Syntheses and characterization of new copper complexes with the heterocyclic thione, AMTTO. X-ray structures of [Cu(AMTTO)Cl2], [Cu(AMTTO)2]Cl, and [Cu(AMTTO)(PPh3)2Cl]: (AMTTO = 4-amino-6-methyl-1,2,4-triazine-

Article abstract of DOI:10.1002/1521-3749(200213)628:13<2887::AID-ZAAC2887>3.0.CO;2-B

The complexes [Cu(AMTTO)Cl₂] (2), [Cu(AMTTO)₂]Cl (3), and [Cu(AMTTO)(PPh₃)₂Cl] (4) have been prepared and characterized by IR spectroscopy and elemental analyses. Also single-crystal X-ray diffraction studies on

Full text of DOI:10.1002/1521-3749(200213)628:13<2887::AID-ZAAC2887>3.0.CO;2-B

Syntheses and Characterization of New Copper Complexes with the
Heterocyclic Thione, AMTTO. X-Ray Structures of [Cu(AMTTO)Cl2],
[Cu(AMTTO)2]Cl, and [Cu(AMTTO)(PPh3)2Cl]
(AMTTO ؍ 4-Amino-6-methyl-1,2,4-triazine-3-thione-5-one)
Mitra Ghassemzadeh*
Tehran/Iran, Chemistry and Chemical Engineering Research Center of Iran
Forough Adhami
Tehran/Iran, Islamic Azad University, Shahr ray Campus
Majid M. Heravi
Vanak, Tehran/Iran, Department of Chemistry, School of Sciences, Azzahra University
Abas Taeb
Tehran/Iran, University of Science and Technology
Soheila Chitsaz and Bernhard Neumüller
Marburg, Fachbereich Chemie der Universität
Received May 27th, 2002.
Abstract. The complexes [Cu(AMTTO)Cl2] (2), [Cu(AMTTO)2]Cl
(3), and [Cu(AMTTO)(PPh3)2Cl] (4) have been prepared and
characterized by IR spectroscopy and elemental analyses. Also sin-
gle-crystal X-ray diffraction studies on compound 2, 3 and 4 re-
vealed that AMTTO acts in 2 as a bidentate ligand via nitrogen
and sulfur atoms, in 3 and 4 as a monodentate via sulfur atoms.
Complex 3 was already mentioned in literature, but the structure
was not described in detail. The molecules in 2 form infinite chains
through additional weak CuϪS interactions along [010] indicating
the Jahn-Teller distortion of the d9 ion Cu2ϩ. The infinite chains
are connected by hydrogen bonding along [100]. Crystal data for 2
at Ϫ80°C: monoclinic, space group P21/m, a ϭ 666.7(1), b ϭ
609.4(1), c ϭ 1132.6(2) pm, b ϭ 95.46(2)°, Z ϭ 2, R1 ϭ 0.0365;
for 3 at Ϫ80°C: orthorhombic, space group Pbcn, a ϭ 1291.2(2),
b ϭ 1146.5(1), c ϭ 1000.5(1) pm, Z ϭ 4, R1 ϭ 0.0315; for 4 at
Ϫ80°C: monoclinic, space group, P21/n, a ϭ 879.4(1), b ϭ
1849.3(2), c ϭ 2293.8(3) pm, β ϭ 92.38(1)°, Z ϭ 4, R1 ϭ 0.0688.
Keywords: Copper; Triazine; Metallacycles
Synthesen and Charakterisierung von neuen Kupfer-Komplexen des heterocyclischen
Thions AMTTO. Die Kristallstrukturen von [Cu(AMTTO)Cl2], [Cu(AMTTO)2]Cl
und [Cu(AMTTO)(PPh3)2Cl]
(AMTTO ؍ 4-Amino-6-methyl-1,2,4-triazin-3-thion-5-on)
Inhaltsübersicht. Über die Darstellung der Komplexe [Cu(AMT-
TO)Cl2] (2), [Cu(AMTTO)2]Cl (3) sowie [Cu(AMTTO)(PPh3)2Cl]
(4) und deren Charakterisierung mittels IR-Spektroskopie and Ele-
mentaranalysen wird berichtet. Die zusätzlich an 2, 3 und 4 durch-
geführten Röntgenstrukturanalysen ergaben, daß der Ligand
AMTTO in 2 als zweizähniger Ligand über Stickstoff- und Schwe-
felatome koordiniert, dagegen in 3 und 4 nur als einzähniger Li-
gand über die Schwefelatome fungiert. Komplex 3 wurde bereits in
der Literatur erwähnt, jedoch wurde der dreidimensionale Aufbau
dort nicht ausführlich beschrieben. Die Moleküle von 2 bilden
durch zusätzliche schwache CuϪS-Kontakte unendliche Ketten
entlang [010], was die Jahn-Teller-Verzerrung des d9-Ions Cu2ϩ be-
legt. Diese Polymerstränge sind untereinander durch Wasserstoff-
brücken-Bindungen entlang [100] verknüpft.Strukturparameter für
2 bei Ϫ80°C: monoklin, Raumgruppe P21/m, a ϭ 666,7(1), b ϭ
609,4(1), c ϭ 1132,6(2) pm, β ϭ 95,46(2)°, Z ϭ 2, R1 ϭ 0,0365;
für 3 bei Ϫ80°C: orthorhombisch, Raumgruppe Pbcn, a ϭ
1291,2(2), b ϭ 1146,5(1), c ϭ 1000,5(1) pm, Z ϭ 4, R1 ϭ 0,0315;
für 4 bei Ϫ80°C: monoklin, Raumgruppe P21/n, a ϭ 879,4(1), b ϭ
1849,3(2), c ϭ 2293,8(3) pm, β ϭ 92,38(1)°, Z ϭ 4, R1 ϭ 0,0688.
