New members in the Nin+1(QO3)nX 2 family: Unusual 3D network based on Ni4ClO3 cubane-like clusters in Ni7(TeO3)6Cl 2

Article abstract of DOI:10.1021/ic060356x

Three new members in the family of nickel(II) tellurium(IV)/selenium(IV) oxyhalides generally formulated as Ni_n+1-(QO₃) _nX₂ (Q = Te, X = Cl, n = 6, 10; Q = Se, X = Br, n = 4) have been synthesized by solid-state reactions of NiX₂, QO ₂, and NiO (or Ni₂O₃) at high temperature. The structure of Ni₇(TeO₃)₆Cl₂ features a novel 3D network based on Ni₄ClO₃ cubane-like clusters with Te atoms located at the cavities of the network. Ni₄ClO ₃ clusters are interconnected into a hexagonal layer through additional O...O edges. The neighboring two layers are further interconnected, via sharing of common Ni(II) atoms, into a novel 3D network. The 3D open framework of Ni₅(SeO₃)₄-Br₂ is built from 2D nickel(II) oxybromide-layers bridged by Se and additional Ni atoms. The structure of Ni₁₁(TeO₃)₁₀-Cl ₂ features a condensed 3D network based on NiO₅Cl, NiO₆, and NiO₅ polyhedra interconnected via corner and edge sharing, as well as O-Te-O bridges. The results of magnetic property measurements indicate that all three compounds display antiferromagnetic interactions between nickel(II) centers.

Full text of DOI:10.1021/ic060356x

Inorg. Chem. 2006, 45, 7593−7599
New Members in the Nin+1(QO ) X Family: Unusual 3D Network Based
3 n
2
on Ni ClO Cubane-like Clusters in Ni (TeO ) Cl
4
3
7
3 6
2
Hai-Long Jiang and Jiang-Gao Mao*
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of
Matter, and the Graduate School of the Chinese Academy of Sciences, Chinese Academy of
Sciences, Fuzhou 350002, P. R. China
Received March 3, 2006
Three new members in the family of nickel(II) tellurium(IV)/selenium(IV) oxyhalides generally formulated as Ni
QO (Q Te, X Cl, n 6, 10; Q Se, X Br, n 4) have been synthesized by solid-state reactions
of NiX , QO , and NiO (or Ni ) at high temperature. The structure of Ni (TeO Cl features a novel 3D network
based on Ni ClO cubane-like clusters with Te atoms located at the cavities of the network. Ni ClO clusters are
interconnected into a hexagonal layer through additional O‚‚‚O edges. The neighboring two layers are further
interconnected, via sharing of common Ni(II) atoms, into a novel 3D network. The 3D open framework of Ni (SeO
Br is built from 2D nickel(II) oxybromide layers bridged by Se and additional Ni atoms. The structure of Ni11(TeO
Cl features a condensed 3D network based on NiO Cl, NiO , and NiO polyhedra interconnected via corner and
edge sharing, as well as O Te O bridges. The results of magnetic property measurements indicate that all three
compounds display antiferromagnetic interactions between nickel(II) centers.
n+1
-
(
3
)
X
n 2
)
)
)
)
)
)
2
2
2
O
3
7
3
)
6
2
4
3
4
3
5
3 4
) -
2
3 10
) -
2
5
6
5
−
−
Introduction
etc, which are susceptible to second-order Jahn-Teller
distortions have been introduced to the selenite or tellurite
Selenites or tellurites can adopt many unusual structures
because of the presence of the stereochemically active lone-
pair electrons. The asymmetric coordination polyhedron
adopted by the Se(IV) or Te(IV) atom may result in
noncentrosymmetric structures with consequent interesting
physical properties, such as nonlinear optical second har-
monic generation (SHG).2 Transition metal ions with d
2
-4
systems to enhance their SHG properties. Recent studies
also indicate that the activation of the selenite or tellurite
anion for lanthanide ions can also produce new luminescent
1
5
materials in the near-IR region. More interestingly, transition
metal Te(IV) or Se(IV) oxyhalides can be regarded as
“
chemical scissors”, and some of them are promising new
-4
0
6
-9
low-dimensional magnets.
