Synthesis, characterization and crystal structures of new 1,2,4-triazole based schiff-bases and their copper(I) complexes

Article abstract of DOI:10.1002/zaac.200500140

The reaction of 4-amino-5-methyl-2H-1,2,4-triazole-3(4H)-thione (AMTT, 1) with 4-methoxy benzaldehyde and 3-methoxybenzaldehyde in methanol led to the iminic derivatives 4-(4-methoxybenzylideneamino)-5-methyl-2H-1,2,4-triazole- 3(4H)-thione (2, L1) and 4-(3-methoxybenzylideneamino)-5-methyl-2H-1,2,4- triazole-3(4H)-thione (3, L2). The reaction of the latter with [(PPh ₃)₂CuCl] in methanol solution gave the first Cu ^I complex of 3, [(PPh₃)₂CuCl(L2)] (4) and in chloroform solution the complex [(PPh₃)₂CuCl(L2)] ·2CHCl₃ (5). All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X-ray diffraction studies. Crystal data for 2 at -80°C: space group P2₁/ c with a = 1351.3(3), b = 399.4(1), c = 2225.2(5) pm, β = 96.50(2)°, Z = 4, R ₁ = 0.0667, for 3 at -80°C: space group R3c with a = b = 3020.4(2), c = 708.2(1) pm, Z = 18, R₁ = 0.0435, for 4 at -80°C: space group P2₁/c with a = 1427.8(1), b = 1129.0(1), c = 2622.8(2) pm, β = 97.19(1)°, Z = 4, R₁ = 0.0517 and for 5 at -80°C: space group P1 with a = 1280.5(1), b = 1316.1(1), c = 1731.4(1) pm, α = 78.14(1)°, β = 86.06(1)°, γ = 64.69(1)°, Z = 2, R₁ = 0.0525.

Full text of DOI:10.1002/zaac.200500140

Synthesis, Characterization and Crystal Structures of new 1,2,4-Triazole based
Schiff-bases and their Copper(I) Complexes
Mitra Ghassemzadeha,*, Masoomeh Tabatabaeeb, Samaneh Soleimanib, and Bernhard Neumüllerc
Tehran/Iran, Chemistry & Chemical Engineering Research Center of Irana; Yazd, Iran; Islamic Azad Universityb
Marburg, Fachbereich Chemie der Universitätc
Received March 18th, 2005.
Abstract. The reaction of 4-amino-5-methyl-2H-1,2,4-triazole-
3(4H)-thione (AMTT, 1) with 4-methoxy benzaldehyde and 3-me-
thoxybenzaldehyde in methanol led to the iminic derivatives 4-(4-
methoxybenzylideneamino)-5-methyl-2H-1,2,4-triazole-3(4H)-
thione (2, L1) and 4-(3-methoxybenzylideneamino)-5-methyl-2H-
1,2,4-triazole-3(4H)-thione (3, L2). The reaction of the latter with
[(PPh3)2CuCl] in methanol solution gave the first CuI complex of
3, [(PPh3)2CuCl(L2)] (4) and in chloroform solution the complex
[(PPh3)2CuCl(L2)]·2CHCl3 (5). All compounds were characterized
by infrared spectroscopy, elemental analyses as well as by X-ray
diffraction studies. Crystal data for 2 at Ϫ80 °C: space group P21/
c with a ϭ 1351.3(3), b ϭ 399.4(1), c ϭ 2225.2(5) pm, β ϭ
96.50(2)°, Z ϭ 4, R1 ϭ 0.0667, for 3 at Ϫ80 °C: space group R3c
with a ϭ b ϭ 3020.4(2), c ϭ 708.2(1) pm, Z ϭ 18, R1 ϭ 0.0435,
for 4 at Ϫ80 °C: space group P21/c with a ϭ 1427.8(1), b ϭ
1129.0(1), c ϭ 2622.8(2) pm, β ϭ 97.19(1)°, Z ϭ 4, R1 ϭ 0.0517
and for 5 at Ϫ80 °C: space group P1 with a ϭ 1280.5(1), b ϭ
1316.1(1), c ϭ 1731.4(1) pm, α ϭ 78.14(1)°, β ϭ 86.06(1)°, γ ϭ
64.69(1)°, Z ϭ 2, R1 ϭ 0.0525.
