Thiosemicarbazone derivatives of copper(I): Influence of substituents (R) at N1 atom of [(C5H4N)HC2=N 3N2H-C1(=S)N1HR] in the formation of 1D or 2D networks of copper(I) complexes

Article abstract of DOI:10.1002/zaac.201000175

Copper(I) halides with N¹-substituted pyridine-2-carbaldehyde thiosemicarbazones [(C₅H₄N)HC²=N ³N²H-C¹(=S)N¹HR] in the presence of Ph₃P have formed complexes of stoichiometry, [CuX(Hpytsc-N ¹HR)(Ph₃P)₂] [X, R; Br, Me (1); Br, Et (2), Cl, Ph (3·CH₃CN)]. All these complexes are characterised by elemental analysis, IR and NMR (¹H, ³¹P) spectroscopy and X-ray crystallography. The role of substituents at N¹ atom of pyridine-2-carbaldehyde thiosemicarbazones in intermolecular interactions in copper(I) complexes is described. A 1D polymer of compound 1 is formed by intermolecular CH_(methyl)···π_(py) interactions. The hydrogen atoms of EtN¹H and ethyl group interact with the phenyl ring of PPh₃ {via EtN ¹H···π_(Ph), H₂CH _(Et)···π_(Ph)} to form a 1D polymer of 2. A 2D sheet arrangement of compound 3 is formed by pyridyl-phenyl (CH _(py)···π_(Ph)) interactions along the a axis and phenyl-phenyl [CH _(Ph)···π_(Ph)] interactions (phenyl at N¹ with phenyl of PPh₃) along the b axis. Copyright

Full text of DOI:10.1002/zaac.201000175

ARTICLE
DOI: 10.1002/zaac.201000175
Thiosemicarbazone Derivatives of Copper(I): Influence of Substituents (R) at
N1 Atom of [(C5H4N)HC2=N3N2H-C1(=S)N1HR] in the Formation of 1D or
2D Networks of Copper(I) Complexes
Tarlok S. Lobana,*[a] Rekha Sharma,[a] Alfonso Castiñeiras,[b] and Ray Jay Butcher[c]
Keywords: Substituent effects; Copper; Thiosemicarbazones; IR spectroscopy; NMR spectroscopy
Abstract. Copper(I) halides with N1-substituted pyridine-2-carbalde- is described. A 1D polymer of compound 1 is formed by intermolecu-
hyde thiosemicarbazones [(C5H4N)HC2=N3N2H-C1(=S)N1HR] in the lar CH(methyl)···π(py) interactions. The hydrogen atoms of EtN1H and
presence of Ph3P have formed complexes of stoichiometry, ethyl group interact with the phenyl ring of PPh3 {via EtN1H···π(Ph)
,
[CuX(Hpytsc-N1HR)(Ph3P)2] [X, R; Br, Me (1); Br, Et (2), Cl, Ph H2CH(Et)···π(Ph)} to form a 1D polymer of 2. A 2D sheet arrangement
(3·CH3CN)]. All these complexes are characterised by elemental analy- of compound 3 is formed by pyridyl–phenyl (CH(py)···π(Ph)) interactions
sis, IR and NMR (1H, 31P) spectroscopy and X-ray crystallography. along the a axis and phenyl–phenyl [CH(Ph)···π(Ph)] interactions (phenyl
The role of substituents at N1 atom of pyridine-2-carbaldehyde thio- at N1 with phenyl of PPh3) along the b axis.
