Stabilization of decatellurium molecules in isolated and concatenated clusters

Article abstract of DOI:10.1002/zaac.201200430

Black, shiny crystals of the molecular cluster compounds (Te ₁₀)[M(TeX₄)(TeX₃)]₂ (M/X = Rh/Cl (1), Ir/Br (2)), (Te₁₀)[Ru(TeI₄)(TeI₂)] ₂ (3), (Te₁₀)[M(TeI₄)(TeI₂)] ₂(TeI₄)(Te₂I₂) (M = Rh (4), Ir (5)) as well as the one-dimensional cluster polymer (Te₁₀I ₂)[Ir(TeI₄)]₂(Te₄)I₂ (6) were synthesized by melting reactions of an electron-rich transition metal M (M = Ru, Rh, Ir) with tellurium and TeX₄ (X = Cl, Br, I). X-ray diffraction on single-crystals revealed that the compounds crystallize in the triclinic space group type P1. 4 and 5 show [3+1]-dimensional modulations of their structures. All compounds contain binuclear complexes with central μ-η⁴:η⁴-bridging Te₁₀ units and terminal halogenidotellurate(II) groups. Each of the transition metal cations is in a slightly distorted octahedral coordination by six tellurium atoms; the two [MTe₆] octahedra share a common edge. With the tellurium atoms acting as electron-pair donors, the 18 electron rule is fulfilled for the electrophilic M atoms. The central tricyclo[5.1.1.1^{3, 5}]- decatellurium molecule consists of two ecliptically stacked Te₄ rings, which are linked through two tellurium atoms. The symmetric or asymmetric 3c4e bonds along these almost linear bridges are in analogy to polyanionic forms of tellurium, while the tricyclic conformation is stabilized by the strong bonding to the transition-metal cations. Multi-center bonding (3c4e) is also present in the terminal square [Te^+IIX₄]^2- and the T-shaped [Te^+IIX₃]^- groups. The crystal structures of 4 and 5 are organized in layers of (Te₁₀)[M(TeI ₄)(TeI₂)]₂ⁿ⁺ clusters (n ≤ 2) that are quite robust upon oxidation or reduction as shown by molecular calculations. These clusters alternate with incommensurately modulated layers that probably consist of TeI₄^2- anions and a previously unknown Te₂I₂ molecule. The uncertainty arises primarily from equal scattering powers of I and Te atoms as well as from the known flexibility of the electron count of the Te₁₀ unit. In 6, neutral Te₄ rings concatenate (Te₁₀I₂)[Ir(TeI ₄)]₂ clusters into chains, which run parallel to the a axis. Copyright

Full text of DOI:10.1002/zaac.201200430

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ARTICLE
DOI: 10.1002/zaac.201200430
Stabilization of Decatellurium Molecules in Isolated and Concatenated
Clusters
Anja Günther,[a,b] Anna Isaeva,[a] and Michael Ruck*[a,b]
Dedicated to Professor Hartmut Bärnighausen on the Occasion of His 80th Birthday
Keywords: Cluster compounds; Donor bonding; Transition metals; Multi-center bonding; Tellurium
Abstract. Black, shiny crystals of the molecular cluster compounds rium molecule consists of two ecliptically stacked Te4 rings, which are
linked through two tellurium atoms. The symmetric or asymmetric
3c4e bonds along these almost linear bridges are in analogy to poly-
anionic forms of tellurium, while the tricyclic conformation is stabi-
lized by the strong bonding to the transition-metal cations. Multi-center
bonding (3c4e) is also present in the terminal square [Te+IIX4]2– and
the T-shaped [Te+IIX3]– groups. The crystal structures of 4 and 5 are
(Te10)[M(TeX4)(TeX3)]2 (M/X = Rh/Cl (1), Ir/Br (2)), (Te10)[Ru(TeI4)-
(TeI2)]2 (3), (Te10)[M(TeI4)(TeI2)]2(TeI4)(Te2I2) (M = Rh (4), Ir (5)) as
well as the one-dimensional cluster polymer (Te10I2)[Ir(TeI4)]2(Te4)I2
(6) were synthesized by melting reactions of an electron-rich transition
metal M (M = Ru, Rh, Ir) with tellurium and TeX4 (X = Cl, Br, I). X-
ray diffraction on single-crystals revealed that the compounds crys-
n+
organized in layers of (Te10)[M(TeI4)(TeI2)]2 clusters (n Յ 2) that
¯
tallize in the triclinic space group type P1. 4 and 5 show [3+1]-dimen-
are quite robust upon oxidation or reduction as shown by molecular
calculations. These clusters alternate with incommensurately modu-
sional modulations of their structures. All compounds contain binu-
clear complexes with central μ-η4:η4-bridging Te10 units and terminal
halogenidotellurate(II) groups. Each of the transition metal cations is
in a slightly distorted octahedral coordination by six tellurium atoms;
the two [MTe6] octahedra share a common edge. With the tellurium
atoms acting as electron-pair donors, the 18 electron rule is fulfilled
for the electrophilic M atoms. The central tricyclo[5.1.1.13,5]-decatellu-
2–
lated layers that probably consist of TeI4 anions and a previously
unknown Te2I2 molecule. The uncertainty arises primarily from equal
scattering powers of I and Te atoms as well as from the known flexibil-
ity of the electron count of the Te10 unit. In 6, neutral Te4 rings concat-
enate (Te10I2)[Ir(TeI4)]2 clusters into chains, which run parallel to the
a axis.
ions of four neighboring [Re6Te8(TeCl3)2] clusters (μ4-
η1:η1:η1:η1 mode).
