Synthesis, characterization, and crystal structure of the new Schiff-bases derived from 1,2,4-triazole and the structure of [(PPh3) 2Cu(AMTT)]NO3·EtOH (AMTT = 4-amino-5-methyl-2H-1,2, 4-triazole-3(4H)-thione)

Article abstract of DOI:10.1002/zaac.200600342

The reactions of 4-amino-5-methyl-2H-1,2,4-triazole-3(4H)-thione (AMTT, L1) with 2-thiophen carbaldehyde, salicylaldehyde and 2-nitrobenzaldehyde in methanol led to the corresponding Schiff-bases (L1a-c). The reaction of L1 with [(PPh₃)₂Cu]NO₃ in ethanol gave the ionic complex [(PPh₃)₂Cu(L1)]NO₃·EtOH (2) All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X-ray diffraction studies. Crystal data for L1a at 20°C: space group P2₁/n with a = 439.6(2), b = 2074.0(9), c = 1112.8(4) pm, β= 93.51(3)°, Z = 4, R₁, = 0.0406, Lib at -80°C: space group P2₁/n with a = 1268.9(2), b = 739.3(1), c = 1272.5(1) pm, β= 117.97(1)°, Z = 4, R₁ = 0.0361, L1c at -80°C: space group P2₁/n with a = 847.8(1), b = 1502.9(2), c = 981.5(2) pm, β= 110.34(1)°, Z = 4, R₁ = 0.0376 and for 2 at -80°C: space group P1 with a = 1247.8(1), b = 1270.3(1), c = 1387.5(1) pm, α = 84.32(1)°, β= 84.71(1)°, γ = 63.12(1)°, Z = 2, R₁ = 0.0539.

Full text of DOI:10.1002/zaac.200600342

DOI: 10.1002/zaac.200600342
Synthesis, Characterization, and Crystal Structure of the New Schiff-Bases derived
from 1,2,4-Triazole and the Structure of [(PPh3)2Cu(AMTT)]NO3·EtOH
(AMTT ϭ 4-Amino-5-methyl-2H-1,2,4-triazole-3(4H)-thione)
Felora Heshmatpoura,*, Mitra Ghassemzadehb, Maryam Semsarhac, and Bernhard Neumüllerd
Tehran/Iran, a Department of Chemistry of K. N. Toosi University of Technology, b Chemistry & Chemical Engineering Research Center
of Iran Qazvin, and c Imam Khomeini University
d Marburg, Fachbereich Chemie der Universität
Received December 3rd, 2006.
Abstract. The reactions of 4-amino-5-methyl-2H-1,2,4-triazole-
3(4H)-thione (AMTT, L1) with 2-thiophen carbaldehyde, salicylal-
dehyde and 2-nitrobenzaldehyde in methanol led to the correspon-
ding Schiff-bases (L1a-c). The reaction of L1 with [(PPh3)2Cu]NO3
in ethanol gave the ionic complex [(PPh3)2Cu(L1)]NO3·EtOH (2)
All compounds were characterized by infrared spectroscopy, ele-
mental analyses as well as by X-ray diffraction studies. Crystal data
for L1a at 20 °C: space group P21/n with a ϭ 439.6(2), b ϭ
2074.0(9), c ϭ 1112.8(4) pm, β ϭ 93.51(3)°, Z ϭ 4, R1 ϭ 0.0406,
L1b at Ϫ80 °C: space group P21/n with a ϭ 1268.9(2), b ϭ 739.3(1),
c ϭ 1272.5(1) pm, β ϭ 117.97(1)°, Z ϭ 4, R1 ϭ 0.0361, L1c at
Ϫ80 °C: space group P21/n with a ϭ 847.8(1), b ϭ 1502.9(2), c ϭ
981.5(2) pm, β ϭ 110.34(1)°, Z ϭ 4, R1 ϭ 0.0376 and for 2 at
Ϫ80 °C: space group P1 with a ϭ 1247.8(1), b ϭ 1270.3(1), c ϭ
1387.5(1) pm, α ϭ 84.32(1)°, β ϭ 84.71(1)°, γ ϭ 63.12(1)°, Z ϭ 2,
R1 ϭ 0.0539.
