Crystal structure of copper(I) thiosemicarbazone complex [CuI(PPh3)(catsc)]

Article abstract of DOI:10.1134/S0022476615050273

In this paper, we report the preparation of a four-coordinated copper(I) thiosemicarbazone complex [CuI(PPh₃)(catsc)] from the reaction of PPh₃ and catsc (3-phenylpropenalthiosemicarbazone) with CuI. The synthesized complex is characterized by elemental analyses (CHNS) and FT-IR spectroscopy. The crystal structure of [CuI(PPh₃)(catsc)] is investigated by single crystal X-ray diffraction. The catsc coordinates to the copper(I) ion as a bidentate ligand via the N and S atoms. The complex has a distorted tetrahedral coordination geometry.

Full text of DOI:10.1134/S0022476615050273

Journal of Structural Chemistry. Vol. 56, No. 5, pp. 1003-1007, 2015.
Original Russian Text © 2015 E. Shahsavani, N. Feizi, V. Eigner, M. Dusek, A. D. Khalaji.
CRYSTAL STRUCTURE OF COPPER(I)
THIOSEMICARBAZONE COMPLEX [CuI(PPh )(catsc)]
3
1
E. Shahsavani , N. Feizi , V. Eigner , M. Dusek ,
1
2,3
3
UDC 541.6:541.49:546.56
4
and A. D. Khalaji
In this paper, we report the preparation of a four-coordinated copper(I) thiosemicarbazone complex
[CuI(PPh3)(catsc)] from the reaction of PPh3 and catsc (3-phenylpropenalthiosemicarbazone) with CuI. The
synthesized complex is characterized by elemental analyses (CHNS) and FT-IR spectroscopy. The crystal
structure of [CuI(PPh3)(catsc)] is investigated by single crystal X-ray diffraction. The catsc coordinates to
the copper(I) ion as a bidentate ligand via the N and S atoms. The complex has a distorted tetrahedral
coordination geometry.
DOI: 10.1134/S0022476615050273
Keywords: copper(I), thiosemicarbazone, crystal structure, single crystal.
Thiosemicarbazones, an important class of N,S-donor ligands, react with a range of transition metals [1, 2]. In recent
years, there was interest in thiosemicarbazones due to their structural diversity [3, 4] and anticancer, antibacterial, antifungal
[5], and ion-sensing abilities [6]. Comparing with other complexes, the coordination chemistry of copper(I)
thiosemicarbazones is less investigated [7-12]. The main reason for limited information on copper(I) thiosemicarbazones is
their insolubility in common organic solvents, such as methanol, chloroform, ethanol etc. In the neutral form,
thiosemicarbazone binds to a metal ion as a monodentate ligand via an S donor atom or as a bidentate ligand via S and N
donor atoms.
Herein, we report the synthesis and crystal structure of a new copper(I) thiosemicarbazone complex
[CuI(PPh3)(catsc)] (Scheme 1).
Scheme 1.
The
chemical
structure of [CuI(PPh3)(catsc)].
Experimental. Material and methods. All reagents and solvents for the synthesis and analysis were commercially
available and used as received without further purifications. Infrared spectra were recorded using KBr disks on a FT-IR
1
2
Department of Chemistry, Payame Noor University, Mashhad, Iran. Department of Solid State Chemistry, Institute
3
4
of Chemical Technology, Prague, Czech Republic. Institute of Physics of the ASCR, Prague 8, Czech Republic. Department
of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran; alidkhalaji@yahoo.com. The text was submitted by the
authors in English. Zhurnal Strukturnoi Khimii, Vol. 56, No. 5, pp. 1061-1065, September-October, 2015. Original article
submitted December 12, 2013.
0022-4766/15/5605-1003 © 2015 by Pleiades Publishing, Ltd.
1003