system, such as Cu
Cu (SeO Cl , Cu
A few compounds in the Cu
(X ) Cl, Br), Cu (TeO Br
, and Cu (SeO Cl , have
The corresponding
4+
5+
6+
6+
electronic configurations, such as Ti , Nb , W , Mo ,
2
Te
2
O
5
X
2
3
3
)
2
2
,
*
To whom correspondence should be addressed. E-mail:
3
3
)
2
2
5
O
2
(SeO
3
)
2
9
O
2
3
)
4
6
mjg@ms.fjirsm.ac.cn.
7,10-11
been structurally characterized.
(
1) (a) Wickleder, M. S. Chem. ReV. 2002, 102, 2011 and references
therein. (b) Harrison, W. T. A.; Dussack, L. L.; Jacobson, A. J. Inorg.
Chem. 1994, 33, 6043. (c) Johnston, M. G.; Harrison, W. T. A. J.
Am. Chem. Soc. 2002, 124, 4576. (d) Irvine, J. T. S.; Johnston, M.
G.; Harrison, W. T. A. Dalton Trans. 2003, 2641. (e) Almond, P. M.;
Albrecht-Schmitt, T. E. Inorg. Chem. 2002, 41, 5495. (f) Almond, P.
M.; Mckee, M. L.; Albrecht-Schmitt, T. E. Angew. Chem., Int. Ed.
(5) (a) Shen, Y.-L.; Jiang, H.-L.; Xu, J.; Mao, J.-G.; Cheah, K.-W. Inorg.
Chem. 2005, 44, 9314. (b) Shen, Y.-L.; Mao, J.-G. Inorg. Chem. 2005,
44, 5328.
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2
002, 41, 3426. (g) Harrison, W. T. A.; Phillips, M. L. F.; Stanchfield,
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(8) Millet, P.; Bastide, B.; Pashchenko, V.; Gnatchenko, S.; Gapon, V.;
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2003, 15, 68.
J.; Nenoff, T. M. Angew. Chem., Int. Ed. 2000, 39, 3808. (h)
Choudhury, A.; Kumar, U.; Rao, C. N. R. Angew. Chem., Int. Ed.
2002, 41, 158.
(
(
(
2) (a) Ra, H.-S.; Ok, K.-M.; Halasyamani, S. H. J. Am. Chem. Soc. 2003,
125, 7764. (b) Ok, K.-M.; Halasyamani, P. S. Inorg. Chem. 2004, 43,
4
248.
(10) (a) Becker, R.; Johnsson, M.; Kremer, R.; Lemmens, P. J. Solid State
Chem. 2005, 178, 2024. (b) Millet, P.; Bastide, B.; Johnsson, M. Solid
State Commun. 2000, 113, 719.
(11) (a) Galy, J.; Bonnet, J. J.; Andersson, S. Acta Chem. Scand. 1979,
A33, 383. (b) Bastide, B.; Millet, P.; Johnsson, M.; Galy, J. Mater.
Res. Bull. 2000, 35, 847.
3) (a) Hart, R. T.; Ok, K.-M.; Halasyamani, P. S.; Zwanziger, J. W. Appl.
Phys. Lett. 2004, 85, 938. (b) Goodey, J.; Broussard, J.; Halasyamani,
P. S. Chem. Mater. 2002, 14, 3174.
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(b) Balraj, V.; Vidyasagar, K. Inorg. Chem. 1999, 38, 5809.