¯
Keywords: 1,2,4-Triazole; Schiff bases; Copper; Crystal structures
1 Introduction
ence of HCl under reflux conditions led to the correspond-
ing iminic compounds L1a-c in high yields (eq. (1)).
In our ongoing interest in the study of the coordination
chemistry of heterocyclic ligands containing nitrogen and
sulfur atoms, such as AMTTO and its Schiff-bases, we have
reported that the AMTTO acts as a unidentate ligand via
its sulfur atom with a weak Ag···N interaction, which leads
to a 2ϩ2 coordination 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 mo-
lar ratio of 2:1 and the additional coordination of the thio-
phene heterocycle caused 2ϩ1 coordination around the me-
tal atom [2]. In addition, we have shown that the ligand
AMTTO acts as a monodentate ligand in a molar ratio 2:1
with Cu(I) ion, while it reacts with Cu(II) as a bidentate
one in a molar ratio 1:1 [3]. We have also reported the reac-
tion of ATT with silver(I) and copper(I) including their mo-
lecular structures [4].
Compound 2 can be obtained by the reaction of L1 with
[(PPh3)2Cu]NO3 in the molar ratio 1:1 in ethanol according
to equation (2).
In this communication, we wish to report the synthesis
and characterization of new Schiff-bases derived from 1,2,4-
triazole and the Cu(I)-complex of AMTT.
2 Syntheses and Characterization of L1a-c and 2
Treatment of 1 with 2-thiophen carbaldehyde, salicylal-
dehyde and 2-nitrobenz-aldehyde in methanol and in pres-
All synthesized compounds are air-stable colorless solid
materials. The IR absorptions νCuS and νCuCl of complex
2 can be observed at 350 and 228 cmϪ1 [5]. The CϭN
functions cause two vibrations at 1617 and 1497 cmϪ1, the
first value is for the endocyclic CϭN group and the latter
can be assigned to the iminic group. P-C vibrations of the
* Dr. Felora Heshmatpour
Department of Chemistry of K.N. Toosi of Technology
Tehran (Iran)
Z. Anorg. Allg. Chem. 2007, 633, 465Ϫ469
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
465

F. Heshmatpour, M. Ghassemzadeh, M. Semsarha, B. Neumüller
moiety PPh3 are found in the range 747-695 cmϪ1. For the
N-H stretching vibrations absorption bands could be found
In all compounds an intermolecular weak hydrogen
bonding links the sulfur atom of one molecule to the NH-
group of the adjacent one (N4-H1···S1a: 331.0(2) pm (L1a),
N3-H1···S1a: 326.3(2) pm (L1b), N4-H1···S1a: 324.0(2) pm
(L1c) and is responsible for the centrosymmetric structure
of the compounds. In addition, there is an intramolecular
hydrogen bonding in L1a (C4-H41···S1: 318.7(3) pm) and
L1b (O1-H2···N2: 267.9(2) pm.
at 3333 w, 3228 s, 3192 w, and 3120 w cmϪ1
.
3 Results and Discussion
Compounds L1a-c and complex 2
Complex
2
consists
of
ionic
molecules
Table 1 shows the crystallographic data of L1a-c and 2.
Selected bond distances and angles are given in Table 2.
Compounds L1a-c crystallize in the monoclinic space group
P21/n. The basic five-membered ring skeleton in all com-
pounds is planar, while the dihedral angle between the best
planes through the triazole ring and the aldehyde rest is 6°
for L1a (Fig. 1), 2° for L1b (Fig. 2) and 5° for L1c (Fig. 3),
The bond distances in the triazole five-membered hetero-
cycles are in well agreement with those observed in iminic
derivatives of 1,2,4-triazole such as 4-(4-methoxybenzylid-
[Cu(PPh3)2(L1)]NO3·C2H5OH (Fig. 4) and show a similar
molecular structure as observed in Cu(I) complex with the
modified AMTTO ligand, C4H4N3SON(ϭCMe2) [9]. In
molecules of 2, the metal atom displays a distorted tetra-
hedral environment with crystallographic C1 site position.
