Polymer and cage-type structures in silver(I) complexes with heterocyclic thiones and bridging diphosphine ligands. Crystal structures of [Ag(μ-dpppent)(tHpymtH)(ONO2)]n and [Ag 2(μ-trans-dppen)3(pymtH)2</s

Article abstract of DOI:10.1016/j.poly.2005.03.009

Reaction of silver(I) nitrate with equimolar amounts of the rigid diphos ligand trans-1,2-bis(diphenylphosphino)ethene (trans-dppen) and some heterocyclic thiones (L) in acetonitrile/methanol solvent gave rise to triply-bridged coordination cages [Ag

Full text of DOI:10.1016/j.poly.2005.03.009

Polyhedron 24 (2005) 853–863
www.elsevier.com/locate/poly
Polymer and cage-type structures in silver(I) complexes
with heterocyclic thiones and bridging diphosphine ligands.
Crystal structures of [Ag(l-dpppent)(tHpymtH)(ONO )] and
2
n
[
Ag (l-trans-dppen) (pymtH) ](NO ) Æ CH CN
2
3
2
3 2
3
a,
P. Aslanidis , S. Divanidis , P.J. Cox , P. Karagiannidis
a
,b
*
a
*
a
Aristotle University of Thessaloniki, Faculty of Chemistry, Inorganic Chemistry Laboratory, P.O. Box 135, GR- 541 24 Thessaloniki, Greece
b
School of Pharmacy, The Robert Gordon University, Schoolhill, Aberdeen AB 10 1FR, Scotland, United Kingdom
Received 22 February 2005; accepted 16 March 2005
Available online 14 April 2005
Abstract
Reaction of silver(I) nitrate with equimolar amounts of the rigid diphos ligand trans-1,2-bis(diphenylphosphino)ethene (trans-
dppen) and some heterocyclic thiones (L) in acetonitrile/methanol solvent gave rise to triply-bridged coordination cages [Ag (l -
2
2
trans-dppen)
dpppent) turned out to be diphosphine-bridged polymers of the type [Ag(l
ing as bridge between two pseudo-tetrahedraly coordinated metal centres. The structures of one representative for each of the two
aforementioned series of complex compounds, namely, [Ag (l -trans-dppen) (pymtH) ](NO (pymtH = pyrimidine-2-thione) and
Ag(l -dpppent)(tHpymtH) (ONO )] (tHpymtH = tetrahydropyrimidine-2-thione) have been established by single-crystal X-ray
diffraction.
2005 Elsevier Ltd. All rights reserved.
L
3 2
](NO
3
)
2
. On the other hand, the complexes produced when using the flexible 1,5-bis(diphenylphosphino)pentane
(
2
-dpppent)(L)(ONO )] with the diphosphine ligand act-
2 n
2
2
3
2
3 2
)
[
2
2 n
ꢀ
Keywords: Silver(I) complexes; Heterocyclic thiones; 1,5-Bis(diphenylphosphino)pentane; trans-1,2-Bis(diphenylphosphino)ethene; Crystal struc-
tures
1
. Introduction
soft acids is virtually limited to the thione-S monoden-
tate and bidentate (l -S) types, thus the majority of the
2
Sulfur donors are known to be good ligands for
Ag(I) complexes bearing simple neutral ligands such as
pyridine-2-thione or pyrimidine-2-thione are mono-
meric or dimeric exhibiting the common trigonal pla-
nar or tetrahedral coordination around the metal
centre [5]. Our previous approach to this area involved
the employment of neutral thioamide ligands in hetero-
leptic phosphane derivatives of Ag(I) halides or Ag(I)
nitrate, whereby some examples of monomers [6,7] or
symmetric dimers [8], with pseudo-tetrahedraly coordi-
nated silver(I) have been structurally characterized. On
the other hand, oligomeric or polymeric Ag(I) species
can be obtained [9–11] for thioamide ligands in their
thionate anionic form, generated by deprotonation. It
monovalent group-11 cations [1], and the research field
concerning silver(I) in sulfur-dominated coordination
spheres is vast and ever expanding. Among the fre-
quently used S-donors, the extended family of hetero-
cyclic thioamides, are of particular interest since their
metal complexes are known to have relevance to bio-
logical systems [2–4]. The coordination mode of the
neutral thioamides, also known as ‘‘thiones’’, towards
*
Corresponding author. Tel.: +32310997694; fax: +32310997738.
E-mail addresses: p.j.cox@rgu.ac.uk (P.J. Cox), aslanidi@chem.
auth.gr (P. Aslanidis).
0
277-5387/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.03.009

854
P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
should be noted, however, that a few silver-thione
polymers of neutral pyridine-2-thione constructed on
the basis of l -S or l -bridges, are also known [12,13].
Bidentate phosphines exhibit excellent ligating prop-
erties towards almost all transition metals [14–16] and
diphosphine containing silver(I) complexes have at-
tracted widespread attention [17]. Taking into account
that the double bridging coordination mode of both
diphosphines and heterocyclic thiones is quite common
for univalent group-11 metal complexes, we recently
vents were purified by respective suitable methods and
allowed to stand over molecular sieves. Infra-red spectra,
ꢀ
3
molar conductivities in 10 M solutions in acetonitrile,
magnetic susceptibility measurements and elemental
analyses for carbon, nitrogen and hydrogen were per-
formed as described previously [22]. Thermogravimetric
analyses were performed on a SETSYS-1200 machine
with DTG facility in dry nitrogen atmosphere. Sample
sizes were in the range 8–10 mg and open Pt crucibles were
used. The heating rate was 10ꢁ/min.
