On the synthesis and structural analysis of some coordination polymers derived from Hg(TeAr)2 involving dithio ligands

Article abstract of DOI:10.1016/j.poly.2012.11.017

Hg(TePh)₂ (Ph = phenyl) reacts with Hg(dedtc)₂ (dedtc = diethyldithiocarbamate), as well as with Hg(dedtp)₂ (dedtp = diethyldithiophosphate) and sodium pyrrolidine dithiocarbamate to give the coordination polymers [Hg(TePh)(S₂CNEt₂)]_n (1), [Hg(TePh){S₂P(OEt)₂}]_n (2), and [Hg(TePh)(S₂CNC₄H₈)]_n (3); Hg{Te(dmb)}₂ (dmb = 2,6-dimethoxybenzene) and Hg{Te(mes)}₂ (mes = 2,4,6-trimethylbenzene) react with NaS₂CNC₄H ₈ to yield the polymers [Hg{Te(dmb)(S₂CNC ₄H₈)}]_n (4) and [Hg{Te(mes)(S ₂CNC₄H₈)}]_n (5), as well as the mononuclear complexes [Hg(dmb)(S₂CNC₄H₈)] (6) and [Hg(mes)(S₂CNC₄H₈)] (7). The compounds 1, 2 and 3 present a helical structure along the Hg-Te bonds, while 4 and 5 show a zigzag arrangement. In 3, 4 and 5 each Hg atom is linked to two sulfur atoms of one dithio ligand. Compounds 6 and 7 are mononuclear, and probably also decomposition products of 4 and 5, respectively.

Full text of DOI:10.1016/j.poly.2012.11.017

Polyhedron 50 (2013) 467–472
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Polyhedron
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On the synthesis and structural analysis of some coordination polymers
derived from Hg(TeAr)2 involving dithio ligands
⇑
⇑
Ernesto Schulz Lang , Gelson Manzoni de Oliveira , Davi Fernando Back, Poliana Reckziegel
Laboratório de Materiais Inorgânicos – LMI, Universidade Federal de Santa Maria – UFSM, Departamento de Química, 97105-900 Santa Maria, RS, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Hg(TePh)2 (Ph = phenyl) reacts with Hg(dedtc)2 (dedtc = diethyldithiocarbamate), as well as with
Hg(dedtp)2 (dedtp = diethyldithiophosphate) and sodium pyrrolidine dithiocarbamate to give the coor-
dination polymers [Hg(TePh)(S2CNEt2)]n (1), [Hg(TePh){S2P(OEt)2}]n (2), and [Hg(TePh)(S2CNC4H8)]n (3);
Hg{Te(dmb)}2 (dmb = 2,6-dimethoxybenzene) and Hg{Te(mes)}2 (mes = 2,4,6-trimethylbenzene) react
with NaS2CNC4H8 to yield the polymers [Hg{Te(dmb)(S2CNC4H8)}]n (4) and [Hg{Te(mes)(S2CNC4H8)}]n
(5), as well as the mononuclear complexes [Hg(dmb)(S2CNC4H8)] (6) and [Hg(mes)(S2CNC4H8)] (7).
The compounds 1, 2 and 3 present a helical structure along the Hg–Te bonds, while 4 and 5 show a
zigzag arrangement. In 3, 4 and 5 each Hg atom is linked to two sulfur atoms of one dithio ligand.
Received 13 September 2012
Accepted 19 November 2012
Available online 29 November 2012
Keywords:
Mercury aryltellurolate polymers
Coordination polymers
Dithio ligands
Compounds
respectively.
6 and 7 are mononuclear, and probably also decomposition products of 4 and 5,
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
However, despite its potential applications [9], CP of mercury
have been less investigated in comparison to other elements, be-
cause these species (Hg–CP) present very low solubility in organic
solvents and also in water. This undesirable property can lead to
serious problems regarding the effective reactivity as well as the
adequate growth of crystals suitable for X-ray measurements
[9,10]. Another solubility limiting factor is the absence of mercury
aryl chalcogenolate polymers with substituted aryl groups: the
only known compounds of mercury aryl chalcogenolate polymers
are those derived from Hg(PhE)2.
With the aim, to show that Hg(TePh)2 and its substituted ana-
logue compounds Hg(TeAr)2 {Ar = 2,4,6-trimethylbenzene (mes);
2,6-dimethoxybenzene (dmb)} are valuable sources for the prepa-
ration of proper coordination polymers by reaction with dithio li-
gands, because the substituted aryl groups improve the solubility
of the resulting CPs, we carried out a series of reactions of
Hg(TePh)2 with the dithiocarbamate NaS2CNC4H8, as well as with
Hg(dedtp)2 (dedtp = diethyldithiophosphate) and Hg(dedtc)2 (ded-
tc = diethyldithiocarbamate). With the bulky species Hg{Te(dmb)}2
and Hg{Te(mes)}2, reactions were carried out only with NaS2CNC4H8,
because their reactions with Hg(dedtp)2 and Hg(dedtc)2 do not
occur under normal conditions.