The coordination sphere around the copper atom in 2 is
occupied with two P atoms of the phosphane molecules, the
S atom of the triazole heterocycle and the nitrogen atom
of the hydrazine moiety. This arrangement is considerable
distorted since the P angle at the metal site, P1-Cu1-P2 with
a value of 124.29(4)° is close to Cu(I) complexes with trig-
onally coordinated copper atoms. The three other selected
angles in the CuP2NS group with P2-Cu1-S1: 102.27(3)°,
S1-Cu1-N2: 86.24(7)° and P1-Cu1-N2: 108.05(8)° are
nearly to those of a regular tetrahedron.
eneamino)-5-methyl-2H-1,2,4-triazole-3(4H)-thione
and
4-(3-methoxybenzylideneamino)-5-methyl-2H-1,2,4-triazole
-3(4H)-thione [6].
In all compounds, the S1-C1 bond lengths of mean
168.04 pm is significant for a high double bond character,
such as observed in AMTT [7]. The iminic C-N bond dis-
tance with mean 129.04 pm lies in the range observed in
similar compounds such as 2-acetylthiophene thiosemicar-
bazone (129.2(3) pm) and 2-acetyl thiophene 4-phenyl
thiosemicarbazone (128.2(3) pm) [8].
The tetrahedral distortion is due to steric hindrance of
the bulky phosphane ligands and was observed in a series
of analogous complexes [10]. The Cu-P bond distances for
2, 224.86(8) and 229.12(9) pm are similar to the observed
Table 1 Crystallographic data for L1a-c and 2.
Compound
L1a
L1b
L1c
2
Empirical formula
Formula mass
Crystal size/mm
Crystal system
Space group
a/pm
C8H8N4S2
448.60
0.65 ϫ 0.09 ϫ 0.09
monoclinic
P21/n
439.6(2)
2074.0(9)
1112.8(4)
Ϫ
93.51(3)
Ϫ
1012.7(7)
4
C10H10N4OS
234.28
0.4 ϫ 0.28 ϫ 0.09
monoclinic
P21/n
1268.9(2)
739.3(1)
1272.5(1)
Ϫ
C10H9N5O2S
263.27
0.28 ϫ 0.25 ϫ 0.2
monoclinic
P21/n
847.8(1)
1502.9(2)
981.5(2)
Ϫ
110.34(1)
Ϫ
1172.6(3)
4
C41H42CuN5O4P2S
826.37
0.39 ϫ 0.31 ϫ 0.06
triclinic
¯
P1
1247.8(1)
1270.3(1)
1387.5(1)
84.32(1)
84.71(1)
63.12(1)
1949.3(3)
2
b/pm
c/pm
α/°
β/°
117.97(1)
γ/°
Volume/pm3·106
Z
1054.3(2)
4
1.476
numerical
2.9
dcalcd./g·cmϪ3
Absorption correction
µ/cmϪ1
1.471
numerical
4.9
1.491
numerical
2.8
1.408
numerical
7.4
Temperature/K
2θmax/°
293
52.77
Ϫ5Ǟ5
Ϫ25Ǟ25
Ϫ13Ǟ13
8766
193
52.5
Ϫ15Ǟ15
Ϫ9Ǟ9
Ϫ15Ǟ15
14831
2131
193
52.73
Ϫ10Ǟ10
Ϫ18Ǟ18
Ϫ12Ǟ12
16880
193
52.55
Ϫ15Ǟ15
Ϫ15Ǟ15
Ϫ17Ǟ17
28587
Index range
h
k
l
Reflections collected
Unique reflections
2036
2373
7848
(Rint
)
(0.0568)
1629
(0.0532)
1668
(0.0615)
1834
(0.1155)
5670
Reflections with Fo > 4σ(Fo)
Parameters
R1
159
185
199
506
0.0406
0.1179a)
0.21
0.0361
0.0956b)
0.28
0.0376
0.1046c)
0.23
0.0539
0.1482d)
0.96
wR2 (all data)
Max. residual electron density/[(e·pmϪ3)·10Ϫ6
]
a) w ϭ 1/[σ2(Fo)2ϩ(0.0815·P)2]; P ϭ [max (Fo2, 0) ϩ 2Fc2] /3. b) w ϭ 1/[σ2(Fo)2ϩ(0.0649·P)2]. c) w ϭ 1/[σ2(Fo)2ϩ(0.0721·P)2]. d) w ϭ 1/[σ2(Fo)2ϩ(0.1017·P)2].
