Synthesis and characterization of new AMTTO-imine-ligands and their silver(I) complexes: Crystal structures of TAMTTO, [Ag2(TAMMTO) 4](NO3)2·4MeOH, [Ag(TAMTTO)(PPh 3)2]NO3·1.5THF, [Ag(FAMTTO)(PPh 3)2]NO3

Article abstract of DOI:10.1016/j.ica.2004.01.027

Reaction of 4-amino-6-methyl-1,2,4-triazin-thione-5-one (AMTTO, 1) with 2-thiophenecarboxaldehyde and 2-furaldehyde led to the corresponding iminic compounds 6-methyl-4-[thiophene-2-yl-methylene-amino]-3-thioxo-[1,2,4]-triazin- 3,4-dihydro(2H)-5-one (TAMTTO, 2) and 4-[furan-2-yl-methylene-amino]-6-methyl-3- thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (FAMTTO, 3). Treatment of 2 with AgNO₃ gave the complex [Ag₂(TAMMTO)₄](NO ₃)₂·4MeOH (4) and of 2 and 3 with [Ag(PPh ₃)₂]NO₃ gave the complexes [Ag(TAMTTO)(PPh ₃)₂]NO₃·1.5THF (5) and [Ag(FAMTTO)(PPh₃)₂]NO₃ (6), respectively. All the compounds have been characterized by elemental analyses, IR spectroscopy and mass spectrometry. Compound 2 and all the complexes have been characterized by X-ray diffraction studies, respectively. In addition, 5 and 6 have been characterized by ³¹P NMR spectroscopy. Crystal data for 2 at -80°C: monoclinic, space group C2/c, a=2319.6(2), b=609.8(1), c=1673.6(2) pm, β=106.14(1)°, Z=8, R₁=0.0523; for 4 at -80°C: triclinic, space group P1?, a=877.6(1), b=1085.2(1), c=1557.7(2) pm, α=77.14(1)°, β=80.87(1)°, γ=78.18(1)°, Z=1, R ₁=0.0407; for 5 at 20°C: triclinic, space group P1?, a=1151.1(2), b=1225.1(2), c=1887.4(3) pm, α=78.04(1)°, β=86.20(1)°, γ=76.03(1)°, Z=2, R₁=0.0662; for 6 at -80°C: triclinic, space group P1?, a=1189.7(2), b=1387.8(2), c=1410.9(2) pm, α=94.74(2)°, β=95.12(2)°, γ=112.41(2)°, Z=2, R₁=0.0511.

Full text of DOI:10.1016/j.ica.2004.01.027

Inorganica Chimica Acta 357 (2004) 2245–2252
www.elsevier.com/locate/ica
Synthesis and characterization of new AMTTO-imine-ligands
and their silver(I) complexes: crystal structures of
TAMTTO, [Ag2(TAMMTO)4](NO3)2 ꢀ 4MeOH,
[Ag(TAMTTO)(PPh3)2]NO3 ꢀ 1.5THF, [Ag(FAMTTO)(PPh3)2]NO3
a,
Mitra Ghassemzadeh , Ali Sharifi , Javad Malakootikhah , Bernhard Neumuller ,
a
a
b
*
€
b
Effat Iravani
a
Inorganic Chemistry, Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Soheil Str. 657,
Shiraz Str., Vanak Tehran, Iran
b
Fachbereich Chemie der Universitaet Marburg, Marburg 35032, Germany
Received 16 August 2003; accepted 28 January 2004
Available online 24 March 2004
Abstract
Reaction of 4-amino-6-methyl-1,2,4-triazin-thione-5-one (AMTTO, 1) with 2-thiophenecarboxaldehyde and 2-furaldehyde led to
the corresponding iminic compounds 6-methyl-4-[thiophene-2-yl-methylene-amino]-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one
(TAMTTO, 2) and 4-[furan-2-yl-methylene-amino]-6-methyl-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (FAMTTO, 3). Treat-
ment of 2 with AgNO3 gave the complex [Ag2(TAMMTO)4](NO3)2 ꢀ 4MeOH (4) and of 2 and 3 with [Ag(PPh3)2]NO3 gave the
complexes [Ag(TAMTTO)(PPh3)2]NO3 ꢀ 1.5THF (5) and [Ag(FAMTTO)(PPh3)2]NO3 (6), respectively. All the compounds have
been characterized by elemental analyses, IR spectroscopy and mass spectrometry. Compound 2 and all the complexes have been
characterized by X-ray diffraction studies, respectively. In addition, 5 and 6 have been characterized by 31P NMR spectroscopy.