Newly we have pointed out, in a kind of review works on recent
results on Hg–E clusters [1,2], that the compounds Hg(EPh)2
(E = Se, Te; Ph = phenyl) are valuable sources of {ME} for the syn-
thesis of binary and ternary clusters, attaining also polymeric
structures by intermolecular Hgꢀ ꢀ ꢀE interactions in the solid state
[3–5], being solubilized only in coordinating solvents [6]. This class
of compounds has been extensively used for the well-designed
syntheses of binary, as well as ternary clusters, acting as templates
to generate new products [4,7,8]. Given our interest in the metal
organochalcogenide cluster chemistry, we have investigated the
reactions of Hg(EPh)2 in different chemical environments and with
diverse reagents. These results led to several publications which
are listed in the first two references of this article.
With regard to coordination polymers (CP), in the last decades it
has been observed an increase involving studies on their synthesis
and structural characterization, since these species can be viewed
as an interface between synthetic chemistry and material sciences.
Coordination polymers attain specific structures, properties and
reactivities, which are not present in mononuclear compounds,
justifying the efforts put worldwide in the search for new materials
(CP) in different areas such as catalysis, molecular sensing, magne-
tism and luminescence, for instance [9].
We discuss in follows the synthesis and the structural
characterization of the coordination polymers [Hg(TePh)(S2CNEt2)]n
(1), [Hg(TePh){S2P(OEt)2}]n (2), [Hg(TePh)(S2CNC4H8)]n (3),
[Hg{Te(dmb)(S2CNC4H8)}]n (4), [Hg{Te(mes)(S2CNC4H8)}]n (5), as
well as the mononuclear compounds [Hg(dmb)(S2CNC4H8)] (6)
and [Hg(mes)(S2CNC4H8)] (7).
⇑
Corresponding authors. Tel.: +55 55 3220 8980; fax: +55 55 3220 8031.
E-mail addresses: eslang@smail.ufsm.br (E. Schulz Lang), manzonideo@smail.
ufsm.br (G. Manzoni de Oliveira).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.11.017

468
E. Schulz Lang et al. / Polyhedron 50 (2013) 467–472
2.3. Preparation of [Hg(TePh){S2P(OEt)2}]n (2)
2. Experimental
2.1. General
To 0.061 g (0.1 mmol) of Hg(PhTe)2 dissolved in 8 mL of dmf,
0.057 g (0.1 mmol) of Hg(dedtp) were added. After 1 h stirring at
40 °C a clear, dark yellow solution was formed. Yellow crystals of
the product were obtained in the course of 6 days. Yield: 85% based
on Hg(PhTe)2.
Properties: Yellow crystalline substance. Melting point: 152–
154 °C. Anal. Calc. for C30H45Hg3O6P3S6Te3 (1771.50): C, 20.34; H,
Solvents were purified and dried according to literature proce-
dures [11] and freshly distilled before use. Since the chalcogeno-
philicity of mercury increases in the sequence S < Se < Te [12]
and this has been considered as one of the factors for the danger
of organometallic mercury species, the manipulation of the
HgTe-containing chemicals was made in a good hood and with a
paper gas mask and gloves. Elemental analyses (CHN) were carried
out with a VARIO EL (Elementar Analysensysteme GmbH) analyzer.
Infrared spectra were measured on a Bruker Tensor 27 mid-IR
spectrometer. Melting points were determined on a Microquímica
MQAPF-301 melting point apparatus and are uncorrected.
2.56. Found: C, 20.52; H, 2.62%. IR (KBr): 3052 [
m
s(C–H)]; 2894
s(C@C)]; 1096 [dip(C@C–H)]; 940 [ s(C–O)];
s(P–S)];
[
m
s(C–H)aliph.]; 1570 [
m
m
778 [
ms(P–O)]; 738 [dop(C@C–H)]; 691 [ms(P@S)]; 557 [m
453 cmꢁ1 [dop(C@C–C)].
2.4. Preparation of [Hg(TePh)(S2CNC4H8)]n (3)
The reaction steps involved in the preparation of the com-
pounds referred in this work are summarized in Chart 1.
