Synthesis and structural aspects of 1-naphthyltellurium(IV) trichloride (1), bis(mesityl)tellurium(IV) dichloride (2) and bis(chlorobis(2-thiophenyl) tellurium)oxide (3)

Article abstract of DOI:10.1016/j.poly.2013.06.044

Chlorination of bis(1-naphthyl)ditelluride (NplTeTeNpl; Npl = 1-C ₁₀H₇) with 3 equiv. of sulfuryl chloride (SO ₂Cl₂) resulted in bright yellow crystals of 1-naphthyltellurium(IV) trichloride (1-NplTeCl₃

Full text of DOI:10.1016/j.poly.2013.06.044

Polyhedron 62 (2013) 227–233
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Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and structural aspects of 1-naphthyltellurium(IV)
trichloride (1), bis(mesityl)tellurium(IV) dichloride (2)
and bis(chlorobis(2-thiophenyl)tellurium)oxide (3)
Poornima Singh a, , Ashok K.S. Chauhan , Ray J. Butcher , Andrew Duthie
⇑
a
b
c
a
Department of Chemistry, University of Lucknow, Lucknow 226007, India
Department of Chemistry, Howard University, Washington, DC 20059, USA
School of Life and Environmental Sciences, Deakin University, Geelong 3217, Australia
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
7
Chlorination of bis(1-naphthyl)ditelluride (NplTeTeNpl; Npl = 1-C10H ) with 3 equiv. of sulfuryl chloride
Received 31 December 2012
Accepted 28 June 2013
Available online 6 July 2013
(
SO
2
Cl
2
) resulted in bright yellow crystals of 1-naphthyltellurium(IV) trichloride (1-NplTeCl
3
; 1).
Bis(mesityl)tellurium(IV) dichloride, Mes
oxidative addition of sulfuryl chloride to bis(mesityl)telluride(II), prepared from detelluration of
bis(mesityl)ditelluride with a freshly prepared electrolytic copper. Bis(chlorobis(2-thiophenyl)tellu-
rium)oxide, (Tpn
between bis(thiophenyl)tellurium(IV) dichloride (Tpn
have been characterized crystallographically. In crystal lattice of 1, an asymmetric unit consists of two
independent molecules and both the molecules form a separate polymeric zig-zag chains via -chloro
bridging. These two polymeric chains are interlinked via CꢁHꢀ ꢀ ꢀCl H-bonding interactions to form a
one dimensional supramolecular array. In case of 2 a dimeric unit has been realized through CꢁHꢀ ꢀ ꢀCl
H-bonding interaction while in 3 a one dimensional supramolecular array has been formed via intermo-
2
TeCl , 2 (Mes = 2,4,6-Me ) has been synthesized by the
2
3 6 2
C H
Keywords:
Sterically hindered organotellurium
2
TeCl)
2
O, 3 (Tpn = 2-C
4
H
3
S) have been obtained serendipitously as a product of reaction
2
TeCl ) and AgCN. All the three compounds 1–3
2
1
-Naphthyltellurium(IV) trichloride
Thiophene moiety
C–Hꢀ ꢀ ꢀCl H-bonding interaction
l
2
lecular Teꢀ ꢀ ꢀCl1 secondary bonding interactions, where both the tellurium atoms exhibit
w-trigonal bipy-
ramidal geometry.
Ó 2013 Elsevier Ltd. All rights reserved.
1
. Introduction
with bridging halides, but with no Teꢀ ꢀ ꢀX secondary bonds [8,13].
