Compositional and structural variety of diphenyllead(IV) complexes obtained by reaction of diphenyllead dichloride with thiosemicarbazones

Article abstract of DOI:10.1021/ic026219r

The reactions of PbPh₂Cl₂ in methanol with acetophenone, salicylaldehyde, pyridine-2-carbaldehyde, 2-acetylpyridine, and 2-benzoylpyridine thiosemicarbazones (HATSC, HSTSC, HPyTSC, HAcPyTSC, and HBPyTSC, respectively) were explored.

Full text of DOI:10.1021/ic026219r

Inorg. Chem. 2003, 42, 2584−2595
Compositional and Structural Variety of Diphenyllead(IV) Complexes
Obtained by Reaction of Diphenyllead Dichloride with
Thiosemicarbazones
Jose´ S. Casas,*,1a Eduardo E. Castellano,1b J. Ellena,1b Mar´ıa S. Garc´ıa Tasende,1a Agust´ın Sa´nchez,1a
Jose´ Sordo,1a and Mar´ıa J. Vidarte1a
Departamento de Qu´ımica Inorga´nica, UniVersidade de Santiago de Compostela,
15782 Santiago de Compostela, Spain, and Instituto de F´ısica e Qu´ımica de Saˆo Carlos,
UniVersidade de Saˆo Paulo, CEP 13560 Saˆo Carlos, Brazil
Received November 28, 2002
The reactions of PbPh Cl2 in methanol with acetophenone, salicylaldehyde, pyridine-2-carbaldehyde, 2-acetylpyridine,
2
and 2-benzoylpyridine thiosemicarbazones (HATSC, HSTSC, HPyTSC, HAcPyTSC, and HBPyTSC, respectively)
were explored. Despite the similarities among these ligands, the reactions afforded solids with very diverse
compositions and structural characteristics, which were in most cases analyzed by X-ray diffractometry (as was the
structure of the free ligand HBPyTSC). In the complexes [PbPh2Cl2(HATSC)]2, [PbPh2Cl2(HSTSC)2], [{PbPh2Cl-
(HPyTSC)}2][PbPh2Cl3(MeOH)]2, and [PbPh2Cl(PyTSC)] the metal atoms are surrounded by more or less distorted
octahedral coordination polyhedra; if both strong and weak interactions are considered, the lead atom in [PbPh2-
Cl(AcPyTSC)] has coordination number 7 and distorted pentagonal bipyramidal coordination geometry, while [{PbPh -
2
(BPyTSC)}2(PbPh2Cl4)]‚2MeOH contains two different types of lead atom, one with octahedral and the other with
pentagonal bipyramidal coordination. The complexes (H AcPyTSC)[PbPh2Cl3] and [PbPh2Cl(HAcPyTSC)][PbPh2-
2
Cl3], which were also isolated, could not be crystallized. All these complexes are soluble in DMSO, and the
1
compositions of these solutions were investigated using conductivity measurements and H and 207Pb NMR
spectroscopy.
1. Introduction
To add to the available information on the coordination
behavior of organolead compounds we have begun to explore
complexes derived from interaction between diphenyllead
dichloride and thiosemicarbazone ligands (HTSCs, Chart 1).
Although phenyllead derivatives are only used in organic
synthesis5 and have little environmental impact, they are
relatively stable and will hopefully provide insight into Rn-
PbIV-ligand interactions.
In recent years there has been a renaissance of interest in
the coordination chemistry of lead2,3 due in part to its intrinsic
richness and also to the toxicological and environmental
importance of this metal. Most of this recent work has been
devoted to lead(II), possibly because it is assumed that this
is the only oxidation state of relevance in biological systems.
There is nevertheless clear evidence that intake of organolead
compounds by mammals is only partly metabolized to and
excreted as “inorganic” Pb(II).4 Furthermore, there is no
therapy for organolead poisoning, the chelating agents used
to reduce the burden of other heavy metals not being effective
against organolead.4
As far as we know, the reactions between PbPh2Cl2 and
thiosemicarbazones have previously been investigated only
by Dixit et al.,6 who used IR and NMR spectroscopy to
identify the complexes isolated. We show in this article that
the solid-state structures of this type of complex, as
determined by single-crystal X-ray crystallography, can be
1
quite complicated, and we report H and 207Pb NMR data
* To whom correspondence should be addressed. E-mail: qiscasas@usc.es.
(1) (a) Departamento de Qu´ımica Inorga´nica, Universidade de Santiago
de Compostela. (b) Instituto de F´ısica de Sa˜o Carlos, Universidade
de Sa˜o Paulo.
throwing light on their structures in DMSO solution.
2. Experimental Section
2.1. Materials. Acetophenone (Ega-Chemie), salicylaldehyde
(Aldrich), pyridine-2-carbaldehyde (Aldrich), 2-acetylpyridine
(2) Parr, J. Polyhedron 1997, 16, 551.
(3) Sigel, H.; Da Costa, C. P.; Mart´ın, R. B. Coord. Chem. ReV. 2001,
219-221, 435.
(4) Scha¨fer, S. G.; Davies, R. L. F.; Elsenhans, B.; Forth, W.; Schu¨mann,
K. In Toxicology; Marquardt, H., Scha¨fer, S. G., McClellan, R. O.,
Welsch, F., Eds.; Academic Press: San Diego, CA, 1999; Chapter
32.
(5) Pinhey, J. T. In ComprehensiVe Organometallic Chemistry II; Abel,
E. W., Stone; F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, U.K.,
1995; Vol. 11, Chapter 11.
2584 Inorganic Chemistry, Vol. 42, No. 8, 2003
10.1021/ic026219r CCC: $25.00 © 2003 American Chemical Society
Published on Web 03/20/2003

Diphenyllead(IV) Complexes
Table 1. Crystal and Refinement Data for HBPyTSC and the HTSC Complexes
[PbPh2Cl2-
(HATSC)]2
[PbPh2Cl2-
(HSTSC)2]
[{PbPh2Cl(HPyTSC)}2]
[PbPh2Cl-
(PyTSC)]
[PbPh2Cl-
[{PbPh2(BPyTSC)}2-
(PbPh2Cl4)]‚2MeOH
HBPyTSC
13H12N4S
[(PbPh2Cl3(MeOH))]2
(AcPyTSC)]
molecular
formula
Mr
temp (K)
λ (Å)
cryst system
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
C
C42H42Cl4N6Pb2S2
C
28H28Cl2N6O2PbS2
C
64H64Cl8N8O2Pb4S2
C
19H17ClN4PbS C20H19ClN4PbS
C64H62Cl4N8O2Pb3S2
256.33
120(2)
1253.12
293(2)
0.710 73
triclinic
P1h
8.5712(2)
9.1760(2)
14.1713(3)
90.6640(10)
94.6720(10)
92.4770(10)
1109.69(4)
1
822.78
293(2)
2153.76
293(2)
0.710 73
triclinic
P1h
9.907(2)
12.604(3)
15.834(4)
109.016(4)
92.413(4)
103.377(4)
1803.6(8)
1
576.07
293(2)
590.09
293(2)
0.710 73
triclinic
P1h
9.5816(17)
10.0802(18)
12.170(2)
95.587(3)
104.252(3)
114.979(2)
1005.2(3)
2
1802.7
120(2)
0.710 73
triclinic
P1h
9.8300(5)
11.8780(6)
14.8020(8)
77.330(2)
85.924(2)
73.693(2)
1618.29(15)
1
0.710 73
monoclinic
C2/c
12.3340(2)
11.6570(2)
17.3750(4)
0.710 73
monoclinic
P21/c
13.817(3)
8.884(2)
12.906(3)
0.710 73
monoclinic
P21/n
13.3359(3)
11.1170(3)
13.5689(2)
90.6540(10)
94.019(5)
93.600(2)
2497.97(8)
8
1580.3(7)
2
2007.69(8)
4
Z
abs coeff
0.246
7.948
5.675
9.707
8.650
8.641
8.062
(mm-1
)
F(000)
1072
600
804
1016
1096
564
864
cryst size (mm) 0.20 × 0.20 × 0.28 0.06 × 0.10 × 0.10 0.23 × 0.17 × 0.06 0.26 × 0.12 × 0.25
0.1 × 0.06 × 0.02 0.19 × 0.26 × 0.37 0.10 × 0.15 × 0.60
θ range for data 2.34-27.49
1.44-25.00
1.48-28.13
-18, 7; -1,
2.58-26.34
2.08-25.00
1.77-26.40
2.06-25.00
0, 11; -13,
collcn (deg)
index ranges
0, 16; 0, 15;
-22, 22
5389
-10, 10; -10,
10; -16, 16
24 792
-12, 12; -15,
14; 0, 19
7344
-15, 15; -13,
13; -16, 16
25 528
-11, 11; -12,
12; 0, 15
4087
11; -17, 16
14; -17, 17
reflcns collcd
8318
1.013
10 405
1.052
goodness-of-fit 1.232
1.288
1.061
1.115
1.072
on F2
R1, wR2
0.0396, 0.1176
0.0245, 0.0731
0.0695, 0.1072
0.0252, 0.0528
0.0279, 0.0664
0.0164, 0.0398
0.0545, 0.1435
[I > 2σ(I)]
largest diff peak 0.376 and -0.540 0.660 and -1.985 2.317 and -1.607 1.044 and -0.948
1.319 and -1.511 0.628 and -1.113 2.14 and -2.41
and hole
(e Å-3
)
Chart 1
2.2. Physical Measurements. Elemental analyses for C, H, N,
and S were performed with a Fisons 1108 microanalyzer. Melting
points were determined with a Gallenkamp electrically heated
apparatus. Conductance measurements were made using a Crison
model microMC 2202 conductivity meter and samples prepared in
anhydrous DMSO (Aldrich) under N2 in a glovebox. NMR spectra
were recorded in DMSO using a Bruker AMX 300 spectrometer
1
at 300.14 MHz for H spectra (with TMS as internal reference)
and a Bruker AMX 500 at 104.58 MHz for 207Pb spectra (using a
saturated solution of PbPh4 in CDCl3, δ ) -178.0 ppm, as external
reference). Elemental analysis and all spectroscopic measurements
were carried out in the RIAIDT services of the University of
Santiago de Compostela. X-ray data were collected at the RIAIDT
services, at the CACTI services of the University of Vigo, and at
the Sao Carlos Institute of Physics of the University of Sao Paulo.
2.3. X-ray Crystallography. Crystal data, experimental details,
and refinement results are listed in Table 1. Data were collected
on an Enraf-Nonius CAD-4 diffractometer (HBPyTSC, [PbPh2Cl2-
(HATSC)]2, [PbPh2Cl(PyTSC)], and [{PbPh2(BPyTSC)}2(PbPh2-
Cl4)]‚2MeOH) or a Bruker Smart CCD1000 apparatus ([PbPh2Cl2-
(HSTSC)2], [{PbPh2Cl(HPyTSC)}2][PbPh2Cl3(MeOH)]2, and [PbPh2-
Cl(AcPyTSC)]). The structures were solved using direct methods
(HBPyTSC, [PbPh2Cl2(HATSC)]2, [PbPh2Cl(PyTSC)], [{PbPh2(B-
PyTSC)}2(PbPh2Cl4)‚2MeOH], and [{PbPh2Cl(HPyTSC)}2][PbPh2-
Cl3(MeOH)]2) or the Patterson method ([PbPh2Cl2(HSTSC)2] and
[PbPh2Cl(AcPyTSC)]), followed by conventional difference Fourier
techniques. All the H atoms were introduced in calculated positions
except H(2A) and H(1S) in [{PbPh2Cl(HPyTSC)}2][PbPh2Cl3-
(MeOH)]2, H(1N1) and H(2N1) in [PbPh2Cl(PyTSC)], and H(1A)
and H(1B) in [PbPh2Cl(AcPyTSC)], which were located in the
Fourier difference map and refined isotropically. The crystal of
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH presented disorder affect-
ing the methanol molecules and the phenyl and pyridine rings of
(6) Dixit, P.; Singh, K.; Tandon, J. P. J. Prakt. Chem. 1988, 330, 835.
Dixit P.; Singh, K.; Tandon, J. P. Indian J. Chem. 1989, 28A, 909.
Dixit, P.; Tandon, J. P. Phosphorus Sulfur Silicon Relat. Elem. 1990,
53, 389.
(Aldrich), 2-benzoylpyridine (Aldrich), thiosemicarbazide (Merck),
and dichlorodiphenyllead (Panreac), all of reagent grade, were used
without further purification.
Inorganic Chemistry, Vol. 42, No. 8, 2003 2585