1 Introduction
Thiosemicarbazone and thiosemicarbazide derivatives like
heterocyclic thiones as ligand in metal complexes exhibit
important biological properties [1a]. The antitumoral, anti-
viral and antibacterial activities of a number of complexes
derived from heterocyclic thiones have also been reported
* Dr. M. Ghassemzadeh
Chemistry and Chemical Engineering Research Center of Iran,
P.O. Box 14335-186
Tehran/Iran
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893  2002 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 0044Ϫ2313/02/628/2887Ϫ2893 $ 20.00ϩ.50/0
2887

M. Ghassemzadeh, F. Adhami, M. M. Heravi, A. Taeb, S. Chitsaz, B. Neumüller
[1bϪd]. These ligands show in their coordination different
4 can be prepared by the reaction of 1, copper(I) chloride
and triphenylphosphane in a molar ratio 1:2 in chloroform/
acetonitrile under reflux conditions [eq (3)].
geometries such as neutal S-monodentate, N-monodentate,
S-bridge, N,S-chelate etc. [2]. From a bio-inorganic point of
view, thiolate complexes are of great importance, mainly
due to the presence of thiolate donors in the coordination
sphere of many metal ions in very diverse metallaproteins
[3].
MeOH/MeCN
1 ϩ CuCl ϩ 2 PPh3
Ǟ [(AMTTO)Cu(PPh3)2Cl]
(3)
4
On the other hand, there is a long standing interest in
the preparation and study of CuI complexes with sulfur-
containing ligands with the awareness of the significance of
copper-sulfur interactions in biological systems [4].
Many attention has been paid to copper(I) complexes be-
cause of their participation in certain biochemical redox re-
actions [5] and provide suitable models for the represen-
tation of several enzymatic sites [6]. Although copper defi-
nitely is an essential element of many life processes in higher
organisms, but its biological relevance and prevalence was
recognized when the bio-inorganic chemistry have been de-
veloped [7]. In our investigation, we have shown that the
heterocyclic thione ligand AMTTO (1) reacts with silver
[8a, b], copper [8bϪd] and palladium [8eϪg] as a mono-
dentate ligand or bidentate chelating agent. In this paper
we wish to report on the behaviour of 1 against copper(I)
and copper(II) ions.
This complex can also be obtained by the reaction of
3 with PPh3 in a molar ratio 1:2 under reflux conditions
[eq (4)].
CHCl3/MeCN; ∆
3 ϩ 2 PPh3
Ǟ [(AMTTO)Cu(PPh3)2Cl] ϩ AMTTO (4)
4
All of the complexes are air-stable crystalline solids. In
the IR spectra of 2Ϫ4, the νCuS absorptions were found at
347, 352 and 345 cmϪ1 and the absorption bands of the
CuϪN streching vibrations at 462 cmϪ1 for 2 and 457 cmϪ1
for 3. The band at 271 cmϪ1 for 2 and at 237 cmϪ1 for 4
can be assigned to νCuCl. νCuP2 of 4 was observed at 159
cmϪ1. Characteristic for the AMTTO ligand are the CϭO
and NϭCring vibrations at 1702 and 1609 cmϪ1 for 2, at
1712 and 1603 cmϪ1 for 3 and 1689 and 1593 cmϪ1 for 4.
Because of the two NH-containing functions in AMTTO
two absorptions νNH or νNH2, respectively, could be veri-
fied in 2Ϫ4. Measured values are 3231 and 3179 cmϪ1 for
2, 3229 and 3126 cmϪ1 for 3, and 3297 as well as 3210 cmϪ1
in 4. The P-C vibrations as well as the δ-CH vibrations of
Scheme 1 Graphic representation of a molecule AMTTO
the moiety PPh3 are found in the range of 690Ϫ750 cmϪ1
.
