New cation-dependent supramolecular arrangements of [RTeI4]- tectons: Synthesis and X-ray structural characterization of the mixed valence complex salts [p-CH3O(C6H4)Te(etu)][p-CH3O (C

Article abstract of DOI:10.1016/j.jorganchem.2006.06.003

(p-CH₃OC₆H₄Te)₂ and (p-PhOC₆H₄Te)₂ react with I₂ and thiourea/ethylenethiourea to give the mixed valence complex salts [p-CH₃O(C₆H₄)Te

Full text of DOI:10.1016/j.jorganchem.2006.06.003

Journal of Organometallic Chemistry 691 (2006) 4006–4011
www.elsevier.com/locate/jorganchem
ꢀ
New cation-dependent supramolecular arrangements of [RTeI4]
tectons: Synthesis and X-ray structural characterization of the
mixed valence complex salts [p-CH O(C H )Te(etu)]-
3
6 4
[
p-CH O(C H )TeI ] (etu = ethylenethiourea) and
3 6 4 4
[
p-PhO(C H )Te(tu)][p-PhO(C H )TeI ] (tu = thiourea)
6 4 6 4 4
Gleison Ant oˆ nio Casagrande , Ernesto Schulz Lang , Gelson Manzoni de Oliveira a,*,
a
a,
*
b
b
Sebasti a˜ o S. Lemos , Viviane A.S. Falcomer
a
LMI – Departamento de Qu ı´ mica, Universidade Federal de Santa Maria, 97.105-900 Santa Maria, RS, Brazil
b
Instituto de Qu ı´ mica, Universidade de Bras ı´ lia, 70904-970, Bras ı´ lia, DF, Brazil
Received 26 April 2006; received in revised form 2 June 2006; accepted 3 June 2006
Available online 15 June 2006
Abstract
(
p-CH
3
OC
)Te(etu)][p-CH
6
H
4
Te)
2
and (p-PhOC
6 4 2 2
H Te) react with I and thiourea/ethylenethiourea to give the mixed valence complex salts [p-
CH
3
O(C
6
H
4
3
O(C )TeI
6
H
4
4
] (1) and [p-PhO(C
6
4
H )Te(tu)][p-PhO(C
6 4
H )TeI
4
] (2). Both compounds confirm the tectonic
ꢀ
2ꢀ
character of the tetraiodo-organyltellurates [RTeI ] with the assembling of polymeric chains of ½p-CH
3
OðC
6
H
4
ÞTeI
4
ꢁ
and
4
2
2ꢀ
½
p-PhOðC
6
H
4
ÞTeI
4
ꢁ
dimers linked through single (1) and double (2) Iꢂ ꢂ ꢂI secondary bonds. The strong covalent character of the cat-
2
3
ion–anion interaction of 2 allows its further representation as the mixed valence molecular species [RTeI (l-I)Te(tu)R] {R = p-
PhO(C H )}.
6
4
ꢀ
2006 Elsevier B.V. All rights reserved.
ꢀ
] ions
Keywords: Organotellurium halides; Tectonic tetraiodo-organyltellurates; Supramolecular assembling of [RTeI
4
1
. Introduction
have found [4] three different packing arrangements in
the crystal lattice of [PhTeCl4] salts, all of them arising
ꢀ
If we consider Simard’s tecton (from Greek, tekton,
from secondary Teꢂ ꢂ ꢂCl bonds (which complete the octahe-
dral coordination at tellurium) and hydrogen–halogen
bonds between the anion and the stabilizing cations (pyri-
donium, for example). When the same, not too bulky
cationic species is maintained for different – and bigger –
builder) definition [1] – any molecule whose interactions
are dominated by particular associative forces that induce
the self-assembly of an organized network with specific
architectural or functional features – and the concept of
ꢀ
ꢀ
supramolecular synthesis [2,3], then the species [RTeX4]
[PhTeX4] (X = Br, I) anions, the polymerization gradu-
(
R = aryl; X = halogen) surely play an important role in
ally increases substantially [5]. Further, in the lattice of
this chemical field, due to their remarkable ability to act
as supermolecule-building tectons. We have already
described some examples with this tendency: initially we
{Cs[PhTeCl ] Æ CH OH]} and Cs[PhTeBr ] the alkali metal
4
3
4
cation interacts secondarily with the chlorine and bromine
Te-ligands holding the structures in tridimensional, supra-
molecular assemblies [6]. In tetraiodo-organyltellurates sta-
bilized by cations without acid N–H functions such as
*
(Et N)[PhTeI ] and (Et N)[(b-naphthyl)TeI ], only the
4 4 4 4
Corresponding authors. Tel.: +55 55 220 8757; fax: +55 55 220 8031.