1
0.1021/ic060356x CCC: $33.50
© 2006 American Chemical Society
Inorganic Chemistry, Vol. 45, No. 19, 2006 7593
Published on Web 08/16/2006

Jiang et al.
nickel system is much less explored, and only Ni
X ) Cl, Br), Ni (SeO Cl , and three other nonstoichio-
metric compounds with approximate compositions of [Ni30
5
(TeO
)
3 4
X
2
manually selected on the basis of their unique colors were used
for IR, TGA, and magnetic measurements. The purities of the
samples were confirmed by XRD powder diffraction studies. IR
(
5
3
)
4
2
-
-
1
9,12
data for Ni
96 (vs), 469 (m). IR data for Ni11(TeO
s), 691 (vs), 624 (m), 589 (m), 482 (w), 459 (w), 431 (w).
Preparation of Ni (SeO Br . Red brick-shaped single crystals
of Ni (SeO Br were prepared by the solid-state reaction of a
mixture containing Ni (0.199 g, 1.2 mmol), NiBr (0.131 g, 0.6
mmol), and SeO (0.266 g, 2.4 mmol). The reaction mixture was
7 3 6 2
(TeO ) Cl (KBr, cm ): 791 (s), 702 (s), 637 (w),
Te32
O
90
X
3
][Ni
were astonished that many compounds in above systems can
be generally formulated to be Mn+1(QO where M, Q,
4
X13] (X ) Cl, Br) have been reported. We
-
1
5
3 2
)10Cl (KBr, cm ): 734
(
3 n 2
) X
5
)
3 4
2
and X represent a transition metal, Se or Te, and a halide
anion, respectively. Our exploration of the missing members
in the nickel system afforded three new compounds, namely,
5
3
)
4
2
O
2 3
2
2
Nin+1(QO
3
)
n
X
2
(Q ) Te, X ) Cl, n ) 6, 10; Q ) Se, X )
thoroughly ground and pressed into a pellet, which was then sealed
into an evacuated quartz tube. The quartz tube was heated at 300
°C for 1 day and 670 °C for 6 days and then cooled to 310 °C at
Br, n ) 4). Herein, we report their syntheses, crystal
structures, and magnetic properties.
4
°C/h before the furnace was switched off. NiSeO
was found to be the only impurity. The Ni/Se/Br molar ratio of
.0:3.7:2.3 measured by microprobe elemental analysis is in good
3
(brick, yellow)
Experimental Section
5
Materials and Instrumentation. All chemicals except NiO were
analytically pure from commercial sources and used without further
purification. Transition metal oxides and halides were purchased
agreement with that determined from single-crystal X-ray structural
analysis. A lot of effort was made to synthesize a single phase
product for Ni
containing NiO/NiBr
temperatures. However, the NiSeO
highest yield of about 85% was obtained by the reaction of a
mixture of Ni /NiBr /SeO in a molar ratio of 2:1:4 at 620 °C
5
(SeO
3
)
4
Br
/SeO
2
by the solid-state reaction of a mixture
in a molar ratio of 4:1:4 at various
impurity always exists. The
from the Shanghai Reagent Factory, and TeO
99+%) were purchased from ACROS Organics. NiO was syn-
thesized by heating Ni in air at 610 °C for 12 h, and its purity
2
(99+%) and SeO
2
2
2
(
3
2
O
3
was confirmed by X-ray powder diffraction (XRD) studies. The
measured XRD pattern is in good agreement with the one simulated
from crystal structure data.13 XRD patterns were collected on a
XPERT-MPD θ-2θ diffractometer. The chemical compositions for
the three compounds were analyzed by a field-emission scanning
electron microscope (FESEM, JSM6700F) equipped with an energy-
dispersive X-ray spectroscope (EDS, Oxford INCA). IR spectra
were recorded on a Magna 750 FT-IR spectrometer as KBr pellets
2
O
3
2
2
for 6 days. Hence, the samples used for its IR, TGA, and magnetic
measurements are single crystals selected on the basis of their
-1
unique color. IR data for Ni
14(m), 777 (s), 736 (vs), 715 (vs), 544 (m), 503 (m).
