Syntheses, characterization and X-ray structure of the first silver(I) complexes with 4-Amino-3-thioxo-3,4-dihydro-1,2,4-triazin-5(2H)-one

Article abstract of DOI:10.1002/zaac.200801417

Reaction of thiocarbohydrazide with glyoxolic acid monohydrate led to 4-amino-3-thioxo-3,4-dihydro-l,2,4-triazin-5(2W)-one (AHTTO, 1). Treatment of 1 with AgNO₃ and PPh₃ gave the complexes [(PPh ₃)₂Ag₂

Full text of DOI:10.1002/zaac.200801417

ARTICLE
DOI: 10.1002/zaac.200801417
Syntheses, Characterization and Xꢀray Structure of the First Silver(I)
Complexes with 4ꢀAminoꢀ3ꢀthioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone
Masoumeh Tabatabaee,*[a] Mitra Ghassemzadeh,[b] and Bernhard Neumüller[c]
Keywords: Nitrogen heterocycles; Sulfur heterocycles; S ligands; N ligands; Silver; Structure elucidation
Abstract. Reaction of thiocarbohydrazide with glyoxolic acid monoꢀ [(PPh3)2Ag(AHTTO)]NO3·MeOH (3) was obtained under different
hydrate led to 4ꢀaminoꢀ3ꢀthioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone conditions. All the compounds have been characterized by elemental
(AHTTO, 1). Treatment of 1 with AgNO3 and PPh3 gave the analyses, IR spectroscopy and Xꢀray diffraction studies.
complexes
[(PPh3)2Ag2(µꢀN,SꢀAHTTO)2](NO3)2
(2)
and
Introduction
There is considerable interest in the coordination chemistry
of heterocyclic thiones. The chemical interest of these thiones
is due to fact that they are potentially ambidentate or multiꢀ
functional using their sulfurꢀ or nitrogen atoms [1]. 1,2,4ꢀThioꢀ
triazines and 1,2,4ꢀthiotriazoles are wellꢀknown heterocyclic
thiones derived from thiocarbohydrazide. Some of their derivaꢀ
tives exhibit biological activity and have been used for various
purposes such as herbicides, neutral antibiotics, antibacterial
agents, etc. [2]. The heterocyclic thione exists in two thione
and thiole tautomeric forms (I and II) as illustrated in
Scheme 1.
Scheme 2. Potential binding modes of AHTTO to metal centers (inꢀ
cluding possible modes for hydrogenꢀbonding selfꢀassembly).
Scheme 1.
Because of the high tendency of silver(I) and copper(I) to
form Metal–Sulfur bonds due to the “Pearson Principle” [4],
we are interested in studying the behavior of these ions toꢀ
wards the above mentioned heterocyclic thiones, especially in
the presence of bulky phosphonic coꢀligands. We reported the
synthesis and characterization of the first copper(I) and silꢀ
ver(I) complexes with ATT (ATT = 6ꢀazaꢀ2ꢀthiothymine) as a
heterocyclic thione ligand [5]. Recently we reported the synꢀ
thesis and characterization of new Schiff base ligands 4ꢀaminoꢀ
6ꢀmethylꢀ1,2,4ꢀtriazinthioxoꢀ5ꢀone (AMTTO) and 4ꢀaminoꢀ3ꢀ
thioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone (AMTT) and their
reaction with silver(I) and copper(I) ions in the presence of
PPh3 as coꢀligand. It has been shown that in the cation of
[Ag(L)(PPh3)2]+, the arrangement around the silver atom (one
sulfur atom from the ligand, two phosphorous atoms from the
coꢀligand and one Ag–N contact) led to a 3+1 coordination
[6].
Therefore, such compounds exhibit various binding modes
to the metal atom (Scheme 2); Sꢀunidentate (A), N,Sꢀchelating
(B), µnꢀN,Sꢀbridging (C, D and E) etc. [3].