To 0.061 g (0.1 mmol) of Hg(PhTe)2 dissolved in 8 mL of di-
methyl sulfoxide (DMSO), 0.017 g (0.1 mmol) of sodium pyrroli-
dine dithiocarbamate were added. After 1 h stirring at 40 °C a
clear, brown solution was formed. Orange crystals of the product
were obtained over the course of 9 days. Yield: 78% based on
Hg(PhTe)2.
2.2. Preparation of [Hg(TePh)(S2CNEt2)]n (1)
Properties: Air stable, orange crystalline substance. Melting
point: 203–205 °C. Anal. Calc. for C11H13HgNS2Te (551.53): C,
23.95; H, 2.38; N, 2.54. Found: C, 23.93; H, 2.42; N, 2.43%. IR (KBr):
To 0.061 g (0.1 mmol) of Hg(PhTe)2 dissolved in 8 mL of dimeth-
ylformamide (dmf), 0.05 g (0.1 mmol) of Hg(dedtc)2 were added.
After 1 h stirring at 40 °C a clear, light brown solution was formed.
Yellow crystals of the product grew over the course of 4 days.
Yield: 89% based on Hg(PhTe)2.
3000 [
m
s(C–H)]; 1568 [
m
s(C@C)]; 1249 [
ms(C–N)]; 1166 [ms(C@S)];
1013 [dip(C@C–H)]; 943 [
m
s(C–S)]; 729 [dop(C@C–H)]; 450 cmꢁ1
[dop(C@C–C)].
Properties: Air stable, yellow crystalline substance. Melting
point: 143–146 °C. Anal. Calc. for C11H15HgNS2Te (553.55): C,
23.87; H, 2.73; N, 2.53. Found: C, 23.91; H, 2.78; N, 2.58%. IR
2.5. Preparation of [Hg{Te(dmb)(S2CNC4H8)}]n (4)
(KBr): 3045 [
[dop(C@C–H)]; 437 [dop(C@C–C)]; 2924 [
N)]; 838 [ s(C@S)]. (dip and dop = in-plane
s(C–S)]; 1202 cmꢁ1
and out-of-plane bendings, respectively).
m
s(C–H)]; 1568 [
m
s(C@C)]; 1074 [dip(C@C–H)]; 730
m
s(C–H)aliph.]; 1264[ s(C–
m
To 0.073 g (0.1 mmol) of Hg{Te(dmb)}2 dissolved in 6 mL of
DMSO, 0.017 g (0.1 mmol) of sodium pyrrolidine dithiocarbamate
were added. After 1 h stirring at 40 °C a brown solution was
m
[m
[Hg(TePh){S2P(OEt)2}]n
2
[Hg(TePh)(S2CNEt2)]n
[Hg(TePh)(S2CNC4H8)]n
Hg(dedtp)2
Ar = Ph
DMF/Δ
3
1
2
8
2
4
(ArTe)2Hg
2
4
8
8
4
2
[Hg{Te(mes)(S2CNC4H8)}]n
[Hg{Te(dmb)(S2CNC4H8)}]n
5
4
24h
24h
[Hg(mes)(S2CNC4H8)]
[Hg(dmb)(S2CNC4H8)]
7
6
dmb = 2,6-dimethoxybenzene
mes = 2,4,6-trimethylbenzene
dedtc = diethyldithiocarbamate
dedtp = diethyldithiophosphate
Chart 1.

E. Schulz Lang et al. / Polyhedron 50 (2013) 467–472
469
Table 1
Crystallographic data and refinement parameters for 1, 2, 3, 4 and 5.