Consistent with the structure of 4, only a sharp singlet
resonance at 32.6 ppm was observed in the 31P{1H} NMR
spectrum.
2 Results and Discussion
2.1 Synthesis and characterization of 2, 3, and 4
2.2 Crystal Structures of 2؊4
Complex 2 can be observed by the addition of equimolar
amount of 1 to CuCl2 in methanol/hydrochloric acid solu-
tion as a green solid at room temperature [eq (1)].
Complex 2
The crystal structure of 2 consists of neutral complex
molecules [(AMTTO)CuCl2] (Fig. 1). AMTTO acts as a bi-
dentate ligand and occupies two equatorial positions in the
Jahn-Teller distorted stretched octahedron. The sites trans
to nitrogen and sulfur atoms, respectively, are occupied by
the chloride ligands. This approximately square planar ar-
rangement around CuII is completed to a distorted octa-
hedron by additional weak CuϪS contacts using the S
atoms of molecules above and below. The Cu1ϪS1 and
Cu1ϪS1a bond lengths are 231.1(3) and 304.7(3) pm,
respectively. The CuϪS distance observed in similar com-
plexes with square planar coordination, lies in the range of
228.4Ϫ229.2 pm [9aϪc] (CuII) and for tetrahedral coordi-
nation in the range of 232.6Ϫ244.4 pm (CuI) [5b, 9g].
MeOH/HCl
1 ϩ CuCl2
Ǟ [(AMTTO)CuCl2]
(1)
2
The reaction of 1 with CuCl in a 2:1 molar ratio in
methanol/hydrochloric acid solution leads to the complex 3
at room temperature [eq (2)]. 3 was already published inde-
pendently by others, using a known literature route [8d, h].
We decided to synthesize 3, because it is an important start-
ing compound for further investigations [see eq (4)].
MeOH/HCl
2 1 ϩ CuCl
Ǟ [(AMTTO)2Cu]Cl
(2)
3
2888
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893

New Copper Complexes with the Heterocyclic Thione
Table 1 Selected bond lengths/pm and bond angles/° in 2Ϫ4a)
2
Cu1...S1a 304.7(3) S1aϪCu1ϪS1b 178.09(9) Cl1ϪCu1ϪCl2 97.3(1)
Cu1ϪCl1 224.6(3) Cl1ϪCu1ϪCl2 97.3(1)
Cl1ϪCu1ϪS1 89.7(1)
Cu1ϪCl2 225.2(3) Cl1ϪCu1ϪN2 174.8(3) Cl2ϪCu2ϪS1 173.0(1)
Cu1ϪS1 231.1(3) Cl2ϪCu1ϪN2 87.9(3)
Cu1ϪN2 203.7(9) Cu1ϪS1ϪC1 97.1(4)
S1ϪCu1ϪN2 85.1(3)
S1ϪC1
173(1)
O1ϪC2 118(2)
3
Cu1ϪS1 225.28(8) S1ϪCu1ϪN2 84.93(8) S1ϪCu1ϪS1a 143.28(4)
Cu1ϪN2 217.9(4) S1ϪCu1ϪN2a 120.22(8) N2ϪCu1ϪN2a 97.6(1)
S1ϪC1
168.1(4) Cu1ϪS1ϪC1 98.8(1)
Cu1ϪN2ϪN1 112.0(2)
O1ϪC2 121.1(4)
4
Cu1ϪCl1 236.7(2) Cl1ϪCu1ϪS1 104.69(6) Cl1ϪCu1ϪP1 115.07(6)
Cu1ϪS1 242.6(2) Cl1ϪCu1ϪP2 105.25(6) S1ϪCu1ϪP1 97.10(6)
Cu1ϪP1 225.9(2) S1ϪCu1ϪP2 106.83(6) P1ϪCu1ϪP2 125.43(7)
Cu1ϪP2 229.5(2) Cu1ϪS1ϪC1 108.5(2) Cu1ϪP1ϪC5 118.1(2)
Fig. 1 Molecular structure of three molecules of 2 (view approxi-
mately perpendicular to string direction [010]; most of the H atoms
are omitted for clarity; thermal ellipsoids 40% probability)
S1ϪC1
168.1(6) Cu1ϪP1ϪC6 114.0(2) Cu1ϪP1ϪC7 110.2(2)
O1ϪC2 122.2(7) Cu1ϪP2ϪC8 118.9(2) Cu1ϪP2ϪC9 120.1(2)
P1ϪC5
P1ϪC6
P1ϪC7
P2ϪC8
P2ϪC9
181.7(6) Cu1ϪP2ϪC10 107.1(2)
182.6(6)
181.4(6)
182.6(6)
183.7(6)
P2ϪC10 181.6(6)
a) Crystallographic data (excluding structure factors) for the crystal structu-
res have been deposited at the Cambridge Crystallographic Data Center with
the numbers CCDC 181959 (2), CCDC 181960 (3) and CCDC 181961 (4).