Casas et al.
the thiosemicarbazone ligand, two atomic sites being observed for
each of the atoms in these fragments. The site occupancy factors
were determined as 0.600 and 0.400 for atoms in the pyridine rings,
0.700 and 0.300 for the phenyl rings, and 0.650 and 0.350 for the
methanol molecules. Only the lengths of bonds between the atoms
with the higher occupancy factors are included in the tables. The
structure solution program used was SHELX 97.7 Molecular
graphics were obtained with ORTEP and PLATON.8 Crystal-
lographic data are available as Supporting Information and as
deposited with the CCDC [CCDC Nos.: 198380 (C13H12N4S1);
198381 (C42H42Cl4N6Pb2S2); 198382 (C28H28Cl2N6O2PbS2); 198383
(C64H64Cl8N8O2Pb4S2); 198384 (C19H17ClN4PbS); 198385 (C20H19-
ClN4PbS); 198386 (C64H62Cl4N8O2Pb3S2].
2.4. Synthesis of the Ligands. HATSC, HSTSC, HPyTSC,
HAcPyTSC, and HBPyTSC (Chart 1) were prepared by following
the general procedure outlined by Anderson et al.9 by reacting the
thiosemicarbazide with the corresponding aldehyde or ketone in
ethanol/water, as described in detail for HATSC elsewhere.10 Only
in the case of HATSC was it necessary for the synthesis to be
carried out in the presence of glacial acetic.
δ[Ho(Ph-Pb)] ) 8.11 dd (4); δ[Hm(Ph-Pb)] ) 7.59 t (4); δ[Hp-
(Ph-Pb)] ) 7.44 t (2); 3J(1H-207Pb) ) 203.4 Hz; 4J(1H-207Pb) )
82.2 Hz. 207Pb NMR (DMSO-d6): -506 ppm. Slow evaporation of
the mother liquor at room temperature gave colorless crystals
suitable for X-ray diffractometry. The same complex was afforded
by 2:1 and 1:1 metal:ligand mole ratios.
PbPh2Cl2/HPyTSC Reaction. PbPh2Cl2 (0.10 g, 0.23 mmol) was
suspended in 10 mL of MeOH and added slowly to a solution of
HPyTSC (0.08 g, 0.46 mmol) in the same solvent (10 mL). PbPh2-
Cl2 rapidly dissolved, giving a clear yellow solution from which a
new solid separated. The crystalline solid formed upon stirring this
heterogeneous system overnight at room temperature was filtered
out and dried under vacuum (yield: 0.12 g). It comprised two types
of crystal, which were separated by hand under a microscope. One
type is stable to air and moisture and proved to be [PbPh2Cl-
(PyTSC)]. Mp: 204 °C. Anal. Calcd for C19H17ClN4PbS: 39.6;
H, 3.0; N, 10.0; S, 5.6. Found: C, 39.6; H, 2.9; N, 9.3; S, 5.4.
1
Molar conductivity (10-3 M in DMSO): 18.5 S cm2 mol-1. H
NMR (DMSO-d6, freshly prepared sample): δ[C(7)H] ) 8.91 d
(1); δ[C(2)H] ) 8.53 s (1); δ[N(1)H2] ) 7.46 s (2); δ[C(4)H] )
7.63 d (1); the [C(5)H] and [C(6)H] signals overlap those of the
phenyl groups; δ[Ho(Ph-Pb)] ) 7.92 dd (4); δ[Hm(Ph-Pb)] ) 7.44
2.4. Synthesis of the Complexes. The complexes were obtained
by reacting PbPh2Cl2 and each thiosemicarbazone in methanol. In
each case, 1:2, 1:1, and 2:1 mole ratios were used. Only syntheses
in 1:2 mole ratio are described in detail.
Caution! Lead is a highly toxic cumulatiVe poison, and lead
compounds should be handled carefully.4
3
4
t (4); δ[Hp(Ph-Pb)] ) 7.31 t (2); J(1H-207Pb) and J(1H-207Pb)
could not be calculated. The 1H NMR spectrum of this compound
rapidly becomes very complicated. 207Pb NMR (DMSO-d6 or DMF-
d6): no signal was observed.
PbPh2Cl2/HATSC Reaction. To a solution of HATSC (0.09 g,
0.46 mmol) in MeOH (3 mL) was slowly added a suspension of
PbPh2Cl2 (0.10 g, 0.23 mmol) in the same solvent (10 mL). The
suspension dissolved partially, and after it was stirred for 24 h, a
white solid formed which was filtered out and vacuum-dried.
Yield: 89.3%. Mp: 200 °C. Anal. Calcd for C21H21Cl2N3SPb
([PbPh2Cl2(HATSC)]2): C, 40.3; H, 3.3; N, 6.7; S, 5.1. Found: C,
40.5; H, 3.9; N, 6.8; S, 5.8. Molar conductivity (10-3 M in
DMSO): 4.4 Ω-1 cm2 mol-1. 1H NMR (DMSO-d6): δ[N(2)H] )
10.20 s (1); δ[N(1)H2] ) 8.26 s (1), 7.90 s (1); δ[C(4,8)H] ) 7.92
m (2); δ[C(5-7)H] ) 7.38 m (3); δ[Ho(Ph-Pb)] ) 8.11 dd (4);
Crystals of the other type became opaque with time and proved
to be [{PbPh2Cl(HPyTSC)}2][PbPh2Cl3(MeOH)]2. Mp: 227 °C.
Anal. Calcd for C32H32Cl4N4SOPb2: C, 35.7; H, 3.0; N, 5.2; S,
3.0. Found: C, 35.6; H, 2.7; N, 5.4; S, 2.7. Molar conductivity
(10-3 M in DMSO): 6.5 S cm2 mol-1 1H NMR (DMSO-d6):
.
δ[N(2)H] ) 11.62 s (2); δ[C(7)H] ) 8.55 d (2); δ[N(1)H2] ) 8.33
s (2), 8.16 s (2); δ[C(4)H] ) 8.26 d (2); δ[C(2)H] ) 8.07 s (2);
δ[C(5)H] ) 7.83 t (2); δ[C(6)H] ) 7.36 dd (2); δ[Ho(Ph-Pb)] )
8.15 d (16); δ[Hm(Ph-Pb)] ) 7.60 t (16); δ[Hp(Ph-Pb)] ) 7.43 t
(8); 3J(1H-207Pb) ) 204.0 Hz; 4J(1H-207Pb) ) 82.7 Hz. 207Pb NMR
(DMSO-d6): -506 ppm.
3
δ[Hm(Ph-Pb)] ) 7.59 t (4); δ[Hp(Ph-Pb)] ) 7.42 t (2); J(1H-
207Pb) ) 205.2 Hz; 4J(1H-207Pb) ) 82.2 Hz. 207Pb NMR (DMSO-
d6): -507 ppm. Crystals suitable for X-ray diffraction analysis were
obtained by crystallization from acetone/MeOH. Reactions in 2:1
and 1:1 mole ratios gave the same complex.
The reaction in 1:1 mole ratio also afforded a mixture of both
complexes, while reaction in 2:1 mole ratio gave only [{PbPh2Cl-
(HPyTSC)}2][PbPh2Cl3(MeOH)]2. Both complexes were studied by
X-ray diffractometry.
PbPh2Cl2/HSTSC Reaction. A suspension of PbPh2Cl2 (0.10
g, 0.23 mmol) in MeOH (7 mL) was added slowly with stirring to
a solution of HSTSC (0.09 g, 0.46 mmol) in the same solvent (10
mL). The suspension was dissolved, and the yellow solution
obtained was stirred for 48 h at room temperature. The white solid
formed was filtered out and vacuum-dried. Yield: 58.2%. Mp: 217
°C. Anal. Calcd for C28H28Cl2N6O2S2Pb ([PbPh2Cl2(HSTSC)2]): C,
40.9; H, 3.4; N, 10.2; S, 7.8. Found: C, 41.2; H, 3.1; N, 10.3; S,
8.1. Molar conductivity (10-3 M in DMSO): 4.5 S cm2 mol-1. 1H
NMR (DMSO-d6): δ[N(2)H] ) 11.35 s (2); δ[N(1)H2] ) 8.08 s
(2), 7.91 s (2); δ[OH] ) 9.87 s (2); δ[C(2)H] ) 8.36 s (2); δ[C(5)H]
) 7.89 s (2); δ[C(6)H] ) 7.20 td (2); δ[C(7,8)H] ) 6.80 m (4);
PbPh2Cl2/HAcPyTSC Reaction. A suspension of PbPh2Cl2
(0.10 g, 0.23 mmol) in MeOH (10 mL) was added with stirring to
a yellow suspension of HAcPyTSC (0.09 g, 0.46 mmol) in the same
solvent (10 mL). The orange solution obtained was stirred for 4 h
at room temperature. The yellow solid formed, probably PbPh2-
Cl2(HAcPyTSC)(HCl) or (H2AcPyTSC)[PbPh2Cl3] (see Discus-
sion), was filtered out and dried in vacuo. Yield: 53%. Mp: 207
°C. Anal. Calcd for C20H21Cl3N4SPb: C, 36.2; H, 3.2; N, 8.5; S,
4.8. Found: C, 37.0; H, 3.3; N, 8.9; S, 5.1. Molar conductivity
(10-3 M in DMSO): 8.2 S cm2 mol-1 1H NMR (DMSO-d6):
.
δ[N(2)H] ) 10.50 s (1); δ[C(7)H] ) 8.64 d (1); δ[N(1)H2] ) 8.51
s (1), 8.33 s (1); δ[C(4)H] ) 8.40 d (1); δ[C(5)H] ) 7.00 t (1);
δ[C(6)H] overlaps signals of the phenyl groups; δ[C(8)H3] ) 2.38
s (3); δ[Ho(Ph-Pb)] ) 8.15 d (4); δ[Hm(Ph-Pb)] ) 7.47 t (4);
δ[Hp(Ph-Pb)] ) 7.40 t (2); 3J(1H-207Pb) ) 206 Hz; 4J(1H-207Pb)
) 82.3 Hz. The fact that water signal is very wide seems likely to
be due to the presence of an unresolved pyridinium proton signal
(the same phenomenon has been also observed in the proton
spectrum of 2-acetylpyridine thiosemicarbazone hydrochloride,
(7) Sheldrick, G. M. SHELX-97, An integrated system for solVing and
refining crystal structures from diffraction data; University of Go¨t-
tingen: Go¨ttingen, Germany, 1997.
(8) Farrugia, J. L. ORTEP III for Windows. J. Appl. Crystallogr. 1997,
30, 565. Spek, A. L. PLATON 99, A multipurpose crystallographic
tool; Utrecht University: Utrecht, The Netherlands, 1999.
(9) Anderson, F. E.; Duca, C. J.; Scudi, J. V. J. Am. Chem. Soc. 1951,
73, 4967.
(10) Lobana, T. S.; Sa´nchez, A.; Casas, J. S.; Garc´ıa-Tasende, M. S.; Sordo,
J. Inorg. Chim. Acta 1998, 267, 169.
2586 Inorganic Chemistry, Vol. 42, No. 8, 2003