Our synthetic approach utilizes electron-rich transition met-
als as an electrophilic component for the coordination of un-
charged tellurium species and TeX4 (X = Cl, Br, I) as Lewis
acids. An abundance of cluster compounds and coordination
Introduction
Selenium and especially sulfur show an impressive struc-
tural diversity, mainly based on molecular allotropes. In con-
trast to its lighter homologues tellurium has only one crystal-
line modification under standard conditions, the gray catena-
polytellurium.[1] On the search for molecular tellurium allo-
tropes, cyclo-tetratellurium in [Te4{Cr(CO)5}4],[2] cyclo-hexa-
tellurium in (AgI)2(Te6),[3] crown-shaped cyclo-octatellurium
polymers with
(a) cyclo-hexatellurium in (Te6)[Ru(TeBr3)(TeBr2)]2
[M(Te6)]X3 (M = Rh, Ir; X = Cl, Br, I),[8,9,10]
[8,9]
and
[4]
in Cs3Te6(Te8)2 and Cs4Te20(Te8),[5] as well as tellurium
(b) cyclo-octatellurium with a hitherto unknown conformation
dumbbells in [(Te2)2](I2)[6] were obtained from reactions in
various solvents (THF, HI, or MeOH). High-temperature reac-
tion of ReCl5 and tellurium yielded Re6Te10Cl6(Te6),[7] in
which a cyclo-hexatellurium molecule with chair conformation
binds to the comparatively electron-poor transition metal cat-
in [Ru(Te8)]Cl2,[9,10]
(c) cyclo-nonatellurium in [Ru(Te9)](InCl4)2,[9,10]
(d) tricyclo-decatellurium in (Te10)[Ir(TeCl4)(TeCl3)]2
(Te10)[Ir(TeBr3)2]2(Te10)[Ir(TeBr2)(TeBr4)]2 (InBr4)2,[9,12]
[9,11]
and
demonstrates the viability of the concept for the stabilization
of cyclic tellurium molecules in a solid. In the case of the
six-, eight- and nine-atomic tellurium rings the binding mode
is μ-η3:η3, while the tricyclic Te10 molecule is μ-η4:η4-bond-
ing. We anticipate that these compounds could be used as start-
ing materials for the isolation of new allotropic forms of the
element at moderate temperature.
Here we report on the synthesis and crystal structures of six
new compounds with either isolated or concatenated clusters
containing the tricyclo-decatellurium unit: (Te10)[Rh(TeCl4)-
* Prof. Dr. M. Ruck
Fax: +49-351-463-33244
E-Mail: michael.ruck@tu-dresden.de
[a] Fachrichtung Chemie und Lebensmittelchemie
Technische Universität Dresden
01062 Dresden, Germany
[b] Max-Planck-Institut für Chemische Physik fester Stoffe
Nöthnitzer Str. 40
01187 Dresden, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200430 or from the au-
thor.
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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A. Günther, A. Isaeva, M. Ruck
ARTICLE
Figure 2. Projection of one polymeric chain in the crystal structure of
(Te10I2)[Ir(TeI4)]2(Te4) (6). Ellipsoids represent 90% probability.
tal tellurium, and TeX4 (X = Cl, Br, I). Furthermore, the reac-
tion of Rh or Ir with Te and TeI4 in the molar ratio of 2:14:12
yielded black, shiny crystals with modulated structures and
composition M2Te17I18 (4 and 5) as by-product (5–10%; main
product RhTe6I3 for 4 and α-TeI4 for 5). Several EDX mea-
surements on crystals of the two compounds verified the
higher quantities of iodine compared to MTe6I3 (Figures S1
and S2).
All compounds crystallize in the triclinic space group type
¯
P1 (including the average structures of 4a and 5a), respectively
Figure 1. Top: The molecular cluster (Te10)[Rh(TeCl4)(TeCl3)]2 (1);
middle: (Te10)[Ru(TeI4)(TeI2)]2 (3); bottom: (Te10I2)[Ir(TeI4)]2(Te4)
(6). Ellipsoids represent 90% probability.
¯
in the [3+1]-dimensional superspace group P1(αβγ)0 for the
modulated structures of 4b and 5b. Tellurium-rich clusters
(Te10)[M(TeXn)m]2 (n = 2–4; m = 1, 2) with rather similar con-
stitutions and Ci symmetry are the dominating components of
all structures. In 1–5, they are isolated species (Figure 1 and
Figure 3) and thereby resemble the previously described
(TeCl3)]2 (1), (Te10)[Ir(TeBr4)(TeBr3)]2 (2), (Te10)[Ru(TeI4)-
(TeI2)]2 (3), (Te10)[Rh(TeI4)(TeI2)]2(TeI4)(Te2I2) with M = Rh
(4a = averaged structure; 4b = modulated structure) or Ir (5a
=
averaged structure; 5b = modulated structure), and
+
(Te10)[Ir(TeCl4)(TeCl3)]2,[11] (Te10)[Ir(TeBr4)(TeBr2)]2 , and
(Te10I2)[Ir(TeI4)]2(Te4) (6). Compound 6 also features a neutral
+ [12]
(Te10)[Ir(TeBr3)2]2 .