Crystal data for 2 at )80 °C: monoclinic, space group C2=c, a ¼ 2319:6ð2Þ, b ¼ 609:8ð1Þ, c ¼ 1673:6ð2Þ pm, b ¼ 106:14ð1Þ°, Z ¼ 8,
ꢀ
R1 ¼ 0:0523; for 4 at )80 °C: triclinic, space group P1, a ¼ 877:6ð1Þ, b ¼ 1085:2ð1Þ, c ¼ 1557:7ð2Þ pm, a ¼ 77:14ð1Þ°, b ¼ 80:87ð1Þ°,
ꢀ
c ¼ 78:18ð1Þ°, Z ¼ 1, R1 ¼ 0:0407; for 5 at 20 °C: triclinic, space group P1, a ¼ 1151:1ð2Þ, b ¼ 1225:1ð2Þ, c ¼ 1887:4ð3Þ pm,
ꢀ
a ¼ 78:04ð1Þ°, b ¼ 86:20ð1Þ°, c ¼ 76:03ð1Þ°, Z ¼ 2, R1 ¼ 0:0662; for 6 at )80 °C: triclinic, space group P1, a ¼ 1189:7ð2Þ,
b ¼ 1387:8ð2Þ, c ¼ 1410:9ð2Þ pm, a ¼ 94:74ð2Þ°, b ¼ 95:12ð2Þ°, c ¼ 112:41ð2Þ°, Z ¼ 2, R1 ¼ 0:0511.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Triazines; S-ligands; Silver; Self-assembly; Crystal structure
1. Introduction
for various purposes such as herbicides, neutral antibi-
otics, antibacterial, etc. The heterocyclic thione exists in
two thione and thiole tautomeric forms and there has
been considerable interest in the coordination properties
of both the neutral thione and of the deprotonated thiol
ligand [3].
Metal complexes of sulfur–nitrogen chelating agents
were reviewed in 1974 [1] and the particular features of
sulfur as a donor atom have been discussed in some
detail in an earlier review [2].
1,2,4-Triazines are well-known heterocyclic thiones
derived from thiocarbo-hydrazide, which some of their
derivatives exhibit biological activity and have been used
It has been found that the thione coordinates exclu-
sively via S atom [3b], while the thiolate shows a variety
of possibilities, namely (I) S-unidentate, (ii) S,N-che-
lating [3b,4,5], (iii) S,N-bridging [4,6] and (iv) S-unid-
entate (with a weak Mꢀ ꢀ ꢀN interaction) [7].
* Corresponding author. Tel.: +98-21-803-61-44; fax: +98-21-803-71-
In our investigations, we have shown that the AM-
TTO reacts with palladium(II) halides such as chloride,
85.
E-mail address: mghassemzadeh@ccerci.ac.ir (M. Ghassemzadeh).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.01.027

2246
M. Ghassemzadeh et al. / Inorganica Chimica Acta 357 (2004) 2245–2252
bromide and iodide as a S,N-chelating ligand [8] and
with silver(I) nitrate according to the ‘‘Pearson Princi-
ples’’ [9] as a unidentate one via its sulfur atom with a
weak Agꢀ ꢀ ꢀN interaction, which leads to a 2 + 2 coor-
dination on the silver atom [10]. We have also studied
the behavior of the AMTTO to the homologous Cu(I)
and Cu(II) ions and found that the AMTTO reacts with
Cu(I) as a monodentate in a ratio 2:1, while it reacts
with Cu(II) as a bidentate one in a ratio of 1:1. In the
latter complex, the ligand occupied two equatorial po-
sitions in the Jahn–Teller distorted streched octahedron
[10c]. We have also studied the behavior of the synthe-
sized complexes against the nucleophile PPh3.
thioamide), 1272, 1045 (mC@S), 935, 854, 793, 771, 732,
720, 629, 588, 569, 514. MS (70 eV) m=z (%): 252(31)[Mþ],
253(13)[Mþ+1], 143(40), 110(55), 102(48), 96(44), 83(14),
70(34), 69(100), 59(35), 56(18), 45(23), 42(34), 39(32),
1
27(22). H NMR (DMSO-d6): d ¼ 2:19 (s, 3H, CH3),
7.14–7.18 (dd, 1H, H-2), 7.58–7.61 (dd, 1H, H-3), 7.74
(dd, 1H, H-1), 8.61 (d, 1H, H-imine), 12.65 (bs, 1H, NH-
thione). 13C NMR (DMSO-d6): d ¼ 16:55 (CH3), 128.29
(C-2), 133.32(C-1), 135.48(C-3), 136.17(C-4), 146.90
(CH@N, imine), 149.60 (C@N, triazine), 166.41 (C@O),
170.50 (C@S).
2.2.2. Synthesis of FAMTTO (3)
As part of our continuing interest in the syntheses
and characterization of heterocyclic thione complexes of
transition metals, specially silver(I), we wish to report on
further thione argentanacycles.