Diphenyllead(IV) Complexes
which is known to contain the [H2AcPyTSC]+ ion in the solid
state11).207Pb NMR (DMSO-d6): -507 ppm.
were eventually isolated. Mixtures in 1:1 and 2:1 mole ratios
were generally suspensions.
Partial evaporation of the mother liquor afforded a small amount
of a mixture containing small plates of the free ligand and orange
crystals suitable for X-ray study that turned out to be [PbPh2Cl-
(AcPyTSC)]. Mp: 195 °C. Anal. Calcd for C20H19ClN4SPb: C,
40.7; H, 3.2; N, 9.5; S, 5.4. Found: C, 40.4; H, 3.3; N, 9.3; S, 5.3.
Although one might expect that the selected thiosemicar-
bazones should all give similar compounds, the results were
amazingly dissimilar.
HATSC and HSTSC were not deprotonated under any of
the mole ratio conditions used, giving only 1:1 HATSC or
1:2 HSTSC adducts.
1
Molar conductivity (10-3 M in DMSO): 23.8 S cm2 mol-1. H
NMR (DMSO-d6): δ[C(7)H] ) 8.96 d (1); δ[C(5)H] ) 7.97 t (1);
δ[C(4)H] ) 7.86 (overlapping Ho); δ[C(6)H] ) 7.45 m (1); δ[N(1)-
H2] ) 7.43 s (2); δ[C(8)H3] ) 2.54 s (3); δ[Ho(Ph-Pb)] ) 7.86
dd (4); δ[Hm(Ph-Pb)] ) 7.41 t (4); δ[Hp(Ph-Pb)] ) 7.28 t (2);
The reactions of PbPh2Cl2 with HPyTSC in 1:2 and 1:1
mole ratios both gave two complexes simultaneously. In one,
the deprotonated ligand has displaced one of the two chlor-
ides from the coordination sphere of the metal, giving the
neutral mixed complex [PbPh2Cl(PyTSC)]. In the other the
chloride ion is also displaced, but HPyTSC retains its proton,
forming the cationic complex [{PbPh2Cl(HPyTSC)}2]2+.
Only this latter was formed when the mole ratio was 2:1.
Reaction of PbPh2Cl2 with HAcPyTSC in 1:2 mole ratio
afforded the [PbPh2Cl(PyTSC)] analogue [PbPh2Cl(AcPy-
TSC)], but (probably due to its greater solubility) it was
isolated only after isolation of a product that seems to be
[H2AcPyTSC][PbPh2Cl3]. The latter seems likely to have
originated from interaction of the excess ligand with the HCl
generated when [PbPh2Cl(AcPyTSC)] formed. Its elemental
analysis agrees with the proposed formula (see Experimental
4
3J(1H-207Pb) ) 196.5 Hz. J(1H-207Pb) could not be calculated.
207Pb NMR (DMSO-d6): -493 ppm.
When PbPh2Cl2 and HAcPyTSC were mixed in 1:1 and 2:1 mole
ratios in the same solvent and stirred overnight, a pale yellow solid
formed which was filtered out and dried in vacuo. Yield: 41%.
Mp: 208 °C. Anal. Calcd for C32H30Cl4N4Pb2S ([PbPh2Cl-
(HAcPyTSC)][PbPh2Cl3]): C, 36.3; H, 2.8; N, 5.3; S, 3.0. Found:
C, 36.4; H, 2.9; N, 5.3; S, 3.0. Molar conductivity (10-3 M in
1
DMSO): 7.5 S cm2 mol-1. H NMR (DMSO-d6): δ[N(2)H] )
10.30 s (1); δ[C(7)H] ) 8.56 d (1); δ[C(6)H] ) 8.42 d (1); δ[N(1)-
H2] ) 7.39 s (1), 8.11 s (1, overlapping Ho); δ[C(5)H] ) 7.77 m
(1); δ[C(6)H] ) 7.37 m (1); δ[C(8)H3] ) 2.54 s (3); δ[Ho(Ph-
Pb)] ) 8.11 dd (8); δ[Hm(Ph-Pb)] ) 7.60 t (8); δ[Hp(Ph-Pb)] )
3
4
7.42 t (4); J(1H-207Pb) ) 204.3 Hz; J(1H-207Pb) ) 82.0 Hz.
207Pb NMR (DMSO-d6): -507 ppm.
1
Section), and its H NMR spectrum in DMSO is coherent
with the presence of the H2AcPyTSC+ cation. Furthermore,
metal complexes containing the counterion [H2AcPyTSC]+
have been reported previously.12,13 Since the protonation
constants of HAcPyTSc and HPyTSC are almost identi-
cal,14,15 it is plausible that a similar complex containing [H2-
PyTSC]+ may have been formed in the reaction of PbPh2Cl2
with HPyTSC, in which case its nonisolation might be due
to it being more instead of less soluble than [PbPh2Cl-
(PyTSC)] ([H2PyTSC]Cl is more soluble than [H2AcPyTSC]-
Cl in MeOH according to our approximate measurements).
When reacted in 1:1 and 2:1 mole ratio, PbPh2Cl2 and
HAcPyTSC afforded a compound that was tentatively formu-
lated as [PbPh2Cl(HAcPyTSC)][PbPh2Cl3] by analogy with
that obtained using PbPh2Cl2 and HPyTSC (vide supra)(bar
the MeOH ligand).
PbPh2Cl2/HBPyTSC Reaction. To a solution of HBPyTSC
(0.15 g, 0.58 mmol) in MeOH (7 mL), a suspension of PbPh2Cl2
(0.13 g, 0.30 mmol) in the same solvent (9 mL) was slowly added
with stirring. The yellow solution obtained was stirred for 4 h at
room temperature, affording after slow evaporation a yellow solid,
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH. Yield: 43.4%. Mp: 194
°C. Anal. Calcd for C64H62Cl4N8O2S2Pb3: C, 42.6; H, 3.5; N, 6.2;
S, 3.6. Found: C, 42.8; H, 3.3; N, 6.4; S, 3.7. Molar conductivity
1
(10-3 M in DMSO): 5.8 S cm2 mol-1. H NMR (DMSO-d6; see
Figure 10): δ[C(7)H] ) 8.96 d (2); δ[C(5)H] ) 7.71 td (2); δ[N(1)-
H2] ) 7.30 s (4); δ[C(9-13)H] ) 7.10-7.50 (overlapping Ph-
Pb); δ[C(4)H] ) 6.80 d (2); δ[C(6)H] overlaps signals of the phenyl
groups; δ[Ho(Ph-Pb)] ) 8.16 d (4), 7.98 d (8); δ[Hm(Ph-Pb)] )
3
7.57 t (4), 7.45 t (8); δ[Hp(Ph-Pb)] ) 7.2-7.5 m; J(1H-207Pb)
) 206.1, 195.5 Hz. 207Pb NMR (DMSO-d6): -504.2 ppm. Crystal-
lization of this yellow solid from a 1:1 EtOH-CH2Cl2 solution
yielded crystals of the complex suitable for X-ray diffraction
analysis. The same complex was isolated by reacting PbPh2Cl2 and
the ligand in 2:1 and 1:1 mole ratios.
Finally, the reaction of HBPyTSC with PbPh2Cl2 afforded
the same product regardless of mole ratio: in all cases the
deprotonated ligand displaced the two chlorides from PbPh2-
Cl2, giving the positively charged fragment [PbPh2(BPyTSC)]+.
The mother liquor subsequently gave crystals of HBPyTSC
which were used in the X-ray study of the free ligand (vide infra).
1H NMR (DMSO-d6): δ[N(2)H] ) 12.52 s (1); δ[C(7)H] ) 8.87
d (1); δ[N(1)H2] ) 8.66 s (1), 8.21 s (1); δ[C(5)H] ) 8.02 t (1);
δ[C(9,13)H] ) 7.66 d (2); δ[C(6)H] ) 7.61 m (1); δ[C(10-12)H]
) 7.46 d (3); δ[C(4)H] ) 7.38 d (1).
2-
Two of these fragments interact weakly with a PbPh2Cl4
moiety (vide infra), giving the final complex [{PbPh2-
(BPyTSC)}2(PbPh2Cl4)], which was isolated solvated with
two molecules of methanol.
The above results suggest that all these reactions involve
complex equilibria including the displacement of chloride
ligand(s) from the coordination sphere of the lead by the
3. Results and Discussion
3.1. Synthesis of the Complexes. All reactions were
performed by mixing a suspension of PbPh2Cl2 in methanol
with a solution of the corresponding HTSC in the same
solvent until a 1:2, 1:1, or 2:1 mole ratio was reached. In
1:2 mole ratio, in all cases except one the halide dissolved,
giving a clear solution from which one or more complexes
(12) Abram, S.; Maichle-Mo¨ssmer, C.; Abram, U. Polyhedron 1998, 17,
131.
(13) Abram, U.; Bonfada, E.; Schulz Lang, E. Acta Crystallogr. 1999, C55,
1479.
(14) Kovala-Demertzi, D.; Domopoulou, A.; Demertzi, M. Polyhedron
1994, 13, 1917.
(11) Kumbhar, A.; Sonawane, P.; Padhye, S.; West, D. X.; Butcher, R. Y.
(15) Kovala-Demertzi, D.; Miller, J. R.; Kourkoumelis, N.; Hadjikakou,
S. K.; Mavroudis Demertzis, A. Polyhedron 1999, 18, 1005.
J. Chem. Crystallogr. 1997, 27, 533.
Inorganic Chemistry, Vol. 42, No. 8, 2003 2587