Perkin–Elmer spectrophotometer. Elemental analyses were carried out using a Heraeus CHN-O-Rapid analyzer. The
thiosemicarbazone ligand catsc was prepared in a high yield following the literature procedure [13].
Synthesis of [CuI(PPh3)(catsc)]. To a solution of 190 mg (1 mmol) CuI in 5 ml⋅l acetonitrile a solution of 262 mg
(1 mmol) of PPh3 in 5 ml⋅l acetonitrile was added dropwise under the air atomsphere at room temperature. The mixture was
stirred for 30 min and then 205 mg (1 mmol) catsc in 5 ml acetonitrile were added and stirred for additional 30 min.
An orange-yellow microcrystalline powder was immediately obtained. Single crystals of [CuI(PPh3)(catsc)] were obtained by
recrystallization from the acetonitrile solution after a few days. The crystals were collected by filtration and dried. Anal.
Calcd. For C28H26CuIN3PS. Calcd. (%) C 51.11, H 3.98, N 6.39, S 4.87. Found (%): C 51.15, H 4.02, N 6.45, S 4.83. FT-IR
–1
(KBr, cm ): 3407, 3274 (NH2), 31.73 (NH), 3042, 2928 (CH aromatic and aliphatic), 2851 (–CH=N), 1621 (C=N), 1604
(NH2), 1578, 1555, 1478 (C=C).
X-ray crystallography. A [CuI(PPh3)(catsc)] single crystal of the dimensions 0.36×0.25×0.08 mm was chosen for
the X-ray diffraction study. Crystallographic measurements were carried out at 120 K on a four-circle Gemini CCD
diffractometer (Oxford diffraction, Ltd.) with mirrors-collimated CuK radiation (λ = 1.54184 Å). Although the quality of the
α
single crystals was low (as indicated by the Rint factor in Table 2 for merging symmetry equivalent reflections) the crystal
structure could be nevertheless easily solved by charge flipping using the SUPERFLIP program [14] and refined using the
2
Jana2006 program package [15] by the full-matrix least-squares technique on F . The molecular structure plots were prepared
by ORTEP III [16]. Hydrogen atoms were mostly discernible in difference Fourier maps and could be refined to a reasonable
geometry. According to the common practice, hydrogen atoms attached to carbon atoms were kept in ideal positions during
the refinement. The isotropic atomic displacement parameters of hydrogen atoms were set to 1-1.2Ueq of their hydrogen
atoms. Crystallographic data and details of the data collection and structure solution and refinements are listed in Table 1.
Results and discussion. The [CuI(PPh3)(catsc)] complex was synthesized by the reaction of CuI, PPh3, and catsc in
acetonitrile in the 1:1:1 molar ratio (Scheme 2). Orange-yellow crystals of the [CuI(PPh3)(catsc)] complex were obtained in
a good yield (83 %). This complex is stable in the air in the solid state.
CH CN
3
CuI + PPh ⎯⎯⎯→CuI(PPh ) + catsc ⎯⎯⎯→CuI(PPh )(catsc)
Stirred
3
3
3
Scheme 2. Synthesis of the [CuI(PPh3)(catsc)] complex.
The complex was purified by recrystallization from acetonitrile and characterized by elemental analyses (CHNS)
and FT-IR spectroscopy. Elemental analyses revealed that the ratio of the PPh3, Cu, I, and catsc in the [CuI(PPh3)(catsc)]
complex is 1:1:1:1.
FT-IR spectroscopy of [CuI(PPh3)(catsc)] confirmed the presence of catsc and PPh3 via their ν(N–H), ν(C–N),
ν(C=C), ν(C=S), ν(C=N), and ν(C–P) bands (Fig. 1). Its FT-IR spectrum showed the presence of the ν(N–H) band at
–1
–1
–1
3407 cm and 3274 cm (due to –NH2) and 3173 cm (due to –NH–). Also, the ν(C=N) and ν(C=S) appeared at 1621 cm