¯
Keywords: 1,2,4-Triazole; Schiff-base; Copper; Crystal structures
1 Introduction
also found that the ligand AMTTO acts as a monodentate
ligand in a molar ratio 2:1 with CuI ion, while it reacts with
CuII as a bidentate one in a molar ratio 1:1 [3]. We have
reported the reaction of ATT with silver(I) and copper(I)
including their molecular structures [4].
4-amino-5-methyl-2H-1,2,4-triazole-3(4H)-thione (AMTT,
1) is a representative of the thio-triazole family, which
shows like the other members of this group the thione-thiol
tautomerism (forms I and II) as shown in Scheme 1.
In this paper, we wish to report the synthesis of Schiff-
bases based on AMTT and their CuI complexes.
2 Syntheses and Characterization of 2, 3, 4, and 5
Treatment of 1 with 4-methoxybenzaldehyde and 3-meth-
oxybenzaldehyde in methanol in presence of HCl under re-
flux conditions led to the corresponding iminic compounds
2 and 3 in high yields [Eq. (1)].
Scheme 1 Tautomeric forms in AMTT
Therefore, they can acts as neutral thione I and the de-
protonated thiol II ligand with the metal atoms.
In our investigations in the study of the coordination
chemistry of N,S-chelating agents, such as AMTTO, ATT
and the Schiff-bases based on AMTTO, we have shown that
AMTTO acts as a unidentate ligand via its sulfur atom with
a weak Ag···N interaction, which leads to a 2ϩ2 coordi-
nation on the silver(I) atom [1]. We have also found that
the 2-thiophene-Schiff-base based on AMTTO reacts with
silver ion via its sulfur atoms in a molar ratio of 2:1. The
additional coordination of the thiophene heterocycle caused
a 2ϩ1 coordination around the metal atom [2]. We have
Compounds 4 and 5 can be obtained by the reaction of
L2 and [(PPh3)2CuCl] in the molar ratio 1:1 in different
solvents according to equations (2) and (3).
* Dr. Mitra Ghassemzadeh
Chemistry and Chemical Engineering Research Center of Iran
P.O. Box 14335-186
Tehran (Iran)
All synthesized compounds are colorless and air-stable.
The absorptions νCuS and νCuCl of complexes 4 and 5 in
Z. Anorg. Allg. Chem. 2005, 631, 1871Ϫ1876
DOI: 10.1002/zaac.200500140
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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M. Ghassemzadeh, M. Tabatabaee, S. Soleimani, B. Neumüller
Table 1 Crystallographic data for 2, 3, 4 and 5
Compound
2 (L1)
3 (L2)
4
5
Empirical formula
Formula mass
Crystal size (mm)
Crystal system
Space group
a/pm
C11H12N4OS
248.30
0.53 x 0.04 x 0.02
monoclinic
P21/c
1351.3(3)
399.4(1)
2225.2(5)
90
96.50(2)
90
1193.2(5)
4
1.382
numerical
2.6 (Mo-Kα)
193
C11H12N4OS
248.30
0.4 x 0.12 x 0.06
trigonal
R3c
3020.4(2)
3020.4(2)
708.2(1)
90
90
120
5595.2(9)
18
1.326
C47H42ClCuN4OP2S
871.89
0.43 x 0.09 x 0.07
monoclinic
P21/c
1427.8(1)
1129.0(1)
2622.8(1)
90
97.19(1)
90
4194.7(6)
4
1.381
numerical
7.5 (Mo-Kα)
193
C49H44Cl7CuN4OP2S
1110.64
0.31 x 0.27 x 0.2
triclinic
¯
P1
1280.5(1)
1316.1(1)
1731.4(1)
78.14(1)
86.06(1)
64.69(1)
2580.8(3)