466
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 465Ϫ469

Schiff-Bases derived from 1,2,4-Triazole and the Structure of [(PPh3)2Cu(AMTT)]NO3·EtOH
Table 2 Selected bond lengths/pm and bond angles/°.a)
L1a
L1b
L1c
2
S1ϪC1
C1ϪN4
N4ϪN3
N3ϪC2
C2ϪN1
N1ϪN2
N2ϪC4
C4ϪC5
C5ϪS2
S2ϪC8
167.9(2)
134.3(3)
137.3(3)
130.2(3)
138.5(6)
139.7(2)
127.4(3)
144.4(3)
171.1(2)
170.7(2)
S1ϪC1
C1ϪN3
N3ϪN4
N4ϪC2
C2ϪN1
N1ϪN2
N2ϪC4
C4ϪC5
C10ϪO1
C2ϪC3
167.9(2)
133.7(2)
137.7(2)
129.7(2)
138.5(2)
139.2(2)
128.4(2)
145.2(2)
135.5(2)
147.6(2)
S1ϪC1
C1ϪN4
N4ϪN3
N3ϪC2
C2ϪN1
N1ϪN2
N2ϪC4
C4ϪC5
C6ϪN5
N5ϪO1
N5ϪO2
167.9(2)
133.3(2)
137.2(2)
129.3(2)
138.5(2)
138.8(2)
127.2(2)
147.3(2)
146.9(2)
122.1(2)
122.5(2)
Cu1ϪN2
Cu1ϪS1
Cu1ϪP1
Cu1ϪP2
S1ϪC1
C1ϪN4
C1ϪN1
N1ϪC2
C2ϪN3
N3ϪN4
N5ϪO1
N5ϪO2
220.0(3)
237.90(9)
224.86(8)
229.12(9)
167.2(4)
134.3(4)
137.4(4)
138.0(4)
129.3(5)
137.7(4)
120.6(4)
124.8(4)
127.3(4)
86.24(7)
102.27(3)
124.29(4)
108.05(8)
92.6(1)
107.3(2)
127.3(2)
129.7(3)
108.4(3)
113.4(3)
110.8(3)
123.0(4)
116.8(3)
120.2(4)
123.0(4)
116.8(3)
120.2(4)
N5ϪO3
S1ϪC1ϪN1
C1ϪN4ϪN3
N4ϪN3ϪC2
N3ϪC2ϪN1
C2ϪN1ϪC1
C1ϪN1ϪN2
N1ϪN2ϪC4
N2ϪC4ϪC5
C4ϪC5ϪS2
130.8(2)
115.0(2)
103.6(2)
110.7(2)
108.9(2)
132.6(2)
119.5(2)
120.5(2)
122.1(2)
S1ϪC1ϪN3
C1ϪN3ϪN4
N3ϪN4ϪC2
N4ϪC2ϪN1
C2ϪN1ϪC1
C1ϪN1ϪN2
N1ϪN2ϪC4
N2ϪC4ϪC5
C5ϪC10ϪO1
126.1(1)
114.5(1)
103.7(2)
110.9(2)
108.3(1)
132.9(2)
119.2(1)
120.7(2)
122.9(2)
S1ϪC1ϪN4
C1ϪN4ϪN3
N4ϪN3ϪC2
N3ϪC2ϪN1
C2ϪN1ϪC1
C1ϪN1ϪN2
N1ϪN2ϪC4
N2ϪC4ϪC5
C6ϪN5ϪO1
C6ϪN5ϪO2
O1ϪN5ϪO2
126.7(1)
114.3(2)
104.2(2)
110.8(2)
107.9(1)
133.1(1)
119.2(1)
117.1(2)
117.7(2)
118.4(2)
123.8(2)
N2ϪCu1ϪS1
S1ϪCu1ϪP2
P2ϪCu1ϪP1
P1ϪCu1ϪN2
Cu1ϪS1ϪC1
Cu1ϪN2ϪN1
S1ϪC1ϪN1
S1ϪC1ϪN4
C1ϪN1ϪC2
C1ϪN4ϪN3
N1ϪC2ϪN3
O1ϪN5ϪO2
O2ϪN5ϪO3
O1ϪN5ϪO3
O1ϪN5ϪO2
O2ϪN5ϪO3
O1ϪN5ϪO3
a) Further details can be obtained free of charge on application to the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.
