[Cd2(Te6O13)][Cd2Cl 6] and Cd7Cl8(Te7O17): Novel tellurium(IV) oxide slabs and unusual cadmium chloride architectures

Article abstract of DOI:10.1021/ic051703q

Initial attempts to prepare new Ln-Cd-Te-O-Cl compounds led to the isolation of two novel cadmium tellurium(IV) oxychlorides with two different types of structures, namely, [Cd₂(Te₆O₁₃)] [Cd₂Cl₆] and Cd₇Cl₈(Te ₇O₁₇). Both compounds feature novel polymeric tellurium(IV) oxide anions and unusual cadmium chloride substructures. The structure of [Cd₂(Te₆O₁₃)][Cd ₂Cl₆] is composed of 1D [Cd₂Cl ₆]^2- double chains and (002) [Cd₂(Te ₆O₁₃)]²⁺ layers. The 1D Te₆O ₁₃^2- slab of the [Cd₂(Te₆O ₁₃)]²⁺ layer is formed by TeO₃, TeO ₄, and TeO₅ groups via corner- and edge-sharing, and it contains six- and seven-membered tellurium(IV) polyhedral rings. The structure of Cd₇Cl₈(Te₇O₁₇) features a 3D network with long-narrow tunnels along the b axis. The two types of structural building blocks are 1D [Te₇O₁₇]^6- anions and unusual corrugated [Cd₇Cl₈]⁶⁺ layers based on cyclohexane-like Cd₃Cl₃ rings.

Full text of DOI:10.1021/ic051703q

Inorg. Chem. 2006, 45, 717−721
[Cd2(Te6O13)][Cd2Cl6] and Cd7Cl8(Te7O17): Novel Tellurium(IV) Oxide
Slabs and Unusual Cadmium Chloride Architectures
Hai-Long Jiang and Jiang-Gao Mao*
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences, and the Graduate School of the Chinese Academy of
Sciences, Fuzhou 350002, P.R. China
Received October 3, 2005
Initial attempts to prepare new Ln−Cd−Te−O−Cl compounds led to the isolation of two novel cadmium tellurium(IV)
oxychlorides with two different types of structures, namely, [Cd2(Te6O13)][Cd2Cl6] and Cd7Cl8(Te7O17). Both compounds
feature novel polymeric tellurium(IV) oxide anions and unusual cadmium chloride substructures. The structure of
2
-
[Cd2(Te6O13)][Cd2Cl6] is composed of 1D [Cd2Cl6]2- double chains and (002) [Cd2(Te6O13)]2+ layers. The 1D Te6O13
slab of the [Cd2(Te6O13)]2 layer is formed by TeO3, TeO4, and TeO5 groups via corner- and edge-sharing, and it
+
contains six- and seven-membered tellurium(IV) polyhedral rings. The structure of Cd7Cl8(Te7O17) features a 3D
6-
network with long-narrow tunnels along the b axis. The two types of structural building blocks are 1D [Te7O17
]
+
anions and unusual corrugated [Cd7Cl8]6 layers based on “cyclohexane-like” Cd3Cl3 rings.
Introduction
and they are promising new low-dimensional magnets.5-9
A number of transition metal Te(IV) oxychlorides have been
reported.5-17 Very recently, a series of lanthanide transition
metal (Cu or Mn) Te(IV) oxychlorides have been prepared
by our group.15 Our exploration of new lanthanide cad-
mium(II) Te(IV) oxychlorides produced two novel cadmium
tellurium(IV) oxychlorides instead, namely, [Cd2(Te6O13)][Cd2-
Cl6] and Cd7Cl8(Te7O17), which display several unusual
structural building blocks: two new types of 1D telluri-
um(IV) oxide anions (Te6O132- and Te7O176-), 1D [Cd2Cl6]2-
double chains, and 2D [Cd7Cl8]6+ sheets. So far, no cadmium
Metal tellurites adopt many unusual structures because of
the presence of the stereochemically active lone pair of
Te(IV) and the existence of a variety of isolated or polymeric
Te(IV)Ox (x ) 3, 4, 5) polyhedra.1 The asymmetric coordi-
nation polyhedron adopted by the Te(IV) atom may also
result in noncentrosymmetric structures with consequently
interesting physical properties, such as nonlinear optical
second harmonic generation (SHG).2-4 Transition metal
Te(IV) oxyhalides can be regarded as “chemical scissors”,
* To whom correspondence should be addressed. E-mail: mjg@
ms.fjirsm.ac.cn.