E-mail address: manzoni@quimica.ufsm.br (G.M. de Oliveira).
Teꢂ ꢂ ꢂI and Iꢂ ꢂ ꢂI secondary bonds behave as structure-
0
022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.06.003

G.A. Casagrande et al. / Journal of Organometallic Chemistry 691 (2006) 4006–4011
4007
forming interactions in the self-organization of the supra-
ionic lattices [7] which are also strongly dependent on the
Te(l-I)Te(etu)Ph][PhTeI ] [9], there are no cation–anion
interactions, and the anions [PhTeI4] appear merely in
4
ꢀ
size of the organic group.
dimeric association through symmetrical and reciprocal
Teꢂ ꢂ ꢂI interactions, which accomplish the octahedral con-
figuration of the Te centres.
ꢀ
Another interesting characteristic of [RTeX ] anions is
4
II
II
their trend to be also stabilized by Se and Te cation com-
plexes to form mixed valence complex salts. We have newly
reported some structures of this kind of complexes, such as
In the light of these experimental studies we now report
on the synthesis and the structural characterization of the
new mixed valence complex salts [p-CH O(C H )-
[
PhSe(tu)][PhTeI ], [PhSe(tu)][PhTeBr ] [8] and [Ph(etu)-
4 4
3
6
4
Te(l-I)Te(etu)Ph][PhTeI ] [9]. In these cases, however, the
Te(etu)][p-CH O(C H )TeI ] (1) and [p-PhO(C H )-
3 6 4 4 6 4
4
ꢀ
IV
tectonic character of the [RTeX ] ion – e.g., its ability to
Te(tu)][p-PhO(C H )TeI ] (2), where the Te anions [p-
6 4 4
4
ꢀ
ꢀ
build supermolecules through secondary interactions – is
very limited, probably due to the stereochemical effects
associated with the size of the cation complex. Thus, in
CH O(C H )TeI ] and [p-PhO(C H )TeI ] confirm their
3 6 4 4 6 4 4
tectonic character. In both compounds the anions are
linked in the well known dimeric association through reci-
procal Teꢂ ꢂ ꢂI secondary interactions which assure the octa-
hedral coordination of the Te atoms. Single Iꢂ ꢂ ꢂI
interactions in 1 generate a polymeric chain, in 2 the dimers
are linked through double Iꢂ ꢂ ꢂI bonding in a curious poly-
meric conformation. The strong cation–anion interaction
in 2 also allows its molecular representation.
[
PhSe(tu)][PhTeI ] there occurs dimeric association of anio-
4
ꢀ
nic [PhTeI4] through reciprocal Teꢂ ꢂ ꢂI interactions, with
+
the participation of two [PhSe(tu)] cationic moieties
through Seꢂ ꢂ ꢂI interactions. Dimeric assembling and strong
covalent cation-anion interactions were also observed in the
‘
‘molecular’’ complexes described in the same report [8],
[
(tmtu)PhTe(l-Br)TeBr Ph] and [(tu)PhTe(l-I)TeI Ph]
2
3
2
3
(
(
tmtu = tetramethylthiourea); on the other hand, in [PhSe-
2. Experimental
ꢀ
tu)][PhTeBr ] (of the same series), the tectons [PhTeBr ]
4
4
are able to achieve a very complex (zigzag) polymeric chain,
additionally reinforced by three secondary bonds of
cationic selenium atoms to the bromine ligands of the sur-
rounding anionic units. Finally, in the lattice of [Ph(etu)-
All manipulations were conducted under nitrogen by the
use of standard Schlenk techniques. Methanol was dried
with Mg/I and distilled before use [10]. The respective ditel-
2
lurides were prepared according literature procedures [11].