Compound 3 was synthesized by a similar procedure
used for 2 using the following amounts: 1 (0.95 g, 6
mmol), furfural-2-carboxaldehyde (1.73 g, 18 mmol,
1.50 mL), 10 drops HCl in MeOH, refluxing time 7.5 h.
Yield: 1.16 g (81%). mp.: 186.8°, Anal. Calc. for
C9H8N4O2S (236.25): C, 45.75; H, 3.41; N, 23.71; S,
13.57. Found: C, 45.54; H, 3.45; N, 22.95; S, 12.64%. IR
2. Experimental
~
2.1. General remarks
(Nujol): t ¼ 3232, 3092 [(NH)], 2982 (C–Ar), 1702
(C@O), 1671, 1613 (C@N, imine), 1547 (C–N, thioam-
ide), 1500 (C@N, triazine), 1477, 1427, 1407, 1378, 1338
(C–N, thioamide), 1287, 1261, 1018 (C@S), 935, 757
(C@S), 730, 436, 407, 354, 333, 313, 270, 238, 214, 186,
113. MS (70 eV) m=z (%): 236(78)[Mþ], 237(18)[Mþ + 1],
143 (35), 110(9), 102(83), 96(54), 93(37), 69(100), 59(22),
AMTTO (1) was prepared according to the literature
procedure [11]. Solvents were purified by standard
methods [12]. IR spectra were recorded on a Perkin–
Elmer spectrometer 883 (KBr pellets, Nujol mulls, 4000–
250 cmꢁ1) or on a Bruker IFS 88 instrument (CsBr discs,
4000–400 cmꢁ1; polyethylene discs, 500–100 cmꢁ1; Nu-
1
52(45), 42(43), 39(34), 29(9), 27(17). H NMR (DMSO-
d6): d ¼ 2:25 (s, 3H, CH3), 7.08 (m, 1H, H-2), 7.12 (d,
1
jol mulls). H, 13C and 31P NMR were recorded on a
Bruker AC 200 spectrometer using TMS and 85%
aqueous H3PO4 as an external standard. 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; silver: decomposition with
HClO4 and X-ray fluorescence analysis. The following
chemicals were purchased from Merck and Fluka and
used without further purification: silver nitrate, furfural-
2-carboxaldehyde, 2-thiophenecarboxaldehyde, metha-
nol, triphenylphosphane.
1H, H-3), 7.51 (d, 1H, H-1), 8.24 (s, 1H, H-imine).
2.2.3. Synthesis of [Ag2(TAMMTO)4](NO3)2 ꢀ 4MeOH
(4)
A solution of 2 (0.50 g, 2 mmol) in dry methanol (25
mL) was treated with silver nitrate (0.17 g, 1 mmol) and
the yellow reaction mixture was stirred at 25 °C for 2 h and
refluxed for further 6 h. The yellow precipitate was filtered
off and washed with cold dry methanol (10 mL). The clear
solution was kept at 4 °C to give colorless crystals of 4.
Yield: 1.21 g (91%). Anal. Calc. for C36H32Ag2N18-
O10S8 (1349.01): C, 32.05; H, 2.39; N, 18.68; S, 19.01.
Found: C, 31.98; H, 2.41; N, 18.99; S, 18.88%. IR
~
2.2. Synthesis of the ligands and complexes
(Nujol): t ¼ 3072 [m(NH)], 2922 (C–Ar), 1673 (mC@O),
1625 (mC@N, imine), 1575 (mC–N, thioamide), 1518
(mC@N, triazine), 1460, 1376 (mNO3), 1298 (mC–N, thi-
oamide), 1281, 1203, 1178, 1079 (mC@S), 865 (C–S–C,
thiophene), 802 (mNO3), 741 (C@S), 724, 480, 435, 404,
2.2.1. Synthesis of TAMTTO (2)
A solution of 1 (0.95 g, 6 mmol) in MeOH (40 mL) was
treated with 2-thiophenencarboxaldehyde (2.01 g, 18
mmol) and the resulting mixture was acidified with 10
drops of hydrochloric acid (37.5%). The reaction mixture
was refluxed for 9 h. The white precipitate formed was
filtered off and was recrystallized from EtOH/THF. Yield:
1.21 g (80%). mp.: 231°. Anal. Calc. for C9H8N4OS2
(252.31): C, 42.84; H, 3.20; N, 22.20. Found: C, 43.05; H,
1
343 (mAg–S), 301 (mAg–S), 262, 195, 166, 139. H NMR
(DMSO-d6): d ¼ 2:14 (s, 3H, CH3), 7.22–7.24 (dd, 1H,
H-2), 7.78–7.80 (d, 1H, H-3), 7.94–7.99 (d, 1H, H-1),
8.77 (s, 1H, H-imine), 9.88(s, 1H, NH-thione).