2
3
introduced
diphosphines Ph P(CH ) PPh as a second soft donor
a
series of oligomethylene-backboned
2.2. X-ray crystallographic study
2
2 n
2
with the aim of provoking some variability in the nucle-
arity of silver-thione complexes. The role of the flexibil-
ity of the bridging phosphine in controlling product
selectivity in the formation of a multisilver complex is al-
ready recognized. Thus, while with long-chained flexible
diphosphines, silver(I) salts with oxo-anions selectively
form dinuclear (2:2) macrocycles, the rigid bis(diph-
enylphosphino) acetylene (dppa) gives stable cationic
disilver complexes with triply-bridging diphosphine
units [18,19]. On the other hand, by proper selection
of thiolato ligands, novel oligonuclear structures can
be constructed for Ag(I) complexes containing short bite
diphosphines like bis(diphenylphosphino)methane [20].
In this context, our related work was initially devoted
to silver(I) nitrate derivatives of some heterocyclic thi-
ones containing bridging 1,2-bis(diphenylphosphino)
ethane (dppe) and 1,4-bis(diphenylphosphino)butane
Single crystals of 3 and 10 suitable for X-ray crystal-
lographic study were grown by slow concentration of
acentonitrile/methanol solutions of the compounds over
several days at ambient temperature. X-ray diffraction
data were collected on an Enraf-Nonius Kappa CCD
area-detector diffractometer. The programs DENZO [23]
and COLLECT [24] were used in data collection and cell
refinement. Details of crystal and structure refinement
are shown in Table 1. The structures were solved using
program SIR97 [25] and refined with program SHELX-97
[26]. Molecular plots were obtained with program
ORTEP-3 [27].
2.3. Synthesis of complexes 1–14
The complexes were prepared according to the fol-
lowing general procedure. A suspension of silver nitrate
(0.5 mmol) and 1,5-bis(diphenylphosphino)pentane or
trans-1,2-bis(diphenylphosphino)ethene (0.5 mmol) in
(
dppb). Interestingly, the only common feature of the
two types of structures was the presence of pseudo-tetra-
hedraly coordinated metal centres exhibiting the same
P S donor set, since the complexes bearing the longer
3
20 cm acetonitrile was stirred at 50 ꢁC until a white pre-
2
2
chained diphosphine (dppb) were found to be quadrou-
bly bridged dimers build by a perfect combination of
two kinds of bridges, whereas polymerization occurred
in the case of dppe [21]. To prove the role of chain
length, bulkines and flexibility of the bidentate phos-
phine and to gain more information concerning the ef-
fect of polymerization, we decided to include further
potentially bidentate/bridging diphosphines in our stud-
ies. In this paper, we present our results on the use of the
long chained 1,5-bis(diphenylphosphino)pentane (dppp)
and the rigid trans-1,2-bis(diphenylphosphino)ethene
cipitation was formed. A solution of the appropriate thi-
one (0.5 mmol) in methanol was then added and the new
suspension was stirred to clearness. The resulting solu-
tion was filtered off and the clear solution was kept at
room temperature. Slow evaporation of the solvent at
room temperature gave the microcrystalline solid, which
was filtered off and dried in vacuo.
2.4. [Ag(l-dpppent)(py2SH)(NO )] (1)
3
n
Pale yellow crystals. Yield: 263 mg (73%), m.p.
177 ꢁC; Anal. Calc. for C H AgN O P S: C, 56.59;
(
trans-dppen).
3
4
35
2
3 2
H, 4.89; N, 3.88. Found: C, 56.49; H, 4.79; N, 3.76%;
2
ꢀ1
ꢀ1
Km (mho cm mol ): 93; IR (cm ): 3452m, 3049w,
2920w, 1707s, 1601s, 1584vs, 1434vs, 1384vs, 1302vs,
2
. Experimental
1
222s, 1139vs, 1098s, 1025vs, 997s, 741vs, 693vs, 617s,
2
.1. Materials and instruments
512vs, 486s, 445s; UV–Vis (kmax, loge): (CHCl ); 260
3
(4.37), 289 (4.29), 361 (3.91).
Commercially available silver nitrate, trans-1,2-
bis(diphenylphosphino)ethene (trans-dppen) and 1,5-
bis(diphenylphosphino)pentane (dpppent) were used as
received while the thiones (Merck or Aldrich) were recrys-
tallized from hot ethanol prior to their use. All the sol-
2.5. [Ag(l-dpppent)(pymtH)(NO )] (2)
3
n
Yellow crystals. Yield: 220 mg (61%), m.p.155 ꢁC;