Casas et al.
Table 2. Selected Bond Lengths (Å) and Angles (deg) in [PbPh2Cl2(HATSC)], [PbPh2Cl2(HSTSC)2], [PbPh2(PyTSC)Cl], and [PbPh2(AcPyTSC)Cl]
a
[PbPh2Cl2(HATSC)]2
[PbPh2Cl2(HSTSC)2]b
2.185(10)
[PbPh2Cl(PyTSC)]
[PbPh2Cl(AcPyTSC)]b
Pb-C(11)
Pb-C(21)
Pb-Cl(1)
Pb-Cl(2)
Pb-Cl(1)i
Pb-S
2.185(5)
2.203(5)
2.8352(11)
2.6511(12)
2.8549(11)
2.7832(12)
2.181(5)
2.192(5)
2.7425(12)
2.191(3)
2.186(3)
2.7949(9)
2.715(3)
2.819(2)
2.5825(13)
2.7345(9)
3.0851(9)
2.585(2)
2.486(2)
Pb-Si
Pb-N(3)
Pb-N(4)
2.494(4)
2.759(4)
C(11)-Pb-C(21)
C(11)-Pb-C(11)i
C(11)-Pb-Cl(2)
C(21)-Pb-Cl(2)
C(11)-Pb-N(3)
C(21)-Pb-N(3)
C(11)-Pb-S
177.18(13)
149.33(19)
176.16(11)
180.0
89.66(13)
90.66(13)
98.67(16)
92.97(14)
105.67(14)
104.88(13)
72.31(9)
87.91(10)
95.07(11)
96.68(9)
86.71(8)
67.37(6)
91.02(12)
86.16(12)
91.9(3)
90.3(3)
C(21)-Pb-S
N(3)-Pb-S
Cl(2)-Pb-S
98.14(4)
N(3)-Pb-Cl(1)
C(11)-Pb-Cl(1)
C(21)-Pb-Cl(1)
Cl(2)-Pb-Cl(1)
S-Pb-Cl(1)
156.17(9)
88.77(13)
91.90(12)
152.39(6)
89.25(9)
86.98(9)
89.89(12)
92.89(12)
93.15(4)
168.68(4)
88.15(12)
91.94(13)
171.18(4)
90.45(4)
92.19(9)
98.7(3)
83.89(5)
140.21(2)
C(11)-Pb-Cl(1)i
C(21)-Pb-Cl(1)i
Cl(2)-Pb-Cl(1)i
S-Pb-Cl(1)i
Cl(1)-Pb-Cl(1)i
C(21)-Pb-Si
C(11)-Pb-Si
N(3)-Pb-Si
78.31(3)
180.0
93.18(9)
86.89(9)
124.47(6)
167.21(6)
61.45(3)
79.75(3)
90.47(10)
88.62(11)
64.86(8)
131.33(6)
84.71(6)
88.1(3)
N(4)-Pb-Si
S-Pb-Si
179.999(1)
87.81(9)
Cl(1)-Pb-Si
C(11)-Pb-N(4)
C(21)-Pb-N(4)
N(3)-Pb-N(4)
S-Pb-N(4)
73.64(15)
86.91(16)
62.89(12)
134.23(9)
140.73(9)
Cl(1)-Pb-N(4)
a Symmetry operations: i ) -x, -y, -z. b Symmetry operations: i ) 1 - x, 1 - y, 1 - z.
HTSC ligand (and probably also by the solvent) and the
deprotonation equilibrium of the thiosemicarbazone. This
1
conclusion is supported by the H NMR spectrum of a 1:1
mixture of PbPh2Cl2 and HAcPyTSC in CD3OH, which
shows a complex pattern of broad bands (the 1:2 mixture is
rather insoluble and quickly produces a precipitate in the
NMR tube). It seems probable that the identity of the solid
complex isolated is determined by the relative solubilities
of the various species in each system together with the small
differences in donor capacity and pKa among the HTSCs.
3.2. Solid-State Structures. Figure 1 shows the molecular
structure and numbering of the adduct [PbPh2Cl2(HATSC)]2.
Selected bond lengths and angles are listed in Table 2. The
compound is a centrosymmetric dimer in which each metal
Figure 1. Molecular structure of [PbPh2Cl2(HATSC)]2.
atom is coordinated to one carbon of each of two phenyl
groups, to one thiosemicarbazone sulfur, to one terminal
chloride [Cl(2)], and to two bridging chlorides [Cl(1) and
Cl(1)i, i ) -x, -y, -z]. The lead atom is thus octahedrally
coordinated, the main distortion of this geometry affecting
the bond angles Cl(1)-Pb-Cl(1)i [78.31(3)°] and S-Pb-
Cl(1) [168.68(4)°]. The Pb-C and bridging Pb-Cl distances
are longer than in the polymeric compound PbPh2Cl2,16
probably because of the strong bond with the terminal Cl.
As might be expected, the Pb-S bond is significantly longer
than in complexes containing the deprotonated thiosemicar-
bazone ligand (vide infra). About the C(1)-N(2) and C(2)-
N(3) bonds HATSC has the EE configuration that is usually
found in free thiosemicarbazones. It is practically planar [SC-
(1)N(1)N(2)N(3)C(2) to C(9), rms ) 0.0337] and forms a
dihedral angle of 67.56(0.04)° with the plane containing Pb,
S, Cl(1), Cl(2), and Cl(1)i (rms ) 0.826). The C(1)-S dis-
tance, though longer than in free thiosemicarbazone ligands,17
indicates the persistence of significant double bond character,
being close to that previously found in [NiCl2(HATSC)].18
The other bond lengths in the thiosemicarbazone chain are
within the ranges of values previously found in neutral
thiosemicarbazones.
(16) Mammi, M.; Busetti, V.; Del Pra, A. Inorg. Chim. Acta 1967, 1, 419.
2588 Inorganic Chemistry, Vol. 42, No. 8, 2003