semicarbazones in intermolecular interactions in copper(I) complexes
investigated. The substituents at the N1 nitrogen atom changed
Introduction
the nature of bridging between two metal atoms and nuclearity
Thiosemicarbazones, an important class of nitrogen, sulfur
of complexes [26]. In continuation, this paper reports the effect
donors, received considerable attention due to their structural
of substituents at the N1 atom of pyridine-2-carbaldehyde thio-
diversity [1, 2], variable-bonding modes [3], metallation prop-
semicarbazone on the nuclearity and intermolecular interac-
erties [4], ion-sensing ability [5, 6], extraction properties [7]
tions of complexes of copper(I) halides. These complexes were
and pharmacological applications [8–10]. Thiosemicarbazones
characterised using elemental analysis, IR and NMR (1H, 31P)
bearing a pyridine ring are known antitumor compounds and
spectroscopy and single crystal X-ray crystallography.
inhibitors of DNA synthesis and this activity is attributed to
their ability to inhibit the DNA topoisomerase II enzyme re-
sponsible for the regulation of the topology of DNA [11, 12].
Since copper(II)-thiosemicarbazone compounds are used in bi-
ological systems, they may involve CuII reduction to CuI in the
cells, thus the stability of CuI species is crucial to the hypo-
toxic reactivity and biological activity of topo-II inhibitors.
Pyridine-2-carbaldehyde thiosemicarbazone (I, Hpytsc-
N1H2) with copper(I) halides in acetonitrile is known to form
tetrahedral complexes, [CuX(η1-S-Hpytsc-N1H2)(Ph3P)2] [25].
In a recent study, the effect of substituents at the N1 nitrogen
atom on nature of bonding and nuclearity in copper(I) com-
plexes with thiophene-2-carbaldehyde thiosemicarbazones was
Experimental Section
Material and Techniques
* Prof. Dr. T. S. Lobana
E-Mail: tarlokslobana@yahoo.co.in
[a] Department of Chemistry
Guru Nanak Dev University
Amritsar-143005, India
Copper(I) bromide was prepared by the reduction of CuSO4·5H2O us-
ing SO2 in the presence of NaBr in distilled water [27]. N1-methyl
thiosemicarbazide, N1-ethyl thiosemicarbazide, pyridine-2-carbalde-
hyde and Ph3P were procured from Aldrich Sigma Ltd. Pyridine-2-
carbaldehyde-N1-methyl-thiosemicarbazone and pyridine-2-carbalde-
hyde-N1-ethyl-thiosemicarbazone ligands were prepared by condensa-
tion of pyridine-2-carbaldehyde with respective thiosemicarbazides. C,
H and N analyses were carried out using a thermoelectron FLASH-
EA1112 analyser. The melting points were determined with a Gallen-
kamp electrically heated apparatus. The IR spectra of the ligands and
the complexes were recorded in the range, 4000–200 cm–1 (using KBr
[b] Departamento De Quimica Inorganica
Facultad de Farmacia
Universidad de Santiago,
15782 Santiago, Spain
[c] Department of Chemistry
Howard University,
Washington DC 20059, USA
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201000175 or from the
author.
2698
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Thiosemicarbazone Derivatives of Copper(I)
pellets) with a FTIR-SHIMADZU 8400 Fourier Transform Spectro- spectively, equipped with a graphite monochromator, and Mo-Kα radia-
photometer and with a Pye–Unicam SP3–300 spectrophotometer. 1H tion (λ = 0.71073 Å). Crystal data were collected at 100 K (1), 296 K
¯
NMR spectra were recorded with a JEOL AL300 FT spectrometer at (2) and 200 K (3·CH3CN). The data were processed with APEX2 [28]
300 MHz in CDCl3 with TMS as the internal reference. 31P NMR and corrected for absorption using SADABS (transmissions factors:
spectra were recorded at 121.5 MHz with o-phosphoric acid as the 1.000–0.856) [29] in 1, processed with SMART and correct with
external reference taken as zero position.