2
b/pm
c/pm
α /°
β /°
γ /°
Volume/pm3·106
Z
Dcalcd./g·cmϪ3
Absorption correction
μ /cmϪ1
1.429
numerical
2.5 (Mo-Kα)
193
numerical
9.3 (Mo-Kα)
193
Temperature/K
2θmax/°
Index range
52.42
52.55
52.53
52.53
h
k
l
Ϫ16Ǟ16
Ϫ4Ǟ4
Ϫ27Ǟ24
7921
Ϫ37Ǟ37
Ϫ37Ǟ35
Ϫ8Ǟ8
18566
Ϫ17Ǟ17
Ϫ14Ǟ12
Ϫ32Ǟ32
26946
Ϫ15Ǟ15
Ϫ16Ǟ16
Ϫ21Ǟ21
37694
Reflections collected
Unique reflections (Rint
Reflections with Fo>4σ(Fo)
Parameters
)
2371 (0.1623)
1176
161
2505 (0.1598)
2108
202
8373 (0.0929)
5157
521
10359(0.0422)
7204
585
Flack-parameter
R1
wR2 (all data)
Ϫ
0.0(1)
Ϫ
Ϫ
0.0667
0.0435
0.0517
0.0525
0.1475[a]
0.27
0.1136[b]
0.18
0.1313[c]
0.97
0.1495[d]
0.94
Max. residual electron
density/(e·pmϪ3)·10Ϫ6
[a] wϭ 1/[σ2(Fo)2ϩ(0.0442·P)2]; P ϭ [max (Fo2, 0)ϩ2Fc2]/3. [b] w ϭ 1/[σ2 (Fo)2ϩ(0.0677·P)2], [c] w ϭ 1/[σ2 (Fo)2ϩ(0.0717·P)2], [d] w ϭ 1/[σ2(Fo)2 ϩ (0.0949·P)2]
the IR spectrum can be observed at 350, 228 cmϪ1 (4) and
346 as well as 225 cmϪ1 (5) [5]. The CϭN functions cause
two vibrations at 1617 and 1497 cmϪ1 (4) and 1615 and
1500 cmϪ1 (5). The first value is for the endocyclic CϭN
group and the latter can be assigned to the iminic group. P-
C vibrations of the moiety PPh3 are found in the range 747-
695 cmϪ1 for both complexes. For the N-H stretching two
broad weak absorptions could be found at 3481 cmϪ1 (4)
and 3485 cmϪ1 (5).
character, such as observed in AMTT [7]. The iminic C-N
bond distance with 129.5(6) pm (2) and 127.6(4) pm (3) lies
in the range observed in similar compounds such as 2-ace-
tylthiophene-thiosemicarbazone (129.2(3) pm) and 2-ace-
tyl-thiophene-4-phenyl-thiosemicarbazone
(128.2(3) pm)
[8]. In 2, a weak hydrogen bonding links the sulfur atom of
one molecule to the NH-group of the adjacent one (N3-
H1···S1a: 330.0(4) pm) and is responsible for the centro-
symmetric geometry of the compound. In 3, three iminic
units are linked through NH-group of one to the endocyclic
nitrogen atom of the adjacent one via medium strong hy-
drogen bonding (N3-H1···N4a: 290.2(4) pm). This coordi-
nation mode caused an interesting arrangement around a
threefold symmetry-axis (Fig. 2) and is responsible for the
building (stacking) of tubes of trimeres along the direction
[001] (Fig. 3).
3 Results and Discussion
Compounds 2 and 3
Table 1 shows the crystallographic data of 2, 3, 4 and 5.
Selected bond lengths and angles are given in Table 2. Com-
pound 2 crystallizes in the monoclinic space group P21/c,
while compound 3 crystallizes in the trigonal non-centro-
symmetric space group R3c with Flack-parameter 0.0(1).
The basic five-membered ring skeleton in both compounds
is planar, while the dihedral angle between the best planes
through the triazole ring and the benzole ring is 57° for 2
(Fig. 1) and 44° for 3 (Fig. 2). The bond distances in the
five-membered heterocycles are in well agreement with
those observed in the cadmium(II) complex of the same
ligand [6].
Complexes 4 and 5
Both complexes 4 and 5 consist of neutral molecules (Fig.