Copies of the data can be obtained on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Fax: int. code
e-mail: deposit@ccdc.cam.ac.uk).
ϩ 44-1223/336-033;
drogen bridge. Additional weak hydrogen bonds were
formed in N2ϪH1···Cl2a with a distance of 351.3(5) pm
for N2···Cl2a.
Complex 3
3 consists of [Cu(AMTTO)2]ϩ ions and ClϪ ions (Fig. 3).
Cuϩ and ClϪ ions lie on identical twofold axes. The cop-
per(I) ion is surrounded by two AMTTO ligands quite simi-
lar to the [Ag(AMTTO)2]ϩ ion [8a]. This means a 2ϩ2 co-
ordination of Cu1 by S1and S1a (225.28(8) pm) as well as
by N2 and N2a (217.9(7) pm). Important for the charac-
terization of the coordination sphere in 3 are the angles
S1ϪCu1ϪS1a (143.28(4)°) and N2ϪCu1ϪN2a (97.6(1)°).
Therefore, the structure of 3 can be described either as dis-
torted linear or distorted tetrahedral [8d, 10e]. The CuϪS
distance lies in the range of values, found for Cu(I) com-
plexes with tetrahedral arrangment (224.4Ϫ230.0 pm) [5b,
6c, 10aϪc]. The CuϪN bonds are rather weak, indicated
by the distances of reference complexes [10c, d], exhibiting
values of 198.1Ϫ210.7 pm. The dihedral angle between the
“best planes” of the five-membered chelate rings in the cat-
Fig. 2 View of the unit cell of 2 in direction [010].
The Cu1ϪCl1, Cu1ϪCl2 and Cu1ϪN2 bond lengths are
224.5(3), 225(3) and 203.5(9) pm. Similar CuII complexes
have CuϪN distances of 196.0Ϫ203.5 pm [9b, 9c, 9f] and
CuϪCl distances of 220.0Ϫ230.1 pm [9b,c]. 2 is stacked
along [010] by the additional CuϪS contacts and the
formed columns are connected by hydrogen bonds, which
extent along [100] (Fig. 2). The N···O distance in
N4ϪH2···O1a of 281(1) pm indicates a medium strong hy-
ion [Cu(AMTTO) ]ϩ is 103° (see Fig. 4). The chelate rings
2
possess a slight distinct envelope conformation, recogniz-
able by the angle Cu1/S1/N2//S1C1/N1/N2 of 11°. The cat-
ions in 3 are connected by strong hydrogen bonds
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893
2889

M. Ghassemzadeh, F. Adhami, M. M. Heravi, A. Taeb, S. Chitsaz, B. Neumüller
Fig. 3 Structure of one unit of 3 (most of the H atoms are omitted
for clarity; thermal ellipsoids 40% probability; only the H···Cl hy-
drogen bonds are given)
Fig. 5 Two molecules of 3 forming a centrosymmetrical dimer by
H···O hydrogen bridges.
Fig. 6 View of the unit cell of 3 along the direction [001].
Fig. 4 Side view of the salt 3 in the direction S1ϪCu1ϪS1a with
H···Cl hydrogen bridges.
224.7Ϫ230.7 pm [5b, 6c, 8b]; CuϪCl: 230.8Ϫ241.0 pm [5b,
6c, 8b, 11a]). The CuϪP bond lengthening of ca. 3.5 pm
reflects the sterical influence of the AMTTO ligand caused
by the orientation through the hydrogen bond network. Be-
cause of the sterical repulsion the angle S1ϪCu1ϪP1 is
smaller (97.10(6)°) than the angle S1ϪCu1ϪP2
(106.83(6)°). The other strong sterical repulsion was ob-
served between the two phosphane ligands, indicated by the
expansion of the angle P1ϪCu1ϪP2 to 125.43(7)° [6c, 10a,
11a, b]. We reported a second Cu(I) complex (5) with ClϪ
and PPh3 ligands but with a modified AMTTO ligand,
C4H4N3SON(ϭCMe2) [8b] which is also bound as monod-
entate ligand via S function. 4 possesses three intramolecu-
lar hydrogen bondings (N2ϪH1···O1, N2···O1: 262.2(6)
pm; N2-H2···S1, N2···S1: 295.3(6); N4ϪH1···Cl1, N4···Cl1:
311.7(6) pm) and one intermolecular hydrogen bridge
(N2ϪH1···Cl1, N2···Cl1: 333.2(6) pm), leading to chains
along [100].
