Syntheses and x-ray crystal structures of new copper(I) and silver(I) complexes containing thione ligands

Article abstract of DOI:10.1002/1521-3749(200105)627:5<815::AID-ZAAC815>3.0.CO;2-V

The reaction of [(Ph₃P)₂CuCl]₂ with 4-amino-6-methyl-1,2,4-triazine-thione-5-one (AMTTO, 1) in methanol and further recrystallization from methanol/acetone solution gives [(C₄H₄N₃SON(=CMe₂)Cu(PPh ₃)₂Cl] (2) as a neutral complex. [(C₄H₄N₃SON(=CMe₂)Ag(PPh ₃)₂]NO₃ (4) can be obtained in excellent yield by the reaction of [(AMTTO)₂Ag]NO₃ (3) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X-ray diffraction studies. Crystal data for 2 at -80°C: space group P1 with a=1233.8(1), b=1389.7(1), c=1417.1(1) pm, α=89.36(1)°; β=65.10(1)°, γ=65.95(1)°, Z=2, R₁=0.0582 and for 4 at -80°C: space group P1, with a=1193.3(1), b=1308.5(1), c=1385.3(1) pm, α=94.69(1)°, β=109.14(1)°, γ=93.42(1)°, Z=2, R₁=0.0716. Wiley-VCH Verlag GmbH, 2001.

Full text of DOI:10.1002/1521-3749(200105)627:5<815::AID-ZAAC815>3.0.CO;2-V

ARTIKEL
Syntheses and X-Ray Crystal Structures of New CopperꢀI)
and SilverꢀI) Complexes containing Thione Ligands
Mitra Ghassemzadeh* a, Forough Adhamib, Majid M. Heravic, and Abas Taebd
Tehran/Iran, a Chemistry and Chemical Engineering Research Center of Iran, b Islamic Azad University, Science and Research
Campus, c Azzahra University, School of Sciences, d Iran University of Science and Technology
Soheila Chitsaz and Bernhard NeumuÈller
Marburg, Fachbereich Chemie der UniversitaÈt
Received September 18th, 2000.
Dedicated to Professor Kurt Dehnicke on the Occasion of his 70th Birthday
Abstract. The reaction of [)Ph3P)2CuCl]2 with 4-amino-6-
methyl-1,2,4-triazine-thione-5-one )AMTTO, 1) in methanol
and further recrystallization from methanol/acetone solution
gives [)C4H4N3SON)=CMe2)Cu)PPh3)2Cl] )2) as a neutral
complex.
[)C4H4N3SON)=CMe2)Ag)PPh3)2]NO3 )4) can be obtained
in excellent yield by the reaction of [)AMTTO)2Ag]NO3 )3)
with triphenylphosphane in methanol/acetone. Both com-
plexes were characterized by infrared spectroscopy, elemental
analyses as well as by X-ray diffraction studies. Crystal data
for at ±80 °C: space group P1 with a = 1233.8)1),
b = 1389.7)1), c = 1417.1)1) pm, a = 89.36)1)°; b = 65.10)1)°,
c = 65.95)1)°, Z = 2, R1 = 0.0582 and for 4 at ±80 °C: space
group P1, with a = 1193.3)1), b = 1308.5)1), c = 1385.3)1) pm,
a = 94.69)1)°, b = 109.14)1)°, c = 93.42)1)°, Z = 2, R1 = 0.0716.
2
Keywords: Triazine; Copper; Silver; Crystal structures
Synthesen und Kristallstrukturen neuer KupferꢀI)- und SilberꢀI)-Komplexe
mit Thion-Liganden
InhaltsuÈbersicht. Die Reaktion von [)Ph3P)2CuCl]2 mit
4-Amino-6-methyl-1,2,4-triazin-thion-5-on )AMTTO, 1) in
Methanol sowie Umkristallisation aus Methanol/Aceton er-
gibt den Neutralkomplex [)C4H4N3SON)=CMe2)Cu)PPh3)2Cl]
)2).