(1) (a) Wickleder, M. S. Chem. ReV. 2002, 102, 2011 and references
therein. (b) Verma, V. P. Thermochim. Acta 1999, 327, 63 and
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10.1021/ic051703q CCC: $33.50
Published on Web 12/16/2005
© 2006 American Chemical Society
Inorganic Chemistry, Vol. 45, No. 2, 2006 717

Jiang and Mao
Table 1. Crystal Data and Structural Refinements for
[Cd2(Te6O13)][Cd2Cl6] and Cd7Cl8(Te7O17)
tellurium(IV) oxychlorides has been reported and only a few
cadmium tellurium(IV) or Te(IV)/Te(VI) mixed metal oxides
have been structurally described.18 Herein, we report the
syntheses and crystal structures of [Cd2(Te6O13)][Cd2Cl6] and
Cd7Cl8(Te7O17).
[Cd2(Te6O13)][Cd2Cl6]
Cd4Te6O13Cl6
Cd7Cl8(Te7O17)
empirical formula
fw
Cd7Te7O17Cl8
2235.67
Pca21 (No. 29)
14.4725(8)
6.7259(4)
28.043(1)
90
90
90
2729.7(3)
4
5.440
1635.94
space group
a (Å)
b (Å)
P1h (No.2)
7.9203(4)
9.9079(5)
13.9864(3)
75.41(1)
74.17(1)
89.98(1)
1019.12(8)
2
5.331
13.378
1.137
0.0461, 0.0964
0.0576, 0.1037
Experimental Section
Materials and Instrumentation. All of the chemicals except
CdCl2 were analytically pure from commercial sources and used
without further purification. Transition metal or lanthanide oxides
were purchased from the Shanghai Reagent Factory; TeO2 (99+%)
was purchased from ACROS ORGANICS. CdCl2 was synthesized
by dehydration of CdCl2‚2H2O at 200 °C for 12 h. X-ray powder
diffraction (XRD) patterns were collected on an XPERT-MPD
θ-2θ diffractometer. IR spectra were recorded on a Magna 750
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
Dc (g cm-3
)
µ(Mo KR) (mm-1
GOF on F2
)
13.534
1.079
0.0250, 0.0511
0.0262, 0.0517
R1, wR2a [I > 2σ(I)]
FT-IR spectrometer as KBr pellets in the range of 4000-400 cm-1
.
R1, wR2a (all data)
Microprobe elemental analyses on Cd, Te, and Cl for both
compounds were performed on a field-emission scanning electron
microscope (FESEM, JSM6700F) equipped with an energy-
dispersive X-ray spectroscope (EDS, Oxford INCA).
a R1 ) ∑||Fo| - |Fc||/∑|Fo|; wR2 ) {∑w[(Fo)2 - (Fc)2]2/∑w[(Fo)2]2}1/2
.
Single-Crystal Structure Determination. Data collections for
the two compounds were performed on a Rigaku Mercury CCD
diffractometer equipped with a graphite-monochromated Mo KR
radiation (λ ) 0.71073 Å) at 293 K. Both data sets were corrected
for Lorentz and polarization factors as well as for absorption by
the multiscan method.19a Both structures were solved by direct
methods and refined by full-matrix least-squares fitting on F2 using
SHELX-97.19b All of the atoms were refined with anisotropic
thermal parameters. Crystallographic data and structural refinements
for the two compounds are summarized in Table 1. Important bond
distances are listed in Table 2. More details on the crystallographic
studies as well as atomic displacement parameters are given as
Supporting Information.