(N2ϪH1···O1b: 279.7(4); N2ϪH2···O1b: 279.8(4) pm) to
each other, forming centrosymmetrical dimers (see Fig. 5).
The chloride ion is coordinated via six hydrogen bondings
to four cations, leading to a 3d-network of cations and
anions (Fig. 6).
Complex 4
The copper(I) ion in 4 is surrounded by two triphenyl
phosphine molecules, one AMTTO ligand and one chloride
ion (Fig. 7). In 4, compound 1 acts as a monodentate ligand
through its sulfur atom. The Cu1ϪS1 bond length is
242.6(2) pm and lies in the range observed in similar com-
plexes with tetrahedral Cu(I) centers [5b, 6c, 10aϪc]. This
shows again the 2ϩ2 character of the coordination sphere
in 3 (CuϪS: 225.28(8) pm!). The atom distances Cu1ϪCl1
(236.7(2) pm), Cu1ϪP1 (225.9(2) pm) and Cu1ϪP2
(229.5(2) pm) are close to those found in literature (CuϪP:
2890
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893

New Copper Complexes with the Heterocyclic Thione
[Cu(AMTTO)Cl2] (2): A methanolic solution (15 mL) of 1 (0.22 g,
1.4 mmol) was added to an aqueous solution (10 mL) of CuCl2
(0.18 g, 1.4 mmol) and 15% hydrochloric acid (3 mL) and was
stirred for 1 h at 20°C. A green precipitate was obtained very fast
and was filtered. The filtrate was kept at 20°C for one week to
give green crystals of 2. The crystalline material was washed with
methanol and dried on air.
Yield: 0.40 g (95%).
Elemental analysis: C4H6Cl2CuN4OS (292.62): C 16.32 (calc.
16.42), H 2.01 (2.07), N 19.19 (19.15), Cl 24.18 (24.23), Cu 21.82
(21.71), S 10.89 (10.96)%.
IR (nujol; cmϪ1): 3231 w (νNH), 3179 w (νNH), 2724 w, 1720 s (νCϭO),
1609 m (νCϭN), 1589 m, 1526 m, 1314 m, 1244 m, 1165, 1113 vw, 1050 vw,
972 vw, 936 vw, 766 w, 748 m, 735 w, 645 m, 595 w, 516 m, 462 m (νCuN),
412 m, 348 m, 311 m (νCuS), 271 m (νCuCl), 237 vw, 178 m (br), 139 vw.
[Cu(AMTTO)2]Cl (3): 0.14 g (1.4 mmol) of CuCl in 10 mL of H2O
and 0.44 g (2.8 mmol) of 1 in 17 mL 15% hydrochloric acid/MeOH
(2 mL/15 mL) were added under stirring at 20°C. The reaction
mixture was stirred for 45 min and a yellow shiny microcrystalline
solid precipitated. The mixture was filtered and dried on air. Suit-
able crystals for X-ray structure determination were obtained by
recrystallization from EtOH/CHCl3/MeCN (1:1:1) at 4°C after sev-
eral days.
Fig. 7 Molecular structure of 4 (most of the H atoms are omitted
for clarity; thermal ellipsoids 40% probability).
Yield: 0.58 g (92%).
3 Experimental Section
Elemental analysis: C8H12ClCuN8O2S2 (415.35): C 23.09 (calc.
23.13), H 2.86 (2.91), N 26.91 (26.98), Cl 8.59 (8.53), Cu 15.21
(15.30), S 15.52 (15.44)%.
IR (nujol; cmϪ1) 3229 m (νNH), 3126 w (νNH), 2853 vs,1712 s (νCϭO),
1603 m (νCϭN), 1509 m, 1297 m, 1168 m, 1139 m, 1080 vw, 932 w, 749 w,
641 m, 587 w, 504 m, 457 m (νCuN), 436 w, 412 m, 352 m (νCuS), 313 vw,
272 w, 223 vw, 171 w, 136 m, 114 m.
General Remarks: All chemicals and solvents were purchased from
Merck and Fluka and were used without further purification or
drying. 1 was prepared according to literature [12]. The IR spectra
were obtained on a Bruker IFS-88 (nujol mulls, CsI disks for the
range 4000Ϫ500 cmϪ1 and polyethylene disks for the range
500Ϫ100 cmϪ1). The 31P NMR spectrum was measured on a
Bruker instrument ARX-200 with 85% aqueous H3PO4 as standard
(δ ϭ 0.0 ppm).