[)C4H4N3SON)=CMe2)Ag)PPh3)2]NO3 )4) kann in sehr
guter Ausbeute erhalten werden, wenn [)AMTTO)2Ag]NO3
)3) mit Triphenylphosphan in Methanol/Aceton umgesetzt
wird. Die Komplexe wurden mittels IR-Spektroskopie, Ele-
mentaranalysen und RoÈntgenstrukturanalysen charakteri-
siert. Kristalldaten fuÈr 2 bei ±80 °C: Raumgruppe P1 mit
a = 1233,8)1), b = 1389,7)1), c = 1417,1)1) pm, a = 89,36)1)°;
b = 65,10)1)°, c = 65,95)1)°, Z = 2, R1 = 0,0582 und fuÈr 4 bei
±80 °C: Raumgruppe P1, mit a = 1193,3)1), b = 1308,5)1),
c = 1385,3)1) pm, a = 94,69)1)°, b = 109,14)1)°, c = 93,42)1)°,
Z = 2, R1 = 0,0716.
1
Introduction
The ligand 4-amino-6-methyl-1,2,4-triazine-thione-5-
one )C4H4N3SONH2, AM TTO,1), which contains the
±N)H)±C)=S)± chromophore exists in two tautomeric
forms I and II )scheme I).
* Dr. Mitra Ghassemzadeh,
Chemistry and Chemical Engineering Research Center of
Iran,
P.O. Box 14335-186,
Tehran )Iran)
Scheme 1 Tautomeric forms in thiosemicarbazides and
thiosemicarbazones.
Z. Anorg. Allg. Chem. 2001, 627, 815±819
Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0044±2313/01/627815±819 $ 17.50+.50/0
815

M. Ghassemzadeh, F. Ashami, M. M. Heravi, A. Taeb, S. Chitsaz, B. NeumuÈller
Consequently, there has been considerable interest
mAgN and mAgS [10]. The C=O and C=N functions
cause two vibrations at 1699 and 1614 cm±1 for 2 and
1700 and 1614 cm±1 for 4, respectively. P±C vibrations
of the moiety PPh3 are found in the range 750±
in the coordination properties of both the neutral
thione I and of the deprotonated thiol II ligand [1, 2].
Crystallographic investigations have shown that the
thione I coordinates exclusively via the S atom [3]. In
contrast, the thiolate of II can adopt a variety of coor-
dination modes, namely: )i) S unidendate [2]; )ii) S,N-
chelating [2, 3 c, 4]; )iii) S,N-bridging [3 c, 5] and )iv) S
unidentate )with a weak M´ ´ ´ N interaction) [6].
In our investigations we have shown that the AMTTO
reacts with palladium)II) halides such as chloride,
bromide or iodide as a S,N-chelating ligand [7] and
with silver)I) nitrate according to the ªPearson Prin-
cipleº [8] as a unidentate one via its sulphur atom
with a weak Ag ´ ´ ´ N interaction, which leads to a
2 + 2 coordination on the silver atom [9].
±
697 cm±1 for 2 and at 761±696 cm±1 for 4. The NO3
anion presents its N±O asymmetric streching mode
)E') at 1377 cm±1 and the out-of-plane absorption
)A'') at 826 cm±1. For the N±H streching vibrations
2
two broad weak absorptions could be found at 3442
)2) and 3439 )4) cm±1, a result of the hydrogen bond-
ing.
3
Results and Discussion
2 consists of a neutral molecule )Fig. 1), while 4 is a
ionic compound which consists of the cation
[)C4H4N3SON)=CMe2)Ag)PPh3)2]+ and the anion
As part of our continuing interest in the sythesis
and characterization of heterocyclic thione complexes
of transition metals, we wish to report on further
thione metallacycles containing copper)I) and silver)I)
ions.