* Dr. M. Tabatabaee
Fax: +98ꢀ3518223313
EꢀMail: tabatabaee45m@yahoo.com
Tabatabaee@iauyazd.ac.ir
[a] Department of Chemistry
Islamic Azad University Yazd Branch
P.O. Box 89195ꢀ155 Yazd, Iran
[b] Chemistry & Chemical Engineering Research Center of Iran
P.O. Box 14335ꢀ189 Tehran, Iran
[c] Fachbereich Chemie
Universität Marburg
HansꢀMeerweinꢀStraße
35032 Marburg, Germany
1620
© 2009 WileyꢀVCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 635, 1620–1625

Silver(I) Complexes with 4ꢀAminoꢀ3ꢀthioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone
mixture was stirred at 25 °C for 4 h. The pale yellow precipitate was
The present study aims at the completion of our research on
the complexes of silver(I) with the heterocyclic thione AHTTO
[4ꢀaminoꢀ3ꢀthioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone (1)].
We herein report on the synthesis and characterization of
two complexes with the formulas [(PPh3)2Ag2(µꢀN,Sꢀ
AHTTO)2](NO3)2 (2) and [(PPh3)2Ag(AHTTO)]NO3·MeOH
(3).
filtered off. The clear solution was kept at 4 °C to give colorless crysꢀ
tals of 2. Yield: 0.49 g (85 %). C42H38Ag2N10O8P2S2 (1152.62): calcd.
C 43.73, H 3.30, N 12.15, S 5.55; found C 43.43, H 3.21, N 12.10, S
5.38. IR (Nujol): ν = 3120 [m, b, ν (NH)], 2924 [s, (C–Ar)], 1712 [s,
˜
(νC=O)], 1597 [m, (νC–N, triazine)], 1508, 1461, 1378 [s, (νNO3), E'],
1302, 1182 (m), 1094 (s), 1018 [m, (νC=S)], 877 (m), 820 [m, (νNO3),
A'2], 751 [s, b, ν(P–C)], 694 [s, ν(C–P)], 593 (s), 516 (m), 503 (s),
442 (m) cm–1. 31P NMR (DMSO): δ = 12.8.
[(PPh3)2Ag(AHTTO)]NO3·MeOH (3): A solution of 1 (0.15 g,
1 mmol) in dry methanol (25 mL) was treated with silver nitrate
(0.17 g, 1 mmol) and the reaction mixture was stirred at 25 °C for 3 h
and triphenylphosphane (0.27 g, 1 mmol) in chloroform (5 mL) was
added to it. Reaction mixture was stirred at 25 °C for 2 h. The pale
yellow precipitate was filtered off and the clear solution was kept at
4 °C to give colorless crystals of 3. Yield: 0.39 g (88 %).
C40H38AgN5O5P2S (870.62): calcd. C 55.13, H 4.36, N 8.04, S 3.68;
Experimental Section
General Remarks
AHTTO (1) was prepared according to literature procedures for
AMTTO [7] and has been recrystallized from ethanol. IR spectra were
recorded with a Perkin–Elmer spectrometer 883 or Bruker IFSꢀ88 (KBr
pellets, Nujol mulls, 4000–400 cm–1), 31P NMR spectra were recorded
with a Bruker AC 200 spectrometer using 85 % aqueous H3PO4 as an
external standard. The following chemicals were purchased from
Merck and Fluka and used without further purification: glyoxolic acid
monohydrate, thiocarbohydrazide, silver nitrate, chloroform, methanol
and triphenylphosphane.
found C 55.07, H 4.22, N 7.99, S 3.38. IR (Nujol): ν = 3202 [m, b, ν
˜
(NH)], 2926 [s, (C–Ar)], 1720 [s, (νC=O)], 1584 [m, (νC–N, thioamꢀ
ide)], 1518 [w, (νC=N, triazine)], 1461, 1377 [s, (νNO3), E'], 1303
[m,(νC–N, thioamide)], 1186 (m), 1095 [m, (νC=S)], 889 (w), 822
[w,(νNO3), A'2], 743 [s, ν(P–C)], 723 [s, ν(C–P)], 692 [s, ν(C–P)], 592
(s), 516 (m), 493 (m) cm–1. 31P NMR (DMSO): δ = 10.8.