3
In contrast to the polymeric chlorides and bromides, PhTeI has
The structural characteristics of several classes of organotellu-
been reported to exist as dimers, having either cis or trans oriented
phenyl groups [9]. Recently, in the coordination chemistry of
organotellurium compounds [14,15], the synthesis and the molec-
rium halides are known. In crystal structures reported for RTeX
3
species, the occurrence of intra- and intermolecular secondary
bonding interactions (SBIs), altered by the presence of additional
secondary bonds to tellurium together with the nature of the or-
ganic groups binding to the tellurium atoms and with the halogen,
oxygen or other donor atoms of adjacent molecules, leads to supra-
molecular self-assembly [1–7]. The intermolecular SBIs of the type
3 3
ular structure of (a-naphthyl)TeI and (a-naphthyl)TeBr has been
reported [16,17]. Though a large number of organotellurium tri-
chlorides have been explored so far, only a few have been studied
crystallographically [3,5,10,13,18,19] including the sterically
encumbered supermesityltellurium(IV) trichloride [20]. The reason
for less exploration of crystallographic studies of such compounds
may be partially attributed to the difficulty encountered in recrys-
tallization of these compounds, which are highly insoluble due to
their polymeric structures.
Teꢀ ꢀ ꢀX and Xꢀ ꢀ ꢀX in various RTeX
meric chains, dimers or monomers. It has been assumed that
among RTeX compounds there is a tendency for the chlorides to
3
leads to the formation of poly-
3
be polymeric, the bromides either polymeric or dimeric, the io-
dides to be dimeric and if R is particularly bulky, monomeric struc-
tures would be the rule. Here the size of the halogen should be the
other determining factor and the preference for dimeric structures
increases as size of the halogen increases [8–12]. The isomorphous
2 2
The geometry of R TeX type of compounds has also been pre-
dicted to be -trigonal bipyramidal with two carbon atoms and an
w
electron pair in the equatorial positions and two halo atoms in the
axial positions. Crystal structures of this type of compounds have
been reported [13,21–26] with a view to study SBIs. Presence of
3 3
PhTeCl and PhTeBr exist as polymers made up of infinite chains
secondary Teꢀ ꢀ ꢀX bonds in many phenyl dihalides, R
Cl or Br) renders them to exist in the form of monomers
13,27,28]. Structural studies on a series of organotellurium
2 2
TeX (X = F,
⇑
Corresponding author. Tel.: +91 9455280547; fax: +91 522 2338531.
E-mail address: poornima05singh@yahoo.co.in (P. Singh).
[
0
277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.06.044

2
28
P. Singh et al. / Polyhedron 62 (2013) 227–233
diiodides have been reported [29–34]. However, the coordination
about tellurium is usually expanded to octahedral by formation
of intermolecular Teꢀ ꢀ ꢀI bonds.
The third compound (Tpn
dipitously in an attempt to recrystallize the reaction product of
bis(thiophenyl)tellurium(IV) dichloride [Tpn TeCl and AgCN.
Attempt was made to synthesize the bis(2-thiophenyl)tellurium(IV)
dicyanide by a metathetical reaction between Tpn TeCl and AgCN
2 2
TeCl) O (3) has been obtained seren-
2
2
]
2 6 5 6 5 6 4
Telluroxides of the type R TeO (R = C H , C F , p-MeOC H )
[
35–38] constitute another important class of Te(IV) compounds.
2
2
They have been characterized structurally very well and used to
prepare oligotelluroxanes [39,40] and macrocyclic multi-telluranes
(excess) in dichloromethane at room temperature. The colorless
crystals of reaction product have been characterized as 3. It may
be assumed that the moisture present in the solid AgCN partially
[
41]. In recent past these compounds have also been used in organ-
ic synthesis as oxidizing agents as well as catalysts and also in
some organometallic reactions as oxygen transfer reagents
2 2 2
hydrolyze (Scheme 3) the Tpn TeCl to the Tpn TeCl(OH) which un-
dergo self condensation (Scheme 3) to yield the telluroxane, 3.