[Cu(AMTTO)(PPh3)2Cl] (4): A solution of 1 (0.22 g; 1.4 mmol) in
MeCN (15 mL) was added to a solution of CuCl (0.14, 1.4 mmol)
Table 2 Crystallographic data of 2Ϫ4.
Compound
Instrument
Radiation
2
3
4
IPDS I (Stoe)
Mo-Kα (λ ϭ 71.073 pm)
C4H6Cl2CuN4OS
261.63
IPDS I (Stoe)
Mo-Kα
C8H12ClCuN8O2S2
415.35
CAD4 (Enraf-Nonius)
Mo-Kα
C40H36ClCuN4OP2S
781.76
Empirical formula
Formula mass/g.molϪ1
Crystal size/mm
Crystal system
Space group (no. [18])
a/pm
b/pm
c/pm
0.32x0.09x0.03
monoclinic
P21/m (11)
666.7(1)
609.4(1)
1132.6(2)
95.46(2)
458.1(1)
2
0.38x0.07x0.04
orthorhombic
Pbcn (60)
1291.2(2)
1146.5(1)
1000.5(1)
0.37x0.11x0.08
monoclinic
P21/n (14)
879.4(1)
1849.3(2)
2293.8(3)
92.38(1)
3727.1(8)
4
β/°
Volume/pm3·106
1481.0(3)
4
1.863
Z
dcalc/g.cmϪ3
2.122
1.393
Absorption correction
numerical
31.6
numerical
19.6
empirical
8.4
µ/cmϪ1
Temperature/K
2θmax
193
51.99
193
52.09
193
50.0
h
k
Ϫ8 Ǟ 8
Ϫ13 Ǟ 13
Ϫ7 Ǟ 7
2797
Ϫ15 Ǟ 15
Ϫ11 Ǟ 11
Ϫ14 Ǟ 14
11008
Ϫ10 Ǟ 0
Ϫ21 Ǟ 0
Ϫ27 Ǟ 27
7237
l
reflection collected
Unique reflections (Rint
Reflections with Fo>4s>(Fo)
Parameters
)
981 (0.083)
560
87
139 (0.0636)
775
114
6540 (0.067)
3326
462
R1 (Fo<4s>(Fo))
0.0365
0.0315
0.0781b)
0.52/Ϫ0.47
0.0688
wR2 (all data)
0.0904a)
0.46/Ϫ0.44
0.1093c)
0.44/Ϫ0.43
Largest diff. peak and hole /[(e.pmϪ3).10Ϫ6
]
a) w ϭ 1/[σ2(Fo)2 ϩ (0.0387·P)2]; P ϭ [max(Fo2, 0) ϩ 2Fc2]/3.b) w ϭ 1/[σ2(Fo)2 ϩ (0.0461·P)2]. c) w ϭ 1/[σ2(Fo)2 ϩ (0.0234·P)2].
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893
2891

M. Ghassemzadeh, F. Adhami, M. M. Heravi, A. Taeb, S. Chitsaz, B. Neumüller
and PPh3 (0.73 g, 2.8 mmol) in CHCl3 (30 mL). The yellow solu-
P. Kennepohl, E. I. Solomon, Chem. Rev. 1996, 96;
2239Ϫ2314. c) J. A. Garcia-Vazquez, J. Romero, A. Sousa,
Coord. Chem. Rev. 1999, 193Ϫ195, 691Ϫ745.
tion was stirred for 3 h and then concentrated to a volume of 10
mL. Colorless crystals were obtained at 20°C after several days,
washed with methanol and dried on air.
[4] a) E. S. Raper, Coord. Chem. Rev. 1985, 61, 115Ϫ184; b) S.
K. Hadjikakou, P. Aslanidis, P. Karagiannidis, A. Aubry, S.
Skoulika, Inorg. Chim. Acta 1992, 193, 129Ϫ135; c) D. R.
Smith, Coord. Chem. Rev. 1997, 162, 155Ϫ240.
Yield: 1.09 g (95%).
Elemental analyses: C40H36ClCuN4OP2S (781.76): C 61.39 (calc.
61.46), H 4.71 (4.64), N 7.21 (7.19), Cl 4.58 (4.50), Cu 8.09 (8.13),
P 7.88 (7.92), S 4.07 (4.10)%.
[5] a) K. B. Karolin, J. Zubieta, Copper Coordination Chemis-
tryϪBio-Chemical and Inorganic Perspective, Adenine, New
York, 1983; b) S. K. Hadjikakou, P. Aslanidis, P. D. Akrivos,
P. Karagiannidis, B. Kojic-Prodic, M. Luic, Inorg. Chim. Acta
1992, 197, 31Ϫ38.