4 and Fig. 5) and show a similar molecular structure as
observed in CuI complex with the modified AMTTO li-
gand, (C4H4N3SON(ϭCMe2) [9]. In molecules of 4 and 5,
the metal atom displays a distorted tetrahedral environment
without crystallographic symmetry (C1). The coordination
spheres around the copper atoms in 4 and 5 are occupied
with two P atoms of the phosphane molecules, one S atom
The S1-C1 bond lengths of 168.9(5) pm for 2 and of
166.5(3) pm for 3 are significant for a high double bond
1872
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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New 1,2,4-Triazole based Schiff-bases and their Copper(I) Complexes
Table 2 Selected bond lengths/pm and bond angles/°a)
2 (L1)
3 (L2)
4
5
S1-C1
168.9(5)
133.8(6)
137.8(5)
130.0(6)
138.5(6)
141.4(5)
129.5(6)
144.9(6)
136.1(5)
142.8(5)
S1-C1
166.5(3)
134.3(4)
137.7(4)
129.9(4)
136.7(3)
139.3(3)
127.6(4)
145.8(4)
136.8(4)
142.7(4)
Cu1-Cl1
Cu1-S1
Cu1-P1
Cu1-P2
S1-C1
C1-N4
C1-N1
N1-C2
C2-N3
N3-N4
N1-N2
N2-C4
C4-C5
C7-O1
O1-C11
Cl1-Cu1-S1
S1-Cu1-P2
P2-Cu1-P1
P1-Cu1-Cl1
Cu1-S1-C1
S1-C1-N1
S1-C1-N4
C1-N1-C2
C1-N1-N2
N1-N2-C4
N2-C4-C5
C7-O1-C11
237.09(9)
237.8(1)
229.8(1)
229.1(1)
169.3(4)
133.7(5)
137.0(5)
136.8(5)
130.7(5)
138.2(5)
140.4(4)
128.2(5)
146.1(6)
137.6(8)
140.7(9)
107.59(4)
109.16(4)
120.93(4)
101.57(4)
109.9(1)
129.1(3)
127.7(3)
109.1(3)
127.8(3)
114.0(3)
121.4(4)
118.6(5)
Cu1-Cl1
Cu1-S1
Cu1-P1
Cu1-P2
S1-C1
C1-N4
C1-N1
N1-C2
C2-N3
N3-N4
N1-N2
N2-C4
C4-C5
C7-O1
O1-C11
Cl1-Cu1-S1
S1-Cu1-P2
P2-Cu1-P1
P1-Cu1-Cl1
Cu1-S1-C1
S1-C1-N1
S1-C1-N4
C1-N1-C2
C1-N1-N2
N1-N2-C4
N2-C4-C5
C7-O1-C11
241.35(9)
237.34(9)
228.77(9)
226.65(9)
169.2(3)
133.7(5)
137.1(4)
138.0(5)
130.3(5)
138.0(4)
140.0(4)
127.0(5)
146.7(5)
136.9(6)
142.3(5)
102.14(3)
107.60(4)
122.78(4)
106.29(4)
105.1(1)
128.8(3)
128.2(3)
108.7(3)
128.8(3)
114.0(3)
121.6(3)
117.4(4)
C1-N3
N3-N4
N4-C2
C2-N1
N1-N2
N2-C4
C4-C5
C8-O1
O1-C11
C1-N3
N3-N4
N4-C2
C2-N1
N1-N2
N2-C4
C4-C5
C7-O1
O1-C11
S1-C1-N3
C1-N3-N4
N3-N4-C2
N4-C2-N1
C2-N1-C1
C1-N1-N2
N1-N2-C4
N2-C4-C5
C8-O1-C11
129.0(4)
114.1(4)
104.0(4)
110.4(4)
108.7(4)
128.3(4)
112.9(4)
119.5(4)
117.8(4)
S1-C1-N3
C1-N3-N4
N3-N4-C2
N4-C2-N1
C2-N1-C1
C1-N1-N2
N1-N2-C4
N2-C4-C5
C7-O1-C11
127.3(2)
113.7(3)
104.6(3)
110.3(3)
109.4(3)
129.4(2)
117.9(2)
118.7(3)
118.2(4)
a) Further details can be obtained from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ by quoting the number CCDC
267577 (2), CCDC 267578 (3), CCDC 267579 (4) and CCDC 267580 (5)(Fax: (ϩ44) 1223-3 36-0 33; e-mail: deposite@ccdc.cam.ac.uk).