[Fax.: (internat.) ϩ44 (0)1223 336033; E-mail: deposit@ccdc.cam.ac.uk] quoting the depository numbers CCDC 632480 (L1a), 632481 (L1b), 632482 (L1c),
and 632483 (2).
Figure 3 Centrosymmetrical dimer of L1c (thermal ellipsoids at
Figure 1 Centrosymmetrical dimer of L1a (thermal ellipsoids at
the 50 % probability level).
the 30 % probability level).
distances in [(C4H4N3SON{ϭCMe2})Cu(PPh3)2Cl] (mean
229.2 pm) and in [(AMTTO)Cu(PPh3)2Cl] (mean 227.7 pm)
[3, 9].
In 2 the nitrate ion and the ethanol solvate molecule act
as bridging agents and link the cations via hydrogen bond-
ings (N2-H1···O4, N2···O4: 293.5(5) pm, N2-H2···O3a,
N2···O3a: 286.5(4) pm, N4-H3···O3, N4···O3: 276.6(4) pm
and O4-H4···O2a, O4···O2a: 295.8(5) pm) and are respon-
sible for the building of chains along [001], which are shiel-
ded by the phenyl rings (Fig. 5 and 6). The Cu1-S1 bond
distance is 237.90(9) pm and lies in the range observed for
complexes with tetrahedral coordinated Cu(I) atoms [11,
12]. The dihedral angle between the “best planes” (S1/N1/
N2/N3/N4/C1/ C2 and Cu1/S1/N2) is 21° (Fig. 5).
Figure 2 Centrosymmetrical dimer of L1b (thermal ellipsoids at
the 40 % probability level).
Z. Anorg. Allg. Chem. 2007, 465Ϫ469
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
467

F. Heshmatpour, M. Ghassemzadeh, M. Semsarha, B. Neumüller
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 Fluka and
used without further purification: copper(I) nitrate, triphenylphos-
phane, 2-thiophen carbaldehyde, salicylaldehyde and 2-nitrobenzal-
dehyde, methanol and ethanol.
Synthesis of L1a-c. General procedure.
A solution of AMTT (1 mmol) in methanol (40 mL) was treated
with corresponding aldehyde (1.5 mmol) and was refluxed for 6 h.
The progress of the reaction was monitored by TLC using ethyl
acetate: petroleum ether (1:2) as eluent. After completion of the
reaction, the solvent was evaporated to 20 mL, the solid crude was
filtered and washed with cold methanol (2 x 5 mL). The clear fil-
trate was kept at 4 °C to give the colorless single crystals of the
corresponding Schiff bases L1a-c.
Figure 4 Structure of 2 (thermal ellipsoids at the 40 % probability
level). The phenyl rings are represented as thin lines. Most of the
hydrogen atoms are omitted for clarity.
Selected data for L1a.
Used amounts for L1: 0.14 g (1 mmol); 2-thiophene carbaldehyde:
0.16 (1.5 mmol).
Yield: 0.20 g (90 %).
Anal. Calc. for C8H8N4S2 (224.31): C 42.82 (calcd. 42.84); H 3.50
(3.59); N 24.88 (24.98); S 28.50 (28.59) %.
IR (KBr disc, cmϪ1): 3418 w (νNH), 3109 s, 3108 s (νCH, Ar), 2954 s, 1597 vs
(νNϭC, imine), 1582 s (νNϭC, triazole), 1532 m, 1499 m (νCϭC), 1427 s,
1407 m, 1316 s (νCϭS), 1274 s, 740 s, 632 m, 606 m, 572 m, 549 w.