Single-Crystal Structure Determination. Data collections were
performed on either a Rigaku Mercury CCD diffractometer (for
5 3 4 2
(SeO ) Br (KBr, cm ): 841 (w),
8
Ni
7
(TeO
3
)
6
Cl
2
5 3 4 2
and Ni (SeO ) Br ) or a Rigaku Saturn70 CCD for
-1
in the range of 4000-400 cm . Thermogravimetric analyses (TGA)
were carried out with a NETZSCH STA 449C unit at a heating
rate of 10 °C/min under an oxygen atmosphere. Magnetic suscep-
tibility measurements were performed on a PPMS-9T magnetometer
in the temperature range of 2-300 K.
Ni11(TeO
3
)
10Cl
2
) equipped with graphite-monochromated Mo KR
radiation (λ ) 0.71073 Å) at 293 K. All three data sets were
corrected for Lorentz and polarization factors. Absorption correc-
tions by the multiscan method were applied for Ni
Ni (SeO Br and by the numerical method for Ni11(TeO
All three structures were solved by the direct methods and refined
7 3 6 2
(TeO ) Cl and
14a
5
)
3 4
2
3 2
)10Cl .
Preparation of Ni
crystals of both compounds were prepared by the solid-state reaction
of a mixture of NiO (0.179 g, 2.4 mmol), NiCl (0.078 g, 0.6 mmol),
and TeO (0.287 g, 1.8 mmol). The reaction mixture was thoroughly
7 3 6 2 3 2
(TeO ) Cl and Ni11(TeO )10Cl . Single
2
14b
by full-matrix least-squares fitting on F by SHELX-97. All atoms
2
were refined with anisotropic thermal parameters. For Ni (TeO ) -
11
3 10
2
2
Cl , Ni(6) is only 50% occupied, and three tellurite oxygen atoms
ground and pressed into a pellet, which was then sealed into an
evacuated quartz tube. The quartz tube was heated at 710 °C for 6
days and then cooled to 310 °C at 4 °C/hr before the furnace was
are disordered and each displays two orientations (O(4) and O(4′),
O(5) and O(5′), O(15) and O(15′)) with 50% occupancy each.
Crystallographic data and structural refinements for the three
compounds are summarized in Table 1. Important bond distances
are listed in Table 2. More details of the crystallographic studies
as well as atomic displacement parameters are given as Supporting
Information.
switched off. The products are Ni
phase, Ni11(TeO (brick, deep red), and previously reported
Ni (TeO Cl (plate, orange), as two impurity phases. Microprobe
elemental analyses gave Ni/Te/Cl molar ratios of 7.0:6.0:2.3 and
1.2:9.8:2.4 for Ni (TeO Cl and Ni11(TeO , respectively,
7 3 6 2
(TeO ) Cl (green, brick) as major
3 2
)10Cl
9
5
)
3 4
2
1
7
3
)
6
2
3 2
)10Cl
Results and Discussion
which are in good agreement with those determined from single-
crystal X-ray diffraction studies. A lot of effort was exerted to
Solid-state reactions of nickel(II)/(III) oxide, nickel(II)
prepare single-phase products for Ni
Cl by the solid-state reactions of corresponding stoichiometric
mixtures of NiO, NiCl , and TeO at different temperatures. A pure
powder sample of Ni11(TeO was obtained quantitatively by
the reaction of a mixture of NiO/NiCl
:1:6 at 760 °C for 6 days. For Ni (TeO
7 3 6 2 3 10
(TeO ) Cl and Ni11(TeO ) -
halides, and TeO
different temperatures yielded three new nickel tellurium-
IV) and selenium(IV) oxyhalides, namely, Ni (TeO Cl
Ni (SeO Br , and Ni11(TeO . All of them belong to
new members in the family of nickel(II) tellurium(IV)/
selenium(IV) oxyhalides with a general formula of Nin+1
(QO (Q ) Te, X ) Cl, n ) 6, 10; Q ) Se, X ) Br, n
) 4).