Anal. Calc. for C H AgN O P S: C, 54.86; H, 4.74;
3
3
34
3
3 2

P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
855
Table 1
Crystal data and structure refinement for [Ag(dpppent)(tHpymtH)(NO
3
)]
n
(3) and [Ag
2 3 2 3 2 3
(trans-dppen) (pymtH)] ](NO ) Æ CH CN (10)
3
10
Chemical formula
Formula weight
Temperature (K)
[C33
H
38AgN
3
O
3
P
2
S]
n
86 2 4 6 2 3 3
C H76Ag N P S .2NO Æ CH CN
726.53 (monomer unit)
120(2)
0.71073
1796.26
120(2)
0.71073
˚
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
monoclinic
C2/c
orthorhombic
Pna2
1
˚
a (A)
36.7814(10)
9.5500(5)
18.8438(8)
90
31.0485(5)
20.5143(3)
13.2654(3)
90
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
99.209(3)
90
90
90
˚
3
Volume (A )
3529.7(7)
8
1.477
8449.2(3)
4
Z
3
D
calc (Mg/m )
1.412
0.683
3680
ꢀ1
Absorption coefficient (mm
F (000)
Crystal size (mm)
)
0.817
2992
0.30 · 0.28 · 0.04
3.03–27.41
0.43 · 0.30 · 0.20
3.05–27.48
h Range for data collection (ꢁ)
Index ranges
Reflections collected
ꢀ46 6 h 6 47, ꢀ12 6 k 6 12, ꢀ24 6 l 6 24
ꢀ39 6 h 6 40, ꢀ20 6 k 6 26, ꢀ17 6 l 6 17
34188
62951
Independent reflections [Rint
Completeness to h = 27.47ꢁ
]
7393 [0.0822]
99.1%
0.9681 and 0.7917
18864 [0.0461]
99.6%
0.8754 and 0.7576
Maximum and minimum transmission
Refinement method
Data/restrains/parameters
2
2
full-matrix least-square on F
7393/11/478
1.009
full-matrix least-squares on F
18864/6/1038
1.045
2
Goodness-of-fit on F (S)
Final R indices [(I) > 2r (I)]
R indices (all data)
R
R
1
= 0.0571, wR
= 0.1215, wR
2
= 0.1160
= 0.1365
R
R
1
= 0.0436, wR
= 0.0655, wR
2
= 0.0911
= 0.0982
1
2
1
2
2
2
2
2
Final weighting scheme
Calc: w ¼1=½r2ðF Þþð0:0491PÞ þð21:1062PÞꢁ
Calc: w ¼1=½r2ðF Þþð0:0433PÞ þð2:2006PÞꢁ
o
o
2
o
2
2
o
2
where P ¼ðF þ2F Þ=3
where P ¼ðF þ2F Þ=3
c
c
˚
3
Largest difference peak and hole (e A )
0.903 and ꢀ0.953
0.926 and ꢀ0.627 (close to solvent)
N, 5.82. Found: C, 54.68; H, 4.81; N, 5.69%; K
(
N, 5.66. Found: C, 52.05; H, 4.78; N, 5.76%; K
m
m
2
mho cm mol ): 79; IR (cm ): 3452w, 3048w,
ꢀ1
ꢀ1
2
ꢀ1
ꢀ1
(mho cm mol ): 93; IR (cm ): 3453w, 3050w,
2924m, 1586s, 1482vs, 1435vs, 1385vs, 1284vs, 1197s,
1098s, 1049s, 998s, 740vs, 694vs, 511vs, 480s, 432s;
2920m, 1707s, 1603s, 1584vs, 1482s, 1434vs, 1384vs,
1302vs, 1222s, 1178vs, 1098s, 1026s, 997s, 741vs,
693vs, 512s, 486s, 445m; UV–Vis (kmax, loge): (CHCl3);
256 (4.33), 291 (3.95), 350 (3.10).
UV–Vis (kmax, loge): (CHCl ); 254 (4.36), 307 (4.29).
3
2
.8. [Ag(l-dpppent)(mftztH)(NO )] (5)
3
n
2
.6. [Ag(l-dpppent)(tHpymtH)(NO )] (3)
3
n
Colorless crystals. Yield: 266 mg (67%), m.p. 249 ꢁC;
Anal. Calc. for C H AgF N O P S: C, 49.95; H, 4.32;
Colorless crystals. Yield: 207 mg (57%), m.p. 230 ꢁC;
Anal. Calc. for C H AgN O P S: C, 54.55; H, 5.27; N,
3
3
34
3
4
3 2
N, 7.06. Found: C, 49.10; H, 3.99; N, 6.90%; K
m
3
3
38
3
3
2
2
ꢀ1
ꢀ1
5
(
.78. Found: C, 54.27; H, 5.24; N, 5.81%; K
mho cm mol ): 96; IR (cm ): 3286m, 3049w,
(mho cm mol ): 104; IR (cm ): 3456w, 3051m,
2924m, 1707m, 1616m, 1483vs, 1435vs, 1384vs, 1283s,
1203s, 1149s, 1090s, 741vs, 693vs, 511s, 479m; UV–Vis
m
2
ꢀ1 ꢀ1
2
1
5
939w, 1707m, 1608m, 1547vs, 1481s, 1435vs, 1384vs,
306vs, 1207s, 1098vs, 1025s, 816s, 741vs, 695vs,
(kmax, loge): (CHCl ); 257 (4.38), 355 (4.09).
3
11vs, 478s, 418s; UV–Vis (kmax, loge): (CHCl ); 253
3
(
4.32), 297 (3.94).
2.9. [Ag(l-dpppent)(bzoxtH)(NO )] (6)
3
n
2
.7. [Ag(l-dpppent)(mtdztH)(NO )] (4)
Brownish crystals. Yield: 291 mg (75%), m.p. 135 ꢁC;
Anal. Calc. for C H AgN O P S: C, 56.77; H, 4.63; N,
3
n
3
6
35
3
4 2
Colorless crystals. Yield: 226 mg (61%), m.p. 145 ꢁC;
Anal. Calc. for C H AgN O P S : C, 51.76; H, 4.61;
3.68. Found: C, 57.26; H, 4.83; N, 3.71%; K
m
2
ꢀ1
ꢀ1
(mho cm mol ): 103; IR (cm ): 3440m, 3051m,
3
2
34
3
3 2 2

856
P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
2
1
4
3
924w, 1616m, 1515vs, 1435vs, 1385vs, 1306vs, 1255s,
198s, 1136vs, 1096vs, 923s, 740vs, 694vs, 605s, 512vs,
1096vs, 1025vs, 998s, 918s, 812s, 742vs, 692vs, 508vs,
465vs, 416s, 350m; UV–Vis (kmax, loge): (CHCl ); 254
(4.32), 279 (3.97), 351 (2.17).
3
82s, 424s; UV–Vis (kmax, loge): (CHCl ); 257 (4.21),
3
05 (4.22), 335 (3.16).