[
42–50]. Hydrolysis of bis(organyl)tellurium dihalides is the main
synthetic strategy for the synthesis of such compounds. The hydro-
lysis products of aryltellurium trihalides are not well characterized
whereas initial studies have revealed that the hydrolysis of phenyl-
and substituted phenyltellurium trihalides in neutral aqueous
medium results in the formation of partially hydrolyzed products
2.2. Spectroscopic studies
All the three tellurium(IV) compounds are sharp melting, bright
yellow to colorless crystalline solids and soluble in chlorinated sol-
vents viz. chloroform and dichloromethane. In the H NMR spectra
1
such as RTe(O)X (R = C
the formation of RTe(OH)
when hydrolysis is carried out under alkaline conditions. More
recently, Comasseto et al. reported that tellurinic anhydride,
6
H
5
, p-EtOC
6
H
4
) (X = Cl and Br). However,
O takes place
of these compounds the ring protons of the naphthyl, mesityl as
well as thiophene moiety appear in the aromatic region. The
appearance of two different signals for the protons of two o-methyl
groups of 2 in the aliphatic region indicates restricted rotation of
3
, RTeO(OH) and (RTeO)
2
(
RTeO)
2
O (R = C
6
H
5
, p-EtOC
6
H
4
) can also be prepared by the alka-
the benzene ring about the TeꢁC(Mes) bond in Mes
2
TeCl
C NMR chemical shifts for the ring carbons (of naphthyl, mesityl
and thiophene moiety) have been found to be in the range
2
. The
1
3
line hydrolysis in the presence of a phase transfer catalyst [51].
Partial or complete hydrolysis of organotellurium trihalides has
been reported in a few cases, but the structural characterization
of products obtained has not been reported. However, very re-
cently Beckmann and coworkers have demonstrated the isolation
and structural characterization of RTe(O)OH and RTe(O)Cl by
kinetic stabilization with a bulky m-ter phenyl substituent which
exist as dimers in the solid state [52].
In the light of these previous results, we extend our studies to
the molecular structures and intermolecular bondings in organo-
tellurium trichloride, dichloride and heteroaryl telluroxane. In this
article we report the preparation and structural characterization
1
25
125–144 ppm. A single
Te NMR resonance (deshielded in com-
parision to that of 2) has been observed (see Table 1) for both
the tellurium(IV) derivatives 1 (d 1373 ppm) and 3 (d 871 ppm),
indicating the presence of only one Te containing species in their
solutions. The magnitude of deshielding is very high (560 ppm)
in case of 1 (see Table 1), probably due to three electronegative
chlorine atoms attached directly to the Te(IV) metal centre in 1.
2.3. Crystal structures
and packing arrangement of the polymeric 1-NplTeCl
meric structure of Mes TeCl (2) and (Tpn TeCl) O (3).
3
(1), mono-
The molecular structures of 1, 2 and 3 have been elucidated
with the help of X-ray diffraction on their single crystals and are
shown in Figs. 1–3 with selected bond parameters collected in
the caption to each figure.
2
2
2
2
Two crystallographically independent molecules are present in
the asymmetric unit of the crystal lattice of 1 and each molecule
2
. Results and discussion
conforms to the usual
w-trigonal bipyramidal geometry in which
2
.1. Synthesis
Cl atom at the equatorial site is closest of the three attached to
each Te atom [d(Te1,Cl12), 2.334(1) Å and d(Te2,Cl22),
2.341(2) Å]. The axial Te–Cl bonds are unequal and substantially
3
Compound 1 (1-NplTeCl ) has been synthesized (Scheme 1) by
the oxidative addition of the sulfuryl chloride to the bis(1-naph-
thyl)ditelluride, prepared similarly as reported in literature [53].
Its bright yellow crystals have been obtained by recrystallization
of the compound in dichloromethane.
longer compared to
R
r
cov(Te,Cl) value of 2.36 Å [58]. Such an al-
most linear Te(IV)Cl
2
fragment among organotellurium(IV) di-
and trihalides is routinely described as a three-centre four-electron
bond (3c–4e), similar to that introduced by Rundle and Pimentel
for trihalide anions [59–62] and explains the hypervalency of tellu-
rium atom without violating the octet rule or invoking ionic bond-
ing. As two of the four electrons are occupied in a non-bonding
molecular orbital, only one bonding pair is available for the two
Compound 2 has been synthesized by the oxidative addition of
Cl to the solution of bis(mesityl)telluride(II) in hexane.