2.2.4. Synthesis of [Ag(TAMMTO)(PPh3)2](NO3) ꢀ
1.5THF (5)
A solution of 2 (0.23 g, 1 mmol) in dry methanol (40
mL) was treated with [Ag(PPh3)2]NO3 (produced in situ
~
3.68; N, 21.98%. IR (Nujol): t ¼ 3146 [(NH)], 2923, 2854
(C–Ar), 1670 (mC@O), 1617 (C@N, imine), 1593 (C–N,
thioamide), 1520 (C@N, triazine), 1462, 1377, 1324 (C–N,

M. Ghassemzadeh et al. / Inorganica Chimica Acta 357 (2004) 2245–2252
2247
from silver nitrate (0.17 g, 1 mmol) and triphenyl
phosphane (0.52 g, 2 mmol) in dry methanol (20 mL))
and the reaction mixture was stirred at 25 °C for 1 h and
refluxed for further 5 h. The yellowish precipitate was
filtered off and washed with cold dry MeOH (15 mL)
and dried in vacuo. Single crystals of 5 suitable for X-
ray diffraction can be obtained from the solution of solid
effects. In addition, absorption corrections were applied
for 2, 4 and 6 (numerical) and for 5 (empirical, 10 psi-
scans). The structures were solved by the direct methods
for 2 (SHELXS-97 [13]), for 4 and 5 (SIR-92 [14]) and by
Patterson method for 6 (SHELXTL-Plus [15]) and refined
against F 2 by full-matrix least-squares using the pro-
gram SHELXL-97 [16]. The hydrogen atoms (C–H) in 4–
6 were calculated in ideal positions (refinement with a
common displacement parameter). The hydrogen atoms
of NH- and OH-groups were fixed at 85 pm (4) or freely
in THF. Yield: 1.21
g (91%). Anal. Calc. for
C45H38AgN5O4P2S2 (946.76): C, 57.07; H, 4.04; N, 7.39;
S, 6.77; Ag, 11.39. Found: C, 56.80; H, 4.18; N, 7.27; S,
~
6.68; Ag, 10.90%. IR (Nujol): t ¼ 3052 [s, m(NH)], 1700
refined (2, 5 and 6). Programs used were SHELXTL-Plus,
1
[s, m(C@O)], 1674 (w), 1608 [w, m(C@N, imine)], 1581 [s,
m(C–N, thioamide)], 1529 [m, mC@N, triazine)], 1479 (s),
1434 (m), 1410 (m), 1379 [w, (mNO3), E0], 1298 [w, d(C–
N, thioamide)], 1094 [s, m(C@S)], 1027 (w), 996 (w), 850
(w), 823 [s, m(NO3), A020], 748 [s, m(P–C)], 694 [s, m(C–P)],
618 (vw), 514(s), 503 (vw), 489 (w), 440 (s), 347 (w), 311
(s), 272 [m, m(Ag–N)], 215 [m, m(Ag–S)], 192 (m), 159
(w), 130 [m, m(AgP2)]. 31P NMR (THF): d ¼ 12:8.
SHELXL-97, SHELXS, ORTEP [17], and PLATON [18].
3. Results and discussion
3.1. Syntheses and characterization of 2–6
Treatment of 1 with 2-thiophenecarboxaldehyde and
2-furaldehyde in dry methanol under reflux conditions
gave the corresponding iminic compounds 2 and 3
2.2.5. Synthesis of [Ag(FAMMTO)(PPh3)2](NO3) (6)
A solution of 3 (0.25 g, 1 mmol) in dry dichlorome-
thane was treated with [Ag(PPh3)2]NO3 (produced in
situ from silver nitrate (0.17 g, 1 mmol) and triphenyl
phosphane (0.52 g, 2 mmol) in dry dichloromethane)
and the reaction mixture was stirred at 25 °C for 1 h.
The yellowish precipitate was filtered off and washed
with cold dry methanol (10 mL) and dried in vacuo.
Suitable single crystals for X-ray diffraction can be ob-
tained from a methanolic solution of 6 at 4 °C. Yield:
0.78 g (84%). Anal. Calc. for C45H38AgN5O5P2S
(930.70): C, 58.07; H, 4.11; N, 7.52; S, 3.44; Ag, 11.58.
Found: C, 57.94; H, 4.18; N, 7.38; S, 3.37; Ag, 11.34%.
CHR
N
N
NH2
N
O
S
H
O
S
H
MeOH, HCl
reflux
H2O
+
+
RCHO
N
S
N
H3C
N
H
3C
N
,
3: R =
2: R =
1
O
ð1Þ
Compound 4 can be obtained by the reaction of 2
with AgNO3 in the molar ratio 2:1 in dry MeOH at 50°
dry MeOH
42 þ 2AgNO3
ƒƒƒƒƒ!