2
.15. [Ag (l-trans-dppen) (bzoxtH) ](NO ) (12)
2
3
2
3 2
2
.10. [Ag(l-dpppent)(mbzimtH )(NO )] (7)
2
3
n
Braunish crystals. Yield: 256 mg (56%), m.p. 210 ꢁC;
Anal. Calc. for C H N Ag O P S : C, 60.33; H, 4.18;
Colorless crystals. Yield: 225 mg (58%), m.p. 152 ꢁC;
Anal. Calc. for C H AgN O P S: C, 57.37; H, 4.94; N,
9
2
76
4
2
8 6 2
N, 3.06. Found: C, 59.87; H, 4.18; N, 2.99%; K
m
3
7
38
3
3
2
2
ꢀ1
ꢀ1
5
(
.42. Found: C, 56.97; H, 4.99; N, 5.34%; K
m
mho cm mol ): 89; IR (cm ): 3435w, 3051m,
(mho cm mol ): 126; IR (cm ): 3438w, 3051w,
1615m, 1515s, 1479s, 1435vs, 1384vs, 1308s, 1257vs,
1182s, 1138vs, 1097vs, 1026s, 925s, 742vs, 694vs, 507s,
2
ꢀ1 ꢀ1
2
1
5
923w, 1617s, 1520s, 1484vs, 1456vs, 1435vs, 1384vs,
307vs, 1185s, 1098s, 1026s, 804s, 740vs, 694vs, 628s,
491s, 423s; UV–Vis (kmax, loge): (CHCl ); 252 (4.32),
3
12vs, 479s, 430m; UV–Vis (kmax, loge): (CHCl ); 255
272 (3.15), 355 (2.98).
3
(
4.37), 303 (4.37).
2
.16. [Ag (l-trans-dppen) (mtdztH) ](NO ) (13)
2
3
2
3 2
2
.11. [Ag(l-dpppent)(pur6SH)(NO )] (8)
3
n
White crystals. Yield: 233 mg (52%), m.p. 221 ꢁC;
Anal. Calc. for C H N Ag O P S : C, 56.25; H, 4.16;
Pale yellow crystals. Yield: 263 mg (69%), m.p.
8
4
74
6
2
6 6 4
1
H, 4.42; N, 9.18. Found: C, 52.98; H, 4.60; N, 8.96%;
Km (mho cm mol ): 86; IR (cm ): 3435w, 3050w,
70 ꢁC; Anal. Calc. for C H AgN O P S: C, 53.55;
N, 4.68. Found: C, 56.01; H, 4.10; N, 4.67%; K
m
2
3
4
34
5
3
2
ꢀ1
ꢀ1
(mho cm mol ): 122; IR (cm ): 3445w, 3050w,
1640s, 1552s, 1480vs, 1435vs, 1384vs, 1308vs, 1197s,
1097vs, 1058vs, 998s, 812m, 741vs, 693vs, 509vs, 476s,
2
ꢀ1
ꢀ1
2
1
7
922w, 1709m, 1594vs, 1570vs, 1482vs, 1435vs, 1384vs,
207vs, 1158s, 1099vs, 1025s, 999vs, 932vs, 856vs,
432s, 344m; UV–Vis (kmax, loge): (CHCl ); 251 (4.11),
3
41vs, 694vs, 590s, 511vs, 481s, 431s; UV–Vis (kmax
,
307 (4.02), 341 (2.87).
loge): (CHCl ); 255 (4.31), 335 (4.25).
3
2
.17. [Ag (l-trans-dppen) (mftztH) ](NO ) (14)
2
3
2
3 2
2
.12. [Ag (l-trans-dppen) (py2SH) ](NO ) (9)
2
3
2
3 2
White crystals. Yield: 270 mg (57%), m.p. 249 ꢁC;
Anal. Calc. for C H N Ag F O P S : C, 54.50; H,
Pale yellow crystals. Yield: 206 mg (47%), m.p.
8
6
74
8
2
6
6 6 2
2
H, 4.37; N, 3.20. Found: C, 59.89; H, 4.19; N, 3.16%;
Km (mho cm mol ): 137; IR (cm ): 3446w, 3048w,
24 ꢁC; Anal. Calc. for C H Ag N O P S : C, 60.35;
3.93; N, 5.91. Found: C, 53.91; H, 4.08; N, 5.75%; K
m
2
8
8
76
2
4
6
6
2
ꢀ1
ꢀ1
(mho cm mol ): 115; IR (cm ): 3.362 w, 3174w,
2965w, 1560vs, 1435vs, 1384vs, 1310vs, 1221vs, 1096s,
997s, 811m, 752s, 742vs, 694vs, 509vs, 479s, 416s; UV–
2
ꢀ1
ꢀ1
2
1
980w, 1583vs, 1481s, 1435vs, 1384vs, 1308vs, 1186s,
098vs, 1024s, 997vs, 741vs, 693vs, 539vs, 519vs, 493s;
Vis (kmax, loge): (CHCl ); 250 (4.40), 298 (4.19).
3
UV–Vis (kmax, loge): (CHCl ); 258 (4.34), 282 (4.22),
3
3
60 (3.20).
3
. Results and discussion
2
.13. [Ag (l-trans-dppen) (pymtH) ](NO ) (10)
2
3
2
3 2
3
.1. Preparative considerations
Yellow crystals. Yield: 197 mg (45%), m.p. 198 ꢁC;
Anal. Calc. for C H N Ag O P S : C, 58.91; H, 4.25;
Before discussing the experimental results, we
8
6
74
6
2
6 6 2
N, 4.79. Found: C, 58.69; H, 4.57; N, 4.58%; K
(
should point out that both, 1,5-bis(diphenylphosph-
ino)pentane (dpppent) and trans-1,2-bis(diphenylphos-
phino)ethene (trans-dppen) showed a marked prefer-
ence for the formation of macrocycles in their reactions
with Cu(I), in the presence of heterocyclic thione li-
gands [28–30], whereas cis-1,2-bis(diphenylphosph-
ino)ethene yielded predominantly chelated monomeric
species [31].
m
2
mho cm mol ): 124; IR (cm ): 3445w, 3050w,
ꢀ1 ꢀ1
2861w, 1600s, 1574vs, 1479vs, 1434vs, 1384vs, 1327vs,
1214s, 1177vs, 1096s, 1026s, 975s, 794m, 743vs, 694vs,
506vs, 488vs, 463s, 335m; UV–Vis (kmax, loge): (CHCl3);
262 (4.30), 286 (4.27), 370 (3.18).