±
NO3 )Fig. 2). The molecules and ions of 2 and 4 pos-
sess only C1-symmetry. The coordination around the
metal is distorted tetrahedral with two P atoms of the
phosphane molecules, one S atom of the thione and
one Cl atom. This arrangement is considerable dis-
torted since the P angle at the metal site, P1±Cu1±P2
with a value of 126.62)5)°, is close to trigonally coor-
dinated Cu)I), while three other selected angles in
the CuP2SCl group with 106.09)5)° )Cl1±Cu1±S1),
105.35)6)° )Cl1±Cu1±P1) and 103.00)6)° )P2±Cu1±S1)
are nearly to those of a regular tetrahedron. The tetra-
hedral distortion is due to steric imposion of the bulky
phosphane ligands and was observed in a series of
analogous complexes [11]. The Cu±P bond distances,
mean 229.2 pm, are within the range of the corre-
sponding distances reported for other copper)I) com-
plexes )227.7±230.7 pm) [12]. Similar Cu±Cl distances,
here 238.0)1) pm, has been observed in four coordi-
nated Cu)I) complexes )233.3±239.1 pm) [13].
2
Syntheses and Characterization of 2 and 4
2 can be obtained by the reaction of CuCl, PPh3 and 1
in a molar ratio 1 : 2 : 1 in methanol at 50 °C and
further recrystallization of the crude from acetone so-
lution at room temperature according to equation )1).
CuCl + 2 PPh3 + C4H4N3SONH2
MeOH=Me2CO
! [)C4H4N3SON)=CMe2)Cu)PPh3)2Cl]
)1)
ÀH2O
2
4 can be prepared by the reaction of [)AMTTO)2Ag]-
NO3 )3) with PPh3 in the molar ratio 1 : 1 in metha-
nol/acetone [eq. )2)].
The nitrogen-bound hydrogen atom in 2 partici-
pates in an intramolecular hydrogen bridge with the
metal-bound chlorine atom; as illustrated in Fig. 1, this
results in the formation of a CuClHNCS six-mem-
bered ring. The non-bonding distance N4 ´ ´ ´ Cl1 of
304.7)5) pm indicates a strong hydrogen bridge )angle:
N4±H1 ´ ´ ´ Cl1 169)5)°). The Cu±S distance of
237.8)1) pm is consistent with the distances usually
found for tetrahedrally coordinated copper)I) ions
with thione-S donors [13, 14].
3 + 2 PPh3
MeOH=Me2CO
! [)C4H4N3SON)=CMe2)Ag)PPh3)2]NO3 + 1 )2)
ÀH2O
4
In both complexes 2 and 4, the NH2-group of the ligand
reacts with the solvent acetone in a Schiff's base reac-
tion to the corresponding imine C4H4N3SON)=CMe2)
according equation )3).
In the cation of 4 the ligand chelates the silver atom
through its sulphur and iminic nitrogen atom )Fig. 2)
forming a five-membered ring. Two PPh3 molecules
are also bound to the central atom and complete the
distorted tetrahedral coordination around the silver
atom. The deviation from perfect tetrahedral coordi-
nation is best illustrated by the P1±Ag1±P2 angle of
124.33)6)° and can be accounted for the steric hin-
drance induced by the two phosphane molecules, con-
sequently compressing the S1±Ag1±N2 angle to
70.6)1)°.
ꢀ3†
2 is a yellowish crystalline solid and 4 is a colorless
one. The absorptions mCuS and mCuCl of complex 2
can be observed at 305 and 208 cm±1. In the IR spec-
tra of 4 a broad band at 286 cm±1 can be assigned to
816
Z. Anorg. Allg. Chem. 2001, 627, 815±819

New Copper)I) and Silver)I) Complexes containing Thione Ligands
Fig. 3 View on the envelope comformation of the central
metallacycle in 4 )without phenyl rings).
Fig. 1 Molecular structure of 2 )only H1 is shown; 50%
probability level).
cantly shorter bond than the 250.4)3) pm in 3. 224 pm
are generally accepted as typical Ag±N distance [15]
but Ag1±N2 is clearly shorter than the sum of van
der Waals radii of silver and nitrogen )155 + 170 =
325 pm) [16].