Syntheses of the Complexes
Crystal Structure Analyses
[(PPh3)2Ag2(µꢀN,SꢀAHTTO)2](NO3)2 (2): A mixture of AHTTO
(0.15 g, 1 mmol), AgNO3 (0.17 g, 1 mmol) and PPh3 (0.27 g, Selected crystals of 1, 2 and 3 were covered with perfluorinated oil
1 mmol)wasdissolvedinmethanol/chloroform(20 mL,1:1)andthereaction and mounted on the tip of a glass capillary under a flow of cold gaseꢀ
Table 1. Crystallographic data for 1, 2 and 3.
Compound
1
2
3
Empirical formula
C3H4N4OS
144.15
C42H38Ag2N10O8S2
1152.63
C40H38AgN5O5.5P2S
870.65
Formula mass
Crystal size /mm
0.36 × 0.33 × 0.21
monoclinic
P21/c
0.32 × 0.25 × 0.1
triclinic
0.27 × 0.17 × 0.14
triclinic
Crystal system
¯
¯
Space group
P1
P1
a /pm
707.3(1)
1308.4(2)
1218.9(1)
90
903.7(1)
1006.4(1)
1390.9(1)
86.20(1)
71.99(1)
68.95(1)
1154.8(2)
1
1180.7(2)
1299.2(2)
1387.9(2)
98.12(1)
112.33(1)
94.10(1)
1931.3(5)
2
b /pm
c /pm
α /°
β /°
103.80(1)
90
γ /°
Volume /pm3´106
1095.4(2)
8
Z
dcalcd. /g·cm–3
1.748
1.657
1.497
Absorption correction
numerical
17.48
numerical
10.7
numerical
7.1
µMo–Kα /cm–1
Temperature /K
183
52.24
173
51.88
173
52.01
2θ range
Index range
h
k
–8→8
–16→16
–14→15
10650
2027 (0.0589)
1640
–11→11
–12→12
–17→17
16449
–14→14
–15→15
–17→17
27328
l
Reflections collected
Unique reflections (Rint)
4494 (0.04)
3811
7492 (0.0559)
5717
Reflections with Fo > 4σ(Fo)
Parameters
195
374
488
R1
0.055
0.0217
0.0521b)
0.48
0.0316
0.0751c)
0.57
wR2 (all data)
0.1478a)
0.722
Largest diff. Peak and hole /e·pm–3´10–6
a) w = 1/[σ2 Fo + (0.1108 P)2]; P = [Max (Fo , O) + 2 Fc ]/3. b) w = 1/[σ2 Fo + (0.0458 P)2]; P = [Max (Fo , O) + 2 Fc ]/3. c) w = 1/[σ2 Fo
2
2
2
2
2
2
2
+ (0.0338 P)2]; P = [Max (Fo , O) + 2 Fc ]/3.
2
2
Z. Anorg. Allg. Chem. 2009, 1620–1625
© 2009 WileyꢀVCH Verlag GmbH & Co. KGaA, Weinheim
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M. Tabatabaee, M. Ghassemzadeh, B. Neumüller
ARTICLE
ous nitrogen. The orientation matrix and the unit cell dimensions were
determined from 4500 (1), 8000 (2) and 10000 (3) reflections (Stoe
IPDS II, graphiteꢀmonochromated MoꢀKα radiation; λ = 71.073 pm).
Results and Discussion
Treatment of 1 with AgNO3 and PPh3 (molar ratio 1:1:1) in
The intensities were corrected for Lorentz and polarization effects. In methanol/chloroform led in a oneꢀpot reaction to the complex
addition, absorption corrections were applied for 1, 2 and 3 (numeriꢀ
cal). The structures were solved by the direct methods for 1, 2
(SHELXSꢀ97 [8]) and 3 (SIRꢀ92 [9]) and refined against F2 by fullꢀ
matrix leastꢀsquares using the program SHELXLꢀ97 [10]. The hydroꢀ
gen atoms in 1 and 2 were included with a free refinement. The hydroꢀ
gen atoms (C–H) in 3 were calculated and refined in calculated posiꢀ
tions with a common displacement parameter (free refinement for H1,
H2 and H3). Programs used were SHELXTLꢀPlus [11], SHELXSꢀ97,
SHELXLꢀ97 and PLATONꢀ98 [12, 13]. Details of the crystal structure
analysis are shown in Table 1 and Table 2.