1
2
3
4
5
Empirical formula
C
11H15HgNS2Te
C30H45Hg3O6P3S6Te3
1771,50
C11H13HgNS2Te
551.53
C26H34Hg2N2O4S4Te2
1223.17
C14H19HgNS2Te
593.61
Fw (g molꢁ1
)
553.55
T (K)
296(2)
293(2)
293(2)
293(2)
296(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
trigonal
P3(2)
11.1272(3)
11.1272(3)
10.5243(4)
90
90
120
1128.48(6)
3, 2.444
12.383
trigonal
P3(1)
19.2466(5)
19.2466(5)
11.2555(3)
90
90
120
3610.80(16)
3, 2.444
11.721
monoclinic
P21/c
9.4120(3)
6.5791(2)
22.4300(8)
90
94.428(2)
90
1384.78(8)
4, 2.645
triclinic
P1
monoclinic
C2/c
46.945(5)
4.462(5)
16.246(5)
90
95.795(5)
90
ꢀ
7.3679(3)
10.5031(4)
22.0348(9)
81.661(2)
88.311(2)
73.326(2)
1616.08(11)
2, 2.514
a
(°)
b (°)
c
(°)
V (Å3)
3386(4)
8, 2.329
11.015
Z, qcalc (g cmꢁ3
l
)
(mmꢁ1
)
13.454
11.551
F(000)
756
2430
1000
1128
2192
Crystal size (mm)
h range (°)
Limiting indices (h, k, l)
0.16 ꢂ 0.15 ꢂ 0.13
2.11ꢁ27.15
ꢁ14 6 h 6 14
ꢁ14 6 k 6 14
ꢁ13 6 l 6 13
7877
0.316 ꢂ 0.081 ꢂ 0.076
1.22ꢁ26.77
ꢁ24 6 h 6 24
ꢁ24 6 k 6 24
ꢁ13 6 l 6 14
39885
0.322 ꢂ 0.088 ꢂ 0.049
1.82ꢁ27.13
ꢁ11 6 h 6 11
ꢁ8 6 k 6 8
ꢁ28 6 l 6 28
18831
0.345 ꢂ 0.046 ꢂ 0.038
0.93ꢁ29.67
ꢁ10 6 h 6 10
ꢁ14 6 k 6 14
ꢁ30 6 l 6 30
48330
0.3 ꢂ 0.03 ꢂ 0.03
2.52ꢁ30.47
ꢁ66 6 h 6 65
ꢁ6 6 k 6 6
ꢁ22 6 l 6 23
28446
Reflections collected
Reflections unique
2988
8475
3031
9112
5159
Completeness to hmax (%)
Absorption correction
92.9
Gaussian
90.0
Gaussian
98.9
Gaussian
99.5
Gaussian
99.8
semi-emp. from
equivls.
Minimum and maximum transmission 0.2420 and 0.2959
0.1480 and 0.4943
8475/2/356
0.905
0.6839 and 0.9716
3031/0/145
1.005
0.7272 and 1.0000
9112/0/361
0.979
1 and 0.9067
5159/0/172
0.997
Data/restraints/parameters
2988/1/146
1.119
Goodness-of-fit on F2
Final R indices [I > 2
r
(I)]
R1 = 0.0673,
wR2 = 0.1467
R1 = 0.0798,
wR2 = 0.1510
3.623 and ꢁ2.068
R1 = 0.0573,
wR2 = 0.1248
R1 = 0.0909,
wR2 = 0.1340
2.790 and ꢁ1.377
R1 = 0.0223,
wR2 = 0.0361
R1 = 0.0396,
wR2 = 0.0404
0.866 and ꢁ0.625
R1 = 0.0350,
wR2 = 0.0475
R1 = 0.0806,
wR2 = 0.0569
0.832 and ꢁ0.926
R1 = 0.0332, wR2
= 0.0587
R1 = 0.0732, wR2
= 0.0689
R indices (all data)
Largest difference in peak and hole
(e Åꢁ3
1.231 and ꢁ0.961
)
Table 2
Crystallographic data and refinement parameters for 6 and 7.
formed. Yellow crystals of the product were obtained from the
solution after 7 days stored. Yield: 62% based on Hg{Te(dmb)}2.
Properties: Air stable, yellow crystalline substance. Melting
point: 151–153 °C. Anal. Calc. for C26H34Hg2N2O4S4Te2 (1223.17):
C, 25.53; H, 2.80, N, 2.29. Found: C, 25.51; H, 2.85; N, 2.24%. IR
6
7
Empirical formula
C
13H17NO2S2Hg
C14H19NS2Hg
466.01
Fw (g molꢁ1
)
483.99
T (K)
296(2)
293(2)
(KBr): 3010 [
s(C–N)]; 1167 [
946 [
s(C–S)]; 749 [dop(C@C–H)], 450 cmꢁ1 [dop(C@C–C)].
m
s(C–H)]; 2952 [
ms(C–H)]; 1582 [ms(C@C)]; 1241
Crystal system
Space group
a (Å)
b (Å)
c (Å)
monoclinic
P21/c
11.6298(5)
8.6838(4)
14.9713(6)
90
92.504(2)
90
1510.52(11)
4, 2.128
10.462
orthorhombic
P212121
7.269(5)
12.438(5)
16.896(5)
90.000(5)
90.000(5)
90.000(5)
1527.6(13)
4, 2.026
[m
m
s(C@S)]; 1103 [
mas(C–O–C)]; 998 [dip(C@C–H)];
m
2.6. Preparation of [Hg{Te(mes)(S2CNC4H8)}]n (5)
a
(°)
b (°)
c
(°)
To 0.069 g (0.1 mmol) of Hg{Te(mes)}2 dissolved in 6 mL of
DMSO, 0.017 g (0.1 mmol) of sodium pyrrolidine dithiocarbamate
were added. After 1 h stirring at 40 °C a yellow solution was
formed. Yellow crystals of the product were obtained after 7 days
laying up of the solution. Yield: 82% based on Hg{Te(mes)}2.