While 1–3 consist only of such clus-
cyclo-tetratellurium molecule in μ-η1:η1 mode.
ters, 4 and 5 contain additional complex structured Te-I layers.
Compound 6 adds a new structural motif to this chemistry
Results and Discussion
(Figure 1, Figure 2 and Figure S3): Uncharged cyclo-tetratel-
2+
The tellurium-rich compounds 1–3 and 6 were obtained by lurium rings link (Te10I2)[Ir(TeI4)]2 clusters into infinite
cooling melts of a transition metal M (M = Ru, Rh, Ir), elemen- chains.
2
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Stabilization of Decatellurium Molecules in Isolated and Concatenated Clusters
In the clusters, a central tricyclo[5.1.1.13,5]-decatellurium earity (172.29(1)° in 1, 171.78(4)° in 2, 174.56(3)° in 3,
molecule coordinates two transition metal cations as a bridging 174.11(6)° in 4a, 174.30(5)° in 5a, 170.55 (2)° in 6)
bis-tetradentate ligand. Terminal halogenido-tellurate(II)
The shape of the fragment resembles the “double-decker“
groups and, in the case of 6, a concatenating bis-monodentate structures (Thex2M2Q2)Q2 (Thex = 1,1,2-trimethylpropyl, M =
cyclo-tetratellurium molecule complete the slightly distorted Si, Ge, Q = S, Se),[16] P4(N-iC3H7)6,[17] or (tBuGe)4S6,[18]. In
4+ [19]
coordination octahedron of each of the transition metal cations. the polycation Te8
,
which misses the bridging atoms, the
The two [MTe6] polyhedra of a cluster share a common edge. Te–Te distances within the folded Te4 rings are slightly shorter
The diverse numbers of halide ions in the clusters balance the (Te–Te: average 277.4 pm) than in the Te10 units (1:
+II or +III oxidation states of the metal cations. In 6, additional 277.94(2)–281.01(2) pm; 2: 279.3(1)–283.6(1) pm; 3:
iodide ions that bind predominantly to tellurium atoms of the 279.1(1)–283.1(1) pm; 4a: 278.9(2)–281.6(2) pm; 5a:
same chain assure charge balance.
279.2(2)–282.1(2) pm; 6: 280.28(8)–291.14(7) pm). Moreover,
4+
The average M–Te bond lengths (1: 266.73 pm; 2: the isolated Te8 polycation is biconcave with the Te4 rings
267.53 pm; 3: 265.47 pm; 4a: 267.55 pm; 5a: 267.16 pm; 6: deviating by about 10° from planarity, whereas strong bonding
268.31 pm; for details see Table 1) are only about 2–3 pm to the transition metal cations forces a biconvex arrangement
longer than those of the corresponding binary phases (RhTe2: in 1–6.
pyrite type, Rh–Te: 264.5 pm;[13] IrTe2: CdI2-type, Ir–Te:
The almost linear, asymmetric [Te2–Te5–Te3i] fragment,
265.0 pm;[14] RuTe2: marcasite type, Ru–Te: 262.9 pm[15]). present in the Te10 units of 1–3 and 6, has previously been
The Te–M–Te angles deviates by 3–8° from 90° (1: 84.86(1)– analyzed with quantum chemical methods for the first example
93.18(1)°; 2: 83.61(3)–93.24(3)°; 3: 83.84(3)–94.70(3)°; 4a: of this class of clusters, (Te10)[Ir(TeCl4)(TeCl3)]2.[11] The evi-
83.86(6)–95.85(6)°; 5a: 83.90(3)–95.68(4)°; 6: 82.18(2)– dence of 3-center 4-electron (3c4e) bonding gave justification
94.39(2)°]. It has already been demonstrated that the tellurium for the interpretation of the Te10 unit as an uncharged molecu-
atoms act as two electron donors for the transition metal cat- lar entity, which is stabilized by the strong bonding to the tran-
ions, thereby fulfilling the 18 electron rule for the d6 cations sition metal cations. Here, only bond-length bond-strength cor-
RhIII, IrIII, and RuII.[11]
relations are applied.[20] Bond valences of 0.59Ϯ0.04 for the
shorter bond Te5–Te3i (294.08(2) pm in 1, 292.9(1) pm in 2,
297.2(1) pm in 3, 298.36(8) pm in 6) and 0.44Ϯ0.02 for the
longer bond Te2–Te5 (305.48(2) pm in 1, 308.4(1) pm in 2,
307.4(1) pm in 3, 304.59(8) pm in 6) corroborate the proposed
binding model. Asymmetric three-atomic units of tellurium are
well known from compounds, in which the tellurium atoms
bear only organic ligands, for example [Sm(TpMe,Me)2(TePh)3]
(TpMe,Me = hydrotris(3,5-dimethyl-pyrazolyl)borate)[21] and
[(Mes2Te)2TeMes][SbF6] (Mes = 2,4,6-Me3C6H3).[22] While in
the samarium compound the tritellurium unit is anionic with
Te–Te distances of 293.9 and 311.3 pm, a tritellurium cation
with Te–Te distances of 297.9 and 304.9 pm is stabilized in
the antimony compound.