Preparation of [Cd2(Te6O13)][Cd2Cl6]. Single crystals of the
title compound (needle-shaped and colorless) were initially prepared
by the solid-state reaction of a mixture of Nd2O3 (0.101 g, 0.3
mmol), MoO3 (0.043 g, 0.3 mmol), CdCl2 (0.055 g, 0.3 mmol),
and TeO2 (0.192 g, 1.2 mmol) in our attempt to obtain a Nd-
Mo-Cd-Te-O-Cl phase. The reaction mixture was thoroughly
ground and pressed into a pellet, which was then sealed into an
evacuated quartz tube. The quartz tube was heated at 750 °C for 6
days and then cooled to 300 °C at 4.5 °C/h before we switched off
the furnace. The results of the single-crystal X-ray diffraction
analysis indicate the absence of both Nd and Mo. Microprobe
elemental analysis on several single crystals gave a Cd/Te/Cl molar
ratio of 3.8/5.8/6.3, which is in good agreement with that from
structural analysis. After crystal structure determination, a colorless
crystalline sample of [Cd2(Te6O13)][Cd2Cl6] was obtained quanti-
tatively by the reaction of a mixture of CdO/CdCl2/TeO2 in a molar
ratio of 1/3/6 at 670 °C for 6 days. The purity of [Cd2(Te6O13)]-
[Cd2Cl6] was confirmed by XRD powder diffraction studies. IR
(KBr, cm-1): 790 (m), 771(m), 748 (s), 733 (s), 691 (s), 659 (s),
615(s), 556 (s), 500 (m), 468 (m), 415 (w).
Preparation of Cd7Cl8(Te7O17). Colorless needle-shaped crystals
of Cd7Cl8(Te7O17) were initially prepared by the solid-state reaction
of a mixture containing Er2O3 (0.096 g, 0.25 mmol), CdO (0.032
g, 0.25 mmol), CdCl2 (0.046 g, 0.25 mmol), and TeO2 (0.240 g,
1.5 mmol) in an attempt to obtain an erbium(III)-cadmium(II)-
tellurium(IV) oxychloride. The reaction mixture was thoroughly
ground and pressed into a pellet, which was then sealed into an
evacuated quartz tube. The quartz tube was heated at 720 °C for 6
days and then cooled to 300 °C at 4 °C/h before we switched off
the furnace. Single-crystal X-ray diffraction studies indicate that
the compound contains no erbium(III) ion. Microprobe elemental
analysis on several single crystals indicate the Cd/Te/Cl molar ratio
is 7.1/6.7/8.4, which is in good agreement with that from structural
analysis. After structural analysis, a colorless crystalline sample of
Cd7Cl8(Te7O17) was then obtained quantitatively by the reaction
of a mixture of CdO/CdCl2/TeO2 in a molar ratio of 3/4/7 at 720
°C for 6 days. The purity of Cd7Cl8(Te7O17) was confirmed by XRD
powder diffraction studies: the mismatch of intensities for several
reflections is probably the result of the orientation effect. IR (KBr,
cm-1): 747 (s), 686 (s), 640 (s), 563 (s), 491 (w), 443 (w), 410
(w).
Results and Discussion
Our initial attempts to prepare new Ln-Cd-Te-O-Cl
phases resulted in the formation of two novel cadmium
tellurium(IV) oxychlorides instead, namely, [Cd2(Te6O13)]-
[Cd2Cl6] and Cd7Cl8(Te7O17), pure samples of which can be
prepared by solid-state reactions of cadmium(II) oxide,
cadmium(II) chloride, and TeO2 in different molar ratios at
different temperatures. Both compounds feature novel poly-
meric tellurium(IV) oxide anions and unusual cadmium
chloride substructures.