[(PPh3)2Ag2(µꢀN,SꢀAHTTO)2](NO3)2 (2) [Equation (1)],
whereas the reaction of AgNO3 and AHTTO (molar ratio 1:1)
in methanol, followed by the addition of a solution of PPh3 in
chloroform, led to [(PPh3)2Ag(AHTTO)]NO3·MeOH (3) accordꢀ
ing to Equation (2).
Table 2. Selected bond lengths/pm and bond angles/° in 1, 2 and 3.
1
S1–C1
N1–C1
N1–N2
N1–C2
C2–C3
O1–C2
N3–C3
N3–N4
S2–C4
N5–C4
N5–N6
N5–C5
O2–C5
N7–C6
165.7(3)
138.4(4)
140.6(3)
138.1(4)
145.3(4)
122.8(4)
128.9(4)
134.9(4)
165.8(3)
138.0(4)
140.8(3)
137.6(4)
123.1(4)
129.0(4)
S1–C1–N1
S1–C1–N4
C1–N1–N2
N2–N1–C2
N3–N4–C1
O1–C2–N1
O1–C2–C3
S2–C4–N5
S2–C4–N8
C4–N5–N6
N6–N5–C5
O2–C5–C6
O2–C5–N5
122.6(2)
122.8(2)
118.6(2)
117.5(2)
126.9(3)
120.6(2)
125.7(3)
123.2(2)
122.5(3)
118.1(2)
117.8(2)
125.6(3)
120.8(2)
All synthesized compounds are colorless crystalline solids
and are airꢀstable. IR spectra of 2 and 3 show the bands for
νN–H and νC=O at 2924 (2), 3202 (3) cm–1 and 1712 (2), 1720
(3) cm–1, which were observed at 2985 and 1690 cm–1 in the
IR spectrum of the free ligand [14]. The P–C vibrations as well
as the δC–H vibrations of the PPh3 moiety are observed in the
range 750–694 cm–1 for 2 and in the range 742–692 cm–1 for
–
3. The NO3 anions in 2 and 3 present their N–O asymmetric
stretching mode (E') at 1378 and 1377 cm–1 and their outꢀofꢀ
plane absorptions (A''2) at 820 and 822 cm–1.
2
Ag1–S1
Ag1–S1a
Ag1–N2
Ag1–P1
Ag1···Ag1a
S1–C1
C1–N1
N1–N2
N1–C2
C2–C3
O1–C2
N3–C3
N5–O2
N5–O3
N5–O4
255.01(6)
284.35(6)
234.80(2)
236.66(6)
314.80(5)
169.0(2)
136.9(3)
142.2(2)
140.1(2)
145.1(3)
121.7(3)
128.1(3)
123.9(2)
124.5(3)
123.7(2)
P1–Ag1–N2
S1–Ag1–N2
S1–Ag1–P1
S1–Ag1–S1a
P1–Ag1–S1a
Ag1–S1–C1
Ag1–N2–N1
C1–N1–N2
S1–C1–N1
O2–N5–O3
O2–N5–O4
O4–N5–O2
125.35(5)
77.45(5)
135.89(2)
108.82(2)
102.46(2)
98.66(7)
115.5(1)
119.5(2)
126.1(2)
119.9(2)
120.2(2)
119.9(2)
Description of the Structures
Compound 1
Table 1 shows the crystallographic data of 1, 2 and 3. Seꢀ
lected bond lengths and angles are given in Table 2.
1 crystallizes in the monoclinic space group P21/c. The title
compound consists of two independent molecules of
C3H4N4OS (Figure 1). A medium hydrogen bonding connects
the oxygen atom of one molecule with the NHꢀgroup of the
adjacent one [N4–H3···O2: 288.1(4) pm]. A number of N–
H···O and N–H···N hydrogen bonds are observed in the moleꢀ
cule (Table 3). These coordination modes caused twoꢀdimenꢀ
sional layers parallel to (10–1) (Figure 2).