SAINT in 2 and processed with CrysAlis CCD [30] and corrected with
SCALE3 ABSPACK scaling algorithm in 3·CH3CN. The structure was
solved by direct methods using the program SHELXS-97 [31] and
refined by full-matrix least-squares techniques against F2 using
SHELXL-97 [32] in 1 and 3·CH3CN and XCAD-49 and SHELXTL
in 2 [32]. Full details have been deposited with the Cambridge Crystal-
lographic Data Centre, CCDC-773785 (1), -773786 (2) -773787
(3·CH3CN), respectively. Copies of this information can be obtained
free of charge from The Director, CCDC, 12 Union Road, Cambridge
Synthesis of Complexes
[CuBr(η1-S-Hpytsc-N1HMe)(Ph3P)2] (1): The ligand Hpytsc-N1HMe
(0.034 g, 0.174 mmol) was added to a solution of copper(I) bromide
(0.025 g, 0.174 mmol) in acetonitrile (15 mL), and contents were
stirred for 3–4 h. To the yellow precipitates thus formed Ph3P (0.091 g,
0.358 mmol) was added followed by stirring for 5–10 min to form a
yellow-coloured solution. On slow evaporation at room temperature
it yielded yellow crystals. Yield, 0.109 g, 73 %, m. p. 200–202 °C.
C44H40BrCuN4P2S (862.28): calcd. C 61.29, H 4.64, N 6.50; found C
CB2
1EZ,
UK
(Fax:
44-1223-336-033;
E-mail:
de-
posit@ccdc.cam.ac.uk; or http:// www.ccdc.cam.ac.uk).
61.17, H 4.59, N 6.47. IR (KBr): ν =ν(N1H), 3410s, ν(N2H), 3200s,
˜
Supporting Information (see footnote on the first page of this article):
Syntheses of HpytscMe and HpytscEt, molecular structures of 2 and
3·CH3CN.
ν(C–H), 3096 w,3059w, 2965w, ν(C=N) + ν(C=C) 1640s, 1575s, ν(C–
1
N), 1070s, 1029s, ν(C–S), 883s, ν(P–CPh) 1093(s). H NMR (CDCl3):
δ = 12.19 (–N2H), 8.80s (C2H), 8.69s (C7H), 8.00s (C4H), 7.83–7.31m
(C5,6H, Ph), 1.34d (NHCH3). 31P NMR (CDCl3): δ = –3.71, Δδ (δ
complex – δ ligand) = 0.99.
Results and Discussion
Compounds 2 and 3 are prepared similarly.
Synthesis and IR Spectroscopy
[CuBr(η1-S-Hpytsc-N1HEt)(Ph3P)2] (2): Yield, 0.114 g, 75 %, m. p.
Scheme 1 represents the reaction of copper(I) halides (bro-
mide or chloride) with pyridine-2-carbaldehyde N1-substituted
thiosemicarbazones. Copper(I) halides reacted with Hpytsc-
N1HMe, Hpytsc-N1HEt or Hpytsc-N1Ph in 1:1 molar ratio and
formed insoluble precipitates. The addition of two mmols of
Ph3P to these precipitates in situ formed clear solutions, which
on slow evaporation yielded compounds of empirical formula,
[CuX(η1-S-Hpytsc-N1HR)(Ph3P)2] [X, R; Br, Me (1); Br, Et (2);
Cl, Ph (3·CH3CN)]. If copper(I) halides were treated with Ph3P
first, the addition of thio-ligands did not form clear solution
and no crystalline product could be obtained and thus first
route was adopted.
The coordination of the neutral ligands in the complexes 1–
3·CH3CN is supported by the presence of ν(N–H) bands in the
ranges 3410–3420 cm–1 (due to –N1HR) and 3200–3265 cm–1
(due to–Ν2Η–). The most characteristic thioamide bands due
to ν(C=S) lie in the range 883–885 cm–1 in complexes and
undergo low energy shifts (free ligands, 895–899 cm–1). The
ν(C–H) and ν(P–CPh) bands appeared in the ranges, 2869–
2975 cm–1 and 1093–1095 cm–1 respectively.