The Ag±P bond distances, 243.0)2) )Ag1±P1) and
249.0)2) pm )Ag1±P2), agree well with the values
242.6±250.4 pm measured for a number of complexes
containing silver atoms coordinated by two Phos-
phanes [17]. The Ag±S bond lengths of 262.9)2) is sig-
nificantly longer than the distance found in
3
[243.50)8) pm], where a 2 + 2 coordination around the
Ag+ center was observed. Although, the value of 4 lies
in the range which was found for AgI complexes with
coordination number four [18]. The hydrogen bridge
causes sligthly different N±O bond lenghts within the
standard deviations in the strictly planar nitrate ion.
So, the distance O2±N5 )127.2)8) pm) including the
oxygen which participates in the H bridge is some-
what longer than the other two N±O bonds )O3±N5:
125.6)8) pm; O4±N5: 118.5)9) pm), whereas the bond
angles are very close to the ideal value of 120°.
The distances C5=N2 of 127.2)6) pm for 2 and of
127.9)9) pm for 4 are characteristic for acetone thio-
semicarbazones )C=N: 126.6)7) pm) and acetone semi-
carbazone )C=N: 127.8 pm). The similar C±C bond
lengths and C±C±C bond angles of the imine groups
for 2 )C5±C6: 149.2)7); C5±C7: 149.3)8); C6±C5±C7:
117.5)5)°) and 4 )C5±C6: 150)1); C5±C7: 150)1);
C6±C5±C7: 117.5)7)°) were measured in acetone thio-
semicarbazone )C±C: 149.1)8), 148.6)7); C±C±C:
117.4)5)) and in acetone semicarbazone )C±C: 149.4,
149.9 pm; C±C±C: 125.0°) [19]. There is no p-electron
conjugation between the AMTTO skeleton and the
imin function in 2 and 4. The dihedral angle between
Fig. 2 Structure of the ion pair 4 )only H1 is shown).
The existance of a medium strong hydrogen bond
between the NH-group of the ligand and an oxygen
atom of the nitrate anion [N4 ´ ´ ´ O2: 275.7)7) pm] also
contributes to the angular distortion about the silver
atom. In contrast to 3, where the ligand bound in a
1 + 1 fashion )strong Ag±S bond; weak and long
Ag ´ ´ ´ N contact) to Ag+ [9], in 4 the ligand acts more
bidentately. This may be caused by the existance of
the iminic group although there should be no back-
bonding effects from Ag+ to the imin function, which
are important for classical d-block ions such as FeIII
or MnIII. However, the Ag±N distance of 245.9)6) pm
indicates still a long and relatively weak but signifi-
Z. Anorg. Allg. Chem. 2001, 627, 815±819
817

M. Ghassemzadeh, F. Ashami, M. M. Heravi, A. Taeb, S. Chitsaz, B. NeumuÈller
Table 1 Crystallographic data for 2 and 4
the AMTTO plane and the plane N2/C5/C6/C7
amounts to 69° in 2 and to 59° in 4. The central me-
tallacycle AgN2CS in 4 possess a envelope conforma-
tion with an angle of 48° enlosed by the planes Ag1/
S1/N2 and S1/C1/N1/N2 )Fig. 3).
Compound
2
4
Formula
C43H40ClCuN4OP2S C43H40AgN5O4P2S
821.83
Formula weight/gmol±1
892.70
Crystal size/mm
a/pm
b/pm
c/pm
0.41 ´ 0.38 ´ 0.12
1233.8)1)
1389.7)1)
1417.1)1)
89.36)1)
65.10)1)
65.95)1)
1974.5)3)
2
0.39 ´ 0.32 ´ 0.15
1193.3)1)
1308.5)1)
1385.3)1)
94.69)1)
109.14)1)
93.42)1)
2028.0)3)
2
4
Experimental Section
a/°
The following chemicals were purchased and used without
further purification: CuCl, AgNO3, MeOH, Me2CO )Merck)
and PPh3 )Fluka). 1 was prepared according to literature
procedures [20]. The IR spectra were obtained on a Bruker
IFS-88 )nujol mulls; CsI disks of the range 4000±500 cm±1;
polyethylen disks for the range 500±100 cm±1).