MS (70 eV) m/z (%): 448 (11) (2M)ϩ, 224 (100) Mϩ, 155 (30), 117 (31), 115
(95), 109 (85), 56 (53), 39 (32), 45 (35), 27 (19), 42 (27).
1H NMR (DMSO-d6): δ ϭ 2.37 (s, 3 H, Me), 7.08, 7.11 (dd, 1 H, H-thi-
ophen), 7.48, 7.51 (dd, 2 H, H-thiophene), 10.52 (s, 1 H, CHϭN).
Figure 5 Perspective view of the unit cell of 2. The ions and the
ethanol molecule of 2 are arranged in the direction [001].
Selected data for L1b.
Used amounts of L1: 0.14 g (1 mmol); salicylaldehyde: 0.18 g
(1.5 mmol).
Yield: 2.1 g (93 %).
Anal. Calc. for C10H10N4OS (234.28): C 50.99 (calcd. 51.27); H
4.28 (4.30); N 23.88 (23.91); S 13.66 (13.69) %.
IR (KBr disc, cmϪ1): 3433 w (νNH), 3105 s (νOH), 3068 m, 2936 s, 2759 s,
1603 vs (νNϭC, imine), 1599 s (νNϭC, triazole), 1504 m, 1488 m, 1412 s,
1346 m, 1315 s (νCϭS), 1293 s, 1264 (νC-N, thioamide), 772 s, 613 m, 564 s,
479 w, 447 m.
MS (70 eV) m/z (%) 235 (31) (Mϩ1)ϩ, 234 (47) (Mϩ), 137 (28), 121 (26), 119
(99), 115 (98), 102 (39), 102 (39), 91 (98), 74 (49), 64 (99), 56 (100), 42 (67),
39 968).
1H NMR (DMSO-d6): δ ϭ 2.42 (s, 3 H, Me), 7.01-7.11 (m, 4 H, Ar), 10.23
(s, 1 H, CHϭN imine), 10.43 (s, 1 H, Ph).
Figure 6 Second view of 2. The phenyl rings and most of the
hydrogen atoms are omitted for clarity.
Selected data for L1c.
Used amounts of L1: 0.14 g (1 mmol); 2-nitrobenzaldehyde:
0.22 g (1.5 mmol).
Yield: 0.24 g (94 %).
Anal. Calc. for C10H9N5O2S (263.27): C 45.56 (calcd. 45.62); H
3.39 (3.45); N 26.57 (26.60); S 12.09 (12.18) %.
4 Experimental Section
AMTT (L1) was prepared according to the literature procedure
[13]. IR spectra were recorded on a Shimadzu spectrometer 470
(KBr pellets 4000Ϫ400 cmϪ1 and CsI pellets 4000-200 cmϪ1).
1H NMR 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.
IR (KBr disc, cmϪ1): 3441 w (νNH), 3068 s (νCH, Ar), 2936 s, 2762 m,
1600 vs (νCϭC, Ar), 1591 s (νNϭC, imine), 1525 (νNϭC, triazole) 1506 m,
1404 m, 1378 m, 1344 m (νNO), 1315 s (νCϭS), 1281 s, 1178 s, 1049 s, 798 s,
746 m, 603 m, 573 m, 550 s, 518 m, 472 m.
MS (70 eV) m/z (%): 264 (34) (Mϩ1)ϩ, 263 (38) (Mϩ), 217 (34), 149 (35),
115 (99), 102 (47), 74 (100), 63 (35), 56 (98), 50 (81), 42 (35), 27 (32).
468
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 465Ϫ469

Schiff-Bases derived from 1,2,4-Triazole and the Structure of [(PPh3)2Cu(AMTT)]NO3·EtOH
1H NMR (DMSO-d6): δ ϭ 2.4 (s, 3 H, Me), 7.91 (m, 1 H, H-benzyl ring),
7.97 (dd, 1 H, H-phenyl), 8.19 (dd, 2 H, phenyl), 11.0 (s, 1 H, H-imine), 13.8
(s, 1 H, NH-thione)
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, Schwingungsspektroskopie,
2. Aufl., G. Thieme Verlag, Stuttgart, 1988.
Synthesis of Complex 2. A solution of AMTT (0.13 g, 1 mmol) in
20 ml ethanol was added to a suspension of [(PPh3)2Cu]NO3
(0.65 g, 1 mmol) (prepared in situ from CuNO3 and PPh3 in a mo-
lar ratio 1:2 in ethanol) and stirred for 5h 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 fil-
trate was kept at 4 °C and colorless crystals of 2 were obtained
after few days.