Diphenyllead(IV) Complexes
Table 3. Selected Bond Lengths (Å) and Angles (deg) in
[PbPh2Cl(HPyTSC)][PbPh2Cl3(MeOH)]a
Pb(1)-C(21)
Pb(1)-C(11)
Pb(1)-N(3)
Pb(1)-N(4)
Pb(1)-S
Pb(1)-Cl(1)
Pb(1)-Cl(1)i
Pb(2)-C(41)
Pb(2)-C(31)
Pb(2)-O(1S)
Pb(2)-Cl(4)
Pb(2)-Cl(3)
Pb(2)-Cl(2)
2.178(5)
2.181(5)
2.606(4)
2.686(4)
2.7890(14)
2.7898(14)
2.9112(13)
2.167(5)
2.168(5)
2.554(5)
S-C(1)
1.682(5)
1.318(6)
1.349(6)
1.260(6)
1.455(7)
1.354(6)
1.367(7)
1.382(8)
1.362(9)
1.377(8)
1.336(7)
1.374(6)
1.421(9)
C(1)-N(1)
C(1)-N(2)
C(2)-N(3)
C(2)-C(3)
C(3)-N(4)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(7)-N(4)
N(2)-N(3)
O(1S)-C(1S)
2.6318(14)
2.6671(14)
2.8147(15)
C(21)-Pb(1)-C(11)
C(21)-Pb(1)-N(3)
C(11)-Pb(1)-N(3)
C(21)-Pb(1)-N(4)
C(11)-Pb(1)-N(4)
N(3)-Pb(1)-N(4)
C(21)-Pb(1)-S
172.59(18)
92.88(15)
82.53(15)
86.25(16)
86.44(16)
61.66(12)
89.04(13)
94.66(14)
68.62(10)
129.68(9)
95.03(13)
92.12(12)
143.05(9)
154.84(9)
75.47(4)
92.23(12)
87.74(13)
140.88(10)
80.04(9)
150.24(4)
74.80(4)
C(41)-Pb(2)-Cl(4)
C(31)-Pb(2)-Cl(4)
O(1S)-Pb(2)-Cl(4)
C(41)-Pb(2)-Cl(3)
C(31)-Pb(2)-Cl(3)
O(1S)-Pb(2)-Cl(3)
Cl(4)-Pb(2)-Cl(3)
C(41)-Pb(2)-Cl(2)
C(31)-Pb(2)-Cl(2)
O(1S)-Pb(2)-Cl(2)
Cl(4)-Pb(2)-Cl(2)
Cl(3)-Pb(2)-Cl(2)
N(3)-C(2)-C(3)
N(4)-C(3)-C(4)
N(4)-C(3)-C(2)
C(4)-C(3)-C(2)
C(3)-C(4)-C(5)
C(6)-C(5)-C(4)
C(5)-C(6)-C(7)
N(4)-C(7)-C(6)
C(1)-N(2)-N(3)
C(2)-N(3)-N(2)
C(7)-N(4)-C(3)
95.53(14)
90.96(13)
87.97(14)
94.90(14)
96.93(13)
176.87(13)
89.97(4)
87.57(14)
87.45(13)
99.22(14)
172.48(5)
82.93(4)
120.8(5)
122.7(5)
116.7(5)
120.6(5)
119.6(6)
118.3(6)
119.3(6)
123.6(6)
121.7(4)
117.3(4)
116.5(5)
C(11)-Pb(1)-S
N(3)-Pb(1)-S
N(4)-Pb(1)-S
Figure 2. Molecular structure of [PbPh2Cl2(HSTSC)2].
C(21)-Pb(1)-Cl(1)
C(11)-Pb(1)-Cl(1)
N(3)-Pb(1)-Cl(1)
N(4)-Pb(1)-Cl(1)
S-Pb(1)-Cl(1)
The Cl atoms, N(3), and the N(1)H2 and N(2)H groups
are all involved in intra- or intermolecular hydrogen bonds
(see Table 5), the latter of which give rise to a polymeric
chain along the x axis as shown in Figure 1S (here and
hereafter, the suffix “S” indicates figures included in the
Supporting Information).
C(21)-Pb(1)-Cl(1)i
C(11)-Pb(1)-Cl(1)i
N(3)-Pb(1)-Cl(1)i
N(4)-Pb(1)-Cl(1)i
S-Pb(1)-Cl(1)i
Cl(1)-Pb(1)-Cl(1)i
C(41)-Pb(2)-C(31)
C(41)-Pb(2)-O(1S)
C(31)-Pb(2)-O(1S)
[PbPh2Cl2(HSTSC)2] (Figure 2) is a centrosymmetric mon-
omer in which the lead atom is coordinated to two phenyl
groups, two chloride anions, and two thiosemicarbazone
sulfur atoms in an octahedral arrangement with a slight de-
gree of distortion [the bond angles around the metal range
from 87.81(9) for Cl-Pb-Si (i ) 1 - x, 1 - y, 1 - z) to
92.19(9)° for S-Pb-Cl (see Table 2)]. The Pb-C bonds
are the same length as in [PbPh2Cl2(HATSC)]2, while the
Pb-Cl distance is between the two displayed by the latter
adduct. However, the Pb-S distance is slightly longer in
the 1:2 adduct.
166.50(19)
82.96(18)
85.47(17)
a Symmetry operations: i ) -x + 1, -y + 2, -z.
The coordination behavior of HSTSC in this adduct (neu-
tral and monodentate) is not common for this ligand, which
is usually bideprotonated and S,N(3),O-tridentate. It has only
been found previously in the X-ray diffraction study of the
Cu(I) adduct [Cu(PPh3)2Br(HSTSC)].19 As in that case,
HSTSC is almost planar and retains the EE conformation
found in the free ligand,20 a small elongation of the C-S
bond being the only significant structural change in the ligand
upon coordination.
Three intramolecular hydrogen bonds help stabilize the
molecules, and one intermolecular hydrogen bond links them
in a two-dimensional network in the y-z plane (see Table 5
and Figure 2S).
The asymmetric unit of [{PbPh2Cl(HPyTSC)}2][PbPh2Cl3-
(MeOH)]2 is shown together with its numbering scheme in
Figure 3, and selected bond lengths and angles are listed in
Figure 3. Molecular structure of [{PbPh2Cl(HPyTSC)}2][PbPh2Cl3-
(MeOH)]2 showing one of the {PbPh2Cl(HPyTSC)}+ moieties and the
[PbPh2Cl3(MeOH)]- anion.
Table 3. Unlike the adducts previously described, there are
two independent units in this compound: one, containing
Pb(1), is a cation in which the central metal of diphenyllead-
(IV) is also coordinated to a chloride and to an undeproto-
nated thiosemicarbazone ligand, while the other, containing
Pb(2), is an anion in which the diphenyllead(IV) center
coordinates to three chlorides and the oxygen of a methanol
molecule. The cationic units are linked in pairs by chloro
(17) Casas, J. S.; Garc´ıa-Tasende, M. S.; Sordo, J. Coord. Chem. ReV. 2000,
209, 197.
(18) Dapporto, P.; De Munno, G.; Tomlinson, A. A. G. J. Chem. Res. 1984,
40, 501.
(19) Zheng, H.-G.; Zeng, D.-X.; Xin, X.-Q.; Wong, W.-T. Polyhedron 1997,
16, 3499.
(20) Chattopadhay, D.; Mazumdar, S. K.; Banerjee, T.; Ghosh, S.; Mak,
T. C. W. Acta Crystallogr. 1988, C44, 1025.
Inorganic Chemistry, Vol. 42, No. 8, 2003 2589