Properties: Air stable, yellow crystalline substance. Melting
point: 169–171 °C. Anal. Calc. for C14H19HgNS2Te (593.61): C,
28.33; H, 3.23; N, 2.36. Found: C, 28.48; H, 3.30; N, 2.34%. IR
V (Å3)
Z, qcalc (g cmꢁ3
l
)
(mmꢁ1
)
10.332
F(000)
920
888
Crystal size (mm)
h range (°)
Limiting indices (h, k, l)
0.16 ꢂ 0.10 ꢂ 0.08
1.75–29.65
ꢁ16 6 h 6 16
ꢁ12 6 k 6 12
ꢁ20 6 l 6 20
43937
0.716 ꢂ 0.057 ꢂ 0.05
2.03–27.22
ꢁ9 6 h 6 8
ꢁ15 6 k 6 15
ꢁ21 6 l 6 21
12084
Reflections collected
Reflections unique
(KBr): 3000 [
m
s(C–H)]; 2962 [
m
s(C–H)]; 1444 [
ms(C@C)]; 1292
4250
3260
[ms(C–N)]; 1165 [ms(C@S)]; 1025 [dip(C@C–H)]; 946 [ms(C–S)]; 844
Completeness to hmax (%)
Absorption correction
Minimum and maximum
transmission
99.7
Gaussian
97.8
Gaussian
[dop(C@C–H)], 450 cmꢁ1 [dop(C@C–C)].
0.2853 and 0.4882 0.1346 and 0.6645
2.7. Preparation of [Hg(dmb)(S2CNC4H8)] (6)
Data/restraints/parameters
4250/0/173
1.015
3260/0/164
0.995
Goodness-of-fit on F2
To 0.073 g (0.1 mmol) of Hg{Te(dmb)}2 dissolved in 6 mL of
DMSO, 0.017 g (0.1 mmol) of sodium pyrrolidine dithiocarbamate
were added. After 24 h stirring at 40 °C a yellow, cloudy solution
was formed. The colorless main crystals isolated were obtained
over the course of 10 days, corresponding to 6. Yield: 73% based
on sodium pyrrolidine dithiocarbamate.
Final R indices [I > 2
R indices (all data)
r
(I)]
R1 = 0.0253,
wR2 = 0.0441
R1 = 0.0475,
wR2 = 0.0499
0.489 and ꢁ0.664
R1 = 0.0282,
wR2 = 0.0515
R1 = 0.0424,
wR2 = 0.0552
0.553 and –0.515
Largest difference in peak and
hole (e Åꢁ3
)

470
E. Schulz Lang et al. / Polyhedron 50 (2013) 467–472
Fig. 1. The polymeric structure and the screw-shaped configuration of the Hg and
Te atoms of [Hg(TePh)(S2CNEt2)]n (1). For clarity, the phenyl groups bound to the
tellurium atoms, as well as the hydrogen atoms are not shown. Symmetry
transformations used to generate equivalent atoms: (0) = 1 ꢁ y, ꢁ1 + x ꢁ y,
ꢁ0.33333 + z; (00) = 2 ꢁ x + y, 1 ꢁ x, 0.33333 + z; (000) = 1 ꢁ y, ꢁ1 + x ꢁ y, 0.66667 + z.
Fig. 3. The polymeric, screw-shaped structure of compound [Hg(TePh)(S2CNC4H8)]n
(3). For clarity, the phenyl groups bound to the Te atoms, as well as the hydrogen
atoms are not shown. Symmetry transformations used to generate equivalent
atoms: (0) = 1 ꢁ x, 0.5 + y, 0.5 ꢁ z; (00) = 1 ꢁ x, ꢁ0.5 + y, 0.5 ꢁ z; (000) = x, 1 + y, z.
Fig. 2. The polymeric structure and the helical organization of mercury and
tellurium of [Hg(TePh){S2P(OEt)2}]n (2). For clarity, the phenyl groups bound to the
Te atoms, as well as the hydrogen atoms are not shown. Symmetry transformations
used to generate equivalent atoms: (0) = 4 ꢁ x + y, 2 ꢁ x, ꢁ0.33333 + z; (00) = 2 ꢁ y,
Fig. 4. The polymeric, zigzag structure of [Hg{Te(dmb)(S2CNC4H8)}]n (4). For clarity,
the hydrogen atoms are not shown. The dashed lines identify the TeꢁO secondary
interactions. Symmetry transformations used to generate equivalent atoms:
(0) = ꢁ1 + x, y, z; (00) = 1 + x, y, z.