½Ag2ðTAMTTOÞ ꢂðNO3Þ ꢀ 4MeOH
ð2Þ
~
IR (Nujol): t ¼ 3138 [(NH)], 3052, 2987 (C–Ar), 1705
4
2
4
(C@O), 1612 (C@N, imine), 1578 (C–N, thioamide),
1537 (C@N, triazine), 1479, 1434, 1401, 1378 (mNO3),
1344 (C–N, thioamide), 1283, 1094 (C@S), 1027, 823
(NO3), 770, 749 (C@S), 725, 695 (C–P, PPh3), 586, 516
(C–P, PPh3), 502 (C–P, PPh3), 488, 439, 406, 360, 322,
264 (Ag–N), 216 (Ag–S), 128 (Ag–P). 31P NMR (THF):
d ¼ 13:5.
Treatment of [Ag(PPh3)2]NO3 with 2 and 3 in a
molar ratio of 1:1 led to the complexes 5 and 6
dry MeOH=THF
2 þ ½AgðPPh3Þ ꢂNO3
ƒƒƒƒƒƒƒƒ!
2
½ðTAMTTOÞAgðPPh3Þ ꢂNO3 ꢀ 1:5THF
ð3Þ
2
5
dry MeOH
3 þ ½AgðPPh3Þ ꢂNO3
ƒƒƒƒ!
2
2.3. Crystal structure analyses of 2, 4–6 (Tables 1 and 2)
½ðFAMTTOÞAgðPPh3Þ ꢂNO3
ð4Þ
2
6
The selected crystals of 2, 4–6 were covered with a
perfluorinated oil and mounted on the tip of a glass
capillary under a flow of cold gaseous nitrogen. The
orientation matrix and preliminary unit cell dimensions
were determined from 2000 (2, Stoe IPDS), 2000 (4, Stoe
IPDS), 15 (5, Enraf-Nonius CAD 4) and 2000 (6, Stoe
IPDS) reflections (graphite-monochromated Mo Ka
radiation in all cases; k ¼ 71:073 pm). The final cell
parameters were determined from 8000 for 2, from
10 000 for 4, from 25 for 5 and from 8000 for 6. The
intensities were corrected for Lorentz and polarization
All synthesized compounds are colorless crystalline
solids and are air-stable.
IR spectra of 4–6 show the bands for mNH and mC@O
at 3072, 3053 and 3138 cmꢁ1 and 1673, 1700 and 1705
cmꢁ1 [19].
1
Further details can be obtained free of charge on application to the
Cambridge Crystallographic Data Center, 12 Union Road, Cambridge
CB2 1EZ, UK. [Fax: (internat.) +44 (0)1223 336033; E-mail: deposite
@ccdc.cam.ac.uk] quoting the depository CCDC nos. 231184 (2),
231186 (4), 231185 (5) and 231187 (6).

2248
M. Ghassemzadeh et al. / Inorganica Chimica Acta 357 (2004) 2245–2252
Two absorption bands at 301 and 347 cmꢁ1 for 4 and
atoms exhibit a delocalization of p-electrons. The
142.0(3) pm for C1–N1 is the highest, 128.0(3) pm for
C3–N3 is the lowest value inside the ring and the ring
atoms possess a planar coordination geometry. The
bond lengths 166.4(2) pm for S1–C1 and 120.1(3) pm for
O1–C2 are significant for a high double bond character.
The similar distances are observed in 1 [8a]. The bond
length C5–N2 with 126.7(3) pm lies in the range ob-
served in similar compounds such as 2-acetylthiophene
thiosemicarbazone (129.2(3) pm) and 2-acetylthiophene
4-phenyl thiosemicarbazone (128.2(3) pm) [20].
two absorption bands at 311 and 323 cmꢁ1 for 5 and 6
can be assigned to m(AgS). The P–C vibrations as well as
the d-CH vibrations of the PPh3 moiety are seen in the
range 748–694 cmꢁ1 ꢁfor 5 and in the range 749–695
cmꢁ1 for 6. The NO3 anions in 4–6 present their N–O
asymmetric streching mode (E0) at 1374, 1379 and 1378
cmꢁ1 and their out-of-plane absorptions (A020) at 865, 823
and 823 cmꢁ1. Consistently, with the structure of 5 and
6 only a sharp singlet resonance at 12.8 ppm and 13.5
were observed in the 31P{1H} NMR spectra.
A weak hydrogen bonding links the sulfur atom of
one molecule to the NH-group of the adjacent one (N4–
H1ꢀ ꢀ ꢀS1 332.2(2) pm) and is responsible for the cen-
trosymmetric geometry of 2.
3.2. X-ray structures
3.2.1. Compound 2
Table 1 shows the crystallographic data of 2, 4–6.
Selected bond lengths and angles are given in Table 2.