2 2
SO
Bis(mesityl)telluride(II) has been prepared by literature methods
detelluration of the corresponding ditelluride, Mes Te ) [44].
The sequential reactions for the synthesis of 2 are presented in
(
2
2
3
Te–Cl bonds in 1 (1-NplTeCl ) as well, thereby accounting for their
Scheme 2. Colorless crystals of Mes
from its dichloromethane solution.
2
TeCl
2
(2) has been obtained
bond orders typically less than 1.0 for a single electron pair bond
(2c–2e) between the same elements. The involvement of one of
the axial Cl atoms in strong intermolecular Teꢀ ꢀ ꢀCl secondary bond-
ing interaction (SBI) may be responsible for the significant dispar-
ity in the Te–Claxial bond distances, found in both the molecules of
Br
Mg
MgBr
TeMgBr
Te
1
. Separate polymeric zig-zag (helical) chains are formed by units
of each of the independent molecules via -chloro bridging
Fig. S1) in the crystal lattice. The intermolecular secondary bonds
THF
l
2
(
[
(
0
0
d(Te1ꢀ ꢀ ꢀCl11 ) = 2.875(2) Å, d(Te2ꢀ ꢀ ꢀCl21 ) = 2.888(1) Å] that are
Supporting information: Fig. S1) only slightly longer (ꢂ5%) than
[
O]
SO Cl
2 2
Te
TeCl3
the two axial Te–Cl bonds [d(Te1ꢀ ꢀ ꢀCl11) = 2.673(1) Å,
2
d(Te2ꢀ ꢀ ꢀCl21) = 2.674(1) Å], are significantly shorter than
R rvdw(Te,Cl) value of 3.90 Å [63]. Thus, in the crystalline state of
Scheme 1.
1, the environment of the five coordinate central tellurium atom

P. Singh et al. / Polyhedron 62 (2013) 227–233
229
Me
TeMgBr
Me
Cl
Me
Br
Me
Me
MgBr
Me
Mg
Te
Me
Me
Me
Me
THF
Me
Me
Te
Me
Me
SO Cl
[
O]
Cu
2
2
Me
Te
Me
Te
Me
2
2
Me
Me
Me Me
Cl
Scheme 2.
S
S
S
S
Cl
Cl
Te
Cl
AgCN
-H O
2
O
Te
S
Cl
Te
S
Te
OH
Cl
S
S
Scheme 3.
Table 1
Chemical shifts (d 125Te, in ppm) of organotellurium(IV) compounds.
the basal plane. Formation of similar square pyramidal, TeX
Y units
4
in the solid state has been observed invariably for the anions
ꢁ
[
TeX
4
Y] (Y = X = Cl [64] or Y = aryl group, X = Cl, Br [65]) and
Compound
R = 1-naphthyl(1-Npl)
R = mesityl(Mes)
among the oligomeric or polymeric supramolecular motifs in the
solid state of similar organotellurium trichlorides [3,10,66] as well
as organotellurium tribromides [8] including the bromo analog of 1
R
R
R
R
2
2
2
2
TeF
TeCl
TeBr
TeI
2
–
–
–
–
1206 [54]
813 [55]
744 [56]
389 [56]
–
2
2
2
[
-
17]. In the case of neutral organotellurium trichlorides and
tribromides formation of planar TeX units takes place when the
RTeCl
RTeBr
RTeI
3
1373
1348 [17]
–
4
3
469 [57]
–
central Te atom is approached by a chloro or bromo ligand of an
adjacent molecule in a direction trans to the equatorial Cl(Br)–Te
bond in preference to that of the C–Te bond resulting in two quasi
linear X–Te–X alignments. Formation of such a planar covalent
3
appears to be square pyramidal with naphthyl moiety at the apical
site with its plane perpendicular to the distorted square basal
plane. The nearly coplanar four Cl atoms along with the Te atom
deviation from the mean plane is limited to 0.1788 Å (Cl12 atom)
and 0.019 Å (Cl23 atom) in molecules I and II respectively} occupy
4
TeX moiety among 12–Te–5 hypervalent species may be said to
represent a five-centre eight-electron bonding (5c–8e) system
where three doubly degenerate molecular orbitals are constituted
by two atomic orbitals from the Te atom and one each from four
halogen atoms. All the four Te–Cl bonds are weaker than a normal
{
Fig. 1. Molecular structure of 1. Selected interatomic distances (Å) and angles (°) for the two independent molecules: Te1–C1A 2.115(5) {2.116(5)}, Te1–Cl11 2.673(1)
{
2.674(1)}, Te1–Cl12 2.334(1) {2.341(2)}, Te1–Cl13 2.382(1) {2.376(2)}, C1A–Te1–Cl11 87.70(14) {87.99(14)}, C1A–Te1–Cl12 96.09(15) {95.14(15)}, C1A–Te1–Cl13 91.80(14)
{
92.30(15)}, Cl11–Te1–Cl12 83.82(5) {84.68(6)}, Cl11–Te1–Cl13 171.93(5) {172.27(6)}, Cl12–Te1–Cl13 88.22(6) {87.60(7)}.