ꢁ2 + x ꢁ y, ꢁ66667 + z;
(
000) = x, y, 1 ꢁ z;
(
0000) = 2 ꢁ y, ꢁ2 + x ꢁ y, 0.33333 + z;
(
00000) = 4 ꢁ x + y, 2 ꢁ x, 0.66667 + z.
in the course of 15 days, corresponding to 7. Yield: 64% based on
sodium pyrrolidine dithiocarbamate.
Properties: Air stable, colorless crystalline substance. Melting
point: 179–181 °C. Anal. Calc. for C14H19NS2Hg (466.01): C, 42.78;
H, 4.87; N, 3.56. Found: C, 42.43; H, 5.02; N, 3.52. IR (KBr): 3100
Properties: Air stable, colorless crystalline substance. Melting
point: 159–161 °C. Anal. Calc. for C13H17NO2S2Hg (483.99): C,
38.00; H, 4.17; N, 3.41. Found: C, 39.45; H, 4.24; N, 3.34%. IR
(KBr): 3100 [
s(C–N)]; 1161 [
946 [
s(C–S)]; 758 [dop(C@C–H)]; 455 cmꢁ1 [dop(C@C–C)].
m
s(C–H)]; 2970 [
m
s(C–H)]; 1582 [
ms(C@C)]; 1237
[m
ms(C@S)]; 1102 [
mas(C–O–C)]; 1000 [dip(C@C–H)];
[
m
m
s(C–H)]; 2954 [
s(C@S)]; 1028 [dip(C@C–H)]; 947 [
m
s(C–H)]; 1568 [
m
s(C@C)]; 1249 [
ms(C–N)]; 1166
m
[
m
s(C–S)]; 703 [dop(C@C–H)],
451 cmꢁ1 [dop(C@C–C)].
2.8. Preparation of [Hg(mes)(S2CNC4H8)] (7)
2.9. X-ray structural determination
To 0.069 g (0.1 mmol) of Hg{Te(mes)}2 dissolved in 6 mL of
DMSO, 0.017 g (0.1 mmol) of sodium pyrrolidine dithiocarbamate
were added. After 24 h stirring at 40 °C a yellow, cloudy solution
was attained. The colorless main crystals isolated were obtained
Data were collected with a Bruker APEX II CCD area-detector
diffractometer and graphite-monochromatized Mo K radiation.
The structures were solved by direct methods using SHELXS-97
a

E. Schulz Lang et al. / Polyhedron 50 (2013) 467–472
471
Table 3
Selected bond lengths (Å) and angles (°) for 1–7.
Bond lengths
Bond angles
1
1
Te–Hg
Te0–Hg
Hg–S1
Hg–S2
2.7566(1)
2.7755(1)
2.6039(0)
2.5909(1)
Hg00–Te–Hg
Te–Hg–Te0
Te–Hg–S1
Te–Hg–S2
S1–Hg–S2
Te0–Hg–S2
Te0–Hg–S1
83.980(1)
112.423(1)
109.633(1)
113.933(1)
93.490(1)
109.476(1)
116.640(1)
2
2
Te1–Hg1
Hg1–Te10
Hg1–S1
Hg1–S20000
2.7441(16)
2.7542(15)
2.590(6)
Hg10000–Te1–Hg1
Te1–Hg1–Te10
Te1–Hg1–S1
Te1–Hg1–S20000
S1–Hg1–S20000
Te10–Hg1–S20000
Te10–Hg1–S1
91.894(1)
114.401(1)
122.624(1)
106.350(1)
86.736(1)
113.527(1)
109.832(1)
2.656(6)
3
3
Te–Hg
Te–Hg0
Hg–S1
Hg–S2
2.7069(1)
2.7879(1)
2.6375(1)
2.6114(1)
Te–Hg–Te00
Te–Hg–S1
Te–Hg–S2
Te00–Hg–S1
Te00–Hg–S2
S1–Hg–S2
Hg–Te–Hg0
123.720(1)
121.915(1)
118.485(1)
105.768(1)
104.347(1)
69.386(1)
96.419(1)
Fig. 5. The polymeric, zigzag structure of compound [Hg{Te(mes)(S2CNC4H8)}]n (5).
For clarity, the hydrogen atoms are not shown. Symmetry transformations used to
generate equivalent atoms: (0) = x, ꢁ1 + y, z; (00) = x, ꢁ2 + y, z; (000) = x, 1 + y, z.