210–212 °C. C45H42BrCuN4P2S (876.31): calcd. C 61.68, H 4.80, N
6.40; found C 61.74, H 4.59, N 6.33. IR (KBr): ν = (ν, N1H) , 3420
˜
(s, ν, N2H) , 3265 (s, ν, C–H) 3075 (w), 2940 (w), 2910 (w), 2873 [w,
ν, C=N) + ν(C=C] 1644 (s), 1570 (s, ν, C–N) , 1068 (s, ν, C–S) 884
1
(s, ν, P–CPh) 1095(s) cm–1. H NMR (CDCl3): δ =12.74 (-N2H), 8.74s
(C2H), 8.24s (C7H), 7.99–7.30m (C4,6H, PPh3, N1H), 7.12s (C5H),
3.53m (–CH2–), 1.36t (–CH3). 31P NMR (CDCl3): δ = –3.34, Δδ (δ
complex – δ ligand) = 1.36.
[CuCl(η1-S-Hpytsc-N1HPh)(Ph3P)2]·CH3CN (3·CH3CN): Yield,
0.174 g, 75 %, m. p. 198–200 °C. C51H45ClCuN5P2S (920.96): calcd.
C 66.45, H 4.88, N 7.60; found C 66.72, H 4.79, N 7.56. IR (KBr):
ν = (ν, N1H) , 3432 (s, ν, N2H) , 3260 (s, ν, C–H) 3180 (w), 3066 (w),
˜
2910 (w), 2869 [w, ν, C=N) + ν(C=C] 1638 (s), 1574 (s, ν, C–N) ,
1066 (s, ν, C–S) 885 (s, ν, P–CPh) 1095(s) cm–1. H NMR (CDCl3):
1
12.33s (-N2H), 8.95s (C2H), 8.54d (C7H), 8.36s (NHPh), 7.54–7.31m
(C4,5,6H, PhN1H, PPh3). 31P NMR (CDCl3): δ = –2.85, Δδ (δ com-
plex – δ ligand) 1.85.
Hpytsc-N1HPh: Pyridine-2-carbaldehyde (1.28 g, 11.9 mmol) was
slowly added to a solution of N-phenylthiosemicarbazide (2.0 g,
11.9 mmol) in methanol (50 mL). The contents were heated under re-
flux for 6–7 h. The light yellow needles formed were dried and recrys-
tallised from methanol. Slow evaporation of the solution gave clear
light yellow crystals. 73 %, m. p. 205–207 °C. C13H12N4S (256.32):
calcd. C 60.94, H 4.69, N 21.87; found C 60.56, H 4.59, N 21.72. IR
Crystal Structures of Complexes 1–3·CH3CN
(KBr): ν = (ν, N1H) , 3415 (s, ν, N2H) , 3250 (s, ν, C–H) 3195 (w),
The complexes 1–3·CH3CN crystallised in monoclinic sys-
tem with space group P2(1)/c. The crystallograhic data and
˜
3045 (w), 2915 (w), 2868 [w, ν, C=N) + ν(C=C] 1630 (s), 1585 (s, ν,
C–N) , 1089 (s), 1051 (s, ν, C–S) 899s cm–1. H NMR (CDCl3): δ = important bond parameters are given in Table 1 and 2 respec-
1
11.34s (-N2H), 8.85s (C2H), 8.62d (C7H), 8.47s (NHPh), 7.50–7.32m
tively. The molecular structure of representative complex 1 is
(C4,5,6H, PhN1H).
given in Figure 1
One thio-ligand, one bromine atom and two Ph3P ligands are
coordinated to copper(I) atom in complexes 1 and 2. The Cu–
X-ray Crystallography
Br bond lengths, {2.5217(3) 1; 2.5302(3) Å 2} are similar to
the analogous complex, [CuBr(Hpytsc-N1H2)(Ph3P)2] (4)
Crystals of 1, 2 and 3·CH3CN were mounted on Bruker X8 KappaA-
PEXII, Enraf–Nonius CAD-4 and Oxford Diffraction Gemini R re- (2.5475(8) Å) [25]. These distances are less than the sum of
Z. Anorg. Allg. Chem. 2010, 2698–2703
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. S. Lobana, R. Sharma, A. Castiñeiras, R. J. Butcher
ARTICLE
Scheme 1.