Compound 2 crystallizes in the monoclinic space group
C2=c. The basic six-membered ring skeleton is planar,
while the dihedral angle between the best planes through
the six-membered ring and the thioheterocycle is 62°
(Fig. 1). The distances between the six-membered ring
3.2.2. Complex 4
The Ag atom in the cation is coordinated to the sulfur
atoms of the two ligands and the sulfur atom of the
thiofural hetero ring of the adjacent complex, which is
responsible for the dimer complex (Fig. 2).
Table 1
Crystallographic data for 2, 4–6
Compound
Empirical formula
Formula mass
Crystal size (mm)
Crystal system
Space group
a (pm)
b (pm)
c (pm)
a (°)
b (°)
2
4
5
6
C9H8N4OS2
252.31
0.65 ꢃ 0.4 ꢃ 0.4
monoclinic
C2=c
2319.6(2)
609.8(1)
1673.6(2)
90
C40H48Ag2N18O14S8
1477.15
C51H50AgN5O5:5P2S2
1054.92
C45H38AgN5O5P2S
930.70
0.36 ꢃ 0.26 ꢃ 0.1
0.45 ꢃ 0.45 ꢃ 0.2
0.53 ꢃ 0.54 ꢃ 0.26
triclinic
ꢀ
triclinic
ꢀ
triclinic
ꢀ
P1
P1
P1
877.6(1)
1085.2(1)
1557.7(2)
77.14(1)
80.87(1)
78.18(1)
1405.7(3)
1
1151.1(2)
1225.1(2)
1887.4(3)
78.04(1)
86.20(1)
76.03(1)
2526.5(7)
2
1189.7(2)
1387.8(2)
1410.9(2)
94.74(2)
95.12(2)
112.41(2)
2127.7(6)
2
106.14(1)
90
c (°)
Volume (pm3 ꢃ 106)
2274.0(5)
8
1.474
Z
Dcalcd: (g cmꢁ3
)
1.745
1.387
1.453
Absorption correction
Mo Ka (cmꢁ1
Temperature (K)
numerical
4.5
193
numerical
10.7
193
empirical
6.0
293
numerical
6.5
193
)
2h range
Index range
51.81
52.49
50.02
51.90
h
k
)28 ! 28
)7 ! 7
)20 ! 20
10 598
)10 ! 10
)13 ! 13
)19 ! 19
20 589
)13 ! 13
0 ! 14
)21 ! 21
10 276
)14 ! 14
)17 ! 17
)17 ! 17
20 973
l
Reflections collected
Unique reflections (Rint
)
2116 (0.0481)
1647
177
5646 (0.0792)
4604
391
8826(0.0751)
5129
552
7721(0.063)
5524
511
Reflections with Fo > 4rðFoÞ
Parameters
R1
0.0523
0.1311a
0.0407
0.1130b
0.77
0.0662
0.1777c
0.46
0.0511
0.1351d
1.09
wR2 (all data)
Largest difference peak and hole 0.43
((e pmꢁ3) ꢀ 10ꢁ6
)
2
a w ¼ 1=½r2ðFo2Þ þ ð0:1001PÞ ꢂ; P ¼ ½maxðFo2; 0Þ þ 2Fc2ꢂ=3.
2
b w ¼ 1=½r2ðFo2Þ þ ð0:0772PÞ ꢂ; P ¼ ½maxðFo2; 0Þ þ 2Fc2ꢂ=3.
2
c w ¼ 1=½r2ðFo2Þ þ ð0:0637PÞ þ ð4:57PÞꢂ; P ¼ ½maxðFo2; 0Þ þ 2Fc2ꢂ=3.
2
d w ¼ 1=½r2ðFo2Þ þ ð0:0501PÞ ꢂ; P ¼ ½maxðFo2; 0Þ þ 2Fc2ꢂ=3.