IR (nujol; cmϪ1): 3298 w (νNH), 3210 w (νNH), 3120 vw, 3049 w, 1689 s
(νCϭO), 1592 m-w (νNϭC), 1524 s, 1436 s, 1405 m, 1311 m, 1250 m, 1218
m, 1181 w, 1093 m, 1066 m, 1026 w, 995 m, 904 w, 856 vw, 829 vw, 743 s,
694 s, 619 vw, 580 vw, 510 s, 482 m, 429 m, 413 w, 390 vw, 366 m, 343 w,
315 m (νCuS), 295 w, 271 m, 237 m (νCuCl), 216 m, 190 m, 159 m, 143 m,
111 m.
[6] a) T. G. Spiro (ed.), Copper Proteins, Wiley, New York, 1981;
b) R. Lontie, Copper Proteins and Copper Enzymes, Vol. IϪIII,
CRC Press, Boca Raton (Fl.), 1984; c) P. J. Cox, P. Aslanidis,
P. Karagiannidis, S. K. Hadjikakou, Polyhedron 1999, 18,
1501Ϫ1506.
31P{1H} NMR (MeOH): 32.6 ppm (s).
[7] a) W. Kaim, J. Rall, Angew. Chem. 1996, 108, 47Ϫ64; Angew.
Chem. Int. Ed. Engl. 1996, 35, 43Ϫ60; b) M. E. Shils, J. A.
Olson, M. Sike, A. C. Ross, Modern in Nutrition in Health and
Diseas, 9th, 1998, 241Ϫ251, Lippincott Williams and Wikins,
Awolters Kluwer Company.
Crystal Structure Analyses of 2Ϫ4
The crystals of 2, 3 and 4 were covered with a perfluorinated poly-
ether and mounted on the top of a glass capillary under a flow of
cold gaseous nitrogen (Ϫ80°C; intruments and graphite monochro-
mated radiation see Table 2). The orientation matrix and prelimi-
nary unit cell dimensions were determined from 1000 (2), 1000 (3)
and 15 (4) reflections. The final cell parameters were determined
from 2000 (2), 8000 (3) and 25 (4) reflections. The intensities were
corrected for Lorentz and polarization effects. Used programs:
SIR-92 [13], SHELXS-97 [14], SHELXL-97 [15], SHELXTL [16]
and PLATON-98 [17].
[8] a) F. Adhami, M. Ghassemzadeh, M. M. Heravi, A. Taeb, B.
Neumüller, Z. Anorg. Allg. Chem. 1999, 625, 1411Ϫ1412; b)
M. Ghassemzadeh, F. Adhami, M. M. Heravi, A. Taeb, S.
Chitsaz, B. Neumüller, Z. Anorg. Allg. Chem. 2001, 627,
815Ϫ819; c) M. F. Iskander, J. Stephanos, N. E. Kady, M. E.
Essawi, A. E. Toukhy, L. E. Sayed, Transition Met. Chem.
1989, 14, 27Ϫ33; d) I. A. Razak, K. Chinnakali, H.-K. Fun,
P. Yang, W.-R. Zeng, F.-X. Xie, Y. P. Tian, H. Zhang, Acta
Crystallogr. 1999, C55, 1092Ϫ 1093; e) M. Ghassemzadeh, K.
Aghapoor, M. M. Heravi, B. Neumüller, Z. Anorg. Allg. Chem.
1998, 624, 1969Ϫ1972; f) B. Neumüller, M. M. Heravi, M.
Ghassemzadeh, Z. Anorg. Allg. Chem. 1999, 625, 1908Ϫ1911;
g) M. Ghassemzadeh, M. Bolourtchian, S. Chitsaz, B.
Neumüller, M. M. Heravi, Eur. J. Inorg. Chem. 2000,
1877Ϫ1882; h) M. F. Iskander, J. Stephanos, N. El Kady, M.
El Essawi, A. El Toukhy, L. El Sayed, Transition Met. Chem.
1989, 14, 27Ϫ33.
H-Atoms: 2, 3: Free refinement of N-H; ideal positions for CϪH
and refinement with common displacement parameter. 4: Free re-
finement of NϪH in positions; ideal positions for CϪH; refine-
ment with common displacement parameter for all H atoms.
Acknowledgments. The work was financially supported by the
Deutsche Forschungsgemeinschaft and the Adolf-Haeuser Foun-
dation (Marburg).
[9] a) J. A. Boyko, W. F. Fury, Jr., R. A. Lalancette, Acta Crys-
tallogr. 1992, C48, 1606Ϫ1609; a) F. Bigoli, M. Lanfranchi,
M. A. Pellinghelli, J. Chem. Research (M) 1990, 1710Ϫ1718;
c) M. B. Biaginicingi, F. Bigoli, M. Lanfranchi, M. A.