The structure of [Cd2(Te6O13)][Cd2Cl6] features (002)
cationic cadmium(II) tellurium(IV) oxide layers and “iso-
lated” anionic cadmium(II) chloride double chains along the
a axis (Figure 1). The [Cd2Cl6]2- double chain passing
through the cell edge is formed by Cd(3), Cd(4), and six
chloride anions. Both ions are octahedrally coordinated by
six chloride anions with Cd-Cl distances ranging from
2.500(3) to 2.821(3) Å. Cl(1) and Cl(3) are bidentate
bridging, and Cl(4) and Cl(5) are tridentate bridging, whereas
Cl(2) and Cl(6) are terminal ligands. Each pair of CdCl6
octahedra are interconnected via edge-sharing into a 1D chain
parallel to a axis and two such chains are further condensed
into a double chain via edge-sharing (Figure 2). Such isolated
(19) (a) CrystalClear, version 1.3.5; Rigaku Corp.: Woodlands, TX, 1999.
(b) Sheldrick, G. M. SHELXTL, Crystallographic Software Package,
version 5.1; Bruker-AXS: Madison, WI, 1998.
(18) (a) Kraemer, V.; Brandt, G. Acta Crystallogr. 1985, C41, 1152. (b)
Weil, M. Solid State Sci. 2004, 6, 29.
718 Inorganic Chemistry, Vol. 45, No. 2, 2006

[Cd2(Te6O13)][Cd2Cl6] and Cd7Cl8(Te7O17)
Table 2. Important Bond Lengths (Å) for [Cd2(Te6O13)][Cd2Cl6] and
Cd7Cl8(Te7O17)a
[Cd2(Te6O13)][Cd2Cl6]
Cd(1)-O(4)#1
Cd(1)-O(1)#1
Cd(1)-O(1)#3
Cd(1)-O(8)
2.339(8)
2.363(8)
2.408(8)
2.550(8)
2.314(7)
2.387(8)
2.511(8)
2.594(3)
2.612(3)
2.776(3)
2.584(3)
2.598(3)
2.821(3)
1.970(7)
2.164(8)
1.959(7)
2.205(7)
1.969(7)
2.167(7)
1.942(7)
2.167(8)
2.014(8)
2.131(7)
1.878(8)
1.957(8)
Cd(1)-O(6)#2
Cd(1)-O(10)
Cd(1)-O(9)
Cd(2)-O(6)#1
Cd(2)-O(11)
Cd(2)-O(8)
Cd(3)-Cl(2)
Cd(3)-Cl(1)
Cd(3)-Cl(4)
Cd(4)-Cl(6)
Cd(4)-Cl(1)#5
Cd(4)-Cl(4)#5
Te(1)-O(1)
Te(1)-O(2)
Te(2)-O(4)
Te(2)-O(2)
Te(3)-O(6)
Te(3)-O(7)
Te(4)-O(8)
Te(4)-O(7)
Te(5)-O(10)
Te(5)-O(9)
Te(5)-O(12)#8
Te(6)-O(11)
2.355(7)
2.388(7)
2.442(8)
2.307(8)
2.329(8)
2.478(8)
2.523(3)
2.609(3)
2.755(3)
2.500(3)
2.591(3)
2.790(3)
1.872(8)
2.010(8)
1.857(7)
1.978(7)
1.852(7)
1.988(7)
1.860(7)
2.156(7)
1.941(8)
2.059(7)
2.365(8)
1.907(7)
Cd(2)-O(8)#1
Cd(2)-O(4)#1
Cd(2)-O(5)#1
Cd(3)-Cl(3)
Cd(3)-Cl(5)
Cd(3)-Cl(5)#4
Cd(4)-Cl(3)#4
Cd(4)-Cl(4)
Cd(4)-Cl(5)
Te(1)-O(3)
Te(1)-O(7)#6
Te(2)-O(5)
Figure 1. View of the structure of [Cd2(Te6O13)][Cd2Cl6] down the a axis.