2
30
P. Singh et al. / Polyhedron 62 (2013) 227–233
Fig. 2. Molecular structure of 2. Selected interatomic distances (Å) and angles (°): Te–C1A 2.147(3), Te–ClB 2.142(2), Te–Cl1 2.5368(7), Te–Cl2 2.4979(8), C1A–Te–C1B
15.34(9), Cl1–Te–Cl2 174.98(2).
1
Fig. 3. Molecular structure of 3. Selected interatomic distances (Å) and angles (°) with higher occupencies of the atoms are shown for the clarity: Te1–C9A 2.186(13), Te1–
C13A 2.086(15), Te2–C1A 2.067(21), Te2–C5B 2.110(16), Te1–O1 1.988(6), Te2–O1 1.971(7), Te1–Cl1 2.691(2), Te2–Cl2 2.611(3), C9A–Te1–C13A 102.8(5), C1A–Te2–C5B
9
7.0(7), Te1–O1–Te2 136.6(4), Cl1–Te1–O1 170.1(2), Cl2–Te2–O1 170.6(2).
2
c–2e bond because of the eight electrons that occupy bonding and
to the Te(IV) atom could lead to subtle modifications in the supra-
molecular motifs (Fig. 4).
non bonding molecular orbitals, only four account for such Te–Cl
bonds. However, the formation of such halo-bridged square pyra-
The asymmetric unit in the crystal lattice of 2 is consist of only
midal CTeX
4
units (formed by intermolecular Teꢀ ꢀ ꢀX SBIs) has not
one independent molecule which conforms to the usual w-trigonal
observed in the crystal structures of the iodo analog of 1-naphthyl-
tellurium(IV) trichloride [16], mesityltellurium tribromide [57], 2-
biphenylyltellurium tribromide [1] and also among those of the
functionalized aryltellurium trihalides possessing intramolecular
Teꢀ ꢀ ꢀA SBI with the central Te atom [7,67–68]. The Addison’s tau
values [69] for the compound 1, 2 and 3 are 1.23, 1.0 and 1.12 &
bipyramidal geometry around Te atom. The axial positions are
occupied by more electronegative chlorine atom while the ipso car-
bon atoms of the mesityl moieties together with a lone pair are
placed in the equatorial positions. The steric demand of the mesityl
ligand in this molecule enlarges the equatorial angle [115.34(9)°]
2 2
which is comparable to 113.5(2)° in Mes TeBr [56]. A zero dimen-
1
.23 respectively which also proved that compound 2 is perfectly
sional dimeric unit has been realized via CꢁHꢀ ꢀ ꢀCl intermolecular
trigonal bipyramidal and 2 and 3 are -trigonal bipyramidal. A di-
w
interactions (Fig. S2).