b/°
c/°
Volume/106 pm3
Z
q/gcm±3
1.382
193
7.9
1.462
193
6.8
Temperature/K
l/cm±1
Crystal system
Space group
No. [26]
2h-range/°
h
triclinic
P1
2
5.8±55.8
±13 £ 0
±16 £ 14
±15 £ 15
7038
triclinic
P1
2
4.6±50.0
±14 £ 13
±15 £ 15
0 £ 16
7623
7120 )0.0474)
5221
[ꢀC4H4N3SONꢀ=CMe2)CuꢀPPh3)2Cl] ꢀ2). A solution of 1
)0.15 g, 1 mmol) in 10 mL of methanol was added dropwise
to a solution of CuCl )0.09 g, 1 mmol) and Ph3P )0.52 g,
2 mmol) in 20 mL of methanol and stirred for 3 h at 60±
70 °C. The solvent was evapourated to a small volume )ca.
10 mL) to give a yellow solid which was dissolved by addi-
tion of 10 mL of acetone at room temperature. The solution
was evapourated again to a small volume, the formed crude
crystalline material was filtered off and the clear solution
was kept at 4 °C to give yellowish crystals of 2.
k
l
No. of reflections
Unique reflections )Rint
Reflections with
Fo > 4r)Fo) for R1
Parameters
R1
)
5574 )0.0477)
4225
483
509
0.0582
0.0716
0.2134b)
1.38/±1.74
Yield: 0.71 g )87%).
wR2 )all Data)
0.1545a)
Elemental analysis: C43H40ClCuN4OP2S )821.83): calcd
C 62.84, H 4.90, N 6.81, Cl 4.31, P 7.53, Cu 7.73, S 3.90; found
C 62.77, H 4.91, N 6.93, Cl 4.20, P 7.33, Cu 7.62, S 3.84%.
Max./min. residual electron 0.57/±0.78
density/e ´ pm±3 ´ 10±6
a) w = 1/[r2)F2o) + )0,0954 ´ P)2]; P = [max)Fo2, 0) + 2 ´ F2c]/3.
b) w = 1/[r2)F2o) + )0,1522 ´ P)2].
IR )Nujol; cm±1): 3442 w )mNH, br), 2757 w, 1729 vw, 1699 s )mC=O),
1614 m )mN=C, imine), 1516 s )mN=C, triazine), 1443 s, 1283 s, 1185 vw,
1152 w, 1092 m, 1077 vw, 1023 w, 1000 vw, 913 w, 847 m, 750 s )mPPh3),
742 w )mPPh3), 697 s )mPPh3), 571 w, 510 m, 500 m, 441 m, 417 m,
345 w )br), 305 w )mCuS), 260 w, 208 m )mCuCl), 149 m )mCuP2).
Table 2 Selected bond lengths/pm and angles/° of 2 and 4a)
[ꢀC4H4N3SONꢀ=CMe2)AgꢀPPh3)2]NO3 ꢀ4). A solution of
Ph3P )0.52 g, 2 mmol) in 20 mL of methanol was added to a
solution of 3 )0.48 g, 1 mmol) in 20 mL methanol/acetone
)1 : 1) and stirred for 2 h at 70±80 °C. The solvent was eva-
pourated to a small volume )ca. 10 mL) to give a colorless
solid. The crude product was filtered off and the clear solu-
tion was kept at room temperature to give colorless crystals
of 4.
2
Cu1±Cl1 238.0)1)
Cu1±S1 237.8)1)
Cu1±P1 227.7)1)
Cu1±P2 230.7)1)
Cl1±Cu1±S1 106.09)5)
Cl1±Cu1±P1 105.35)6)
Cl1±Cu1±P2 104.89)5)
S1±Cu1±P1 109.35)5)
S1±Cu1±P2 103.00)6)
P1±Cu1±P2 126.62)5)
Cu1±S1±C1 106.5)2)
S1±C1±N1 123.7)4)
N1±N2±C5 115.3)4)
C6±C5±C7 117.5)5)
N2±N1±C1 115.3)4)
N2±N1±C2 118.0)5)
C1±N1±C2 124.0)4)
S1±C1
167.7)5)
C1±N1 135.3)6)
N1±N2 143.5)6)
N2±C5 127.2)6)
C5±C6 149.2)7)
C5±C7 149.3)8)
Yield: 0.81 g )91%).