Cd, Te, Cl, and O atoms are drawn as cyan, pink, blue, and green circles,
respectively.
Te(2)-O(3)
Te(3)-O(5)
Te(3)-O(3)#3
Te(4)-O(9)
Te(4)-O(11)
Te(5)-O(13)#3
Te(5)-O(10)#7
Te(6)-O(12)
Te(6)-O(13)
Cd7Cl8(Te7O17)
Cd(1)-O(5)#1
Cd(1)-O(16)#3
Cd(1)-Cl(4)
Cd(2)-O(10)
Cd(2)-O(5)#1
Cd(2)-O(11)#5
Cd(2)-Cl(4)
Cd(3)-O(3)
Cd(3)-Cl(6)
Cd(3)-Cl(3)
Cd(4)-O(2)#5
Cd(4)-Cl(5)
Cd(4)-Cl(3)#1
Cd(5)-O(7)#8
Cd(5)-Cl(2)
Cd(5)-Cl(3)
Cd(6)-O(12)#5
Cd(6)-Cl(7)
Cd(6)-Cl(4)
Cd(7)-O(15)#9
Cd(7)-O(1)#7
Cd(7)-Cl(2)#1
Cd(7)-Cl(5)
Te(1)-O(17)
Te(1)-O(2)
Te(2)-O(1)#5
Te(2)-O(7)
Te(3)-O(14)#11
Te(3)-O(6)
Te(4)-O(5)#11
Te(4)-O(6)#12
Te(5)-O(2)#12
Te(5)-O(9)#12
Te(6)-O(12)
Te(6)-O(15)
Te(7)-O(7)
2.244(5)
2.399(6)
2.635(2)
2.230(6)
2.528(6)
2.595(5)
2.868(2)
2.369(6)
2.582(2)
2.723(2)
2.328(5)
2.592(2)
2.736(2)
2.349(5)
2.541(2)
2.734(2)
2.460(5)
2.498(2)
2.676(2)
2.247(6)
2.492(6)
2.551(2)
2.866(2)
1.908(6)
2.226(5)
1.887(5)
2.221(6)
1.860(5)
2.161(5)
1.872(5)
2.219(5)
1.874(5)
2.357(5)
1.939(6)
2.443(6)
1.903(6)
Cd(1)-O(9)#2
Cd(1)-Cl(6)#4
Cd(1)-Cl(1)#1
Cd(2)-O(13)#1
Cd(2)-Cl(7)#1
Cd(2)-Cl(8)
Cd(3)-O(16)
Cd(3)-O(14)#6
Cd(3)-Cl(1)#6
Cd(4)-O(1)#7
Cd(4)-O(3)
2.338(5)
2.620(2)
2.702(2)
2.289(5)
2.556(2)
2.650(2)
2.206(5)
2.380(6)
2.654(2)
2.248(6)
2.542(5)
2.624(2)
2.303(6)
2.385(5)
2.634(2)
2.245(6)
2.488(6)
2.508(5)
2.803(2)
2.330(5)
2.535(6)
2.673(2)
1.874(5)
1.998(5)
1.865(5)
2.073(6)
1.856(5)
2.103(6)
1.857(5)
2.073(6)
1.866(5)
1.965(5)
1.876(5)
2.022(5)
1.892(5)
1.915(6)
Figure 2. 1D double chain of cadmium chloride in [Cd2(Te6O13)][Cd2-
Cl6] along the a axis.
Cd(4)-Cl(6)
Cd(5)-O(3)
Cd(5)-O(1)#9
Cd(5)-Cl(5)
Cd(6)-O(14)
Cd(6)-O(10)
Cd(6)-O(5)
Cd(6)-Cl(1)
Cd(7)-O(11)#7
Cd(7)-O(13)#8
Cd(7)-Cl(8)#10
Te(1)-O(3)#11
Te(1)-O(8)
Figure 3. (002) 2D layer of {Cd2(Te6O13)} in [Cd2(Te6O13)][Cd2Cl6]. Cd,
Te, and O atoms are drawn as cyan, pink, and green circles, respectively.