verse combination of crystal packings has been observed among
organotellurium trihalides and it is not surprising because a slight
variation in the steric and electronic features of the ligands bound
2 2
In case of (Tpn TeCl) O (3), an asymmetric unit also contains
one crystallographically independent molecule in the crystal lat-
tice and ring atoms of each of thiophenyl moieties in the molecule

P. Singh et al. / Polyhedron 62 (2013) 227–233
231
via bridging Cl atom. In 1 and 2 supramolecular architects were
formed through CꢁHꢀ ꢀ ꢀCl H-bonding interaction. 1D supramolecu-
lar array has been realized in case of 3 via bifurcated Teꢀ ꢀ ꢀCl1 inter-
molecular interactions.
3
. Experimental
3.1. General procedures
All solvents were purified and dried before use. Te powder was
purchased from Sigma Aldrich (USA). The starting materials 2-bro-
mo naphthlene, 2-bromo mesitylene and 2-bromo thiophene were
used as procured from Merck KGaA, Germany. Melting points were
1
recorded in capillary tubes and are uncorrected. H NMR spectra
were recorded at 300.13 MHz in CDCl
3
on a Bruker DRX300 spec-
13
1
trometer using Me Si as the internal standard.
4
C{ H}
Te{ H} (126.19 MHz) NMR spectra were re-
on a JEOL Eclipse Plus 400 NMR spectrometer,
Si and Me Te respectively as internal standards. Microa-
nalyses were carried out using a Carlo Erba 1108 analyzer.
1
25
1
(
100.54 MHz) and
corded in CDCl
using Me
3
4
2
3
3
.2. Syntheses
3
.2.1. Synthesis of 1-naphthyltellurium(IV) trichloride, 1-NplTeCl (1)
2 2
Dropwise addition of a solution of SO Cl (0.16 mL, 2.0 mmol) in
dichloromethane (5 mL) to a stirred red solution of bisnaphthyldi-
telluride (0.26 g, 0.50 mmol) in the same solvent (10 mL) at 0 °C
followed by stirring at room temp (2 h), resulted in the precipita-
tion of 1 as a bright yellow solid that was recrystallized from
dichloromethane to afford bright yellow single crystals. Yield:
0.33 g (91%). M.p.: 180 °C (lit. 175–180 °C [70]). Anal. Calc. for C10-
Fig. 4. One dimensional array was realized via C7BꢁH7BAꢀ ꢀ ꢀCl12 interactions in
between the two independent molecules of 1. Only relevant hydrogen atoms are
shown for clarity.
Te (361.12): C, 33.26; H, 1.95. Found: C, 33.14; H, 1.87%. 1
H
3
7
H Cl
NMR: d 7.65 (t, 1H), 7.72 (t, 1H), 7.81 (t, 1H), 8.05 (d, 1H), 8.14
1
3
1
(
d, 2H), 8.69 (s, 1H) ppm. C{ H} NMR: d 124.7, 127.1, 127.3,
1
27.5, 128.3, 129.7, 129.8, 130.0, 133.1, 133.3 (aromatic carbons)
are twofold disordered with occupancies 57:43, 58:42 for the rings
attached to Te1 and 69:31, 44:56 for rings attached to Te2. The
geometry around each Te atom is pseudo-trigonal bipyramidal
and the axial sites are occupied by the more electronegative chloro
and oxo ligands while the carbon atoms of the thiophenyl moieties
together with a lone pair are placed in the equatorial positions. The
equatorial C–Te–C angles are 102.8(5)° for Te1 and 97.0(7)° for Te2
atom and are significantly smaller than the putative value of 120°
for a trigonal bipyramidal geometry owing to the stereochemical
activity of the lone pair on the central Te atom. The Te1–O1–Te2
angle is 136.6(4)°. The Te1–Cl1 bond [2.691(2) Å] is slightly longer
than Te2–Cl2 bond [2.611(3) Å]. It is presumably due to the
involvement of Cl1 atom in the intermolecular secondary bonding
interaction. Formation of one-dimensional supramolecular
array has been observed in this case via bifurcated TeꢀꢀꢀCl1 inter-
molecular interactions [d(Te1ꢀ ꢀ ꢀCl1) = 3.300(2) Å, d(Te2ꢀ ꢀ ꢀCl1) =
1
25
1
ppm.