[6] M. Ghassemzadeh, M. Tabatabaee, S. Soleimani, B. Neu-
müller, Z. Anorg. Allg. Chem. 2005, 631, 1871.
Yield: 0.70 g (85 %); mp.: 190 °C.
[7] J. L. Escobar-Valderrama, J. H. Garcia-Tapia, J. Ramirez-
Ortiz, M. J. Rosales, R. A. Toscano, J. Valdes-Martinez, Can.
J. Chem. 1989, 67, 198.
[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.
Anal. Calc. for C41H42CuN5O4P2S (826.37): C 59.29 (calcd. 59.59);
H 5.08 (5.12); N 8.46 (8.47); S 3.79 (3.88); Cu 7.53 (7.69) %.
IR (KBr disc, cmϪ1): 3333 w (νNH2), 3228 s (νNH2), 3192 w, 3120 w (νNH),
3061 w, 2936 m, 1687 w, 1639 s (νCϭN, imine), 1601 m, 1584 m, 1497 s (νCϭN,
triazole), 1387 m (νasNO3), 1350 m, 1328 s (νCϭS), 1200 m, 1182 m, 1169 m,
1158 m, 1120 m, 1088 s, 1072 sh w, 995 m, 930 m, 882 m, 817 m, 745 w
(νPPh3), 723 m (νPPh3), 695 m (νPPh3), 420 m (νCuN), 380 s (νCuS), 338 s
(νCuP), 247 s , 240 w, 234 sh m, 223 m, 215 m.
31P NMR (DMSO): δ ϭ 26.1.
[11] P. Karagiannidis, P. Aslanidis, S. Papastefanou, D. Mentzafos,
A. Hountas, A. Terzis, Inorg. Chim. Acta 1989, 156, 265;
[12] 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): Cu(I) 60 (coordination num-
ber (CN) 2), Cu(I) 74 (CN 4), N 75, S 104; d) R. R. Conry,
W. S. Strejewske, A. A. Tipton, Inorg. Chem. 1999, 38, 1833.
[13] H. Beyer, C.-F. Kröger, Chem. Ber. 1960, 637, 135.
[14] G. M. Sheldrick, SHELXS-97, Universität Göttingen, 1997.
[15] A. Altmore, G. Cascarano, C. Giacovazzo, A. Guagliardi, M.
C. Burla, G. Polidori, M. Camalli, SIR-92, Bari, Perugia,
Rome, 1992.
Crystal structure analyses of L1a-c and 2
The crystals of L1a-c and 2 were covered with perfluorinated oil
and mounted on the top of a glass capillary. In addition, L1b-c and
2 were hold under a flow of cold gaseous nitrogen. The orientation
matrix and unit cell dimensions were determined from ca. 5000
(L1a, L1b, Stoe IPDS II), ca. 7000 (L1c, Stoe IPDS II), and from
ca. 10000 (2; Stoe IPDS II) reflections (graphite-monochromated
Mo-Kα radiation, λ ϭ 71.073 pm). The intensities were corrected
for Lorentz and polarization effects. In addition, absorption correc-
tions were applied for L1a-c and 2 (numerical). The structures were
solved by direct methods for L1a-c (SHELXS-97) and for 2 (SIR-
92) 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 were calculated for ideal positions and re-
fined with a common displacement parameter. H1 atoms in 2 were
included with a free refinement. All hydrogen atoms in L1a-c were
freely refined. Programs used were SHELXS-97 [14], SIR-92 [15],
SHELXL-97 [16], SHELXTL-Plus [17], and PLATON [18].
[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] A. L. Spek, PLATON-98, Utrecht, 1998.
Z. Anorg. Allg. Chem. 2007, 465Ϫ469
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
469