Te(2)-O(13)#1
Te(2)-O(4)#1
Te(3)-O(9)#4
Te(3)-O(17)#4
Te(4)-O(11)#12
Te(4)-O(12)
Te(5)-O(16)#11
Te(5)-O(8)
Te(6)-O(10)#11
Te(6)-O(6)
Te(7)-O(15)#5
Te(7)-O(4)
double chains have only been reported in an organically
templated cadmium chloride, [C3H7N2S][CdCl3].20
The (002) cadmium(II) tellurium(IV) oxide layer in
[Cd2(Te6O13)][Cd2Cl6] is formed by novel 1D slabs of
2-
Te6O13 anions interconnected by Cd(II) ions (Figure 3).
Among its two unique Cd atoms, Cd(1) is coordinated by
seven oxygen atoms, whereas Cd(2) is octahedrally coordi-
nation by six oxygen atoms. The Cd-O distances fall in the
range of 2.307(8)-2.550(8) Å, which are comparable to
those reported for other cadmium tellurium(IV) oxides.18 It
is interesting to note that the TeOx (x ) 3, 4, 5) polyhedra
are not isolated but interconnected via edge- and corner-
a Symmetry transformations used to generate equivalent atoms. For
[Cd2(Te6O13)][Cd2Cl6]: #1 -x + 1, -y + 1, -z + 1; #2 -x, -y + 1, -z
+ 1; #3 x - 1, y, z; #4 -x, -y, -z + 2; #5 -x + 1, -y, -z + 2; #6 x +
1, y, z; #7 -x, -y + 2, -z + 1; #8 -x + 1, -y + 2, -z + 1. For
Cd7Cl8(Te7O17): #1 x, y + 1, z; #2 x - 1, y, z + 1; #3 x, y + 1, z + 1; #4
x, y, z + 1; #5 x - 1, y, z; #6 x, y, z - 1; #7 -x + 1, -y + 2, z - 1/2; #8
-x, -y + 1, z - 1/2; #9 -x + 1, -y + 1, z - 1/2; #10 -x + 1/2, y, z -
1/2; #11 x + 1, y, z; #12 x, y - 1, z.
2-
sharing into a novel 1D slab of the Te6O13 anion (Figure
(20) Kubiak, M.; Glowiak, T.; Kozlowski, H. Acta Crystallogr. 1983, C39,
1637.
Inorganic Chemistry, Vol. 45, No. 2, 2006 719

Jiang and Mao
Figure 4. 1D slab of the [Te6O13]2- anion in [Cd2(Te6O13)][Cd2Cl6].
Figure 6. Corrugated 2D cadmium chloride sheet in Cd7Cl8(Te7O17).
Figure 7. 1D slab of the [Te7O17]6- anion in Cd7Cl8(Te7O17).
Figure 5. View of the structure of Cd7Cl8(Te7O17) down the b axis. Cd,
Te, Cl, and O atoms are drawn as cyan, pink, deep blue, and green circles,
respectively.
oxygens and three chloride anions, whereas Cd(2), Cd(6),
and Cd(7) atoms are seven coordinated (four oxygens and
three chloride anions). The Cd-O and Cd-Cl distances are
in the range of 2.206(5)-2.595(5) and 2.498(2)-2.866(2)
Å, respectively (Table 2), which are comparable to those in
[Cd2(Te6O13)][Cd2Cl6]. In constrast to those in [Cd2-
(Te6O13)][Cd2Cl6], the Cd and Cl atoms in Cd7Cl8(Te7O17)
form a novel corrugated 2D layer (Figure 6). The layer is
based on Cd3Cl3 rings. The Cl-Cd-Cl and Cd-Cl-Cd
angles within the rings fall in the ranges of 83.70(5)-
96.46(6) and 87.88(6)-99.57(7)°. Hence, such Cd3Cl3 rings
are of the distorted cyclohexane type rather than of the “BN”
type in which the B-N-B angles are 120°.22 These 2D
layers can be viewed as the result of removing 1/8 of Cd(II)
ions from a perfect “Cd8Cl8” 2D layer leaving vacant Cd6-
Cl6 12-member rings with two larger Cd-Cl-Cd (Cd(2)-
Cl(8)-Cd(7)) angles of 130.38(7)°. This type of cadmium
chloride layer has not yet been reported.