–1
–1 –1
and 989 cm , respectively. A band due to ν(C–P) at 1093 cm indicates the presence of PPh3 [11].
An ORTEP view of [CuI(PPh3)(catsc)] is shown in Fig. 2 and selected bond lengths and angles are given in Table 2.
The [CuI(PPh3)(catsc)] complex crystallized in the triclinic system with the space group P-1. In this complex, the copper ion
is bonded to the bidentate N,S-chelate ligand catsc, the triphenylphosphine P atom, and the I atom, forming a distorted
tetrahedral environment coordination geometry. The Cu1–S1, Cu1–N3, Cu1–I1, and Cu1–P1 distances are 2.3237(10) Å,
2.060(3) Å, 2.6356(6) Å, and 2.2095(2) Å respectively, and they are similar to the literature reports. The bond angles around
the copper(I) ion in this structure are in the range from 85.42° (S1–Cu1–N3) to 124.94° (P1–Cu1–N3), confirming a distorted
tetrahedral geometry around the copper(I) ion.
From the molecular structure of [CuI(PPh3)(catsc)] (Fig. 2), it can be seen that two hydrogen
atoms of triphenylphosphine are engaged in the intramolecular hydrogen bonding. One hydrogen atom forms
an intramolecular hydrogen bond with the iodine atom (C21–H1c21⋯I1, 3.098 Å) and another hydrogen atom forms
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TABLE 1. Crystallographic and Refinement Data for [CuI(PPh3)(catsc)]
Empirical formula
Formula weight
C28H26Cu1I1N3P1S1
658
Crystal system, space group
a, b, c, Å
Triclinic, P-1
7.9954(4), 12.9402(7), 13.1156(8)
91.234(5), 92.261(5), 100.516(5)
α, β, γ, deg
3
V, Å
1332.57(13)
2
Z
−1
11.78
μ, mm
T, K
120
Crystal size, mm
0.36×0.25×0.08
0.084, 0.506
31600 / 4739 / 4332
0.127
Tmin, Tmax
Meas. / independent / reflections with I > 3σ(I)
Rint
2 2
R[F > 3σ(F )]
0.033
2
wR(F )
0.087
S
1.52
Reflections / parameters
4739 / 317
1.10, –0.75
3
Δρmax, Δρmin, e/Å
an intramolecular hydrogen bond with the catsc sulphur atom (C10–H1c10⋯S1, 2.878 Å). There is also an intermolecular
hydrogen bond (N2–H1N2…I1, 2.7759(2) Å) which connects the molecules of the complex into a chain along a.
We acknowledge the Golestan University (GU) and Payame Noor University (PNU) for partial support of this work
and the project 15-12653S of the Czech Sciense Foundation for supporting its crystallographic part.
Crystallographic data (excluding structure factors) for the structure reported in this paper has been deposited with
the Cambridge Crystallographic Center, CCDC No. 984807. Copies of the data can be obtained free of charge on application
to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, fax: +44 1223 336 033, e-mail: deposit@ccdc.cam.ac.uk
or http:www.ccdc.cam.ac.uk.
Fig. 1. FT-IR spectrum of [CuI(PPh3)(catsc)].
1005

Fig. 2. Molecular structure of [CuI(PPh3)(catsc)].
TABLE 2. Selected Bond Distances (Å) and Angles (deg) for [CuI(PPh3)(catsc)]
I1–Cu1
Cu1–P1
Cu1–S1
Cu1–N3
N3–C14
S1–C17
N1–C17
N2–N3
2.6356(6)
2.2095(9)
2.3237(10)
2.060(3)
1.290(5)
1.689(3)
1.330(4)
1.384(4)
1.354(4)
I1–Cu1–P1
I1–Cu1–S1
110.71(3)
105.69(3)
124.94(9)
129.5(2)
119.8(3)
122.3(2)
111.17(8)
P1–Cu1–S1
S1–Cu1–N3
Cu1–N3–N2
N2–N3–C14
S1–C17–N1
N1–C17–N2
115.27(4)
85.42(8)
114.7(2)
115.8(3)
122.2(3)
115.4(3)
P1–Cu1–N3
Cu1–N3–C14
N3–C14–C15
S1–C17–N2
I1–Cu1–N3
N2–C17
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