Fig. 1 Graphical representation (thermal ellipsoids at the 40 % probability level) of L1.
of the Schiff-base and one Cl atom. This arrangement is
considerable distorted since the P angles at the metal site,
P1-Cu1-P2 with a value of 120.93(4)° for 4 and 122.78(4)°
for 5, is close to trigonally coordinated CuI, while three
other selected angles in the CuP2SCl group with 107.59(4)°
(4) and 102.14(3)° (5) (Cl1-Cu1-S1), 101.57(4)° (4) and
106.29(4)° (5) (Cl1-Cu1-P1) and 109.16(4)° (4) and
107.60(4)° (5) (P2-Cu1-S1) are close to those of a regular
tetrahedron. The tetrahedral distortion is due to steric hin-
drance of the bulky phosphane ligands and was observed
in a series of analogous complexes [10]. The Cu-P bond
distances, mean 230 (4) and 228 pm (5), are within the
range of the corresponding distances reported for other
copper(I) complexes (227.7Ϫ230.7 pm) [11]. Similar Cu-Cl
distances, here 237.09(9) pm (4) and 241.35(9) pm (5), have
been observed in four coordinated CuI complexes
(233.3Ϫ239.1 pm) [12].Both complexes can be devided in
two planar sequences, C1/N1/C2/N3/N4 and N2/C4/C5/C6/
C7/C8/C9/C10. The dihedral angle between the two planes
were measured to be 38° and 48°.
4 and 5 possess intramolecular hydrogen bondings (N4-
H1···Cl1, N4···Cl1 303.3(4) pm (4) and 307.0(3) pm (5)),
which caused a CuClHNCS six-membered ring.
The Cu1-S1 bond distance is 237.8(1) pm (4) and
237.34(9) pm (5) and lies in the range observed for com-
plexes with tetrahedral CuI centers [12b, 13].
4 Experimental Section
AMTT (1) was prepared according to the literature procedure [14].
IR spectra were recorded on a Shimadzu spectrometer 470 (KBr
pellets 4000Ϫ400 cmϪ1 and CsI pellets 4000Ϫ200 cmϪ1). 1H NMR
Z. Anorg. Allg. Chem. 2005, 631, 1871Ϫ1876
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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M. Ghassemzadeh, M. Tabatabaee, S. Soleimani, B. Neumüller
Fig. 4 Molecular structure (thermal ellipsoids at the 40 % prob-
ability level) of 4.
Fig. 2 Molecular structure (thermal ellipsoids at the 40 % prob-
ability level) of L2.
Fig. 5 Molecular structure (thermal ellipsoids at the 40 % prob-
ability level) of 5.
methoxybenzaldehyde, 4-methoxybenzaldehyde, chloroform, meth-
anol and ethanol.
Synthesis of L1 (2). A solution of 1 (1.3 g, 10 mmol) in ethanol
(20 mL) was treated with 3-methoxybenzaldehyde (2 mL, 15 mmol)
and the resulting mixture was acidified with 5 drops of hydrochloric
acid (37.5 %). The reaction mixture was refluxed for 6 h. The pro-
gress of the reaction was monitored by TLC. After completion of
the reaction (6 hrs), the solid crude was filtered and washed with
cold ethanol (2 x 5 mL). The clear filtrate was kept at 4 °C to give
the colorless single crystals of L1.
Fig. 3 Perspective view of the crystal structure of L2. The L2 trim-
eres are stacked in the [001] direction.
spectra were recorded on the Bruker-AQS advance 300 MHz.
Standard was TMS (external) with δ ϭ 0.0 ppm. Mass spectra were
recorded on a GC mass QP 1100 EX spectrometer.
Yield: 2.3 g (94 %), mp.: 196 °C.
Anal. calc. for C11H12N4OS (248.30): C 53.11 (calcd. 53.21); H 4.87
(4.85); N 22.56 (22.57); S 12.80 (12.91) %.
IR ν˜(KBr disk, cmϪ1) 3470 w (νNH), 3200 s, 2930 s, 1606 vs (νNϭC, imine),
1564 s (νNϭC, triazole), 1514 m, 1491 m, 1468 m, 1421 s, 1376 m, 1348 m,
1315 s (νCϭS), 1260 s, 1210 vw, 1166 s, 1107 m, 1018 s (νC-O), 986 m, 961 w,
882 m, 823 s, 728 s, 659 m, 630 m, 572 s, 519 s, 479 w.