The Te7O176- anion features a 1D structure different from
that of the Te6O132- anion in [Cd2(Te6O13)][Cd2Cl6] (Figure
7). Only two types of tellurium(IV) oxide polyhedra are
found: TeO3 for Te(7) and TeO4 for the remaining six
tellurium atoms. The Te-O distances are in the range of
1.856(5)-2.443(6) Å, which are comparable to those in
[Cd2(Te6O13)][Cd2Cl6] (Table 2). The calculated total bond
valences for the tellurium atoms are in the range of 3.59-
4.08, indicating that all of the tellurium atoms have oxidation
states of 4+.21 TeO3 and TeO4 groups are interconnected
4). The Te-O distances are in the range of 1.852(7)-
2.365(8) Å, which are comparable to those reported in other
tellurium(IV) compounds.5-18 Bond valence calculations
indicate that all six tellurium atoms are 4+, the calculated
total bond valences are in the range of 3.57-3.99.21 Te(1)-
O4, Te(2)O4, and Te(3)O4 groups are interconnected via
corner- and edge-sharing into a trinuclear unit, and neighbor-
ing units are corner-shared (O(5)) into a 1D chain along the
a axis. Two Te(5)O5 and two Te(6)O3 groups form a
tetranuclear unit via corner- and edge-sharing. The above
1D chains and tetranuclear units are bridged by Te(4)O4
2-
groups, through corner-sharing, into a 1D Te6O13 slab,
forming six- and seven-member polyhedral rings (Figure 4).
The width of the slab is about 14.6 Å. Such tellurium(IV)
oxide anion slabs have not been reported before. The lone
pair electrons of the Te(IV) atoms are oriented in the open
space between the cadmium chloride chains and cadmium
tellurium(IV) oxide layers (Figure 1).
The structure of Cd7Cl8(Te7O17) features a 3D network
with long narrow tunnels along the b axis with different
tellurium(IV) oxide and cadmium chloride substructures
(Figure 5). The two structural building blocks are 1D
[Te7O17]6- anions and unusual corrugated [Cd7Cl8]6+ layers
based on cyclohexane-type Cd3Cl3 rings. Cd(1), Cd(3), Cd(4),
and Cd(5) atoms are octahedrally coordinated by three
(21) (a) Brown, I. D.; Altermatt, D. Acta Crystallogr. 1985, B41, 244. (b)
Brese, N. E.; O’Keeffe, M. Acta Crystallogr. 1991, B47, 192.
(22) Pease, R. S. Acta Crystallogr. 1952, 5, 356.
720 Inorganic Chemistry, Vol. 45, No. 2, 2006

[Cd2(Te6O13)][Cd2Cl6] and Cd7Cl8(Te7O17)
2-
4-
via corner-sharing into another type of 1D slab, forming two
types of six-member polyhedral rings and one type of three-
member polyhedral ring (Figure 7). The three-member ring
is composed of three TeO4 groups. One type of the
six-member ring is formed by solely TeO4 groups in a “pear”
shape, whereas the other type is made of two TeO3 and four
TeO4 groups. The width of this 1D slab is 12.1 Å, which is
as layered Te4O9 in K2Te4O9‚3.2H2O and 3D Te2O6 in
KGaTe2O6.3d A few compounds containing extended tellu-
rium(IV) oxide anions were prepared by solid-state reactions
2-
at high temperature (T > 600 °C), such as layered Te2O5
in Ln(Te2O5)X (Ln ) Nd, X ) Cl, Br; Ln ) Gd, X ) Cl).24
Therefore we conclude that the reaction temperature plays
an important role in the polymerization of Te(IV)Ox (x ) 3,
4, 5) groups and the formation of tellurium(IV) oxide anions
with extended structural motifs.