3
Ag1–S1
Ag1–P1
Ag1–P2
Ag1–N2
S1–C1
C1–N1
N1–N2
N1–C2
C2–C3
O1–C2
N3–C3
N5–O2
N5–O3
N5–O4
264.5(8)
242.8(8)
2.47.3(8)
246.3(3)
167.9(3)
136.1(3)
141.7(3)
139.9(4)
145.5(4)
121.3(4)
127.8(4)
126.5(4)
122.1(5)
123.3(5)
P1–Ag1–P2
P1–Ag1–N2
P2–Ag1–N2
S1–Ag1–P1
S1–Ag1–P2
S1–Ag1–N2
Ag1–S1–C1
Ag1–N2–N1
C1–N1–N2
S1–C1–N1
O2–N5–O3
O2–N5–O4
O4–N5–O2
127.82(3)
120.07(9)
101.36(8)
111.68(3)
110.36(3)
71.87(6)
96.4(9)
110.1(2)
118.9(2)
124.6(2)
121.0(3)
116.7(3)
122.3(4)
Complex 2
In 2, each silver atom is coordinated to the sulfur atom of
the thione group of the ligand, the nitrogen atom of the hydraꢀ
zine moiety and one phosphorous atom of the bulky triphenylꢀ
phosphane molecule, forming a [(µꢀN,SꢀAHTTO)Ag(PPh3)]ꢀ
unit. To complete the coordination sphere around the silver
atom, two of these units dimerize over the sulfur atom to form
a centrosymmetric molecule. In the planar Ag2S2 core, each
silver atom displays a distorted tetrahedral coordination (Figꢀ
ure 3). The coordination mode can be described as form C in
Scheme 2. The Ag1–S1 bond length of 255.01(6) pm is
1622
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Z. Anorg. Allg. Chem. 2009, 1620–1625

Silver(I) Complexes with 4ꢀAminoꢀ3ꢀthioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone
values 242.6–250.4 pm measured for a number of complexes
containing silver atoms coordinated by phosphanes [16b].
Figure 1. Molecular structure of 1 (40 % probability level).
Table 3. Hydrogen bonding in 1.
D–H···A
D···A /pm
N2–H1···N3a
N2–H2···O3a
N4–H3···O2
N6–H4···N7b
N6–H5···O1b
N8–H6···O1c
307.3(4)
303.8(4)
288.1(4)
309.9(4)
313.2(4)
287.8(4)
Figure 3. Molecular structure of the cation of 2 (50 % probability
level).
The Ag–N distance of 234.80(2) pm is in the order expected
for such Ag–N bonds [17a] and are in well agreement with the
Ag–N distances observed for the trinuclear silver(I)ꢀtriphenylꢀ
phosphane complex [Ag3(µꢀbim)3(PPh3)5] (bim = benzimidaꢀ
zole) [17b]. Therefore, the arrangement around the silver atom
in the [(µꢀN,SꢀAHTTO)Ag(PPh3)] subunit can be described as
trigonal planar and the arrangement around the silver atoms in
the dimerized molecule as distorted tetrahedral. The deviation
from perfect tetrahedral coordination is best illustrated by the
P1–Ag1–N2 angle of 125.35(5)° and P1–Ag1–S1 of
135.89(2)° can be accounted for the steric hindrance induced
by the phosphane molecule and by the dimerization of two
subunits, consequently compressing the S1–Ag1–N2 angle to
77.45(5)°.
The Ag1···Ag1a distance of 314.80(5) pm is shorter than the
sum of the van der Waals radii of the silver atoms (170 + 170 =
340 pm). Therefore, a weak dispersive metal–metal contact in
the fourꢀmembered ring might occur [18].
The dihedral angle formed by the planar fourꢀmembered
Ag2S2ꢀcore (A: Ag1/Ag1a/S1/S1a) and the planes through the
fiveꢀmembered metal heterocycle (B: Ag1/S1/C1/N1/N2 10/
–11/6/–13/8 pm) is 77°.