Table 1
Crystal data and structure refinement for 1 and 2
1
2
Empirical formula
Formula weight
T (ꢁK)
Radiation, k (A)
Crystal system, space group
C
17
H
20
I
4
N
2
O
2
STe
50 44 8 4 4 2 4
C H I N O S Te
1079.21
273(2)
0.71
2354.61
296(2)
0.71
˚
ꢀ
ꢀ
Triclinic, P1
Triclinic, P1
Unit cell dimensions
˚
a (A)
8.9778(2)
10.1681(2)
15.4585(4)
74.7630(10)
85.3610(10)
89.5750(10)
1356.96(5)
2, 2.641
13.7100(3)
13.7489(2)
18.3665(3)
69.2470(10).
81.4250(10)
79.4890(10)
3169.63(10)
2, 2.467
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
˚
3
V (A )
ꢀ
3
Z, Calculated density (g cm
Absorption coefficient (mm
F(000)
)
ꢀ1
)
6.792
968
5.827
2136
Crystal size (mm)
h Range (ꢁ)
0.24 · 0.14 · 0.04
1.37–30.87
0.12 · 0.11 · 0.09
1.19–28.38
Index ranges
ꢀ12 6 h 6 12,
ꢀ17 6 h 6 18,
ꢀ18 6 k 6 18,
ꢀ24 6 l 6 24
62,531
15834 [Rint = 0.0258]
99.6%
Semi-empirical
0.6221 and 0.5415
Full-matrix least-squares on F
15834/0/649
ꢀ
14 6 k 6 14,
22 6 l 6 22
ꢀ
Reflections collected
Reflections unique
Completeness to theta max.
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
45,165
8454 [Rint = 0.0279]
98.8%
Semi-empirical
0.7728 and 0.2925
Full-matrix least-squares on F
8454/0/253
2
2
2
Goodness-of-fit on F
1.161
1.118
Final R indices [I > 2r(I)]
R indices (all data)
Largest diff. peak and hole (e A
R
R
1
1
= 0.0261, wR
= 0.0415, wR
2
= 0.0811
= 0.1004
R
R
1
= 0.0276, wR
= 0.0479, wR
2
2
= 0.0759
= 0.0982
2
1
˚
ꢀ3
)
1.695 and ꢀ1.280
1.664 and ꢀ1.481

4008
G.A. Casagrande et al. / Journal of Organometallic Chemistry 691 (2006) 4006–4011
2
.1. [p-CH O(C H )Te(etu)] [p-CH O(C H )TeI ] (1)
3
tered. The slow evaporation of the solvent yielded black-
reddish crystals.
6
4
3
6
4
4
To a solution of 0.047 g (0.1 mmol) of (p-CH OC H Te)
2
Properties:
air
stable
black-reddish
crystals;
3
6
4
-
(
2
(
dianisylditelluride - in 30 ml of methanol, 0.0253 g
0.1 mmol) of resublimed I were added. After stirring for
C H I N O S Te (2354.61). Yield: 65% based on (p-
5
0
44 8
4
4
2
4
PhOC H Te) ; Melting point: 125–127 ꢁC; C, H, N-analy-
2
6
4
2
min, to the p-CH OC H TeI solution 0.0204 g
sis: Calc.: C, 25.86; H, 1.91; N, 2.41. Found: C, 25.92; H,
1.80; N, 2.59%.
3
6
4
0.2 mmol) of ethylenethiourea was added and the black
II
color turned red instantaneously {formation of the Te
intermediary p-CH OC H Te(etu)I}. To the red mixture
3
6
4
Table 3
0
.123 g (0.2 mmol) of p-CH OC H TeI was added and
3 6 4 3
˚
Selected bond lengths [A] and angles [ꢁ] for 2
the solution was refluxed mildly at 50 ꢁC for 1 h. After
cooling at room temperature the mixture was filtered and
the slow evaporation of the solvent gave black-reddish
crystals of the product.
