hyde thiosemicarbazone and triphenylphosphine formed
compounds of formula, [CuX(η1-S-H1L) (Ph3P)2] (X =
I, 1; Br, 2; Cl, 3). X-ray structure of complex 3 revealed
a distorted tetrahedral geometry, in contrast to sulfur-
bridged dimer with benzaldehydethiosemicarbazone.19
Reason for change in nuclearity could be the absence
of solvent in the lattice. The intermolecular H-bonding,
Cl· · · HCph, 2.733 Å and π interactions, {CHph · · · π,
2.796; 2.776 Å} led to the formation of 1D chain.
Two such 1D chains were cross-linked via H-bonding,
Cl· · · HCph, 2.896 Å to form 2D network.
Supplementary Information (SI)
All details have been deposited with the Cambridge
Crystallographic Data Centre, CCDC for 3 is 1042089.
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