Figure 2. Packing diagram of 1, showing the intermolecular
hydrogen bonds in the twoꢀdimensional layers parallel to the direction
¯
(101).
slightly longer than the observed distance in silver complexes
The dimeric centrosymmetric cations are linked together
with coordination number (c.n.) three (246.4–253.7 pm) [15] through hydrogen bonds between one of the hydrogen atoms
and is slightly shorter than the Ag–S bond lengths in of 256.8– of the NH2ꢀgroup of the heterocycle in the first cation and the
272.1 pm complexes with c.n. four [15e, 16], whereas the oxygen atom of the second one [N2–H2···O1c: 292.1(3) pm,
Ag1–S1a bond length of 284.35(6) is somewhat longer than 168(3)°], directly. In addition, the nitrate ions act as bridging
the maximum distance generally accepted for Ag–S bonds of agents and link the N–H groups of a dimeric centrosymmetric
272.1 pm [17], but it is clearly shorter than the sum of the van cation to the second hydrogen atoms of the NH2ꢀgroups of the
der Waals radii of silver and sulfur (170 + 180 = 350 pm) [18]. adjacent cation using their three oxygen atoms through hydroꢀ
The Ag1–P1 bond length of 238.66(6) pm is shorter than the gen bonds [N4–H3···O2: 297.7(3) pm, N4–H3–O2: 127(2)°,
Z. Anorg. Allg. Chem. 2009, 1620–1625
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M. Tabatabaee, M. Ghassemzadeh, B. Neumüller
ARTICLE
N4–H3···O3: 280.1(3) pm, N4–H3–O3 165(3)° and N2–
H1···O4b: 282.0(3) pm, N2–H1–O4b: 172(3)°]. However,
there is no hint for different N–O bond lengths and O–N–O
bond angles within the standard deviation in the strictly planar
nitrate ions (Table 2). These observations lead to the formation
of a 3D network of cations and anions in 2 (Figure 4).
Figure 5. Molecular structure of 3 (40 % probability level).
In complex 3, one of the oxygen atoms of the nitrate ion
(O2) links the NHꢀgroup of one cation to one of the hydrogen
atoms of the NH2ꢀgroup of the adjacent one through hydrogen
bonding (Scheme 2, N4–H3···O2: 275.2(3) pm and N2–
H1···O2a: 305.6(4) pm) and the same hydrogen atom is also
linked to another oxygen atom of the same nitrate ion [N2–
H1···O4a: 314.0(5) pm]. The hydrogen bonds caused slightly
different N–O bond lengths and O–N–O bond angles within
the standard deviation in the nitrate ions (Table 2). The solvate
molecule acts also as bridging agent and links the second hyꢀ
drogen atom of the NH2ꢀgroup to the oxygen atom of the adjaꢀ
cent solvate molecule through hydrogen bonds [N2–H2···O5:
Figure 4. Packing diagram of 2. Hydrogen bonds lead to formation of
a 3D network of cations and anions in 2.
Complex 3
Complex 3 is an ionic compound, which consists of
[(PPh3)2Ag (AHTTO)]+cations and NO3– anions (Figure 5). In
the cation of 3, the ligand is coordinated to the silver atom
through its sulfurꢀ and nitrogen atom. The distorted tetrahedral
coordination around the metal is completed by two phosphorꢀ
ous atoms of the two phosphane molecules. The deviation from
perfect tetrahedral coordination is best illustrated by the P1–
Ag1–P2 angle of 127.82(3)° and can be accounted for the
steric hindrance induced by the two phosphane molecules, conꢀ
sequently compressing the S1–Ag1–N2 angle to 71.87(6)°.
The Ag–S bond length of 264.54(8) pm is longer than the Ag–
S distances found in silver complexes with c.n. three (246.4–
253.7 pm) and lies in the range of c.n. four silver complexes
(256.8–272.1 pm) [16b, 17]. The Ag–P bond lengths of
242.85(8) and 247.32(8) pm are in the range of AgI complexes
containing two PPh3 molecules [6c, 6f]. The Ag–N distance of
246.30(3) pm is clearly longer than the generally as typical
accepted Ag–N distance of 234 pm [17a]. It compare well with
the Ag–N distance of 245.9(2) pm observed in the silver comꢀ
plex with the modified AMTTO–acetone ligand [6a], but it is
clearly shorter than the sum of van der Waals radii of silver
and nitrogen (170 + 155 = 325 pm) [18]. Therefore, the coordiꢀ
nation around silver atom can be described as 3 + 1.
Figure 6. Packing diagram of 3. hydrogen bonds linking layers parallel
to [010].