Casas et al.
Figure 4. View of [{PbPh2Cl(HPyTSC)}2][PbPh2Cl3(MeOH)]2 showing the doubly charged dinuclear cation [{PbPh2Cl(HPyTSC)}2]2+ and the weak
association of the [PbPh2Cl3(MeOH)]- anions in pairs.
bridges [Pb(1)‚‚‚Cl(1)i ) 2.9112(13) Å; i ) -x + 1, -y +
2, -z], giving rise to the doubly charged dinuclear cation
[{PbPh2Cl(HPyTSC)}2]2+ (Figure 4). The formation of this
dimer gives a coordination number of 7 to Pb(1), which has
a distorted pentagonal bipyramidal coordination polyhedron
with both phenyl groups axial. The HPyTSC ligand, though
undeprotonated, suffers the usual conformational change
from EE to ZZ to allow S,N(3),N(4)-tridentate coordination,
and its plane (rms ) 0.0714) makes an angle of 11.44(0.12)°
with the equatorial plane of the complex [Pb(1)SN(3)N(4)-
Cl(1)Cl(1)i, rms ) 0.1071]. Its placing three donor atoms in
the coordination sphere of the lead atom displaces one of
the PbPh2Cl2 chlorides, which then probably coordinates to
another PbPh2Cl2 molecule to form a [PbPh2Cl3]- anion that
evolves to [PbPh2Cl3(MeOH)]- by coordination to the
oxygen atom of a solvent molecule. This gives Pb(2) octa-
hedral coordination with Cl(2), Cl(3), Cl(4), and O(1S) equa-
torial (rms ) 0.0484). The main distortion of the octahedral
symmetry affects the angle C(31)-Pb(2)-C(41), which
deviates about 14° from linearity. Two Cl‚‚‚H-O hydrogen
Figure 5. Molecular structure of [PbPh2Cl(PyTSC)].
bonds weakly link the anions in pairs (Figure 4), and other
hydrogen bonds involving N(1)H2, N(2)H, O(1S)H, Cl(2),
and Cl(3) groups (see Table 5) connect the dimeric cations
with pairs of anions, giving rise to a two-dimensional
network (Figure 4S).
tonation and coordination to the metal cause the usual
changes in the thiosemicarbazone ligand,17 namely a switch
from E to Z conformation with respect to C(1)-N(2) and
significant evolution of the C(1)-S bond from the thione to
the thiol form. In keeping with the latter change, the Pb-S
bond in this complex is significantly shorter than in the two
adducts with undeprotonated ligands described above (see
Table 3). The plane of the pyridine ring (rms ) 0.008) makes
a dihedral angle of 13.35(0.26)° with that of the chain SC-
(1)C(2)N(1)N(2)N(3) (rms ) 0.0317). Two intermolecular
hydrogen bonds involving the N(1)H2 group and N(2) and
Cl atoms link the molecules in zigzag layers (see Table 5
and Figure 5S).
The asymmetric unit of [PbPh2Cl(AcPyTSC)] is shown
together with the numbering scheme in Figure 6, and selected
bond lengths and angles are listed in Table 2. Despite the
similarity of HPyTSC and HAcPyTSC, their interactions in
the solid state with [PbPh2Cl]+ differ somewhat. As in [Pb-
Ph2Cl(PyTSC)], the thiosemicarbazonate ligand in [PbPh2Cl-
(AcPyTSC)] coordinates to the metal through its S, N(3),
and N(4) atoms, but the shortest metal-ligand bond is in
The molecular structure of [PbPh2Cl(PyTSC)] is shown
together with the numbering scheme in Figure 5, and selected
bond lengths and angles are listed in Table 2. In this complex
the Ph2PbIV moiety is coordinated to a Cl and to the S, N(3),
and N(4) atoms of a pyridine-2-carbaldehyde thiosemicar-
bazonato ligand. The geometry of the coordination sphere
around the metal can be described as a distorted pentagonal
bipyramid with one vacant equatorial position, the phenyl
groups being axial and the lead atom about 0.11 Å from the
equatorial plane defined by S, N(3), N(4), and Cl (rms )
0.0947). The main distortion from the ideal geometry is prob-
ably imposed by the strong coordination of the metal to the
S and N(3) atoms and by the small bite of the ligand, all of
which bends C-Pb-C toward the vacant space in the equa-
torial plane, narrowing this angle by ca. 30° from linearity.
There are no other interactions involving the metal. Depro-
2590 Inorganic Chemistry, Vol. 42, No. 8, 2003

Diphenyllead(IV) Complexes
deprotonation and coordination to the metal the free ligand21
undergoes changes similar to those of PyTSC- in [PbPh2-
Cl(PyTSC)], although the longer Pb-S bond in the AcPyTSC-
complex entails a slightly shorter C(1)-S bond indicative
of less evolution toward the thiol form (see Table 2). As in
[PbPh2Cl(PyTSC)], there are two intermolecular hydrogen
bonds involving the N(1)H2 group, Cl, and N(2) (see Table
5 and Figure 7), although in this case one of these bonds
stabilizes the dimer originated by the Pb‚‚‚Si interaction and
the second links the dimers in one-dimensional chains.
Figure 8 shows the molecular structure and numbering
scheme of HBPyTSC. Bond lengths and bond angles are
listed in Table 4. The S-C(1), N(1)-C(1), N(2)-C(1),
N(2)-N(3), and N(3)-C(2) bond lengths are similar to the
mean values found among the free HTSC structures in the
CSD.17,22 Comparison of these parameters with typical
lengths of single and double bonds23 shows that in the
thiosemicarbazone moiety of HBPyTSC there is extensive
electron delocalization.
As in other thiosemicarbazones, an intramolecular hydro-
gen bond involving N(1)H2 and N(3) [N(1)‚‚‚N(3) ) 2.576-
(2), N(1)-H(1A) ) 0.880, H(1A)‚‚‚N(3) ) 2.202 Å; N(1)-
H(1A)‚‚‚N(3) ) 105.1°] stabilizes the E configuration with
respect to the C(1)-N(2) bond (Figure 8), while another in-
tramolecular hydrogen bond involving N(2)H and N(4) [N-
(2)‚‚‚N(4) ) 2.635(19), N(2)-H(2A) ) 0.880, H(2A)‚‚‚N(4)
) 1.979 Å; N(2)-H(2A)‚‚‚N(4) ) 130.4°] doubtless helps
stabilize the Z configuration about the C(2)-N(3) bond (E
configuration is found in most unsubstituted pyridine-derived
thiosemicarbazones,21,24-28 and this intramolecular bond has
been observed only once before on unsubstituted ligand of
this type29). Besides these intramolecular hydrogen bonds,
there is an intermolecular hydrogen bond between the sulfur
atom and the N(1)H2 group which links the molecules in
pairs (see Figure 8, N(1)-H(1B)‚‚‚Si [i ) -x, -1 - y, -z;
Figure 6. Molecular structure of [PbPh2Cl(AcPyTSC)] showing the
monomer.
this case Pb-N(4), while Pb-S and Pb-N(3) are longer
than in the PyTSC- complex. This weakening of Pb-S al-
lows a weak S‚‚‚Pbi interaction with the metal atom of a
neighboring molecule to link the complexes in pairs (Figure
7; i ) 1 - x, 1 - y, 1 - z). Thus [PbPh2Cl(AcPyTSC)], un-
like [PbPh2Cl(PyTSC)], has all the positions of its pentagon-
al bipyramidal coordination sphere occupied, and the C-Pb-C
angle deviates only ca. 4° from linearity. By contrast, the
equatorial plane PbSSiN(3)N(4)Cl is rather distorted (rms )
0.1388), mainly due to the S and N(3) atoms. The chelate
rings SC(1)N(2)N(3)Pb (rms ) 0.078) and PbC(2)C(3)N(3)N-
(4) (rms ) 0.0469) form a dihedral angle of 7.54(0.08)°,
and neither is exactly coplanar with the pyridine ring. Upon
Figure 7. Molecular structure of [PbPh2Cl(AcPyTSC)] showing the weak S‚‚‚Pbi interaction (i ) 1 - x, 1 - y, 1 - z) and some hydrogen bonds that
reinforce and link the dimers.
Inorganic Chemistry, Vol. 42, No. 8, 2003 2591