In contrast, the Te10 units in 4 and 5 show symmetrical brid-
ges with bond lengths of 301Ϯ1 pm (bond valence of
0.52Ϯ0.01 for the shorter bond and 0.49Ϯ0.01 for the longer
bond). A similar symmetrical arrangement (299Ϯ2 pm) has
recently been reported for the quaternary cluster compound
{(Te10)[Ir(TeBr3)2]2}{(Te10)[Ir(TeBr4)(TeBr2)]2}(InBr4)2,
which hosts Te10· – radical anions.[12] Since 4 and 5 were only
accessible as minor by-products, ESR spectra could not be
measured. Thus, it can neither be proved nor excluded that the
clusters in the two compounds deviate from the optimum elec-
tron count, i.e. cluster charge 2+.
Table 1. Selected interatomic distances /pm for (Te10)[M(TeX4)
(TeX3)]2 (M = Rh, Ir; X = Cl, Br) and (Te10)[Ru(TeI4)(TeI2)]2 and
(Te10I2)[Ir(TeI4)]2(Te4). (i) = –x, –y, –z for 1–3 and (i*) = 1–x, –y, –z
for 6.
M = Rh
M = Ir
M = Ru
M = Ir
X = Cl
X = Br
X = I
X = I
M – Te1
268.73(2)
264.03(2)
266.25(2)
267.92(2)
268.06(2)
265.38(2)
279.84(2)
281.01(2)
277.94(2)
279.10(2)
305.48(2)
294.08(2)
275.44(7)
250.75(6)
244.23(7)
261.57(6)
256.37(7)
233.88(6)
255.16(7)
307.18(6)
316.90(6)
325.55(6)
332.59(7)
294.16(6)
293.31(7)
–
268.2(1)
265.8(1)
267.7(1)
269.3(1)
268.9(1)
265.3(1)
281.0(2)
282.8(1)
279.3(1)
283.6(1)
308.4(1)
292.9(1)
290.6(2)
267.5(2)
260.6(2)
278.2(2)
279.5(2)
251.0(2)
269.2(2)
310.7(2)
337.6(2)
336.9(2)
334.7(2)
299.1(2)
307.8(2)
–
266.3(1)
261.8(1)
271.3(1)
272.5(1)
261.1(1)
259.8(1)
282.1(1)
280.3(1)
279.1(1)
283.1(1)
307.4(1)
297.2(1)
290.8(1)
296.4(1)
315.4(1)
307.0(1)
286.7(1)
284.4(1)
12
267.04(7)
268.25(7)
269.01(6)
267.80(6)
267.72(7)
270.04(6)
282.27(8)
291.14(7)
285.09(7)
280.28(8)
304.59(8)
298.36(8)
318.29(8)
291.05(8)
284.82(8)
309.83(9)
–
–
–
–
–
–
–
–
–
M – Te4i*
M – Te5
M – Te5i*
M – Te6
M – Te7
Te1 – Te2
Te1 – Te3
Te2 – Te4
Te3 – Te4
Te2 – Te5
Te5 – Te3i
Te6 – X1
Te6 – X2
Te6 – X3
Te6 – X4
Te7 – X5
Te7 – X6
Te7 – X7
X1 ··· Te3i
X1 ··· Te4i
X4 ··· Te1
X4 ··· Te2
X5 ··· Te4i
X7 ··· Te1
X1 ··· Te2i*
344.44(1)
–
–
337.71(1)
–
–
Molecular quantum-chemical calculations demonstrate that
the cluster could withstand a substantial range of charges (be-
tween 0 and 4+) without destruction (Table S13). No dramatic
changes in atomic coordinations occur, yet the cluster flexibly
adjusts towards hypothetical oxidation or reduction (Figure
S4). Three molecular orbitals (Figure S5) are involved as
HOMOs in the successive oxidation from 0 to 4+, therefore the
–
321.76(9)
The central Te10 molecule consists of two ecliptically
stacked four-membered rings (Te1–Te4) linked by a slightly
angled bridge (Te5). The homonuclear bond angles at the geometrical changes in the cluster reflect bonding–antibonding
bridging atoms, Te2–Te5–Te3i, deviate less than 10° from lin- interactions represented by these MOs. Upon reduction from
Z. Anorg. Allg. Chem. 0000, 0–0
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2+ towards 0, rectangular distortion of the Te4 rings of the Table 2. Selected interatomic distances /pm for the averaged structures
of (Te10)[M(TeI4)(TeI2)]2(TeI4)(Te2I2). (i) = –x, –y, –z; (ii) = 1 –x,
1 –y, 1 –z.