2
.14. [Ag (l-trans-dppen) (tHpymtH) ](NO ) (11)
2
3
2
3 2
The reaction between equimolar quantities of silver(I)
nitrate and 1,5-bis(diphenylphosphino) pentane (dpp-
pent) followed by the addition of one equivalent of the
apropriate thione (L) [L = pyridine-2-thione (py2SH),
pyrimidine-2-thione (pymtH), tetrahydropyrimidine–
thione (tHpytH), 5-methyl-1,3,4-thiadiazole-2-thione
White crystals. Yield: 247 mg (56%), m.p. 256 ꢁC;
Anal. Calc. for C H N Ag O P S : C, 58.64; H, 4.69;
8
6
82
6
2
6 6 2
N, 4.77. Found: C, 58.01; H, 4.49; N, 4.54%; K
m
2
ꢀ1
ꢀ1
(
mho cm mol ): 121; IR (cm ): 3060w, 1564vs,
480vs, 1435vs, 1384vs, 1296vs, 1220vs, 1157vs,
1

P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
857
(
5
mtdztH),
benz-1,3-oxazoline-2-thione
-methyl-benz-1,3-imidazole-2-thione (mbzimtH ), 4-
(bzoxtH),
phine was shown to predominantly form dimers of type
[M(l-dpppent)(l-X)]2 (M = Cu, Ag and X = Br, I).
Likewise, treating an acetonitrile solution of Cu(I) chlo-
ride with stoichiometric amounts of dpppent and a het-
erocyclic thione ligand, the complexes formed were of
the formula [CuCl(dpppent)L], whereby the thione-free
2
methyl-5-trifluoromethyl-4H-1,2,4-triazoline-3(2H)-thi-
one (mftztH), and 6-mercaptopurine (pur6SH) in dry
acetonitrile/methanol solution at 30 ꢁC afforded micro-
crystalline solids which, on analysis were found to be of
composition [AgNO (dpppent)L] (compounds 1–8).
3
dimer [Cu(l-dpppent)(l-Br)] was found to be the only
2
According to our previous experience with thione/
+
phosphine complexes of Ag(I) nitrate, Ag tends to
product of the analogous reactions when copper(I) bro-
mide was used [30]. Consequently, the formation of the
polymers under investigation was considered as unpre-
dictable with respect to the geometrical features of the
diphos ligand applied. Moreover, it contrasted, regard-
ing the stoichiometric composition of the products
formed, with the findings of our recent work on analo-
adopt a tetrahedral coordination whith the counterion
kept outside the coordination sphere, despide its strong
coordination ability. Within the meaning of this crite-
rion, two structures (structures a and b, Scheme 1) come
into question that reproduce the above given
stoichiometry.
gous AgNO compounds, where the use of 1,2-bis(diph-
3
On the other hand, if the coordination of the nitrate
anion is weak, the formation of a monomeric, dimeric or
polymeric complex (structures c–e, respectively), could
be possible, but formation of c is unlikely as it is less
compatible with the stereochemical characteristics of
the long-chained diphosphine applied. Indeed, the struc-
ture determination of the tetrahydropyrimidine-2-thione
complex (compound 3) by X-ray diffraction confirmed
compounds 1–8 to be coordination polymers of type
enylphosphino)ethane (dppe) afforded polymers of
general formula [Ag(dppe)(L) ] (NO ) [21], with the
2
n
3 n
latter containing ionic outer-sphere nitrate groups.
Thus, following the same procedure, we repeated the
reactions using the apropriate thione in a twofold ex-
cess, aiming to attain cationic complexes, but we ob-
tained once more compounds 1–8. Likewise, we
treated compounds 1–8 with two equivalents of an apro-
priate thione per formula unit, however the products
isolated in all the cases turned out to be once more the
polymeric complexes initially used as starting materials.
The second series of mixed ligand complexes
obtained on treating silver(I) nitrate with equimolar
quantities of trans-1,2-bis(diphenylphosphino)ethene
(trans-dppen) and the same set of heterocyclic thiones
was of the composition [(AgNO ) (trans-dppen) (L) ].
[
Ag(l-dpppent)(L)(ONO )] .
2
n
In general, diphosphines bearing a long-chained flex-
ible backbone, are expected to bridge metal centres
forming dimeric macrocycles of type [M(diphos) M]
2
rather than polymeric adducts, the later being continu-
ously favoured upon decreasing the diphosphine chain
length. Indeed, the ability of 1,5-bis(diphenylphosph-
ino)pentane to serve as a bridge between two metal cen-
tres in monovalent coinage metal complexes is well
documented, among others in a recent publication of
Pettinari and co-workers [32], where the flexible diphos-
3
2
3
2
On the basis of the above composition it was presumed
that these compounds could be phosphine-bridged dinu-
clear cages. This was indeed found for six of the thiones
applied (compounds 9–14), but not for mbzimtH or
2
NH
Ph2P
S
PPh2
S
Ph2P
S
PPh2
Ag+
Ph2P
Ph2P
S
S
PPh2
PPh2
HN
Ag+
Ag+
Ag
HN
ONO2
HN
Ag+
Ph2P
PPh2
HN
(
a)
(b)
(c)
NH
Ph2P
PPh2
S
S
O2NO
ONO2
Ph2P
NH
__
Ag
Ag
CH2
P
Ag
P
(CH2)4
NH
S
PPh2
ONO2
n
(
d)
(e)
Scheme 1.

858
P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
pur6SH, where the reaction, carried out under the same
experimental conditions as usual, gave in both cases a
powder of uncertain stoichiometry.