Te{ H} NMR: d 1373 ppm.
3
.2.2. Synthesis of bis(mesityl)tellurium(IV) dichloride, Mes
Sulfuryl chloride (0.08 mL, 1.0 mmol) in hexane (5 mL) was
added dropwise to a cooled (0 °C) solution of bis(mesityl)telluride
0.366 g, 1.0 mmol) in hexane (5 mL) and the reaction mixture was
2 2
TeCl (2)
(
stirred for 5 min to obtain a white precipitate. It was filtered and
recrystallized from dichloromethane to yield colorless needles of
2
. Yield: 0.41 g (89%). M.p.: 179 °C (lit. 178–179 °C [71]). Anal. Calc.
for C18 22TeCl (436.87): C, 49.49; H, 5.08. Found: C, 49.42; H,
.21%. H NMR: d 2.33 (s, 3H, p-Me), 2.56 (s, 3H, o-Me), 2.91 (s,
H, o-Me), 7.01 (s, 1H, m-H mesityl ring), 7.05 (s, 1H, m-H mesityl
H
2
1
5
3
13
1
ring) ppm. C{ H} NMR: d 20.9 (p-Me), 24.0 (o-Me), 24.9 (o-Me),
30.5, 130.9, 135.1, 140.6, 141.8, 144.4 (aromatic carbons) ppm.
1
3
.293(2) Å] which are appreciably shorter than
R rvdw(Te,Cl) value
of 3.90 Å (Fig. 5).
3.2.3. Isolation of bis(chlorobis(2-thiophenyl)tellurium)oxide;
Tpn TeCl) O (3)
2
A solution of Tpn TeCl (0.36 g, 1.0 mmol) [34] in 25 ml chloro-
(
2
2
2
2
.4. Conclusion
form was stirred with AgCN (0.27 g, 2.0 mmol) for 36 h. The reac-
tion mixture was filtered and the filtrate was passed through a
short silica column. Filtrate was concentrated to ꢂ5 mL and hexane
was added to afford a white solid that was recrystallized from
dichloromethane/hexane (10:1) to give colorless crystals of 3.
Oxidative addition of the sulfuryl chloride to bisnaphthylditel-
luride and bismesityltelluride gave 1-naphthyltellurium(IV) tri-
chloride (1) and bismesityltellurium(IV) dichloride (2)
respectively. Compound 3 (Tpn
dipitously in crystalline form by the reaction between bis(thio-
phenyl)tellurium(IV) dichloride (Tpn TeCl and AgCN. The
2
TeCl)
2
O has been obtained seren-
Yield: 0.21 g (62%). M.p.: 168 °C. Anal. Calc. for C16
H
12Cl
2 4 2
OS Te
1
(674.63): C, 28.49; H, 1.79. Found: C, 28.43; H, 1.68%. H NMR: d
1
3
1
2
2
)
7.23 (t, 1H), 7.79 (d, 1H), 8.15 (d, 1H) ppm. C{ H} NMR: d
125
1
crystal structures of these three compounds have been crystallo-
128.7, 135.7, 138.2, 140.1 (aromatic carbons) ppm.
Te{ H}
graphically studied. In case of 1, a polymeric chain was observed
NMR: d 871 ppm.

2
32
P. Singh et al. / Polyhedron 62 (2013) 227–233
Fig. 5. 1D supramolecular array realized via Teꢀ ꢀ ꢀCl intermolecular secondary bonding interactions in the crystal lattice of 3. Hydrogen atoms are omitted for clarity.
Table 2
Crystal data and structure refinement details of 1, 2 and 3.