The structure of Ni (TeO ) Cl features a novel 3D
2 2
or SeO in different molar ratios and at
2
2
2
(
7
3
)
6
2
,
3 2
)10Cl
5
3
)
4
2
3 2
)10Cl
2
/TeO in a molar ratio of
2
Cl , the highest purity
2
6
7
3
)
6
-
of about 90% was obtained by the reaction of a mixture of Ni
NiCl /TeO in a molar ratio of 3:1:6 at 620 °C for 6 days; a small
amount of Ni11(TeO was found as the impurity phase based
on XRD powder studies. Hence, single crystals of Ni (TeO Cl
2
2 3
O /
3 n 2
) X
2
2
3 2
)10Cl
7
3
)
6
7
3 6
2
4 3
network based on Ni ClO cubane-like clusters with Te atoms
(
12) (a) Shen, Y.-L.; Mao, J.-G.; Jiang, H.-L. J. Solid State Chem. 2005,
78, 2942. (b) Johnsson, M.; Lidin, S.; T o¨ rnroos, K. W.; B u¨ rgi, H.-
1
(14) (a) CrystalClear, version 1.3.5; Rigaku Corp.: The Woodlands, TX,
1999. (b) Sheldrick, G. M. SHELXTL, version 5.1; Bruker-AXS:
Madison, WI, 1998.
B.; Millet, P. Angew. Chem., Int. Ed. 2004, 43, 4292.
(13) Barrett, C. A.; Evans, E. B. J. Am. Ceram. Soc. 1964, 47, 533.
7594 Inorganic Chemistry, Vol. 45, No. 19, 2006

3 n 2
New Members in the Nin+1(QO ) X Family
Table 1. Crystal Data and Structure Refinements for Ni7(TeO3)6Cl2,
Ni5(SeO3)4Br2, and Ni11(TeO3)10Cl2
Table 2. Important Bond Lengths (Å) for Ni7(TeO3)6Cl2,
Ni5(SeO3)4Br2, and Ni11(TeO3)10Cl2a
Ni7(TeO3)6Cl2 Ni5(SeO3)4Br2 Ni11(TeO3)10Cl2
Ni7(TeO3)6Cl2
Ni(1)-O(3)#1
Ni(1)-O(2)#3
Ni(1)-O(1)
1.987(5)
2.047(4)
2.096(4)
2.076(4)
2.076(4)
2.076(4)
1.831(5)
1.945(4)
Ni(1)-O(2)#2
Ni(1)-O(1)#4
Ni(1)-Cl(1)
Ni(2)-O(1)#5
Ni(2)-O(1)#6
Ni(2)-O(1)#2
Te(1)-O(2)
2.015(4)
2.076(4)
2.487(2)
2.076(4)
2.076(4)
2.076(4)
1.878(4)
empirical formula
fw
space group
a (Å)
b (Å)
c (Å)
Cl2Ni7O18Te6
1535.47
R 3h (No. 148)
11.151(4)
11.151(4)
13.450(6)
90.0
90.0
120.0
1448.4(9)
3
5.281
Br2Ni5O12Se4
961.21
Cl2Ni11O30Te10
2472.71
P 1h (No. 2)
9.281(3)
9.423(3)
10.113(3)
100.218(1)
99.068(4)
115.880(2)
755.0(4)
1
5.438
16.450
1.059
0.0232,
0.0556
0.0272,
0.0567
P 1h (No. 2)
6.430(3)
7.632(3)
7.658(3)
68.017(16)
74.181(16)
81.465(19)
334.8(3)
1
4.767
23.798
1.034
0.0393,
0.0940
Ni(2)-O(1)#7
Ni(2)-O(1)
Ni(2)-O(1)#4
Te(1)-O(3)
Te(1)-O(1)
R (deg)
â (deg)
γ (deg)
Ni5(SeO3)4Br2
3
V (Å )
Ni(1)-O(6)#1
Ni(1)-O(4)
Ni(1)-O(3)#4
Ni(2)-O(1)#3
Ni(2)-O(5)#6
Ni(2)-Br(1)
Ni(3)-O(4)
Ni(3)-O(2)
Ni(3)-O(5)#2
Se(1)-O(2)
Se(1)-O(3)
Se(2)-O(5)
2.012(5)
2.032(5)
2.121(5)
2.010(5)
2.043(5)
2.676(1)
2.007(5)
2.040(5)
2.075(5)
1.707(5)
1.711(5)
1.707(5)
Ni(1)-O(6)#2
Ni(1)-O(1)#3
Ni(1)-Br(1)
Ni(2)-O(1)#5