Elemental analyses were performed by the following methods: C,
H, N analyses; combustion method; sulfur analyses: combustion
and titration with Ba(ClO4)2; Phosphorus: decomposition with
HClO4 and photometric analysis of the molybdophosphate. The
following chemicals were purchased from Merck and used without
further purification: copper(I) chloride, triphenylphosphane, 3-
1874
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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Z. Anorg. Allg. Chem. 2005, 631, 1871Ϫ1876

New 1,2,4-Triazole based Schiff-bases and their Copper(I) Complexes
MS (70 eV) m/z (%): 248 (89), 133 (100) (M)ϩ, 115 (90), 103 (75), 90 (75),
77 (60), 56 (50).
tion corrections were applied for all compounds (numerical). The
structures were solved by the direct methods for 2, 3 and 5
(SHELXS-97) and by the Patterson method for 4 (SHELXTL-
Plus) and refined against F2 by full-matrix least-squares using the
program SHELXL-97. The position of carbon bonded hydrogen
atoms (except H1) in 2, 4 and 5 were calculated for ideal positions
and refined with a common displacement parameter. H1 in 2, 4 and
5 and all hydrogen atoms in 3 were included with a free refinement.
Programs used were SHELXS-97 [15], SHELXL-97 [16],
SHELXTL-Plus [17], SHELXTL [18] and PLATON-98 [19].
1H NMR δ (CDCl3) 2.49 (s, 3 H, CH3), 3.89 (s, 3H, OCH3), 6.97 (d,
3J(HH) ϭ 8.73 Hz, 2H, phenyl), 7.83-7.86 (d, 3J(HH) ϭ 8.73 Hz, 2H, phe-
nyl), 7.26 (s, 1H, CHϭN), 10.07 (s, 1H, NH)
Synthesis of L2 (3). Compound L2 was prepared by a similar pro-
cedure used for L1 using following amounts: 1 (1.3 g, 10 mmol), 4-
methoxybenzaldehyde (2 mL, 15 mmol), 10 drops HCl in 40 mL
ethanol, refluxing time 4 hrs.
Yield: 1.98 g (79 %), mp.: 163 °C.
Anal. calc. for C11H12N4OS (248.30): C 53.11 (calcd. 53.21); H 4.76
(4.85); N 22.56 (22.57); S 12.80 (12.91) %.
IR ν˜(KBr disk, cmϪ1): 3440 w (νNH), 3135 s, 2950 s, 2825 m, 1611 vs (νCϭ
N, imine), 1527 s (νCϭN, triazole), 1503 m, 1479 s, 1449 m, 1414 m, 1374 m,
1343 s, 1317 s (νCϭS), 1285 s, 1249 m, 1194 m, 1151 m, 1101 m, 1044 s (νC-
O), 1000 m, 948 m, 885 m, 810 m, 773 s, 737 w, 683 m, 628 w, 604 m, 574 m,
537 m, 467 w.
References
[1] F. Adhami, M. Ghassemzadeh, M. M. Heravi, A. Taeb, B.
Neumüller, Z. Anorg. Allg. Chem. 1999, 625, 1411.
[2] M. Ghassemzadeh, A. Sharifi, J. Malakootikhah, B. Neu-
müller, E. Iravani, Inorg. Chim. Acta 2004, 357, 2245.
[3] M. Ghassemzadeh, F. Adhami, M. M. Heravi, A. Taeb, S.
Chitsaz, B. Neumüller, Z. Anorg. Allg. Chem. 2002, 628, 2887.
[4] M. Ghassemzadeh, M. M. Pooramini, M. Tabatabaee, M. M.
Heravi, B. Neumüller, Z. Anorg. Allg. Chem. 2004, 630, 403.
[5] J. Weidlein, U. Müller, K. Dehnicke, Schwingungsspektrosko-
pie, 2. Aufl., G. Thieme Verlag, Stuttgart 1988.
[6] M. Hakimi, M. Yazdanbakhsh, M. M. Heravi, M. Ghas-
semzadeh, B. Neumüller, Z. Anorg. Allg. Chem. 2002, 628,
1899.
[7] J. L. Escobar-Valderrama, J. H. Garcia-Tapia, J. Ramirez-Or-
tiz, M. J. Rosales, R. A. Toscano, J. Valdes-Martinez, Can. J.
Chem. 1989, 67, 198.
MS (70 eV) m/z (%): 248 (100) (M)ϩ, 134 (96), 133 (96), 115 (90), 103 (93),
90 (75), 77 (65), 56 (85).