4
4
Te1–Hg1
Te1–Hg200
Te2–Hg2
Te2–Hg1
Hg1–S1
Hg1–S2
Hg2–S3
Hg2–S4
Te1ꢀ ꢀ ꢀO1
Te1ꢀ ꢀ ꢀO2
Te2ꢀ ꢀ ꢀO3
Te2ꢀ ꢀ ꢀO4
2.8008(1)
2.7387(1)
2.7998(1)
2.7413(1)
3.0263(1)
2.5170(1)
2.9251(1)
2.5426(1)
3.1888(1)
3.0904(1)
3.2075(1)
3.0708(1)
Hg200–Te1–Hg1
Hg200–Te1ꢀ ꢀ ꢀO1
Hg200–Te1ꢀ ꢀ ꢀO2
Hg1–Te1ꢀ ꢀ ꢀO1
Hg1–Te1ꢀ ꢀ ꢀO2
Hg1–Te2–Hg2
Hg1–Te2ꢀ ꢀ ꢀO3
Hg1–Te2ꢀ ꢀ ꢀO4
Hg2–Te2ꢀ ꢀ ꢀO3
Hg2–Te2ꢀ ꢀ ꢀO4
Te1–Hg1–Te2
S1–Hg1–S2
86.64(2)
80.302(2)
110.991(2)
59.166(1)
147.678(2)
87.871(2)
80.108(2)
110.009(2)
60.661(1)
148.584(2)
110.822(2)
64.033(2)
97.645(2)
124.927(2)
124.215(2)
122.524(2)
111.265(2)
65.318(2)
97.883(2)
121.317(2)
123.692(2)
125.019(2)
Fig. 6. Molecular structure of [Hg(dmb)(S2CNC4H8)] (6). Dashed lines are secondary
interactions. For clarity, the hydrogen atoms are not shown.
Te1–Hg1–S1
Te1–Hg1–S2
Te2ꢁHg1ꢁS1
Te2ꢁHg1ꢁS2
Te2–Hg2–Te10
S3–Hg2–S4
Te2–Hg2–S3
Te2–Hg2–S4
Te10–Hg2–S3
Te10–Hg2–S4
Fig. 7. Molecular structure of [Hg(mes)(S2CNC4H8)] (7). For clarity, the hydrogen
5
5
atoms are not shown.
Hg–Te
Te0–Hg0
Hg–S1
Hg–S2
Te–C1
2.6241(16)
3.131(2)
2.7293(15)
2.4841(16)
2.131(5)
Hg–Te–Hg0
Te000–Hg–S1
Te000–Hg–S2
Te–Hg–S1
Te–Hg–S2
S2–Hg–S1
101.30(6)
82.53(5)
98.88(6)
134.15(3)
150.49(3)
69.69(4)
[13]. Subsequent Fourier-difference map analyses yielded the posi-
tions of the non-hydrogen atoms. Refinements were carried out
with the SHELXL-97 package [13]. All refinements were made by
full-matrix least-squares on F2 with anisotropic displacement
parameters for all non-hydrogen atoms. Hydrogen atoms were in-
cluded in the refinement in calculated positions. Crystal data and
more details of the data collections and refinements are contained
in Tables 1 and 2.
6
6
Hg–C1
Hgꢀ ꢀ ꢀO2
Hgꢀ ꢀ ꢀO1
Hg–S1
Hg–S2
2.0596(4)
3.0615(3)
3.0698(1)
2.3731(2)
2.9611(1)
S2–Hg–C1
S1–Hg–C1
S1–Hgꢀ ꢀ ꢀO2
S1– Hgꢀ ꢀ ꢀO1
S2–Hgꢀ ꢀ ꢀO1
S2–Hgꢀ ꢀ ꢀO2
S1–Hg–S2
O1ꢀ ꢀ ꢀHgꢀ ꢀ ꢀO2
117.430(2)
175.396(2)
129.007(2)
131.623(1)
110.703(3)
103.966(4)
66.970(3)
99.087(1)
3. Discussion
7
7
Hg–C1
Hg–S1
Hg–S2
Hgꢀ ꢀ ꢀC7
Hgꢀ ꢀ ꢀC9
2.0646(8)
2.397(1)
2.9208(8)
3.2168(8)
3.2898(9)
S1–Hg–C1
S2–Hg–C1
S1–Hg–S2
S2– Hgꢀ ꢀ ꢀC7
S2–Hgꢀ ꢀ ꢀC9
171.594(26)
121.428(14)
66.97(1)
170.68(1)
71.16(1)
Figs. 1–5 show the polymeric structure of compounds 1–5, and
Figs. 6 and 7 display the mononuclear molecules of 6 and 7. Table 3
resumes selected bond angles and lengths for the reactions prod-
ucts 1–7.