Ni(2)-O(5)
Ni(2)-Br(1)#6
Ni(3)-O(2)#7
Ni(3)-O(3)#4
Ni(3)-Br(1)#8
Se(1)-O(1)
Se(2)-O(6)
Se(2)-O(4)
2.026(5)
2.112(5)
2.690(2)
2.010(5)
2.043(5)
2.676 (1)
2.032(5)
2.056(5)
2.972(2)
1.708(5)
1.690(5)
1.709(5)
Z
Dc (g cm-3)
µ(Mo KR) (mm-1) 15.926
2
GOF on F
1.323
R1, wR2
0.0314,
0.0799
0.0325,
0.0807
a
[
I > 2σ(I)]
R1, wR2
0.0461,
0.0975
a
(all data)
a
R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2 ) {∑w[(Fo) - (Fc) ] /∑w[(Fo) ] }1/2.
2
2 2
2 2
located at the cavities of the network (Figure 1). The
asymmetric unit of Ni (TeO Cl contains a Ni(1) atom in
Ni11(TeO3)10Cl2
7
3
)
6
2
Ni(1)-O(5′)#1
Ni(1)-O(14)#1
Ni(1)-O(3)
2.035(2)
2.059(4)
2.094(4)
2.482(2)
2.021(4)
2.060(4)
2.308(4)
2.063(4)
2.087(4)
2.104(4)
2.030(4)
2.083(2)
2.156(4)
1.910(2)
2.075(4)
2.202(19)
2.366(9)
2.009(8)
2.087(5)
1.848(4)
1.926(4)
1.842(4)
1.85(2)
Ni(1)-O(9)#1
Ni(1)-O(14)#2
Ni(1)-O(5)#1
Ni(2)-O(6)
Ni(2)-O(8)#1
Ni(2)-O(7)#3
Ni(3)-O(13)
Ni(3)-O(10)
Ni(3)-O(9)
Ni(4)-O(11)#1
Ni(4)-O(3)
Ni(4)-O(5)#1
Ni(4)-O(12)#5
Ni(5)-O(8)
Ni(5)-O(2)
Ni(5)-O(9)
2.046(4)
2.072(4)
2.095(2)
1.984(4)
2.054(4)
2.072(4)
2.060(4)
2.064(4)
2.094(4)
2.029(4)
2.074(4)
2.140(15)
2.168(4)
1.984(4)
2.164(4)
2.254(4)
1.951(8)
2.042(4)
2.100(4)
1.882(4)
1.817(16)
1.84(3)
the general position, a Ni(2) atom in a site of -3 symmetry,
one tellurite group on general sites, and one Cl atom in a
site of -1 symmetry. Ni(1) is octahedrally coordinated by
five oxygen atoms and one chloride anion, whereas Ni(2) is
octahedrally coordinated by six oxygen atoms. The Ni-Cl
distances (2.487(2) Å) are significantly longer than the Ni-O
bond lengths (1.987(5)-2.096(4) Å). The Te atom is in a
Ni(1)-Cl(1)
Ni(2)-O(1)#3
Ni(2)-O(12)#1
Ni(2)-O(1)#1
Ni(3)-O(7)
Ni(3)-O(2)#1
Ni(3)-O(2)
Ni(4)-O(10)
Ni(4)-O(5′)#1
Ni(4)-O(12)#4
Ni(5)-O(4)#1
Ni(5)-O(10)#1
Ni(5)-O(4′)#1
Ni(5)-O(5)
ψ-TeO
3
trigonal pyramidal geometry with the lone pair of
Te(IV) occupying the pyramidal site. Each TeO
bridges with six nickel(II) ions: O(1) is monodentate, and
O(2) is bidentate, whereas O(3) connects with three nickel-
3
group
(II) ions. Each chloride anion also bonds with three Ni(II)
Ni(6)-O(15)#6
Ni(6)-O(11)#5
Ni(6)-O(7)#3
Te(1)-O(1)
ions. Bond-valence calculations indicate that the nickel and
tellurium atoms are 2+ and 4+, respectively. The calculated
total bond valences are 1.86 (Ni(1)), 1.92 (Ni(2)), and 3.88
Ni(6)-O(15′)#3
Ni(6)-O(6)
Te(1)-O(3)
Te(1)-O(2)
Te(2)-O(5′)
Te(2)-O(4′)#8
Te(2)-O(5)
1
5
(
Te(1)).