Bond lengths
C(11)–Te(1)
S(1)–Te(3)
2.148(4)
2.4895(18)
3.0750(4)
2.8672(5)
2.8371(4)
3.0151(4)
3.8422(5)
2.8785(5)
2.9177(4)
2.9607(5)
2.9661(4)
3.654(2)
3.3000(6)
3.4315(6)
3.637(2)
4.0595(5)
3.6367(5)
4.0595(5)
Te(1)–I(1)
Properties: air stable, black-reddish crystalline sub-
stance; C H I N O STe (1079.21). Yield: 83% based on
Te(1)–I(2)
Te(1)–I(3)
Te(1)–I(4)
1
7
20 4
2
2
(
p-CH OC H Te) ; Melting point: 118–120 ꢁC; C, H, N-
3
6
4
2
Te(1)ꢂ ꢂ ꢂI(4)#1
analysis: Calc.: C, 18.92; H, 1.87; N, 2.60. Found: C,
Te(2)–I(7)
1
8.79; H, 1.62; N, 2.65%.
Te(2)–I(6)
Te(2)–I(8)
Te(2)–I(5)
2
.2. [p-PhO(C H )Te(tu)] [p-PhO(C H )TeI ] (2)
6
4
6
4
4
Te(2)ꢂ ꢂ ꢂI(5)#2
I(1)ꢂ ꢂ ꢂTe(3)
I(6)ꢂ ꢂ ꢂTe(4)
I(3)#1ꢂ ꢂ ꢂI(5)#1
I(1)ꢂ ꢂ ꢂI(7)#1
I(3)ꢂ ꢂ ꢂI(5)
To a red solution of 0.1186 g (0.2 mmol) of (p-
PhOC H Te) – diphenoxyphenylditelluride – in 30 ml of
6
4
2
methanol, 0.0506 g (0.2 mmol) of resublimed I was added
2
and the color turned black. After the addition of 0.0152 g
I(1)#1ꢂ ꢂ ꢂI(7)#2
(
(
0.2 mmol) of thiourea and supplementary 0.0506 g
0.2 mmol) of resublimed I the temperature was kept at
Bond angles
2
4
0 ꢁC for 40 min. At room temperature the mixture was fil-
C(11)–Te(1)–I(3)
C(11)–Te(1)–I(2)
I(3)–Te(1)–I(2)
C(11)–Te(1)–I(4)
I(3)–Te(1)–I(4)
I(2)–Te(1)–I(4)
C(11)–Te(1)–I(1)
I(3)–Te(1)–I(1)
92.69(12)
92.35(12)
91.031(15)
90.49(12)
88.328(13)
177.112(15)
89.26(12)
177.306(14)
87.028(14)
93.519(13)
171.09(12)
91.854(11)
79.902(12)
97.302(11)
85.969(11)
82.70(1)
90.31(12)
92.82(12)
93.60(12)
90.95(12)
90.186(14)
89.478(15)
175.441(14)
175.167(16)
93.295(13)
86.786(14)
178.11(14)
88.14(1)
Table 2
˚
Selected bond lengths [A] and angles [ꢁ] for 1
Bond lengths
Te(1)–C(11)
Te(1)–I(3)
Te(1)–I(4)
Te(1)–I(2)
2.144(4)
2.8741(4)
2.9303(4)
2.9679(4)
3.0251(4)
3.7800(4)
3.6660(6)
2.114(4)
I(2)–Te(1)–I(1)
I(4)–Te(1)–I(1)
Te(1)–I(1)
C(11)–Te(1)ꢂ ꢂ ꢂI(4)#1