Table 1. Crystallographic data of complexes 1–3.
1
2
3·CH3CN
Empirical formula
C44H40BrCuN4P2S
C45H42BrCuN4P2S
monoclinic
P21/c
C51H45ClCuN5P2S
monoclinic
P121/c1
18.8154(14)
11.2125(10)
21.6783(15)
90
Crystal system
monoclinic
P 21/c (No. 14)
10.10030(10)
17.1516(2)
22.7050(3)
90
Space group
a /Å
9.9659(5)
17.5745(8)
22.9750(11)
90
b /Å
c /Å
α /°
β /°
94.4200(10)
90
95.3760(10)
90
96.450(7)
90
γ /°
V /Å3
3921.63(8)
4
4006.3(3)
4
4544.5(6)
4
Z
Dcalcd. /g·cm–3
μ (Mo) /mm–1
λ (Mo-Kα) /Å
F(000)
1.460
1.453
1.346
1.748
1.713
0.697
0.71073
1768
0.71073
1800
0.71073
1912
T /K
100(2)
100(2)
9925
200(2)
Reflections collected
Reflections observed, [I > 2σ(I)]
Parameters
94055
8095
6813
8566
3057
478
488
551
R (all data)
0.0381
0.0605
1.049
0.0389
0.0855
1.049
0.2080
0.0936
0.898
Rw (all data)
Goodness-of-fit on F2
Table 2. Bond lengths /Å and bond angles /° of complexes 1–3.
[CuBr(η1-S-Hpytsc-N1HMe)(Ph3P)2] (1)
Cu(1)–Br(1)
2.5217(3)
2.2700(5)
2.2860(5)
2.4123(6)
104.004(16)
109.513(15)
126.28(2)
S(1)–C(17)
1.693(2)
Cu(1)–P(1)
C(17)–N(14)
1.325(3)
Cu(1)–P(2)
Cu(1)–S(1)
Br(1)–Cu(1)–P(1)
Br(1)–Cu(1)–P(2)
P(1)–Cu(1)–P(2)
N(13)–C(17)
N(13)–N(12)
P(2)–Cu(1)–S(1)
S(1)–Cu(1)–P(1)
S(1)–Cu(1)–Br(1)
1.340(3)
1.370(12)
94.373(19)
109.273(19)
113.221(15)
[CuBr(η1-S-Hpytsc-N1HEt)(Ph3P)2] (2)
Cu(1)–Br(1)
2.5302(3)
S(1)–C(39)
1.6957(19)
1.326(2)
Cu(1)–P(1)
2.2996(5)
C(39)–N(1)
Cu(1)–P(2)
Cu(1)–S(1)
Br(1)–Cu(1)–P(1)
Br(1)–Cu(1)–P(2)
P(1)–Cu(1)–P(2)
2.2842(5)
2.4081(5)
108.860(15)
105.418(14)
127.095(18)
N(2)–C(39)
N(2)–N(3)
P(2)–Cu(1)–S(1)
S(1)–Cu(1)–P(1)
S(1)–Cu(1)–Br(1)
1.353(2)
1.366(2)
107.363(17)
94.721(17)
113.133(14)
[CuCl(η1-S-Hpytsc-N1HPh)(Ph3P)2] (3)
Cu–P(1)
2.2669(14)
2.3016(18)
2.3892(17)
2.4041(15)
123.09(7)
103.60(6)
107.98(6)
S–C(1)
1.680(6)
1.349(6)
1.380(5)
1.276(6)
112.61(6)
100.32(6)
108.77(6)
Cu–P(2)
N(1)–C1
Cu–Cl
Cu–S
P(1)–Cu–P(2)
P(1)–Cu–Cl
P(2)–Cu–Cl
N(1)–N(2)
N(2)–C(2)
P(1)–Cu–S
P(2)–Cu–S
Cl–Cu–S
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Thiosemicarbazone Derivatives of Copper(I)
three complexes and is influenced by the substituents at N1
atom of the thio-ligand.