Te10 molecule is observed, in full accordance with the scheme
exemplified earlier.[12] Upon oxidation from 2+ towards 4+,
the Te10 unit is twisted and the peripheral Te–I bond lengths
are subject to main deformations as influenced by depopulation
of Te–I bonding states (MO 122 Au in Figure S5b).
M = Rh (4)
M = Ir (5)
M – Te1
M – Te4
M – Te5
M – Te5i
M – Te6
M – Te7
Te1 – Te2i
Te1 – Te3
Te2 – Te4
265.6(2)
268.5(2)
268.3(2)
268.1(2)
267.0(2)
267.8(2)
265.9(1)
267.6(1)
268.9(1)
268.5(1)
265.9(1)
266.2(1)
Ϯ0
A second molecular tellurium species is found in 6, a Te4
ring, which binds with opposing atoms to iridium cations of
two clusters (μ-η1:η1 mode). The assignment of charges/oxi-
dation states in 6 is based on the assumption that there is no
significant electron transfer from the planar, almost square
281.5(2)
279.5(2)
278.9(2)
281.6(2)
299.6(2)
301.4(2)
282.0(1)
279.2(2)
279.5(2)
282.1(2)
299.9(2)
302.9(2)
Ϯ0
Ϯ0
Te4
ring (Te–Te–Te: 89.28(2) – 90.72(2)°] to the Te10
unit. The first coordinative stabilization of a cyclo-tetratel- Te3 – Te4i
Te2 – Te5
Te3 – Te5
lurium ring had been achieved in the organometallic compound
[Te4{Cr(CO)5)4].[2] There, the homonuclear ring is slightly
folded with Te–Te–Te angles of 83.8–86.9°. Extended Hückel
molecular orbital (EHMO) calculations showed only small dif-
ferences of about 0.2 eV between the total energies of the
square-planar (D4h) and the butterfly structure (D2d) for a cy-
clo-Te4.[1] The Te–Te distances in the planar ring of 6
Te6 – I1
Te6 – I2
Te6 – I3
Te6 – I4
Te7 – I5
Te7 – I6
311.8(2)
298.1(2)
287.4(2)
298.5(2)
281.4(2)
288.0(2)
310.6(2)
299.0(2)
288.6(2)
298.2(2)
281.7(2)
287.5(2)
(280.81(9) and 284.57(9) pm) are slightly shorter than in the
butterfly structure (281.8(2)–289.5(2) pm). Te4 polycations Te8 – I8
also show only slight distortion from D4h symmetry but about
10 pm shorter bond lengths.[23]
Te8 – I7
294.4(2)
302.6(4)
290(1)
293.8(2)
303.4(4)
290(1)
2+
Te9a – Te9aii
Te9a – I9
306.9(7)
308.7(7)
The terminal halogenidotellurate(II) groups vary in the
number of the halide ions according to the oxidation state of
the metal cations, rendering the central Te10 unit an electron
precise, neutral molecule, at least in 1–3 and 6. Ligands of
this type are known from a series of tellurium-rich rhenium
complexes[24]. The terminal ligands at the metal cations are
0.856/0.144(6) in 4a and 0.861/0.139(5) in 5a. The here pre-
sented preliminary crystal structure description ignores the
2–
minority position Te9b and thus interprets the layer as TeI4
anions and previously unknown Te2I2 molecules. The latter is
[25]
a heavy homologue of S2Cl2
and a stable molecule accord-
2–
–
2–
ing to quantum chemical calculations (Figure S6).[9] The in-
teratomic distances in the almost planar TeI4 anions of 4a
TeX4 and TeX3 (X = Cl, Br) groups in 1 and 2, TeI4 and
2–
2–
uncharged TeI2 groups in 3–5, but TeI4 and a concatenating
Te4 ring in 6. In general, the Te–X distances (Table 1 and
Table 2) show the same bond lengths differentiation as a func-
tion of the bonding situation as those of the compound
(Te10)[Ir(TeCl4)(TeCl3)]2.[11] As can be expected, 3c4e bonds
in the linear [X–Te–X] sequences of the (TeX4)2– and (TeX3)–
ligands are longer than the 2c2e bonds of the TeX2 groups.
Secondary bonds of the halide ions to tellurium atoms of other
terminal groups and/or the central Te10 unit influence the con-
formation of the TeXn ligands as well as their bonding dis-
tances. In 6, additional iodide ions that bind predominantly to
tellurium atoms of the same chain assure charge balance
(shortest distance: Te1···I5, 313.98(7) pm). As has been dis-
cussed above, the terminal ligands are quite sensitive towards
changes in charge on the isolated clusters, but since the effects
of packing strongly affect Te–I bond lengths there is no evident
correlation to be traced between theoretically predicted (Table
S1) and experimentally observed molecules.