1
2
3
Empirical formula
Formula mass (g molꢁ1)
T (K)
Wavelenth, k (Å)
Crystal system
Crystal size (mm)
Space group
a (Å)
C
10
H
7
Cl
3
Te
C
18
H
22Cl
2
Te
C
16 2 4 2
H12Cl OS Te
361.11
123(2)
0.71073
436.86
123(2)
0.71073
674.60
123(2)
1.54178
monoclinic
monoclinic
monoclinic
0.53 ꢃ 0.47 ꢃ 0.35
0.49 ꢃ 0.31 ꢃ 0.25
0.3034 ꢃ 0.2404 ꢃ 0.0160
P 2
1
/c
1
P 2 /c
C 2/c
19.6060(16)
7.3478(3)
17.3811(17)
90
115.988(12)
90
2250.8(3)
8
2.131
10.7833(4)
21.6413(7)
8.2536(3)
90
111.034(4)
90
1797.76(11)
4
1.614
19.0326(8)
8.0139(2)
29.0158(12)
90
109.663(4)
90
4167.6(3)
8
2.150
b (Å)
c (Å)
a
(°)
b (°)
(°)
c
3
V (Å )
Z
ꢁ
q
calc (Mg m 3
)
Absorption coefficient (mmꢁ1)
F(000)
3.310
1360
1.944
864
28.239
2544
h, k, l ranges collected
ꢁ31 ? 30
ꢁ15 ? 10
ꢁ20 ? 32
ꢁ10 ? 12
12674
ꢁ22 ? 23
ꢁ
ꢁ
11 ? 11
28 ? 27
ꢁ9 ? 6
ꢁ35 ? 36
13966
Reflection collected
43876
Independent reflections
h range (°)
Completeness to hmax (%)
Absorption correction
Maximum, minimum transmission
Refinement method
9590 [Rint = 0.0531]
5.24–35.22
99.0
Semi-empirical from equivalents
1.00000, 0.45619
Full-matrix least-squares on F2
9590/0/254
5882 [Rint = 0.0291]
5.03–32.69
99.1
4158 [Rint = 0.0556]
3.23–74.04
99.8
Analytical
0.645, 0.019
1.00000, 0.58408
Data/restraints/parameters
5882/0/197
1.054
4158/296/290
1.057
Goodness-of-fit (GOF) on F2
1.139
Final R indices (I > 2
r
(I))
R
R
1
= 0.0498, wR
= 0.0630, wR
2
= 0.1044
= 0.1109
R
R
1
= 0.0310, wR
= 0.0486, wR
2
= 0.0722
= 0.0759
R
R
1
= 0.0573, wR
= 0.0626, wR
2
2
= 0.1535
= 0.1601
R indices (all data)
1
2
1
2
1
Largest diff peak and hole (e Åꢁ3)
Extinction coefficient
1.930 and ꢁ1.075
0.922 and ꢁ0.557
2.745 and ꢁ1.578
0.0001(3)
3
.2.4. Crystallography
Single crystals of 1 and 2 suitable for X-ray crystallography
tion for 1 and 2 while at 1.54178 Å for 3. Data were reduced and
corrected for absorption using spherical harmonics, implemented
in SCALE3 ABSPACK scaling algorithm in the CrysAlisPro, Oxford
Diffraction Ltd., Version 1.171.33.34d program. The structures
were solved by direct methods and difference Fourier synthesis
were grown by slow evaporation of its dichloromethane solution
while 3 by mixture of dichloromethane/hexane solution. Intensity
data were collected on an Oxford Diffraction Gemini CCD diffrac-
2
tometer with graphite-monochromated Mo K
a
(0.71073 Å) radia-
using SHELXS-97 [72]. Full-matrix least-squares refinements on F ,

P. Singh et al. / Polyhedron 62 (2013) 227–233
233
using all data, were carried out with anisotropic displacement
parameters applied to non-hydrogen atoms. Hydrogen atoms at-
tached to carbon were included in geometrically calculated posi-
tions using a riding model and were refined isotropically. Crystal
data and structure refinement details are given in Table 2. The
molecular structures are depicted in Figs. 1 and 3, showing 30%
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