In complex 1, methyl substituent at the N1 atom interacts
intermolecularly with pyridyl ring at the C2 atom of the second
molecule through CH(methyl)···π(py) (2.888, 2.867 Å), which
generates a linear 1D polymer (Figure 2).
In complex 2, replacement of methyl group with the ethyl
group at N1 changed the intermolecular interactions. In com-
plex 2, the phenyl rings of Ph3P molecule are bonded intermo-
lecularly to EtN1H, CH3 of ethyl group and phenyl ring of
second Ph3P molecule through EtN1H···π(Ph) (2.858 Å),
CH(Et)···π(Ph) (2.805 Å) and CH(Ph)···π(Ph) (2.862 Å). These in-
teractions result in the formation of a linear polymer (Fig-
ure 3). Interestingly, in the earlier reported complex
[CuBr(Hpytsc-N1H2)(Ph3P)2] (4) [25], no intermolecular inter-
actions were observed.
Figure 1. Molecular structure of [CuBr(η1-S-Hpytsc-N1HMe)(Ph3P)2]
(1) (structures of 2 and 3 are similar).
ionic radii of Cu+ and Br– (2.73 Å) [33]. Similar coordination
is found in complex 3·CH3CN. In this complex, the Cu–Cl
distance of 2.3892(17) Å is shorter than 2.4097(6) Å in
[CuCl(Hpytsc-N1H2)(Ph3P)2]·CH3CN (5). The Cu–P distances
in 1–3·CH3CN are close to the literature values [25]. Table 3
shows a comparison of some important bond parameters of
copper(I) halide complexes with pyridine-2-carbaldehyde thio-
semicarbazones. Keeping the halogen constant, Cu–S and C–
S bond show a gradual change with the change of substituent
at N1 atom. The bond angles around the copper atom revealed
distorted tetrahedral arrangement. The P–Cu–P bond angles are
affected by substitution, largest being with Hpytsc-N1HEt (2)
ligand and smallest being with Hpytsc-N1H2 (4 [25]). The Cu–
S–C bite angles are large in complexes 1–3·CH3CN relative to
literature reports [25].
Intermolecular interactions are different in complex
3·CH3CN. Both the pyridyl ring at the C2 carbon atom and
phenyl ring at the N1 nitrogen atom take part in the intermolec-
ular interactions. A linear chain is formed by the interaction of
the pyridyl ring with the phenyl ring of PPh3 by CH(py)···π(Ph)
(2.875 Å). The two linear chains are further connected by the
following interactions: phenyl ring at N1 atom with phenyl ring
of PPh3 (CH(Ph)···π(Ph), 2.830 Å) and amino hydrogen with phe-
nyl ring of PPh3 (PhN1H···π(Ph), 2.864 Å). This results in the
formation of a sheet structure (Figure 4). In contrast, [CuCl(η1-
S-Hpytsc-N1H2)(Ph3P)2]·CH3CN (5) formed
a hydrogen
bonded trimer [25]. The acetonitrile molecules are forming
H2CH···Cl bonds (2.886 Å) and are lying between the chains.