The structures of compounds 1, 2 and 3 are very similar, since
these three polymers, although containing different dithio groups,
show all a helical pattern of the bound Hg–Te atoms. While the
tetrahedral configuration of the Hg atoms in 1 and 2 is attained
(continued on next page)

472
E. Schulz Lang et al. / Polyhedron 50 (2013) 467–472
Hg(dmbTe)2} and the side products (mesTe)2 and (dmbTe)2 were
present [1].
In the species 6 and 7 the Hg atoms show its typical (mainly)
linear bonds, S1–Hg–C1 {175.396(2)°, 6 and 171.594(26)°, 7}. Such
linear bonds are not observable when Te is one of the terminal
atoms, as shown by the compounds 1–5.
Table 3 (continued)
Bond lengths
Bond angles
S1–Hgꢀ ꢀ ꢀC9
S1–Hgꢀ ꢀ ꢀC7
C7ꢀ ꢀ ꢀHgꢀ ꢀ ꢀC9
137.743(19)
120.405(13)
101.835(8)
Symmetry transformations used to generate equivalent atoms: 1: (0) = 1 – y, –
1 + x – y, –0.33333 + z; (00) = 2 – x + y, 1 – x, 0.33333 + z. 2: (0) = 4 – x + y, 2 – x, –
0.3333 + z; (0000) = 2 – y, –2 + x – y, 0.3333 + z. 3: (0) = 1 – x, 0.5 + y, 0.5 – z; (00) = 1 – x,
–0.5 + y, 0.5 – z. 4: (0) = –1 + x, y, z; (00) = 1 + x, y, z. 5: (0) = x, –1 + y, z; (000) = x, 1 + y, z.
Acknowledgments
This work was supported with funds from CNPq, CAPES and FA-
PERGS (Brazilian agencies).
by two sulfur atoms assigned to two dithio groups, in compound 3
(and also in 4, 5, 6 and 7) single dithio groups provide two sulfurs
atoms for each Hg, allowing the metal atoms maintain their tetra-
hedral arrangement. The sulfur atoms of the ligands dedtc, dedtp
and pyrrolidine dithiocarbamate can act as bridge-forming or
bidentate ligands. Factors influencing either function are: the con-
ditions of the reaction, the presence of co-ligands and the stereo-
chemistry of the end products. These effects are also observable
with the dithio ligand R2N–CS2 [14] and with the thio ligand 4,6-di-
methyl-2-pyrimidinethiolate [15]. In compounds 1, 2 and 3 the
medium distances Hg–S1/Hg–S2 are respectively 2.6105 and
2.6194 Å, but, on the contrary, the Hg–S1/Hg–S2 bonds in 4, 5, 6
and 7 are very asymmetrical (see Table 3).
Appendix A. Supplementary data
CCDC 900906–900912 contain the supplementary crystallo-
graphic data for 1–7, respectively. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
References
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(2012), http://dx.doi.org/10.1016/j.poly.2012.06.058.
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(1982) 607.
While in the polymers 1, 2 and 3 the Hg–Te distances are
around 2.75 Å, in the zigzag configured compound
4 the
Te1(Te2)–Hg1 distances reach 2.8008 Å, whereas the Te1(Te2)–
Hg2 bonds retain the ‘‘normal’’ distances, approximately 2.735 Å.
In the also zigzag configured polymer 5 the asymmetry of the
Hg–Te distances achieve the maximum values: 2.6242 (Hg–Te)
and 3.1350 Å (Hg–Te0). As the sum of the Hg/Te van der Waals radii
is 3.61 Å, the Hg–Te0 interactions can be considered as effective
bonds.
The polymeric structures of compounds 1–5 are not observed in
the complexes [Hg(dmb)(S2CNC4H8)] (6) and [Hg(mes)(S2CNC4H8)]
(7). Since these two compounds were prepared by extended
stirring at 40 °C of the mother solutions of 4 and 5, respectively,
they (6 and 7) are supposed to be decomposition products of poly-
mers 4 and 5. It is not wrong to assert that, at the end of the reac-
tions, only the products (6 and 7), starting materials {Hg(mesTe)2,
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Pergamon Press, Oxford, EUA, 1998.
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[13] G.M. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112.
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Tiekink, Inorg. Chem. 30 (1991) 192.
[15] E. Schulz Lang, G. Manzoni de Oliveira, G.A. Casagrande, E.M. Vázquez-López,
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