M. Ghassemzadeh et al. / Inorganica Chimica Acta 357 (2004) 2245–2252
2249
Table 2
Selected bond lengths (pm) and bond angles (°) in 2, 4–6
2
4
5
6
S1–C1
C1–N1
C1–N4
N1–N2
N2–C5
C5–C6
C6–S2
S2–C9
C2–O1
166.4(2) Ag1–S1
137.0(3) Ag1–S3
134.5(3) S1–C1
142.0(3) S3–C10
126.7(3) C1–N1
143.7(3) N1–N2
171.9(3) N2–C5
171.0(3) C5–C6
120.1(3) C6–S2
S2–C9
248.64(9) N6–C14
246.69(9) C14–C15
129.6(4)
143.3(4)
170.8(3)
168.7(4)
314.77(7)
125.6(4)
122.8(4)
120.9(4)
141.9(5)
141.0(5)
287.92(8)
Ag1–S1
Ag1–P1
Ag1–P2
Ag1ꢀ ꢀ ꢀN2
S1–C1
259.2(2)
245.8(2)
250.7(2)
267.5(6)
168.1(7)
135.2(8)
143.4(7)
128.9(8)
144.3(9)
171.3(7)
170.6(8)
122.1(9)
122.2(9)
118.9(9)
Ag1–S1
Ag1–P1
Ag1–P2
Ag1–N2
S1–C1
263.9(1)
243.6(1)
244.9(1)
250.4(4)
167.6(5)
137.6(5)
143.3(4)
125.6(6)
143.7(6)
136.8(6)
136.0(5)
127.7(6)
123.0(5)
120.3(6)
168.8(3)
168.9(3)
136.7(4)
142.5(3)
129.1(4)
143.4(4)
172.5(3)
170.9(3)
136.9(4)
141.8(4)
C15–S4
S4–C18
Ag1ꢀ ꢀ ꢀAg1a
N9–O3
C1–N1
N1–N2
N2–C5
C5–C6
C6–S2
C1–N1
N1–N2
N2–C5
C5–C6
C6–O2
O2–C9
N5–O3
N5–O4
N5–O5
N9–O4
N9–O5
O6–C19
O7–C20
Ag1–S2A
C10–N5
N5–N6
S2–C9
N5–O2
N5–O3
N5–O4
S1–C1–N1
S1–C1–N4
123.7(2) S1–Ag1–S3
121.8(2) S2A–Ag–S3
159.88(3) S3–C10–N5
104.58(3) C10–N5–N6
95.51(3) N5–N6–C14
124.4(2)
117.4(2)
113.1(3)
119.8(3)
121.7(3)
91.4(2)
P1–Ag1–P2
P2–Ag1–S1
S1–Ag1–P1
Ag1–S1–C1
C1–N1–N2
N1–N2–C5
N2–C5–C6
C6–S2–C9
O2–N5–O3
O3–N5–O4
O4–N5–O2
123.72(6) P1–Ag1–P2
108.99(6) P2–Ag1–S1
122.37(7) S1–Ag1–P1
131.59(4)
111.69(4)
109.59(4)
98.9(1)
C1–N1–N2 115.9(2) S2A–Ag–S1
N1–N2–C5 114.4(2) Ag1–S1–C1
N2–C5–C6 121.0(2) Ag1–S3–C10
96.6(1)
97.2(1)
N6–C14–C15
C14–C15–S4
C15–S4–C18
C19–O6–H3
C20–O7–H4
O3–N9–O4
O3–N9–O5
O4–N9–O5
98.9(3)
118.3(5)
109.4(5)
121.8(7)
91.2(4)
Ag1–S1–C1
C1–N1–N2
N1–N2–C5
N2–C5–C6
C6–O2–C9
O3–N5–O4
O4–N5–O5
O5–N5–O3
118.2(2)
113.0(4)
122.1(4)
105.7(4)
119.6(5)
119.1(5)
121.2(7)
C6–S2–C9
91.2(2) S1–C1–N1
124.0(2)
117.3(2)
111.8(2)
120.5(3)
123.5(2)
91.4(2)
C1–N4–N3 127.6(2) C1–N1–N2
N1–C2–O1 122.2(2) N1–N2–C5
N2–C5–C6
113(3)
103(3)
118.3(3)
121.9(8)
115.3(8)
122.8(8)
C5–C6–S2
C6–S2–C9
118.2(3)
123.5(4)
Fig. 1. Molecular structure of 2.
The S1–Ag1–S3-pseudoaxis with an S–Ag–S angle of
159.88° is characteristic for a distorted linear coordina-
tion sphere, caused by additional Ag–S contact. The
sum of the angles around metal atom is 360° and the
complex is planar. The Ag–S bond distances of
246.69(9) and 248.64(9) pm are significantly longer than
the Ag–S distances found in silver complexes with co-
ordination number two (236.2–241.8 pm) [21] and lie
within the range expected for c.n. three (246.4–253.4
pm) [22].
The other Ag–S distances of 287.92(8) and 374.2(1)
pm are longer than the maximum atom distance gener-
ally accepted for Ag(I)–S bonds of 261 pm [23] and the
latter is clearly longer than the sum of van der Waals
radii of silver and sulfur (170 þ 180 ¼ 350 pm) [24], in-
Fig. 2. Molecular structure of 4.
dicating a 2 + 1 coordination sphere for the metal cen-
ters in 4. The Agꢀ ꢀ ꢀAg distance is 314.77(7) pm and is
shorter than the sum of the van der Waals radii of 340
pm, but there is no interaction between the silver atoms,
due to the planar environment of the Agþ ions.ꢁ
Medium strong hydrogen bonds link the NO3 anion
over oxygen atoms of the methanol molecules to the
NH-groups of the adjacent ligands. The contacts
N4ꢀ ꢀ ꢀO7 (272.7(4) pm), N8ꢀ ꢀ ꢀO6a (278.6(4) pm),
O6ꢀ ꢀ ꢀO3 (299.4(4) pm), O6ꢀ ꢀ ꢀO5 (322.5(5) pm) and

2250
M. Ghassemzadeh et al. / Inorganica Chimica Acta 357 (2004) 2245–2252
O7ꢀ ꢀ ꢀO3 (290.7 pm) are responsible for an interesting
aureole (ring) around the cation via self assembly.