Solution-Phase Behaviour
The N2H NMR spectroscopic signal of the ligands appear at
Packing Networks
In complexes 1–3·CH3CN, imino hydrogen atoms form intra- 12.19 ppm, 12.74 ppm and 12.33 ppm in the complexes 1, 2
molecular hydrogen bonding with the halogen atoms, and 3 respectively, which are at low field relative to uncoordi-
(–N2H···X), which is similar to that in 4 and 5 [25]. However, nated ligands (Hpytsc-N1HMe, 11.26; Hpytsc-N1HEt, 11.21;
the intermolecular hydrogen bonding is different in all the Hpytsc-N1HPh, 11.34 ppm). This indicates coordination of
Table 3. Comparison of important bond parameters /Å, ° of copper(I) halide complexes.
Complex
Cu–S
C–S
Cu–P
Cu–S–C
P–Cu–P
[CuBr(Hpytsc-N1H2)(Ph3P)2] (4)[25]
[CuBr(Hpytsc-N1HMe)(Ph3P)2] (1)
[CuBr(Hpytsc-N1HEt)(Ph3P)2] (2)
[CuCl(Hpytsc-N1H2)(Ph3P)2] (5)[25]
2.4142(3)
2.4123(6)
2.4081(5)
2.4063(6)
1.690(5)
1.693(2)
1.6957(19)
1.706(2)
1.680(6)
2.2785(19) 2.2995(13)
2.2700(5), 2.2860(5)
2.2996(5), 2.2842(5)
2.2622(6), 2.2911(6)
2.2669(14), 2.3016(18)
105.82(15)
110.81(7)
111.79(6)
103.13(8)
110.2(2),
122.39(5)
126.28(2)
127.095(18)
121.53(2)
123.09(9)
[CuCl(Hpytsc-N1HPh)(Ph3P)2] (3)·CH3CN 2.4041(15)
Z. Anorg. Allg. Chem. 2010, 2698–2703
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T. S. Lobana, R. Sharma, A. Castiñeiras, R. J. Butcher
ARTICLE
Figure 2. Packing diagram of [CuBr(η1-S-Hpytsc-N1HMe)(Ph3P)2] (1).
Figure 3. Packing diagram of [CuBr(η1-S-Hpytsc-N1HEt)(Ph3P)2] (2).
Figure 4. Packing diagram of [CuCl(η1-S-Hpytsc-N1HPh)(Ph3P)2]·CH3CN (3·CH3CN).
neutral ligands to copper(I) metal atom. Furthermore, the C2H (3.53 ppm, CH2); and one triplet signal (1.36 ppm, CH3) in
signals at 8.80 ppm(1); 8.74 ppm(2) and 8.95 ppm (3·CH3CN) complex 2. The C4H and C6H at pyridyl ring protons in com-
also showed lowfield shifts. The methyl protons of –N1HCH3 plex 1 and C4H, C5H and C6H of pyridyl ring protons in 2 and
appeared as a doublet signal at 1.34 ppm in 1. The ethyl pro- 3·CH3CN merged with ring protons of Ph3P (7.31–7.83 ppm).
tons of –N1HC2H5 group appeared as two sets, one multiplet The 31P NMR spectrum of each complex showed one signal
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Z. Anorg. Allg. Chem. 2010, 2698–2703

Thiosemicarbazone Derivatives of Copper(I)
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It is concluded here that there is no effect of substitution at
N1 on the nuclearity of complexes. However, the presence of
the groups at the N1 atom changed intermolecular interactions,
which resulted in the formation of 1D and 2D networks. The
latter behaviour is in contrast to the unsubstituted (at N1) pyri-
dine-2-carbaldehyde thiosemicarbazone. The molecular struc-
ture remains unchanged in the solution state as revealed by 1H
and 31P NMR spectroscopy.
Acknowledgement
Financial assistance (RS) from Council of Scientific and Industrial Re-
search (CSIR) (Scheme No.: 01(1993)/05/EMR-II), New Delhi is
gratefully acknowledged. The authors thank Professor Dr. Matthias
Zeller of Youngstown State University, USA for X-ray crystallography.
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Received: April 27, 2010
Published Online: July 15, 2010
Z. Anorg. Allg. Chem. 2010, 2698–2703
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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