(294.4(2)–302.6(4) pm) and 5a (293.8(2)–303.4(4) pm) are in
the same range as in the compounds (ET)4TeI4,
(EDT-TTF)4TeI4, and (TMTTF)2TeI4, which consist of cation
2–
radical salts of organic donors and TeI4 groups (Te–I: 289–
302 pm; ET = bis(ethylenedithio)tetra-thiafulvalene, EDT-TTF
= ethylenedithiotetrathiafulvalene, TMTTF = tetramethyltet-
rathiofulvalene).[26]
The model of the crystal structures in the [3+1]-dimensional
¯
superspace group P1(αβγ)0 was developed with the modula-
tion vectors q = (0.376(1), 0, 0.045(1)) for 4b and q =
(0.383(1), 0, –0.251(1)) for 5b. The Fourier plots are in reason-
able agreement with the refined structures (Figures S7–S10).
The modulation mainly affects the almost planar layer, which
is a distorted 44 net of atoms with ordered vacancies (Figure
2–
S11). The interatomic Te–I distances in the TeI4 groups
(Te8–I7: 301 pm; Te8–I8: 294 pm) are within the range found
in the averaged structures. The assignment of the remaining
atoms of the layer is questionable, but we interpreted those as
Te2I2 molecules that are dissociated in some cases. The
average distances between Te9a atoms are 282.2(1) pm in 4b
and 284.4(9) pm in 5b; in general they are 8 pm shorter than
in the averaged structures. The interatomic distances Te9a–I9
vary over a very wide range from bonding to non-bonding
The precise constitution of the Te-I layer in 4 and 5 (Fig-
ure 3) could neither be determined by X-ray single crystal dif-
fraction (equal scattering powers of I and Te atoms) nor by
chemical analysis (minor contribution of the layer to the over-
all content of the two elements). Yet multiple EDX measure-
ments on crystals of 4 and 5 verified the nominal composition
M2Te17I18 (Figures S1 and S2). The refinement of the averaged (270.7(8)–351.0(9) pm in 4b and 266.3(7)–360.4(8) pm in 5b).
structures resulted in occupations of the position Te9a/b of The model of the modulated structures M2Te17I18 is still not
4
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Stabilization of Decatellurium Molecules in Isolated and Concatenated Clusters
further components of the structures may vary considerably.
With respect to their sum formulas, these compounds could
be (mis)interpreted as tellurium monohalides including some
transition metal impurities. Yet, the chemical needs of the latter
dominate the crystal and molecular structures.
Experimental Section
The starting materials were handled in an argon filled glove box (M.
Braun; c(O2) Ͻ 1 ppm, c(H2O) Ͻ 1 ppm). Black crystals of 1–3 were
obtained in high yield by reacting a mixture of Rh (prepared from
RhCl3·3H2O, which was treated with hydrogen at 400 °C and heated
to 1000 °C under nitrogen) or Ir (99.9%, Chempur) or Ru (99%, Rie-
del de Haën), Te (Ͼ99.999%, Fluka) and TeX4 (TeCl4 and TeBr4:
99.9%, Strem, sublimated twice; TeI4 was synthesized by reacting a
molar mixture of Te and I2 in a fused evacuated silica ampoule at
500 °C) with the target composition (1–3) or with the molar ratio of
M : Te: I = 2 : 14 : 12 (4 and 5) and total mass of about 1 g in a
fused evacuated silica ampoule (l = 120 mm, d = 15 mm). To improve
crystallization an excess of 40% TeCl4 to 1, a thin-walled glass am-
poule with 100 μL Br2 (Ͼ99,0%, Sigma–Aldrich) to 2 and 200 mg I2
(Merck, twice sublimated over BaO2) to 3 were added to the reaction
mixture. The reaction of Ir (99.9%, Chempur), Te (Ͼ99.999%, Fluka)
and I2 (Merck, twice sublimated over BaO2) with the target composi-
tion and total mass of about 1 g in a fused evacuated silica ampoule
(l = 80 mm, d = 12 mm) yielded in a few crystals of 6. The ampoules
were heated to 523 K (1 and 6) or 573 K (2–5) with 25 K/h, left at
this temperature for about seven days, and then cooled down to room
temperature with 10 K/h. The products obtained were purified by
washing several times with absolute ethanol. The compounds are stable
in air over a long period of time and inert to water and alcoholic
solvents.
Analysis: The phase purity of the samples 1–3 were checked by X-ray
powder diffraction (Figures S12–S14). The powder diffraction patterns
were measured using an XЈPert powder diffractometer (PANalytical)