I(3)–Te(1)ꢂ ꢂ ꢂI(4)#1
I(2)–Te(1)ꢂ ꢂ ꢂI(4)#1
I(4)–Te(1)ꢂ ꢂ ꢂI(4)#1
I(1)–Te(1)ꢂ ꢂ ꢂI(4)#1
Te(1)–I(4)ꢂ ꢂ ꢂTe(1)#1
C(31)–Te(2)–I(5)
C(31)–Te(2)–I(7)
C(31)–Te(2)–I(6)
C(31)–Te(2)–I(8)
I(7)–Te(2)–I(6)
Te(1)ꢂ ꢂ ꢂI(2)#1
I(3)ꢂ ꢂ ꢂI(3)#1
Te(2)–C(21)
Te(2)–S(1)
Te(2)ꢂ ꢂ ꢂI(3)
2.5163(14)
4.1772(4)
Bond angles
C(11)–Te(1)–I(3)
C(11)–Te(1)–I(4)
I(3)–Te(1)–I(4)
C(11)–Te(1)–I(2)
C(11)–Te(1)ꢂ ꢂ ꢂI(2)#1
I(3)–Te(1)–I(2)
I(4)–Te(1)–I(2)
C(11)–Te(1)–I(1)
I(3)–Te(1)–I(1)
I(4)–Te(1)–I(1)
I(2)–Te(1)–I(1)
I(2)–Te(1)ꢂ ꢂ ꢂI(2)#1
C(21)–Te(2)–S(1)
C(21)–Te(2)ꢂ ꢂ ꢂI(3)#1
S(1)–Te(2)ꢂ ꢂ ꢂI(3)#1
90.85(11)
4.42(12)
89.587(12)
93.59(12)
169.74(12)
90.409(11)
171.990(13)
89.48(11)
175.146(13)
85.559(12)
94.404(11)
78.55(1)
I(7)–Te(2)–I(8)
I(6)–Te(2)–I(8)
I(7)–Te(2)–I(5)
I(6)–Te(2)–I(5)
I(8)–Te(2)–I(5)
C(31)–Te(2)ꢂ ꢂ ꢂI(5)#2
I(5)–Teꢂ ꢂ ꢂI(5)#2
I(7)–Te(2)ꢂ ꢂ ꢂI(5)#2
I(6)–Te(2)ꢂ ꢂ ꢂI(5)#2
I(8)–Te(2)ꢂ ꢂ ꢂI(5)#2
Te(2)–I(5)ꢂ ꢂ ꢂTe(2)#2
88.66(1)
93.295(13)
86.786(14)
91.860(12)
92.19(12)
160.41(11)
74.70(3)
Symmetry transformations used to generate equivalent atoms: #1 ꢀx + 1,
Symmetry transformations used to generate equivalent atoms: #1 ꢀx + 2,
ꢀy, ꢀz + 1; #2 ꢀx, 1 ꢀ y, 1 ꢀ z.
ꢀ
y + 1, ꢀz + 1.

G.A. Casagrande et al. / Journal of Organometallic Chemistry 691 (2006) 4006–4011
13 125
4009
1
.4. H, C, and Te NMR
2
The NMR spectral data were obtained in a Varian Mer-
1
cury Plus 7.05 T spectrometer with 300.07 MHz ( H),
1
3
125
7
5.46 MHz ( C) and 94.74 MHz ( Te). The samples were
dissolved in a 9:1 mixture of acetone-d and DMSO-d ,
6
6
respectively. The solutions were measured in NMR tubes
1
13
of 5 mm, at 300 ꢁK. The H NMR and C NMR chemical
shifts are relative to Si(CH ) as internal reference. The
3
4
1
25
Te NMR spectra were taken with reference to (CH ) Te.
3
2
A capillary containing Ph Te dissolved in CDCl (d 450)
2
2
3
was used as external reference.