250–260 and 282–307 nm regions, as well as an addi-
tional rather broad band with maximum at 335–370
nm. The first two bands can be attributed to intraligand
Complexes 1–14 are diamagnetic, air stable, micro-
crystalline solids, only slightly soluble in common or-
ganic solvents. In accordance with their polymeric
nature, the molar conductivities of complexes contain-
ing dpppent (compounds 1–8) in dry acetonitrile solu-
tions are somewhat lower than those of the dinuclear
compounds 9–14, but still fairly high to suggest com-
plete ionization in solution.
p*
p transitions on the phenyl group of the phosphine
ligands, since the uncoordinated 1,5-bis(diphenylphos-
phino)pentane and trans-1,2-bis(diphenylphosphino)
ethene both reveal two strong absorptions at 259 and
287.5 nm and 258.5 and 296 nm, respectively, which
are known to undergo small shifts upon coordination
to Ag(I). The lower energy band lies in the region where
the free thiones absorb, expressing a small red shift as a
consequence of the coordination to Ag(I) and should be,
therefore, considered as a thione-originating intraligand
transition which possess some MLCT character [33,34]
(Fig. 1).
3
.2. Spectroscopic characterization
The solid state FT-IR spectra of complexes 1–14,
recorded in the range 4000–250 cm
ꢀ1
provide useful
information regarding the mode of thione ligand coordi-
nation. They show the disappearance of the S–H stretch-
3.3. Thermal decomposition
ꢀ
1
ing band around 2560 cm due to the ‘‘free’’ ligands and
Thermal analysis in nitrogen atmosphere shows the
complexes 1–8 decompose in three or four stages. Fig.
2 illustrates TG and DTA data curves for the polymeric
[Ag(NO )(dpppent)(tHpymtH)] (compound 3). The
ꢀ1
the presence of the m(NH) band in the 3190–3230 cm re-
gion, suggesting M–S bond formation. Moreover, they
contain all of the bands required by the presence of het-
erocyclic thioamides occurring in their thione form, with
shifts indicating the exclusive S-coordination mode of
these ligands. Further, they show all the expected strong
phosphine bands, which remain practically unshifted
upon coordination. The asymmetric N–O stretching
mode (m ) of the NO anion appears as a band of medium
3
n
three low temperature initial stages involve a weak
endothermic and a very strong exothermic effect in the
temperature range 240–360 ꢁC and are connected with
an overall weight loss of ꢂ16% which is consistent with
gradually thermal breakdown of the tetrahydropyrimi-
dine-2-thione ligand. Note that the very strong exother-
mic effect is an attribute of the decomposition of
complexes bearing non-aromatic thione ligands, where-
by the corresponding DTA courve in the case of aro-
matic thione compounds allways show endothermic
events instead.
1
3
ꢀ1
intensity in the 1375–1285 cm range, in some cases not
recognizable because of overlapping with strong absorp-
tions due to the thione and phosphine ligands. Unfortu-
nately, nothing certain can be stated about the
coordination mode of the nitrate ion since the thione li-
gands strongly absorb in the regions where the bands
associated with coordinated nitrate occur.
The observed mass loss (ꢂ67%) in the final, slightly
endothermic stage, show excellent agreement for simul-
taneous loss of the diphosphine molecule and conver-
sion of the resultant silver nitrate to Ag O under NO
The electronic absorption spectra of the complexes in
chloroform solutions appear to be mainly of intraligand
character, consisting of two intense sharp bands in the
2
2
evolution. However no clear distinction between these
H
CH3
CF3
N
N
N
N
N
S
S
N
H
N
H
S
S
N
S
CH3
H
py2SH
pymtH
mtdztH
mftztH
S
H
H
H
N
O
CH3
N
N
N
N
S
S
N
N
H
H
bzoxtH
mbzimtH2
pur6SH
Fig. 1. The heterocyclic thione ligands used with their abbreviations.

P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
859
Fig. 2. TG and DTG curves for compound 3.
two processes can be made, thus this stage must be
somewhat complicated in character.
Complex 3 is a coordination polymer consisting of
Ag(I) cations linked through the phosphorous atoms
of the 1,5-bis(diphenylphosphino)pentane ligand. Each
silver nucleus completes the familiar tetrahedral coordi-
nation environment considering the S-atom from the
tetrahydropyrimidine-2-thione ligand, one O-atom from
the weakly coordinated nitrate anion and the two bridg-
ing P-atoms belonging to two different diphosphine
units. The repeating unit extends into an infinite one-
dimensional chain formed by linking Ag and P1 atoms
by unit cell translations along the b axis, in which the
tetrahydropyrimidine-thione units are ordered in a syn
configuration.
Complexes 9–14 show an analogous decomposition
patern but they are in general thermally less stable,
decomposition being usually completed at 450 ꢁC.
Noticeable is the particular short final stage, that ex-
tends over a temperature range of only 60 ꢁC. In the
majority of the cases solvent retention occurs at the tem-
perature of 190 ꢁC indicated by a strong exothermic ef-
fect connected with a weight loss corresponding to one
molecule of CH CN per formula unit.