using Cu-Kα1 radiation. The composition of selected single crystals
of 4–6 were determined by semi-quantitative energy dispersive X-ray
analysis (Figures S1, S2 and S15) using a Digital Scanning Microscope
982 Gemini (Zeiss).
X-ray crystal structure determination: Intensity data of single-crys-
tals of the compounds 1–3 and 6 were collected at 293(2) K with a
four-circle diffractometer Kappa APEX II (Bruker AXS) with CCD
detector using graphite-monochromated Mo-Kα radiation. The frames
were integrated with the Bruker SAINT software package[27] using a
narrow-frame algorithm. Data were corrected for absorption effects
using the numerical method with the SADABS program.[28] The collec-
tion of reflection intensities of 4 and 5 were carried out with an im-
aging plate diffraction system IPDS-II (Stoe) using graphite-mono-
chromated Mo-Kα radiation. The raw-data were corrected for back-
ground, polarization and Lorentz factors. Numerical absorption correc-
tions[29] were performed based on optimized crystal descriptions.[30]
Structure solution for 1–6 with direct methods[31] was followed by
refinements against Fo2 including anisotropic displacement parameters
for all atoms (Tables S1 – S12 of the Supporting Information). The
superstructure refinement for 4 and 5 was performed with the
JANA2006 program package.[32] The occupation modulation of the
atom Te9a/b was handled by a crenel function, and the positional mod-
ulation was fitted by one harmonic function for each of the other
atoms. During the refinement the occupation of Te9a/b was fixed at
Figure 3. The averaged crystal structure of (Te10)[Rh(TeI4)(TeI2)]2-
(TeI4)(Te2I2) (4): the unit cell projected along the a axis (top), the
molecular cluster (Te10)[Rh(TeI4)(TeI2)]2 (middle), and the nearly
planar layer projected along the c axis (bottom). Ellipsoids represent
90% probability.
satisfying. For further exploration the synthesis of the yet hy-
pothetical isostructural chlorine or bromine compounds would
be advantageous.
Conclusions
The here presented molecular clusters demonstrate that the
transition-metal stabilized Te10 unit is not exotic but a common
motif in this type of tellurium-rich compounds. While the clus-
ter cores differ only in detail, the terminal ligands as well as 0.9/0.1. Graphics of the structures were generated with Diamond.[33]
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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5

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/KAP1
Date: 19-12-12 15:21:57
Pages: 8
A. Günther, A. Isaeva, M. Ruck
ARTICLE
¯
1: Rh2Te14Cl14: triclinic, space group P1 (no. 2), a = 916.54(2) pm, 3σ(Io)] = 0.137 / R1 = 0.078, wR2(all Io) = 0.139; first-order satellites:
b = 1000.65(2) pm, c = 1126.83(3) pm, α = 69.310(1)°, β = 67.081(1)°, R1 = 0.186, wR2[Io Ͼ 3σ(Io)] = 0.348 / R1 = 0.491, wR2(all Io) = 0.429;
γ = 66.766(1)°, V = 849.98(3) ϫ 106 pm3; Z = 1; ρcalcd. = 4.86 g cm–3;
μ(MoKα) = 13.9 mm–1; 2θmax = 78.84°; 51603 measured, 10018
unique reflections, Rint = 0.028, Rσ = 0.030; 137 parameters; extinction
parameter x = 53.0(2) ϫ 10–5; R1(7794 Fo Ͼ 4σ(Fo)) = 0.028, wR2(all
Fo ) = 0.033, GooF = 1.35; min./max. residual electron density: –1.32 /
1.40 e ϫ 10–6 pm–3.
No. of parameters: 514; min./max. residual electron density: –7.11 /
7.25 e ϫ 10–6 pm–3.
¯
6: Ir2Te16I10: triclinic, space group P1 (no. 2), a = 963.61(3) pm, b =
2
1015.04(4) pm, c = 1162.65(4) pm, α = 76.148(2)°, β = 63.525(2)°, γ
= 87.989(2)°, V = 984.96(6) ϫ 106 pm3; Z = 1; ρcalcd. = 6.23 g cm–3;
μ(MoKα) = 26.2 mm–1; 2θmax = 46.50°; 7738 measured, 2809 unique
reflections, Rint = 0.033, Rσ = 0.035; 128 parameters; extinction param-
¯
2: Ir2Te14Br14: triclinic, space group P1 (no. 2), a = 952.40(4) pm, b
2
eter x = 1.7(2) ϫ 10–4; R1(2461 Fo Ͼ 4σ(Fo)) = 0.021, wR2(all Fo ) =
= 1014.17(4) pm, c = 1179.38(5) pm, α = 67.957(2)°, β = 65.619(2)°,
γ = 67.967(2)°, V = 928.43(7) ϫ 106 pm3; Z = 1; ρcalcd. = 5.88 g cm–3;
μ(MoKα) = 33.0 mm–1; 2θmax = 52.88°; 18447 measured, 3735 unique
reflections, Rint = 0.044, Rσ = 0.033; 137 parameters; extinction param-
0.041, GooF = 1.02; min./max. residual electron density: –0.81 / 0.87
e ϫ 10–6 pm–3.
2
Further details of the crystal structure investigation can be obtained
from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-
Leopoldshafen, Germany (Fax: +49-7247-808-666; E-Mail:
crysdata@fiz-karlsruhe.de, http://www.fiz-karlsruhe.de/request for de-
posited data.html) on quoting the depository numbers CSD-425194
(1), CSD-425195 (2), CSD-425196 (3), CSD-425197 (4a), CSD-
425198 (4b), CSD-425199 (5a), CSD-425200 (5b) and CSD-425201
(6).
eter x = 62(9) ϫ 10–5; R1(3494 Fo Ͼ 4σ(Fo)) = 0.046, wR2(all Fo ) =
0.123, GooF = 1.11; min./max. residual electron density: –3.88 / 2.68
e ϫ 10–6 pm–3.