The dihedral angles formed by the planes of the li-
gands (A: N5–N7–N8–C10–C11–C12 and B: S4–C15–
C16–C17–C18) and (C: N1–N3–N4–C1–C2–C3 and D:
S2–C6–C7–C8–C9) are 66° and 75°. The latter is sig-
nificantly wider than the angle observed in the ligand.
The other observed dihydral angles between the planes
(C,D) and (E,A) are 44° and 52°.
within the range expected for c.n. three complexes
(246.4–253.4 pm) [22].
The dihedral angle formed from the planes S2–C6–
C7–C8–C5 and N1–N3–N4–C1–C2–C3 is 67°. The Ag–
P bond distances, 245.8(2) and 250.7(2) pm, agree well
with the distances observed in the acetone complex
[(C4H4N3SON(@CMe2)Ag(PPh3)2]NO3 (243.0(2) and
249.0(2) pm).
There are two weak hydrogen bondings between two
oxygen atoms of the nitrate ion and the NH-group of
the heterocycle (308.2(9) and 292.7(9) pm), which caused
the reduction of the O–N–O angle to 115°.
3.2.3. Complex 5
In the cation of 5, the ligand is coordinated to the
silver atom through its sulfur atom (Fig. 3). Two PPh3
molecules are also bound to the central atom and
complete the trigonal coordination around the silver
atom. The sum of the angles around the central atom is
355° and it shows a slightly pyramidalization of the
trigonal coordination.
3.2.4. Complex 6
Complex 6 is an ionic compound which consists of
the cation [(FAMTTO)Ag(PPh3)2]þ and the anion
ꢁ
NO3 (Fig. 4). The molecules of the cationic complexes
possess only C1-symmetry. In the cation of 6, the ligand
chelates the silver atom through its sulfur and iminic
nitrogen atom forming a five-membered ring. The dis-
torted tetrahedral coordination around the metal is
completed by two P atoms of the phosphane molecules.
The deviation from perfect tetrahedral coordination is
best illustrated by the P1–Ag1–P2 angle of 131.59(4)°
and can be accounted for the steric hindrance induced
by the two phosphane molecules, consequently com-
pressing the S1–Ag1–N2 angle to 71.3(1)°. The exis-
tence of a medium strong hydrogen bond between the
NH-group of the ligand and an oxygen atom of
the nitrate anion [N4ꢀ ꢀ ꢀO3: 273.1(6) pm] contributes to
the angular distortion about the silver atom. In con-
trast to 5, where the sulfur-nitrogen ligand bound in a
3 + 1 fashion (strong Ag–S bond; weak and long
Agꢀ ꢀ ꢀN contact) to Agþ, in 6 the ligand acts more
bidentately. However, the Ag–N distance of 250.4(4)
The Ag–S bond lengths of 259.2(2) pm are longer than
the Ag–S distances found in complexes with c.n. three
(246.4–253.4 pm) [22] and lies in the range of c.n. four
silver complexes [21]. It is slightly shorter than the Ag–S
distance obtained in the acetone complex [262.9(2) pm],
where a distorted tetrahedral coordination around the
Agþ center was observed [10b]. The Ag–N distance is
267.5(6) pm and is longer than the generally as typical
accepted Ag–N distance of 224 pm and the Ag–N dis-
tance of 245.9(2) pm observed in similar acetone complex
[10b] and 250.4(3) pm in the AMTTO-complex [10a], but
it is clearly shorter than the sum of van der Waals radii of
silver and nitrogen (170 þ 155 ¼ 325 pm) [24]. Therefore,
the coordination around silver atom is 3 + 1.
The Ag–S bond distances of 246.69(9) and 248.64(9)
pm are significantly longer than in silver complexes with
coordination number two (236.2–241.8 pm) [21] and lie
Fig. 3. Structure of 5.
Fig. 4. Molecular structure of 6.

M. Ghassemzadeh et al. / Inorganica Chimica Acta 357 (2004) 2245–2252
2251
pm indicates still a long and relatively weak bond, even
if significantly shorter than 267.5(6) pm, as found in 5.
The 224 pm is generally accepted as typical Ag–N
distance [23], but Ag1–N2 is clearly shorter than the
sum of van der Waals radii of silver and nitrogen
(155 þ 170 ¼ 325 pm) [24].
teresting for further studies, espcecially in the absence of
strong donor ligands like phosphanes.
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