3
3
.4. Crystal structures
Colorless crystals of 3 suitable for X-ray were ob-
tained by slow evaporation of a CH CN/CH OH solu-
Table 2
3
3
˚
Selected bond lengths (A) and angles (ꢁ) for 3
tion of the compound. The complex crystallizes in the
monoclinic space group C2/c, with eight monomer units
in the unit cell. Details regarding the crystal data collec-
tion and refinement for the complex are reported in
Table 1. Bond lengths and angles around the Ag(I) are
listed in Table 2. Fig. 3 shows the monomeric unit of
the complex with the labelling of the atoms, and Fig. 4
the resultant polymer. The structure is substantially dis-
ordered, with each of the individual components of the
monomeric entity being affected in some degree. Four
of the five carbon atoms (C5–C8) in the pentane chain
are disordered over two sites, whereas disorder in the
thione ligand involves three carbons (C3–C5). Similarly
˚
Bond lengths (A)
Ag–P(2)
Ag–P(1)
Ag–S(1)
2.4541(14)
2.4666(14)
2.5623(15)
2.535(8)
P(1)–C(9)
1.837(5)
1.70(3)
a
P(2)–C(5B)
N(3)–O(1A)
N(3)–O(2A)
N(3)–O(3A)
1.232(9)
1.148(8)
1.227(9)
Ag–O(1A)
S(1)–C(1)
1.712(6)
Bond angles (ꢁ)
P(2)–Ag–P(1)
P(2)–Ag–S(1)
a
a
P(1) –Ag–O(1A)
132.75(5)
110.07(6)
108.25(6)
103.6(3)
99.7(2)
Ag–S(1)–C(1)
113.92(19)
120.7(9)
125.2(9)
113.9(8)
a
P(1) –Ag–S(1)
O(2A)–N(3)–O(1A)
O(2A)–N(3)–O(3A)
O(3A)–N(3)–O(1A)
P(2)–Ag–O(1A)
S(1)–Ag–O(1A)
94.64(18)
Hydrogen bridges
O(1A)ꢃꢃꢃN(1)
O(1A)ꢃꢃꢃH(1)
2.721(9)
1.90
N(1)–H(1)
O(1A)ꢃꢃꢃH(1)–N(1)
0.88
155ꢁ
0.88
153ꢁ
the three oxygen atoms in the NO ion are highly disor-
3
dered. Moreover, there are high displacement parame-
ters associated with an aryl group attached to P2,
which had to be restricted to a hexagon with ideal bond
lengths and angles.
b
O(2A) ꢃꢃꢃN(2)
3.034(11)
2.23
N(2)–H(2)
b
b
O(2A) ꢃꢃꢃH(2)
O(2A) ꢃꢃꢃH(2)–N(2)
a
Atom coordinates transposed by x, y ꢀ1, z.
b
Atom coordinates transposed by x, ꢀ2 ꢀy, 0.5 + z.

860
P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
2
Fig. 3. The monomeric unit [Ag(l-dpppent)(tHpymtH)(ONO )] of 3 with atom labels (disorder removed). Displacement ellipsoids are shown in the
50% probability level.
Fig. 4. A view of the polymeric chain [Ag(dpppent)(tHpymtH)(NO
at the 50% probability level.
3
)]
n
with hydrogen atoms removed for clarity. Displacement ellipsoids are shown
Considering the angles involving the central metal
atom, there are considerable distortions from the ideal
tetrahedral geometry, the most remarkable being the
P(1)#ꢀAg–P(2) angle, with a large value of 132.75(5)ꢁ
which can be partly accounted for the steric hindrance
induced by the bulky phenyl-rings of the two phosphine
units, but probably also for the presence of the weakly
coordinated nitrate. Namely, the weak anion-cation
silver atoms bonded to two phosphorus atoms [35,36]
and vary little [Ag(1)–P(1) = 2.4501(5), [Ag(1)– P(2) =
˚
2.4658(5) A]. Finally, the geometrical characteristics of
the tetrahydropyrimidine-thione ligand, where the sex-
membered ring adopts an envelope conformation, are
not altered noticeable upon coordination.
Compound 10 crystallizes in the orthorhombic space
group Pna2 , with 4 discrete molecules in the unit cell as
1
interaction, indicated by the large Ag–O distance of
˚
well as four lattice CH CN molecules. Main bond
3
2
.535(8) A, is associated with angles involving the coor-
lengths and angles are given in Table 3 and a perspective
drawing showing the atom numbering is shown in
Fig. 5.
dinated nitrate oxygen-atom that are less than the ideal
tetrahedral value of 109.4ꢁ, thus allowing an appropriate
opening up of the angle between the sterically demand-
ing groups. Another remarkable feature in the structure
of 3 is the quite large Ag–S–C angle of 113.92(19)ꢁ,
which may be attributed to the presence of a strong
hydrogen N–HꢃꢃꢃO bridge (Table 2).
The crystal structure of 10 is built by dinuclear units
in which the two tetrahedral silver centres are linked by
three bridging diphosphine units, whereby the fourth
position of each tetrahedron is occupied by the S-atom
of a thione unit. Interestingly, the two thione rings are
almost parallel to each other adopting a relative cis ori-
entation. Each of the two nitrate anions is placed near to
a thione unit and is adjusted to its nitrogen-bound
hydrogen atom via hydrogen bonding interactions (see
Table 3). Furthermore, each of these counterions is close
˚
The Ag–S bond distance of 2.5623(15) A, coincident
with the sum of the corresponding atomic radii, is typi-
cal for this bonding arrangement. Likewise, the two Ag–
˚
P distances lie within the limits of 2.426–2.504 A found
for a number of complexes containing tetracoordinated

P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
861
Table 3
˚
Selected bond lengths (A) and angles (ꢁ) for 10
˚
Bond lengths (A)
Ag(1)–P(1)
Ag(1)–P(2)
Ag(1)–P(3)
Ag(1)–S(1)
Ag(2)–P(5)
Ag(2)–P(4)
Ag(2)–P(6)
Ag(2)–S(2)
S(1)–C(1)
2.4979(14)
2.5131(11)
2.5211(13)
2.5660(10)
2.5123(12)
2.5370(12)
2.5379(11)
2.5923(10)
1.693(4)
P(2)–C(13)
P(3)–C(11)
P(4)–C(10)
P(5)–C(12)
P(6)–C(14)
O(1)–N(5)
O(2)–N(5)
O(3)–N(5)
O(4)–N(6)
O(5)–N(6)
O(6)–N(6)
1.804(4)
1.813(4)
1.808(4)
1.808(4)
1.810(4)
1.264(7)
1.236(6)
1.253(5)
1.191(6)
1.247(8)
1.332(7)
S(2)–C(5)
P(1)–C(9)
1.689(4)
1.825(4)
Bond angles (ꢁ)
P(1)–Ag(1)–P(2)
P(1)–Ag(1)–P(3)
P(2)–Ag(1)–P(3)
P(1)–Ag(1)–S(1)
P(2)–Ag(1)–S(1)
P(3)–Ag(1)–S(1)
P(5)–Ag(2)–P(4)
P(5)–Ag(2)–P(6)
P(4)–Ag(2)–P(6)
P(5)–Ag(2)–S(2)
111.56(4)
113.12(4)
100.39(4)
109.69(4)
104.65(3)
116.71(4)
111.00(4)
114.65(4)
108.78(4)
109.75(5)
P(4)–Ag(2)–S(2)
P(6)–Ag(2)–S(2)
C(1)–S(1)–Ag(1)
C(5)–S(2)–Ag(2)
O(2)–N(5)–O(3)
O(2)–N(5)–O(1)
O(3)–N(5)–O(1)
O(4)–N(6)–O(5)
O(4)–N(6)–O(6)
O(5)–N(6)–O(6)
110.82(4)
101.48(3)
102.78(13)
103.60(14)
123.1(5)
119.9(4)
117.1(5)
124.0(7)
119.3(7)
116.6(5)
Fig. 5. A view of [Ag
2 3 2 3 2 3
(trans-dppen) (tHpymtH) ](NO ) Æ CH CN
(10) with hydrogen atoms and disorder removed for clarity. Displace-
ment ellipsoids are shown at the 50% probability level.