1H NMR δ (CDCl3) 2.49 (s, 3H, CH3), 3.87 (s, 3H, OCH3), 7.07-7.10 (d,
3J(HH) ϭ 7.71, 1H, phenyl), 7.83-7.86 (m, 3H, phenyl), 7.26 (s, 1H, CHϭ
N), 10.31 (s, 1H, NH).
Complex 4. A solution of L2 (0.24 g, 1 mmol) in 20 ml solvent was
added to a suspension of [(PPh3)2CuCl] (0.62 g, 1 mmol) (prepared
in situ from CuCl and PPh3 in a molar ratio 1:2 in methanol) and
stirred for 5 h at room temperature. After completion of reaction,
which was monitored by TLC using petroleum ether/ethyl acetate
(2/1) as eluent, the crude product was filtered and washed with cold
methanol (2 x 15 mL). The filtrate was kept at 4 °C and colorless
crystals of 4 were obtained after few days.
Yield: 0.74 g (85 %), mp.: >300 °C.
Anal. calc. for C47H42ClCuN4OP2S (871.89): C 64.74 (calcd.
64.68); H 4.87 (4.85); N 6.35 (6.42); S 3.51 (3.67); Cu 7.11 (7.28) %.
[8] G. M. de Lima, J. L. Neto, H. Beraldo, H. G. L. Siebald, D.
J. Duncalf, J. Mol. Struct. 2002, 604, 287.
[9] M. Ghassemzadeh, F. Adhami, M. M. Heravi, A. Taeb, S.
Chitsaz, B. Neumüller, Z. Anorg. Allg. Chem. 2001, 627, 815.
[10] S. Skoulika, A. Aubru, P. Karagiannidis, P. Aslanadis, P. Papa-
stefanou, Inorg. Chim. Acta 1991, 183, 207.
IR ν˜(KBr disk, cmϪ1): 3481 w (νNH), 3075 s, 3061 w, 2936 w, 2855 w,
2759 vw, 1687 w, 1617 s (νCϭN, imine), 1601 m, 1581 w, 1497 s (νCϭN, tria-
zole), 1468 m, 1437 s, 1414 m, 1384 m, 1351 m, 1328 s (νCϭS), 1300 s,
1290 s, 1270 s, 1203 m, 1184 m, 1165 m, 1158 m, 1119 m, 1095 m,
1072 (sh) w, 1040 m (νC-O), 995 m, 970 m, 843 m, 817 m, 794 m, 780 sh m,
747 w (;gPh3), 721 PPh3), 695 m (νPPh3), 350 (νCuS), 247 s, 240 w, 234 sh m,
228 s (νCuCl), 223 m, 215 s, 210 sh m, 205 s.
[11] a) K. K. Pandey, M. Noltemeyer, G. M. Sheldrick, R. Saheb,
Z. Naturforsch. 1984, 39b, 586; b) M. B. Ferari, G. G. Fava,
C. Pelizzi, P. Tarasconi, Inorg. Chim. Acta 1985, 98, L49; c)
P. Leoni, M. Pasquali, C. A. Ghilardi, J. Chem. Soc., Chem.
Commun. 1983, 240; d) A. P. Gaughan (Jr.), Z. Dori, J. A.
Ibers, Inorg. Chem. 1974, 13, 1657; e) S. L. Lippard, K. M.
Melmed, J. Am. Chem. Soc. 1967, 89, 3929; f) F. Takusagawa,
A. Fumagalli, T. F. Koetze, S. G. Shore, T. Schmitkons, A. V.
Fratini, K. W. Morse, C. Y. Wei, R. Bau, J. Am. Chem. Soc.
1981, 103, 5165; g) S. L. Lippard, K. M. Melmed, Inorg.
Chem. 1969, 8, 2755; h) J. Bojes, T. Chivers, P. W. Codding, J.
Chem. Soc., Chem. Commun. 1981, 1171.
[12] a) B. E. Green, C. H. L. Kennard, G. Smith, B. D. James, A.
H. White, Acta Crystallogr. 1984, C40, 426; b) P. Karagian-
nidis, P. Aslanidis, S. Papastefanou, D. Mentzafos, A.
Hountas, A. Terzis, Inorg. Chim. Acta 1989, 156, 265; c) T. S.