. Results and discussion
The crystal data and experimental conditions are given in
3
Table 1. Selected bond distances and angles of [p-
CH O(C H )Te(etu)][p-CH O(C H )TeI ] (1) and [p-
3
6
4
3
6
4
4
PhO(C H )Te(tu)][p-PhO(C H )TeI ] (2) are listed in
6
4
6
4
4
Tables 2 and 3, with dashed lines representing the secondary
bonds. Figs. 1 and 3 display the asymmetric units of com-
pounds 1 and 2, with the secondary interactions also identi-
fied by dashed lines. Fig. 2 represents the dimeric
ꢀ
Fig. 1. Asymmetric unit of [p-CH
3 6 4 3 6 4 4
O(C H )Te(etu)][p-CH O(C H )TeI ]
association of the anions [p-CH O(C H )TeI ] in com-
3
6
4
4
(
1). The dashed line identifies the secondary interaction.
pound 1 and their polymeric assembling through single
Iꢂ ꢂ ꢂI secondary bonds. Fig. 4 shows the dimerization of
ꢀ
2
.3. Crystallography
X-ray data were collected on a Bruker SMART CCD
the [p-PhO(C H )TeI ] anions of 2 and the attainment of
6
4
4
a polymeric chain through double Iꢂ ꢂ ꢂI secondary interac-
tions. The significant long interionic distance
˚
diffractometer. The crystallographic structures of [p-
CH O(C H )Te(etu)][p-CH O(C H )TeI ] (1) and [p-
{Te(2)ꢂ ꢂ ꢂI(3) = 4.1772(4) A, see Fig. 1} in [p-CH O(C H )-
3
6
4
Te(etu)][p-CH O(C H )TeI ] (1) and consequently the weak
3
6
4
3
6
4
4
3
6
4
4
PhO(C H )Te(tu)][p-PhO(C H )TeI ] (2) were solved by
cation–anion interaction should exclude the possibility to
represent this compound in a molecular way, such as
[RTeI (l-I)Te(etu)R] {R = p-CH O(C H )}, for example.
6
4
6
4
4
direct methods (SHELXS-97) [12]. Refinements were carried
out with the SHELXL-97 [13] package. All refinements were
3
2
3
6
4
2
made by full-matrix least-squares on F with anisotropic
In [p-PhO(C H )Te(tu)][p-PhO(C H )TeI ] (2) there occurs
6 4 6 4 4
displacement parameters for all non-hydrogen atoms.
Hydrogen atoms were included in the refinement in calcu-
lated positions.
a strong cation–anion interaction {I(1)ꢂ ꢂ ꢂTe(3) = 3.3000(6),
˚
I(6)ꢂ ꢂ ꢂTe(4) = 3.4315(6) A} (see Fig. 3); therefore, and
according to previous results [8], the representation of the
ꢀ
Fig. 2. Dimeric association of the anions [p-CH
3
O(C
6
H
4
4
)TeI ]
in compound 1 and their polymeric assembling along the b axis through I–I secondary
interactions (dashed lines). Symmetry transformations used to generate equivalent atoms: #1 ꢀx + 2, ꢀy + 1, ꢀz + 1.

4010
G.A. Casagrande et al. / Journal of Organometallic Chemistry 691 (2006) 4006–4011
This asymmetry is evident in the apparent irregular con-
tour of the chain, which, despite this, shows in the middle
of the Te(1)–Te(1)#1 dimers inversion centres which,
respectively, enclose the two neighbored dimers, achieving
vicinal sequences of 12-atom rings.
Attempts to study the dissociation of the title complexes
in solution by means of multinuclear NMR spectra were
limited by the fact that the crystals of 1 and 2 are soluble
only in coordinating solvents like dimethylsulfoxide
(DMSO). Another limiting factor represents the occurrence
of dynamic equilibrium in solution due to the exchange
between ligand and solvent molecules, predominantly with
1
13
125
DMSO. To minimize this effect H, C, and Te NMR
studies were conducted in solutions of acetone-d6 and
DMSO-d in a 9:1 proportion, respectively. Complex 1
6
25
Fig. 3. Asymmetric unit of [RTeI
Secondary interactions and bonds as dashed lines.
3 6 4
(l-I)Te(tu)R] {R = p-PhO(C H )}.