2-
slightly narrower than that of the Te6O13 anion in [Cd2-
(Te6O13)][Cd2Cl6].
The above two types of building units are interconnected
via Te-O-Cd bridges into a 3D network with long narrow
tunnels along the b axis (Figure 5). Alternatively, the
structure of Cd7Cl8(Te7O17) can be viewed as (200) and (100)
layers of Cd7Cl7(Te7O17) further cross-linked by the eighth
chloride anion (Cl(8)) via Cd(2)-Cl(8)-Cd(7) bridges. The
stereoactive lone pairs of the Te(IV) atoms are oriented
toward the narrow tunnels.
Cd7Cl8(Te7O17) crystallizes in the acentric space group
Pca21; hence, it may possess the NLO property. However,
the results of our measurements on a homemade instrument
using an Nd:YAG laser as the light source indicate that its
SHG signal is very weak.
It is interesting to note the polymerization of the Te(IV)
polyhedral groups and the formation of novel 1D slabs of
tellurium(IV) oxide anions in both [Cd2(Te6O13)][Cd2Cl6] and
Cd7Cl8(Te7O17). The Te(IV) polyhedral groups in the organi-
cally templated or organically covalently bonded metal
tellurites prepared under normal hydrothermal conditions
(120-200 °C) are normally nonpolymerized.23 Under su-
percritical hydrothermal methods (T > 374 °C, P >218 atm)
meta-stable compounds may be formed, and a few examples
of polymeric tellurium(IV) oxide anions are observed, such
Conclusion
In summary, the syntheses and crystal structures of two
new cadmium tellurium(IV) oxychloride complexes have
been described. It is interesting to note that the Te-O
polyhedra in both compounds are condensed into 1D anionic
slabs via edge- and corner-sharing. The cadmium chloride
substructures in both compounds are also interesting. In Cd7-
Cl8(Te7O17), the interconnection of cadmium(II) ions by
bridging chloride anions led to a novel corrugated “defect”
2D layer based on Cd3Cl3 rings, whereas the cadmium(II)
and chloride anions in [Cd2(Te6O13)][Cd2Cl6] form a double
chain. It is anticipated that many other new cadmium
tellurium(IV) oxyhalides with interesting architectures will
be discovered in the future.
Acknowledgment. This work was supported by the
National Natural Science Foundation of China (No. 20371047)
and NSF of Fujian Province (No. E0420003).
Supporting Information Available: X-ray crystallographic files
in CIF format and simulated and experimental XRD powder patterns
for Cd7Cl8(Te7O17) and [Cd2(Te6O13)][Cd2Cl6]. This material is
available free of charge via the Internet at http://pubs.acs.org.
IC051703Q
(23) (a) Xiao, D.-R.; Li, Y.-G.; Wang, E.-B.; Wang, S.-T.; Hou, Y.; De,
G.; Hu, C. Inorg. Chem. 2003, 42, 7652. (b) Xie, J.-Y.; Mao, J.-G.
Inorg. Chem. Commun. 2005, 8, 375. (c) Feng, M.-L.; Mao, J.-G. J.
Solid State Chem. 2005, 178, 2256.
(24) (a) Nikiforov, G. B.; Kusainova, A. M.; Berdonosov, P. S.; Dolgikh,
V. A.; Lightfoot, P. J. Solid State Chem. 1999, 146, 473. (b) Meier,
S. F.; Schleid, T. Z. Anorg. Allg. Chem. 2003, 629, 1575.
Inorganic Chemistry, Vol. 45, No. 2, 2006 721