Lobana, P. K. Bhatia, E. R. T. Tiekink, J. Chem. Soc., Dalton
Trans. 1989, 749; d) L. P. Battaglia, A. Bonamartini Conradi,
M. Nardelli, M. E. Vidoni Tani, J. Chem. Soc., Dalton Trans.
1976, 143.
Complex 5. Compound 5 was prepared by a similar procedure used
for complex 4 using a mixture of chloroform/methanol (1:1)
(40 mL) as solvent. The reaction time was 6h and the obtained
single crystals suitable for X-ray diffraction were colorless. Yield:
0.70 g (80 %), mp. 163 °C.
Anal. calc. for 5 as powder C47H42ClCuN4OP2S (871.89): C 64.68
(calcd. 64.74); H 4.87 (4.85); N 6.35 (6.42); S 3.51 (3.67); Cu 7.11
(7.28) %.
IR ν˜(KBr disk, cmϪ1) of the solid crude: 3485 w (νNH), 3077 s, 3064 w,
2940 w, 2854 w, 2762 w, 1684 vw, 1615 s (νCϭN, imine), 1601 m, 1581 w,
1500 s (νCϭN, triazole), 1468 m, 1439 s, 1418 m, 1390 m, 1361 m, 1331 s
(νCϭS), 1298 s, 1290 s, 1273 s, 1203 m, 1180 m, 1165 m, 1158 m, 1119 m,
1100 m, 1074 sh w, 1038 m (νC-O), 995 m, 970 m, 846 m, 815 m, 794 m,
780 sh m, 747 w (νPPh3), 721 m (νPPh3), 695 m (νPPh3), 346 (νCuS), 245 s,
238 w, 232 sh m, 225 s (νCuCl), 216 s, 211 sh m, 206 s.
Crystal structure analyses of 2, 3, 4, and 5
The crystals of 2, 3, 4, and 5 were covered with perfluorinated oil
and mounted on the top of a glass capillary under a flow of cold
gaseous nitrogen. The orientation matrix and the unit cell dimen-
sions were determined from ca. 3500 (2; Stoe IPDS II) from ca.
9000 (3, Stoe IPDS II), ca. 13000 (4; Stoe IPDS II) and ca. 15000
(5; Stoe IPDS II) reflections (graphite-monochromated Mo-Kα
radiation (λ ϭ 71.073 pm) for all compounds. The intensities were
corrected for Lorentz and polarization effects. In addition, absorp-
[13] a) S. K. Hadjikakou, P. Aslanidis, P. D. Akrivos, P. Karagian-
nidis, B. Kojic-Prodic, M. Luic, Inorg. Chim. Acta 1992, 197,
31; b) P. J. Cox, P. Aslanidis, P. Karagiannidis, S. K. Hadjiko-
kou, Polyhedron 1999, 18, 1501; c) International Tables for X-
Ray Crystallography, Vol. IV, Kynoch Press, Birmingham
(U.K.) 1974: Covalent radii (pm): CuI 60 (coordination num-
ber (CN) 2), CuI 74 (CN 4), N 75, S 104; d) R. R. Conry, W.
S. Strejewske, A. A. Tipton, Inorg. Chem. 1999, 38, 1833.
Z. Anorg. Allg. Chem. 2005, 631, 1871Ϫ1876
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1875

M. Ghassemzadeh, M. Tabatabaee, S. Soleimani, B. Neumüller
[14] H. Beyer, C.-F. Kröger, Chem. Ber. 1960, 637, 135.
[15] G. M. Sheldrick, SHELXS-97, Universität Göttingen 1997.
[16] G. M. Sheldrick, SHELXL-97, Göttingen 1997.
[17] G. M. Sheldrick, SHELXTL-Plus, Release 5.05/VMS for Sie-
mens R3 Crystallographic Research Systems, Siemens Analit-
ical X-Ray Instruments Inc., Madison (WI), 1996. Göttingen
1997.
[18] G. M. Sheldrick, SHELXTL, Release 5.05/VMS for Siemens
R3 Crystallographic Research Systems, Siemens Analytical X-
Ray Instruments Inc., Madison (WI), 1996.
[19] A. L. Spek, PLATON-98, Utrecht 1998.
1876
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 1871Ϫ1876