1
gives a Te NMR broad signal at 933.5 ppm, 2 generates
1
13
a wide peak localized in 894.6 ppm. The H and C NMR
1
signals of compounds 1 and 2 are: H NMR 1: 8.93 (broad,
mixed valence complex salt [p-PhO(C H )Te(tu)][p-
2N–H), 8.25 (d, 4C–Harom.), 6.81 (d, 4C–Harom.), 3.90 (s,
6
4
PhO(C H )TeI ] (2) which corresponds to the real (molecu-
4H CH etu), 3.82 ppm (s, 6H CH –O–); 2: 8.5 (broad,
6
4
4
2
3
1
3
lar) atomic aggregation of the compound would be
RTeI (l-I)Te(tu)R] {R = p-PhO(C H )}. This spell way
4H N–H), 6.8–7.5 ppm (multiplet, 18Harom.). C NMR
1: 176.3 (C@S), 160.89 (C4), 143.95 (C2 and C6), 115.3
(C3 and C5), 108.6 (s, weak, C –Te), 55.56 (CH –O–),
[
3
6
4
does not exclude the dimerization tendency of the [RTeI4]
1
3
moieties, where the reciprocal Teꢂ ꢂ ꢂI secondary bonds mea-
46.3 ppm (2CH etu); 2: 171.0 (C@S), whole aromatic sig-
nals 158.6, 157.9, 156.8, 144.3, 140.3, 130.9, 130.7, 130.6,
124.7, 124.0, 120.6, 120.2, 119.4, 119.3, 118.8 ppm,
2
˚
sure 3.8422(5) A {Te(1)ꢂ ꢂ ꢂI(4)#1}, somewhat longer than
the equivalent distances observed in compound
1
˚
{
Te(1)ꢂ ꢂ ꢂI(2)#1 = 3.7800(4) A}.
In both compounds the tectonic character of the RTeI4
moieties is remarkably strong. The Iꢂ ꢂ ꢂI (secondary) dis-
112.07 ppm (s, weak, C –Te).
1
4. Supplementary material
2
4 2
ꢀ
tances of the dimers ½p-CH OðC H ÞTeI ꢁ
in 1 is
3
6
4
˚
3
.6660(6) A {I(3)ꢂ ꢂ ꢂI(3)#1}. In compound 2 the supramo-
Crystallographic data for the structural analyses have
been deposited with the Cambridge Crystallographic Data
Centre CCDC nos. CSD 609607 and 609608 for com-
pounds 1 and 2. Further details of the crystal structure
investigations are available free of charge via www.ccdc.
cam.ac.uk/conts/retrieving.html (or from the CCDC, 12
lecular tectonic assembling of the type [RTeI (l-I)-
3
Te(tu)R] {R = p-PhO(C H )} is achieved through double,
n
6
4
asymmetric Iꢂ ꢂ ꢂI secondary interactions (see Fig. 4):
I(3)#1ꢂ ꢂ ꢂI(5)#1 = 3.637(2), I(1)ꢂ ꢂ ꢂI(7)#1 = 4.0595(5),
I(3)ꢂ ꢂ ꢂI(5) = 3.6367(5) and I(1)#1ꢂ ꢂ ꢂI(7)#2 = 4.0595(5) A.
˚
Fig. 4. Supramolecular lattice of [RTeI
3 n 6 4 6 4 4
(l-I)Te(tu)R] {R = p-PhO(C H )}; for clarity only the [p-PhO(C H )TeI ] dimers are represented. Secondary
interactions in dashed lines. Symmetry transformations used to generate equivalent atoms: #1 ꢀx + 1, ꢀy, ꢀz + 1; #2 ꢀx, 1 ꢀ y, 1 ꢀ z.

G.A. Casagrande et al. / Journal of Organometallic Chemistry 691 (2006) 4006–4011
4011
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223
36033; e-mail: deposit@ccdc.cam.ac.uk).
[7] E. Schulz Lang, G. Manzoni de Oliveira, G.N. Ledesma, Z. Anorg.
Allg. Chem. 631 (2005) 1524.
3
[
8] E.S. Schulz Lang, G.A. Casagrande, G. Manzoni de Oliveira, G.N.
Ledesma, S.S. Lemos, E.E. Castellano, U. Abram, Eur. J. Inorg.
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