Pellinghelli, A. Vera, E. Buluggiu, J. Chem. Soc., Dalton Trans.
1992, 3145Ϫ3151; d) T. U. Fessler, R. Hübener, J. Strähle, Z.
Anorg. Allg. Chem. 1997, 623, 1367Ϫ1374; e) O. J. Parker, S.
L. Aubol, G. L. Breneman, Polyhedron 2000, 19, 623Ϫ626; f)
N. Matsumoto, Y. Motada, T. Matsuo, T. Nakashima, N. Re,
N. F. Dahan, J. P. Tuchagues, Inorg. Chem. 1999, 38,
1165Ϫ1173; g) T. C. Deivaraj, G. X. Lai, J. J. Vittal, Inorg.
Chem. 2000, 39, 1028Ϫ1034.
Literature
[1] a) D. X. West, A. E. Liberta, S. B. Padhye, R. C. Chikate, P.
B. Sonawane, A. S. Kumbhar, R. G. Yerande, Coord. Chem.
Rev. 1993, 123, 49Ϫ71; b) D. X. West, M. A. Lockwood, A.
Castineriras, Transition Met. Chem. 1997, 22, 366Ϫ371; c) D.
Kovala-Demertzi, A. Domopoulou, M. A. Demertzis, G.
Valle, A. Papageorgiou, J. Inorg. Biochem. 1997, 68, 147Ϫ155;
d) F. Hueso-Urena, N. A. Illan-Cabeza, M. N. Moreno-Carre-
tero, A. L. Penas-Chamorro, R. Faure, Polyhedron 2000, 19,
689Ϫ693.
[2] a) M. Akbar Ali, S. E. Livingstone, Coord. Chem. Rev. 1974,
13, 101Ϫ132; b) E. S. Raper, Coord. Chem. Rev. 1996, 153,
199Ϫ255; c) P. Perez-Lourido, J. A. Garcia-Vazquez, J.
Romero, M. S. Louro, A. Sousa, J. Zubieta, Inorg. Chim. Acta
1998, 271, 1Ϫ8.
[10] a) T. S. Lobana, P. K. Bhatia, E. R. T. Tiekink, J. Chem. Soc.,
Dalton Trans. 1989, 749Ϫ751; b) International Tables for X-
Ray Crystallography, Vol. IV, Kynoch Press, Birmingham
(U.K.), 1974: Covalent radii (pm): Cu(I) 60 (coordination
number (CN) 2), Cu(I) 74 (CN 4), N 75. c) R. R. Conry, W.
S. Striejewske, A. A. Tipton, Inorg. Chem. 1999, 38,
2833Ϫ2843; d) P. K. Santra, D. Das, T. K. Misra, R. Roy, C.
Sinha, S.-M. Peng, Polyhedron 1999, 18, 1909Ϫ1915; e) M.
Albrecht, K. Hübler, S. Zalis, W. Kaim, Inorg. Chem. 2000,
39, 4731Ϫ4734.
[3] a) W. H. Armstrong in: L. Que, Jr. (ed.), Metal Clusters in
Proteins, ACS, Washington (D.C.), 1998, p. 1; b) R. H. Holm,
2892
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893

New Copper Complexes with the Heterocyclic Thione
[11] a) J. K. Bera, M. Nethaji, A. G. Samuelson, Inorg. Chem.
1999, 38, 218Ϫ228; b) F. Marchetti, C. Pettinari, R. Pettinari,
A. Cingolani, M. Camalli, R. Spagna, Inorg. Chim. Acta 2000,
299, 65Ϫ79.
[12] A. Dornow, H. Menzel, P. Marx, Chem. Ber. 1964, 97,
2173Ϫ2178.
[13] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi,
M. C. Burla, G. Polidori, M. Camalli, SIR-92, Bari, Perugia,
Rome, 1992.
[14] G. M. Sheldrick, SHELXS-97, University of Göttingen, 1997.
[15] G. M. Sheldrick, SHELXL-97, University of Göttingen, 1997.
[16] G. M. Sheldrick, SHELXTL, Release 5.05/VMS for Siemens
R3 Crystallographic Research Systems, Siemens Analytical X-
Rax Instruments Inc., Madison (WI), 1996.
[17] A. L. Spek, PLATON-98, University of Utrecht, 1998.
[18] International Tables for Crystallography, 2nd ed., Vol. A,
Kluwer Academic Publishers, Dordrecht, 1989.
Z. Anorg. Allg. Chem. 2002, 628, 2887Ϫ2893
2893