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© 2009 WileyꢀVCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1620–1625

Silver(I) Complexes with 4ꢀAminoꢀ3ꢀthioxoꢀ3,4ꢀdihydroꢀ1,2,4ꢀtriazinꢀ5(2H)ꢀone
45, 10998; d) R. M. Silva, M. D. Smith, J. R. Gardinier, Inorg.
Chem. 2006, 45, 2132; e) J. Bailey, M. Lanfranchi, L. Marchiò,
S. Parsons, Inorg. Chem. 2001, 40, 5030.
299.4(6) pm, N2–H2–O5: 137(3)° and O5–H4···O5b: 305.9(7)
pm, O5–H4–O5b: 133°]. There also exists intramolecular hyꢀ
drogen bonding between the oxygen atom of the heterocycle
and the endocyclic NHꢀgroup [N2–H2···O1: 269.6(4) pm, N2–
H2–O1: 113(3)°]. This coordination mode is responsible for
the formation of layers parallel to (010) (Figure 6). The diheꢀ
dral angle formed by the planes of A and B (A: Ag1/N2/S1
and B: S1/C1/N1/N2 5/1/–2/–7 pm) is 142°. The solvate moleꢀ
cule is disordered at two positions, which are refined with the
occupation parameter 0.6/0.4 for C41/C42.
In both complexes, the C1–S1 and N1–N2 bond lengths
[169.0(2) pm and 142.2(2) pm for 2 and 167.9(3) pm and
141.7(3) pm for 3] are slightly longer than the observed bond
lengths in the free ligand [C1–S1: 165.7(3) pm and N1–N2:
140.6(3) pm]. These bond lengthenings are caused by the coorꢀ
dination of the sulfur atom and the hydrazine nitrogen atom to
the metal atoms. No further difference is observed in all other
bond lengths comparing free heterocycles and the complexes.
[5] M. Ghassemzadeh, M. M. Pooramini, M. Tabatabaee, M. M. Herꢀ
avi, B. Neumüller, Z. Anorg. Allg. Chem. 2004, 630, 403.
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müller, Z. Anorg. Allg. Chem. 2001, 627, 815; b) M. Ghassemzaꢀ
deh, M. Tabatabaee, S. Solimani, B. Neumüller, Z. Anorg. Allg.
Chem. 2005, 631, 1871; c) M. Ghassemzadeh, M. Tabatabaee,
M. M. Pooramini, M. M. Heravi, A. Eslami, B. Neumüller, Z.
Anorg. Allg. Chem. 2006, 632, 786; d) M. Tabatabaee, M. Ghasꢀ
semzadeh, B. Zarabi, B. Neumüller, Z. Naturforsch. 2006, 61b,
1421; e) M. Tabatabaee, M. Ghassemzadeh, B. Zarabi, M. M.
Heravi, M. AnaryꢀAbbasinejad, B. Neumüller, Phosphorus Sulfur
Silion Relat. Elements 2007, 182, 677; f) M. Ghassemzadeh, A.
Sharifi, J. Malakootikhah, B. Neumüller, E. Iravani, Inorg. Chim.
Acta 2004, 357, 2245.
[7] A. Dornow, H. Menzel, P. Marx, Chem. Ber. 1964, 97, 2173.
[8] G. M. Sheldrick, SHELXS 97, Göttingen, 1997.
[9] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. C.
Burla, G. Polidori, M. Camalli, SIR 92, Bari, Perugia, Rome,
1992.
[10] G. M. Sheldrick, SHELXL 97, Göttingen, 1997.
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Acknowledgement
The authors are grateful to Islamic Azad University, Yazd Branch for
the support of this work.
[12] A. L. Spek, PLATON 98, Utrecht, 1998.
[13] Further details can be obtained free of charge on application to
the Cambridge Crystallographic Data Center, 12 Union Road,
Cambridge CB2 1EZ, U. K. [Fax: + 441223 336033; Eꢀmail: deꢀ
posit@ccdc.cam.ac.uk] quoting the depository nos. CCDCꢀ
679273 (1), ꢀ679274 (2) and ꢀ679275 (3).
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Received: December 24, 2008
Published Online: July 8, 2009
Z. Anorg. Allg. Chem. 2009, 1620–1625
© 2009 WileyꢀVCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wileyꢀvch.de
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