Casas et al.
Table 4. Selected Bond Lengths (Å) and Angles (deg) in HBPyTSC
and [{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOHa
Table 5. Intra- and Intermolecular Hydrogen Bonds in the Complexes
(Å, deg)
HBPyTSC
D-H
H‚‚‚A
D‚‚‚A
D-H‚‚‚A
S-C(1)
1.6790(16)
1.330(2)
1.367(2)
N(3)-C(2)
C(2)-C(3)
N(4)-C(7)
N(4)-C(3)
1.297(2)
1.488(2)
1.337(2)
1.355(2)
a
[PbPh2Cl2(HATSC)]2
N(1)-C(1)
N(2)-C(1)
N(2)-N(3)
N(1)-H(1A)‚‚‚N(3)
N(2)-H(2)‚‚‚Cl(2)
N(1)-H(1B)‚‚‚Cl(1)ii
N(1)-H(1A)‚‚‚Cl(2)ii
0.860
0.860
0.860
0.860
2.250
2.763
3.020
2.818
2.606(7)
3.576(4)
3.373(5)
3.532(5)
140.4
158.4
107.0
141.4
1.3684(18)
C(1)-N(2)-N(3)
C(2)-N(3)-N(2)
N(2)-C(1)-N(1)
N(2)-C(1)-S
117.12(13)
121.09(13)
115.92(14)
119.37(12)
N(1)-C(1)-S
N(3)-C(2)-C(8)
N(3)-C(2)-C(3)
124.71(13)
112.44(13)
127.36(14)
[PbPh2Cl2(HSTSC)2]b
O(1)-H(1)‚‚‚N(3)
N(1)-H(1A)‚‚‚N(3)
N(1)-H(1B)‚‚‚Cl(1)ii
N(2)-H(1A)‚‚‚Cl(1)
0.820
0.860
0.860
0.860
2.002
2.384
2.489
2.374
2.710(12)
2.702(14)
3.314(11)
3.233(9)
145.9
102.3
160.9
178.0
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH
Pb(1)-C(31)
Pb(1)-C(21)
Pb(1)-N(3)
Pb(1)-S
Pb(1)-N(4)
Pb(1)-Cl(1)
Pb(1)-Cl(2)
Pb(2)-C(41)
Pb(2)-Cl(2)
2.190(12)
2.196(13)
2.457(9)
2.577(3)
2.585(10)
2.974(3)
3.448(3)
2.196(11)
2.727(3)
Pb(2)-Cl(1)
S-C(1)
2.751(3)
1.703(13)
1.362(15)
1.337(15)
1.361(13)
1.307(14)
1.535(15)
1.3900
c
[{PbPh2Cl(HPyTSC)}2][PbPh2Cl3(MeOH)]2
N(2)-H(2A)‚‚Cl(3)
O(1S)-H(1S)‚‚Cl(2)ii
N(1)-H(1B)‚‚Cl(2)iii
N(1)-H(1A)‚‚Cl(3)iii
0.87(5)
0.66(6)
0.86
2.28(5) 3.144(4)
2.46(6) 3.107(5)
173(4)
166(7)
168.1
117.3
N(1)-C(1)
N(2)-C(1)
N(2)-N(3)
N(3)-C(2)
C(2)-C(3)
N(4)-C(7)
N(4)-C(3)
2.45
2.83
3.292(5)
3.311(4)
0.86
[PbPh2(PyTSC)Cl]d
0.889(19) 2.26(2) 3.135(6)
0.88(2) 2.49(3) 3.306(5)
N(1)-H(1N1)‚‚‚N(2)i
N(1)-H(2N1)‚‚‚Clii
168(5)
154(5)
1.3900
[PbPh2(AcPyTSC)Cl]e
C(31)-Pb(1)-C(21)
C(31)-Pb(1)-N(3)
C(21)-Pb(1)-N(3)
C(31)-Pb(1)-S
159.2(5)
91.1(4)
98.8(4)
101.8(3)
98.5(3)
73.6(2)
82.3(5)
85.0(5)
66.4(4)
139.9(4)
85.0(3)
96.4(4)
146.0(2)
74.21(9)
145.5(4)
88.2(3)
77.9(3)
143.3(2)
142.2(9)
77.2(4)
Cl(1)-Pb(1)-Cl(2)
C(41)i-Pb(2)-C(41)
C(41)i-Pb(2)-Cl(2)
C(41)-Pb(2)-Cl(2)
Cl(2)-Pb(2)-Cl(2)i
C(41)-Pb(2)-Cl(1)
Cl(2)-Pb(2)-Cl(1)
C(41)-Pb(2)-Cl(1)i
Cl(2)-Pb(2)-Cl(1)i
Cl(1)-Pb(2)-Cl(1)i
Pb(2)-Cl(1)-Pb(1)
C(1)-S-Pb(1)
C(1)-N(2)-N(3)
C(2)-N(3)-N(2)
N(2)-C(1)-N(1)
N(2)-C(1)-S
N(1)-C(1)-S
N(3)-C(2)-C(8)
N(3)-C(2)-C(3)
70.46(7)
180.0
90.2(3)
89.8(3)
180.0
91.5(3)
85.66(8)
88.5(3)
94.34(8)
180.0
107.44(9)
99.7(4)
115.2(10)
115.9(10)
113.6(11)
130.2(9)
116.3(9)
126.6(15)
115.9(11)
N(1)-H(1A)‚‚‚Cli
0.81(4)
0.92(5)
2.57(4) 3.367(3)
2.28(5) 3.149(4)
167(4)
157(4)
N(1)-H(1B)‚‚‚N(2)ii
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOHf
C(21)-Pb(1)-S
N(1)-H(1A)‚‚‚O(1S)ii 0.880
N(1)-H(1B)‚‚‚Cl(1)iii 0.880
1.974
2.661
2.8268(16)
3.426(11)
162.80
145.97
N(3)-Pb(1)-S
C(31)-Pb(1)-N(4)
C(21)-Pb(1)-N(4)
N(3)-Pb(1)-N(4)
S-Pb(1)-N(4)
a-f Symmetry operations: (a) ii ) 1 + x, y, z; (b) ii ) 1 - x, 0.5 + y,
0.5 - z; (c) ii ) 2 - x, 1 - y, 1 - z, iii ) 2 - x, 2 - y, 1 - z; (d) i )
-x, 1 - y, 1 - z, (ii) ) -0.5 - x, -0.5 + y, 0.5 - z; (e) i ) 1 - x, 1 -
y, 1 - z, (ii) 2 - x, 2 - y, 1 - z; (f) ii ) x, 1 + y, z, (iii) ) 1 - x, 2 -
y, -z.
C(31)-Pb(1)-Cl(1)
C(21)-Pb(1)-Cl(1)
N(3)-Pb(1)-Cl(1)
S-Pb(1)-Cl(1)
those of HBPyTSC. The complex is trinuclear and cen-
trosymmetric, containing two {PbPh2(BPyTSC)} units linked
by a {PbPh2Cl4} unit. In the latter the Pb(2) atom is
octahedrically coordinated to two phenyl groups and four
chloride ions, the Pb-C distance [2.196(11) Å] being shorter
and the Pb-Cl distances [Pb(2)-Cl(2) ) 2.728(3), Pb(2)-
Cl(1) ) 2.751(3) Å] slightly longer than the sums of the
corresponding covalent radii (2.37 and 2.59 Å, respec-
tively23). The environment of the lead atom is similar in
PbPh2Cl2,16 but in the {PbPh2Cl4} unit the Pb-C bonds are
slightly shorter, while Pb(2)-Cl(2) is shorter and Pb(2)-
Cl(1) longer than the Pb-Cl bonds in PbPh2Cl2.16 The
chlorine atoms also coordinate, albeit weakly, to the two Pb-
(1)-based units [Pb(1)‚‚‚Cl(1) ) 2.974(3), Pb(1)‚‚‚Cl(2) )
3.447(3) Å]. The Cl- ligand that is the more strongly bound
to Pb(2), Cl(2), is the more weakly bound to Pb(1), the Pb-
(1)-Cl(2) bond length being close to the sum of the van
der Waals radii of the atoms (3.70 Å23). Together with the
two chlorides, a carbon atom of each of the two phenyl
groups and the sulfur atom and two nitrogen atoms of the
thiosemicarbazonate ligand make the coordination number
of Pb(1) up to 7, giving a coordination sphere that is best
N(4)-Pb(1)-Cl(1)
C(31)-Pb(1)-Cl(2)
C(21)-Pb(1)-Cl(2)
N(3)-Pb(1)-Cl(2)
S-Pb(1)-Cl(2)
N(4)-Pb(1)-Cl(2)
a Symmetry operations: i ) -x + 2, -y + 1, -z.
Figure 8. Molecular structure of HBPyTSC showing the intra- and
intermolecular hydrogen bonds.
N(1)‚‚‚Si ) 3.341(15), N(1)-H(1B) ) 0.88, H(1B)‚‚‚Si )
2.492 Å; N(1)-H(1B)‚‚‚Si ) 162.5°].
Figure 9 shows the molecular structure and numbering
scheme of [{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH. Bond
lengths and bond angles are listed in Table 4 together with
(24) Brown, J. N.; Yang, C. H. Cryst. Struct. Commun. 1979, 8, 879.
(25) Brown, J. N.; Agrawal, K. C. Acta Crystallogr., Sect. B 1978, 34,
2038.
(26) Byushkin, V. N.; Chumakov, Y. M.; Samus, N. M.; Baka, I. O. Zh.
Strukt. Khim. (Engl. Transl.) 1987, 28, 119.
(27) Brown, J. N.; Agrawal, K. C. Acta Crystallogr. 1978, B34, 1002.
(28) Taishang, H. Xiamen Dax. Xuebao, Zir. Kex. (J. Xi. Uni (Nat. Sci.))
1993, 32, 741.
(29) Duan, C. Y.; Wu, B. M.; Mak, T. C. M. J. Chem. Soc., Dalton Trans.
1996, 3489.
(21) Carcelli, M.; Delledonne, D.; Fochi, A.; Pelizzi, G.; Rodr´ıquez-
Argu¨elles, M. C.; Russo, U. J. Organomet. Chem. 1997, 544, 29.
(22) Allen, F. H.; Kennard, O. Chem. Des. Autom. News 1993, 8, 1.
(23) Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry:
Principles of Structure and ReactiVity, 4th ed.; Harper Collins College
Publishers: New York, 1993.
2592 Inorganic Chemistry, Vol. 42, No. 8, 2003