Hydrogen bridges
a
O(2) ꢃꢃꢃN(2)
2.831
1.956
3.063
2.539
2.871
2.018
3.102
2.532
N(2)–H(2)
a
0.88
173ꢁ
bearing the rigid bis-(diphenylphosphino)acetylene
(dppa) [19]. Some examples of such cages with more
or less strong anion–cation interactions, thus exhibiting
tetrahedrally coordinated Ag(I) centres have been also
reported recently [41]. Further related [Ag L ] com-
a
O(2 )ꢃꢃꢃH(2)
O(2) ꢃꢃꢃH(2)–N(2)
a
O(1) ꢃꢃꢃN(2)
a
a
O(1) ꢃꢃꢃH(2)
O(1) ꢃꢃꢃH(2)–N(1)
119
b
O(3) ꢃꢃꢃN(4)
N(4)–H(4)
O(3)ꢃꢃꢃH(4)–N(4)
0.88
163ꢁ
b
O(3) ꢃꢃꢃH(4)
2
3
b
O(1) ꢃꢃꢃN(4)
plexes involve 2,6-bis(diphenylphosphino)pyridine [42],
,6-bis(diphenylphosphino)pyridazine [42] and 2,9-
bis(diphenylphosphino)-1,8-naphthyridine [43]. With
b
b
O(1) ꢃꢃꢃH(4)
O(1) ꢃꢃꢃH(4)–N(4)
123
3
a
Atom coordinates transposed by ꢀx + 1, ꢀy + 1, z + 0.5.
b
Atom coordinates transposed by ꢀx + 1, ꢀy, z + 0.5.
trans-dppen, evidence for the formation of discrete
Ag L ] cages was found in solution, although, on crys-
2 3
[
to a lattice CH CN molecule, which will not be further
3
tallization, only the corresponding ring-opened poly-
meric structures could be obtained [41].
discussed as there is no evidence of any specific interac-
tion involving this latter solvent molecule. One of the
nitrate ions is hydrogen bonded to both thione units
The geometrical characteristics of the structure un-
der investigation generally refer to those of other
silver(I) complexes tetrahedrally coordinated by phos-
phine and thione ligands. There are six different Ag–P
bond distances around the two Ag(I) centres, each of
them within the limits expected for a complex contain-
ing a tetracoordinated silver atom bearing phosphorus
and sulfur donor ligands [44]. Likewise the two Ag–S
(
3
Fig. 6). As well as the N–HꢃꢃꢃO bonds (Fig. 6, Table
) there is also evidence of N–HꢃꢃꢃN interactions.
trans-1,2-Bis(diphenylphosphino)ethene (trans-dppen)
is well known to serve as a phosphorus(r) donor bridge
between metal centres in coordination compounds
[
28,29,37,38]. However, in view of the rigidity of the
˚
diphosphine backbone, the formation of the three-fold
bridging motif realized in the complex under discussion
should be considered as quite strained, the more so as
this rigidity is accompanied with a remarkable accumu-
lation of stericaly demanding Ph PCH -units around the
distances [2.5660(10) and 2.5923(10) A] are typical for
this type of ligation. Interestingtly, the formation of
the Ag(PP) Ag cage does not require significant con-
3
formational rearrangements on the part of the diphos-
phine ligands; upon coordination the two P atoms of
each diphosphine unit twist about the ethene bridge
altering the dihedral angle through the four atoms
by about 8ꢁ, taken as the average of the torsion angles
P(1)–C(9)–C(10)–P(4), P(3)–C(11)–C(12)–P(5) and
P(2)–C(13)–C(14)–P(6), with respect to the corre-
sponding value (176.6ꢁ) in the free trans-dppen [45],
thus only moderately modifying the bite size of the
diphosphine.
2
2
metal centres. Nevertheless, some related triply bridged
M L ] complexes with rigid bridging diphosphines such
[
2
3
as Ph PAC„CAPPh [39] and Ph PAC„CAC„
2
2
2
CAPPh [40] have been characterised in the solid state.
2
Among the Ag(I) complexes, this cage structure is
known to exist, with no terminal ligands and thus with
trigonal coordination of the two metal atoms, in the tri-
2
+
ply-bridged disilver helical complexes [Ag (l -dppa) ]
2
2
3

862
P. Aslanidis et al. / Polyhedron 24 (2005) 853–863
Fig. 6. Plot showing the N–HꢃꢃꢃO hydrogen bonds linking a nitrate ion to two thione units. Phenyl rings and hydrogen atoms are removed for
clarity.
4
. Conclusion
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spectroscopically characterised. The complexes bearing
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[
[
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