¯
3: Ru2Te14I12: triclinic, space group P1 (no. 2), a = 994.93(4) pm, b
= 1015.23(4) pm, c = 1322.72(5) pm, α = 63.484(2)°, β = 56.756(2)°,
γ = 69.277(2)°, V = 989.18(7) ϫ 106 pm3; Z = 1; ρcalcd. = 5.90 g cm–3;
μ(MoKα) = 20.3 mm–1; 2θmax = 58.36°; 11923 measured, 5304 unique
reflections, Rint = 0.046, Rσ = 0.082; 128 parameters; extinction param-
Quantum chemical calculations: Geometry optimizations for the
(Te10)[Rh(TeI4)(TeI2)]n+ cluster proceeded from the experimental con-
figuration were performed using the ADF software[34a] within the
framework of DFT. The cluster charge n has been varied between 0
and 4. The relevance of each resultant configuration has been con-
firmed by an absence of imaginary frequencies. The exchange-corre-
lation functional from Becke and Perdew (BP86)[34b] for the general-
ized gradient approximation (GGA) was applied. Relativistic effects
were taken into account by employing the scalar zero-order regular
approximation (ZORA).[34c] A quadruple-zeta Slater-type orbitals aug-
mented with four sets of polarization functions were used as the basis
set to describe all electrons. Molecular orbitals were retrieved from the
ADF output data and visualized using the DGrid software.[34d]
2
eter x = 6.0(2) ϫ 10–5; R1(3481 Fo Ͼ 4σ(Fo)) = 0.038, wR2(all Fo ) =
0.056, GooF = 0.95; min./max. residual electron density: –1.89 / 1.60
e ϫ 10–6 pm–3.
¯
4: average structure: Rh2Te17I18: triclinic, space group P1 (no. 2), a =
1002.12(1) pm, b = 1250.79(1) pm, c = 1267.41(1) pm, α = 67.10(1)°,
β = 72.68(1)°, γ = 72.22(1)°, V = 1364.2(2) ϫ 106 pm3; Z = 1; ρcalcd.
= 5.67 g cm–3; μ(MoKα) = 19.7 mm–1; 2θmax = 53.44°; 15628 mea-
sured, 5519 unique reflections, Rint = 0.075, Rσ = 0.059; 180 param-
eters; extinction parameter x = 86(2) ϫ 10–5; R1(4015 Fo Ͼ 4σ(Fo)) =
2
0.073, wR2(all Fo ) = 0.207, GooF = 1.27; min./max. residual electron
density: –3.21/ 4.50 e ϫ 10–6 pm–3.
¯
superstructure: superspace group: P1(αβγ)0; modulation vector: q =
Supporting Information (see footnote on the first page of this article):
Powder diffractogram, coordinates and displacement parameters of 1–
3; coordinates, displacement parameters and EDX spectrum of 4–6.
(0.376(1), 0, 0.045(1)); No. of measured reflections: 93190; No. of
independent reflections: 16589; 5035 with Io Ͼ 3σ(Io); No. of main
reflections: 5528; 3976 with Io Ͼ 3σ(Io); No. of first-order satellites:
11061; 1059 with Io Ͼ 3σ(Io); Rint = 0.075, Rσ = 0.033; Refinement
on F2; all reflections: R1 = 0.071, wR2[Io Ͼ 3σ(Io)] = 0.163 / R1
0.166, wR2(all Io) 0.188; main reflections: R1 0.064,
=
Acknowledgments
=
=
wR2[Io Ͼ 3σ(Io)] = 0.152 / R1 = 0.085, wR2(all Io) = 0.158; first-order
satellites: R1 = 0.171, wR2[Io Ͼ 3σ(Io)] = 0.303 / R1 = 0.516, wR2(all
Io) = 0.158; No. of parameters: 514; min./max. residual electron den-
sity: –3.55/ 4.93 e ϫ 10–6 pm–3.
This work was supported by the Deutsche Forschungsgemeinschaft
(DFG). We are indebted to ZIH TU Dresden for the computational
facilities provided within the framework of the project “Chemical
Bonding Analysis of Novel Inorganic Compounds with Real-Space
Indicators”.
¯
5: average structure: Ir2Te17I18: triclinic, space group P1 (no. 2), a =
1004.13(8) pm, b = 1248.74(1) pm, c = 1267.16(1) pm, α = 66.96(1)°,
β = 72.72(1)°, γ = 72.04(1)°, V = 1362.4(2) ϫ 106 pm3; Z = 1; ρcalcd.
= 5.90 g cm–3; μ(MoKα) = 24.0 mm–1; 2θmax = 60.92°; 20700 mea-
sured, 7859 unique reflections, Rint = 0.081, Rσ = 0.062; 180 param-
eters; extinction parameter x = 34(3) ϫ 10–4; R1(6129 Fo Ͼ 4σ(Fo)) =
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Received: September 27, 2012
Published Online: ᭿
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7

Job/Unit: Z12430
/KAP1
Date: 19-12-12 15:21:57
Pages: 8
A. Günther, A. Isaeva, M. Ruck
ARTICLE
A. Günther, A. Isaeva, M. Ruck* ...................................... 1–8
Stabilization of Decatellurium Molecules in Isolated and Con-
catenated Clusters
8
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0