Elemental analysis: C43H40AgN5O4P2S )892.70): calcd
C 57.85, H 4.03, N 7.84, P 6.93, Ag 12.08, S 3.59; found
C 57.21, H 4.03, N 8.09, P 6.71, Ag 11.98, S 3.34%.
4
IR )Nujol; cm±1): 3439 vw )mNH, br), 2731 w, 1700 s )mC=O), 1614 m
)mN=C, imine), 1527 m )mC=N, triazine), 1435 s, 1401 s, 1377 s )E', mNO3),
1298 s, 1250 s, 1196 m, 1174 m, 1152 m, 1098 s, 1073 m, 1043 w, 1030 m,
Ag1±S1 262.9)2)
Ag1±P1 243.0)2)
Ag1±P2 249.0)2)
Ag1±N2 245.9)6)
S1±Ag1±P1 118.24)6)
S1±Ag1±P2 112.64)6)
P1±Ag1±P2 124.33)6)
S1±Ag1±N2 70.6)1)
P1±Ag1±N2 116.9)2)
P2±Ag1±N2 99.6)2)
Ag1±S1±C1 95.0)2)
Ag1±N2±N1 109.1)4)
N1±N2±C5 115.1)5)
N2±C5±C6 115.4)6)
N2±C5±C7 127.1)7)
C6±C5±C7 117.5)7)
O2±N5±O3 118.6)7)
O2±N5±O4 119.7)7)
O3±N5±O4 121.6)8)
N2±N1±C1 116.1)5)
N2±N1±C2 119.3)5)
C1±N1±C2 123.5)6)
1000 m, 977 w, 935 w, 848 w, 825 w )A'', mNO3), 815 w, 761 vs )mPPh3), 750 vs
2
)mPPh3), 742 vs )mPPh3), 695 vs )mPPh3), 636 vw, 618 vw, 588 vw, 576 m,
516 s, 501 s, 498 s, 394 m )br), 286 m )br, mAgN, mAgS), 144 s )mAgP2).
S1±C1
167.3)7)
C1±N1 137.9)9)
N1±N2 141.9)7)
N2±C5 127.9)9)
C5±C6 150)1)
C5±C7 150)1)
O2±N5 127.2)8)
O3±N5 125.6)8)
O4±N5 118.5)9)
Crystal structure analyses of 2 and 4
The crystals of 2 and 4 were covered with a perfluorinated
polyether and mounted on the top of a glass capillary under
a flow of cold gaseous nitrogen. The orientation matrix and
preliminary unit cell dimensions were determined from 15
)CAD4, Enraf-Nonius) reflections )graphite-monochromated
MoKa radiation; k = 71.073 pm). The final cell parameters
were determined from 25 reflections. The intensities were
corrected for Lorentz and polarization effects. In addition
a) Further details can be obtained from the Cambridge Crystallographic
Data Center, 12 Union Road, Cambridge CB21EZ by quoting the num-
bers CCDC 158749 )2) and 158750 )4) )Fax: )+44)12 23-3 36-0 33; e-mail:
deposit@ccdc.cam.ac.uk).
818
Z. Anorg. Allg. Chem. 2001, 627, 815±819

New Copper)I) and Silver)I) Complexes containing Thione Ligands
absorption corrections were performed in both cases )em-
pirical, 10 u-scans, for further details see Table 1). The struc-
tures were solved by direct methods for 2 )SHELXTL [23])
and by the Patterson method for 4 )SHELXTL-Plus [21])
and refined against F2 by full-matrix least-squares using the
program SHELXL-97 [22]. The N±H hydrogen atoms in
both complexes are freely refined. The C±H hydrogen atoms
were calculated for ideal positions and refined with a
common displacement parameter. Used programs were
SHELXTL, SHELXTL-Plus, SHELXL-97, ORTEP [24] and
PLATON-98 [25].
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