Diphenyllead(IV) Complexes
Figure 9. Molecular structure of [{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH.
described as a distorted pentagonal bipyramid. Unfortunately,
the disorder shown by the pyridine and phenyl rings of the
BPyTSC- ligand prevents thorough analysis of all the
changes undergone by HBPyTSC (vide supra) upon the
formation of the complex. However, in the thiosemicarbazone
chain deprotonation and coordination to the metal basically
bring about the same changes as in the thiosemicarbazonate
ligand in [PbPh2Cl(PyTSC)]: a switch to Z conformation
about the C(1)-N(2) bond, a lengthening of the C(1)-S and
C(1)-N(1) bonds, and a shortening of C(1)-N(2). The Pb-S
and Pb-N(3) bonds are slightly shorter in the BPyTSC-
complex than in [PbPh2Cl(PyTSC)] and significantly shorter
than in [PbPh2Cl(AcPyTSC)], while Pb-N(4) is longer than
in the latter complex but shorter than in the former. An
intermolecular hydrogen bond between N(1)-H(1B) and a
Cl(1) (see Table 5) links the molecules in a polymeric chain
(see Figure 9S), while the solvent molecules are bound by
hydrogen bonds involving N(1)-H(1A) [or N(1)i-H(1A)i]
and their oxygen atom (Table 5, Figure 9S).
shifts and coupling constants corresponding in all cases with
those of PbPh2Cl2 and the free HTSC ligands in DMSO.
[PbPh2Cl(PyTSC)] turned out to be unstable in DMSO
solution, decomposing within a few minutes and so allowing
only the 1H NMR spectrum to be recorded (see Experimental
Section). This spectrum shows changes relative to the free
ligand and diphenyllead chloride which are in keeping with
the deprotonation and coordination of HPyTSC: (i) The
N(2)-H signal at 11.65 ppm in the spectrum of HPyTSC
disappears. (ii) The two signals associated with N(1)H2 in
the free ligand, at 8.37 and 8.10 ppm, merge into one because
in the complex this group can rotate freely as a consequence
of the change in the charge distribution in the thioamide
group when the S-Pb bond forms. (iii) The C(2)-H signal
(at 8.07 ppm in the free ligand) shifts downfield due to the
coordination of N(3) to the metal. (iv) The C(7)-H signal
(at 8.53 ppm in the free ligand) also shifts downfield, due
to the inductive effect of the Pb-N(4) bond. (v) All the pro-
tons of the phenyl groups are more shielded than in PbPh2-
Cl2.
For [PbPh2Cl(AcPyTSC)], both 1H and 207Pb NMR spectra
in DMSO were obtained. In the proton spectrum, the changes
in the ligand signals upon deprotonation and coordination
are basically the same as those described above for [PbPh2-
Cl(PyTSC)], suggesting similar coordination via S, N(3), and
N(4). Surprisingly, the 207Pb NMR signal is located at only
slightly lower field than that of PbPh2Cl2, at -493 as against
-508.4 ppm. Since the kernels of these compounds are
different, this similarity is probably due to their lead atoms
also having different coordination numbers: 6 in PbPh2Cl2-
(solv) and 7 in [PbPh2Cl(AcPyTSC)], in which even if the
dimer-forming Pb‚‚‚Si bonds (vide supra) are broken in
solution they are probably replaced by bonds to DMSO
molecules.
3.3. Studies in DMSO Solution. The new compounds are
all insoluble in CHCl3 but soluble in DMSO. The molar con-
ductivity of 10-3 M solutions is <10 S cm2 mol-1 in all
cases except those of [PbPh2Cl(PyTSC)] and [PbPh2Cl(Ac-
PyTSC)], which have values of 18.5 and 23.8 S cm2 mol-1,
respectively, that are still far less than those expected for
1:1 electrolytes in this solvent (50-70 S cm2 mol-1 30) and
hence rule out extensive ionogenous dissociation.
The high receptivity and abundance of 207Pb facilitate
NMR spectroscopy.31 The spectrum of a 2 × 10-2 M solution
of PbPh2Cl2 in DMSO shows a single signal at -508.4 ppm
which may be due to the previously described adduct [PbPh2-
Cl2(DMSO)2].32 The 207Pb NMR data for the HTSC com-
plexes containing neutral thiosemicarbazone ligands suggest
that they all dissociate in DMSO in accordance with the
equation
1H and 207Pb NMR spectra were also recorded for the
complex formed by the deprotonated HBPyTSC ligand,
[PbPh2Cl2(HTSC)n] + 2DMSO f [PbPh2Cl2(DMSO)2] +
nHTSC
(30) Geary, W. J. Coord. Chem. ReV. 1971, 7, 81.
(31) Wrackmeyer, B.; Horchler, K. Annu. Rep. NMR Spectrosc. 1989, 22,
249.
(32) Hills, K.; Henry, M. C. J. Organomet. Chem. 1965, 3, 159. Yatsenko,
A. V.; Aslanov, L. A.; Schenk, H. Polyhedron 1995, 14, 2371.
their signals all lying close to that of PbPh2Cl2. The 1H NMR
data are also coherent with this conclusion, the chemical
Inorganic Chemistry, Vol. 42, No. 8, 2003 2593

Casas et al.
Scheme 1
ppm and 195.5 Hz, agree well with values obtained for these
protons in the complexes in which the [PbPh2]2+ unit
coordinates to both thiosemicarbazonate and chloride anions.
These data suggest that the following process must take place
in DMSO solution:
[{PbPh2(BPyTSC)}2(PbPh2Cl4)] DMSO8
[PbPh2Cl2(DMSO)2] + 2[PbPh2Cl(BPyTSC)]
The position of the only signal in the 207Pb NMR spectrum
of this complex in DMSO shows that it corresponds to
[PbPh2Cl2(DMSO)2]. No signal for [PbPh2Cl(BPyTSC)] was
obtained even though the solution seems to be stable (the
1H NMR spectrum remained unaltered for several days). The
Pb-NPy bond being weaker than in [PbPh2Cl(AcPyTSC)],
it seems possible that the solvent displaces the N(4) atom
from the coordination sphere and thereby allows the con-
formation of the ligand with respect to the C(2)-N(3) bond
to vary, thus providing a relaxation mechanism for the 207Pb
nucleus via the influence of the π charge of the phenyl and
pyridinyl groups.
3.4. Conclusions. The reaction of PbPh2Cl2 with thiosemi-
carbazones in methanol proceeds without observable dephen-
ylation, giving a variety of diphenyllead(IV) complexes with
diverse compositions and configurations in the solid state
(see Scheme 1). Only the HTSCs which include a pyridine
ring as an additional donor center are able to displace the
chloride ligand from the coordination sphere of the metal.
This displacement can be accompanied by deprotonation of
the HTSC, giving thiosemicarbazonates. The other HTSCs
investigated only form adducts.
Figure 10. 1H NMR spectrum of [{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH
from 6.6 to 9.2 ppm. An asterisk indicates a signal corresponding to Ho(Pb-
Ph) in PbPh2Cl2, and a plus sign indicates a signal corresponding to Ho(Pb-
Ph) in [PbPh2Cl(BPyTSC)].
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]‚2MeOH. In the 1H spectrum
(Figure 10), the changes in the ligand signals with respect
to those of the free ligand are similar to those observed in
the spectra of [PbPh2Cl(PyTSC)] and [PbPh2Cl(AcPyTSC)],
suggesting deprotonation and a similar coordination mode
(as was also observed crystallographically). Among the
organometallic signals, however, the presence and intensities
of two clearly different signals for the ortho protons, with
their corresponding coupling constants, indicate the existence
of two different kernels in 2:1 ratio. The chemical shift and
coupling constant of the less intense signal, 8.16 ppm and
206.1 Hz, coincide with data for PbPh2Cl2 in DMSO,
suggesting the formation of this species, while the chemical
shift and coupling constant of the more intense signal, 7.98
2594 Inorganic Chemistry, Vol. 42, No. 8, 2003

Diphenyllead(IV) Complexes
In keeping with its size, in all these compounds the lead
atom has coordination number 6 or 7, often using Cl- as a
bridging ligand in order to increase the number of available
donor atoms. The C-Pb-C angle of the PbPh2 unit can
narrow to only 150° but usually remains close to the 180°
of PbPh2Cl2.
The solvent MeOH seems to compete poorly with the
chloride and thiosemicarbazone ligands, because only once
was it included in the coordination sphere of lead in the solid
state.
The complexes containing undeprotonated HTSC ligands
dissociate in DMSO, giving the starting materials. Those
containing thiosemicarbazonate ligands either persist or
evolve to new complexes, but the ligand remains coordinated
to the metal atom.
for financial support under Projects PGIDT00PX120301PR
and BQU2002-04524-C02-01.
Supporting Information Available: X-ray crystallographic files
in CIF format for [PbPh2Cl2(HATSC)]2, [PbPh2Cl2(HSTSC)2],
[PbPh2Cl(PyTSC)], [PbPh2Cl(AcPyTSC)], [{PbPh2Cl(HPyTSC)}2]-
[PbPh2Cl3(MeOH)]2, HBPyTSC, and [{PbPh2(BPyTSC)}2(PbPh2-
Cl4)]‚2MeOH, Figure 1S (polymeric chains along the x axis in the
[PbPh2Cl2(HATSC)]2 lattice formed by intermolecular hydrogen
bonds), Figure 2S (intra- and intermolecular hydrogen bonds in
[PbPh2Cl2(HSTSC)2]), Figure 4S (hydrogen bonds connecting the
dimeric cations with pairs of anions in [{PbPh2Cl(HPyTSC)}2]-
[PbPh2Cl3(MeOH)]2), Figure 5S (intermolecular hydrogen bonds
in [PbPh2Cl(PyTSC)]), and Figure 9S (the intermolecular hydrogen
bond between N(1)-H(1b) and Cl(1) which links [{PbPh2-
(BPyTSC)}2(PbPh2Cl4)] molecules in polymeric chains and also
the hydrogen bonds with the MeOH solvent molecules). This
material is available free of charge via the Internet at http://pubs.
acs.org.
Acknowledgment. We thank the Secretaria Xeral de
Investigacio´n e Desenvolvemento, Xunta de Galicia, Galicia,
Spain, and the Ministerio de Ciencia y Tecnolog´ıa of Spain
IC026219R
Inorganic Chemistry, Vol. 42, No. 8, 2003 2595