Three Ni(1)O
ClO cubane-like cluster via O‚‚‚O and O‚‚‚Cl edge
Te(2)-O(6)#8
Te(2)-O(4)#8
Te(3)-O(8)
1.889(15)
1.900(4)
1.866(4)
1.960(4)
1.659(9)
1.851(4)
5
6
Cl moities and one Ni(2)O unit forms a
1.888(4)
1.934(4)
1.938(4)
2.450(4)
1.771(8)
1.877(4)
Te(3)-O(7)
Ni
4
3
Te(3)-O(9)
Te(4)-O(11)#9
Te(4)-O(12)
Te(5)-O(15)#10
Te(5)-O(14)
sharing (Figure 2a). The four nickel(II) ions within a cluster
form a slightly distorted tetrahedron with Ni(1)‚‚‚Ni(1) and
Ni(1)‚‚‚Ni(2) separations of 3.302(1) and 3.044(1) Å,
Te(4)-O(10)#8
Te(4)-O(13)#8
Te(5)-O(15′)
Te(5)-O(13)
respectively. Such M
4 3
O Cl cluster units have been reported
a
Symmetry transformations used to generate equivalent atoms.
Ni7(TeO3)6Cl2: #1 -x + 1, -y + 2, -z; #2 y - 1/3, -x + y + 1/3, -z +
1/3; #3 -y + 4/3, x - y + 5/3, z - 1/3; #4 -x + y, -x + 1, z; #5 -x +
in a number of manganese(II) and copper(II) coordination
16
complexes. Most of the cubane clusters in the above metal
complexes are isolated, but they can form a Cu dimeric
For nickel(II) com-
2
1
/3, -y + 4/3, -z + 1/3; #6 -y + 1, x - y + 1, z; #7 x - y + 2/3, x +
/3, -z + 1/3. Ni5(SeO3)4Br2: #1 x - 1, y, z; #2 -x + 1, -y, -z + 1; #3
x, y - 1, z; #4 -x, -y + 1, -z + 1; #5 -x + 1, -y + 1, -z; #6 -x + 1,
y, -z; #7 -x + 1, -y + 1, -z + 1; #8 x, y, 1 + z. Ni11(TeO3)10Cl2: #1
7
6 2
O X
unit in the copper(II) complexes.1
6d,16e
-
(
15) (a) Brown, I. D.; Altermatt, D. Acta Crystallogr. 1985, B41, 244. (b)
-x + 1, -y + 1, - z + 1; #2 x, y, z + 1; #3 x + 1, y, z; #4 -x, -y + 1,
-z + 1; #5 x, y - 1, z; #6 -x + 1, -y, -z + 1; #7 -x + 1, -y, -z; #8
x, y + 1, z; #9 x - 1, y, z; #10 x, y, z - 1.
Brese, N. E.; O’Keeffe, M. Acta Crystallogr. 1991, B47, 192.
16) (a) Bashkin, J.; Chang, H.-R.; Streib, W. E.; Huffman, J. C.;
Hendrickson, D. N.; Christou, G. J. Am. Chem. Soc. 1987, 109, 6502.
(
(
b) Hendrichson, D. N.; Christou, G.; Schmitt, E. A.; Libby, E.;
plexes, an isolated Ni
of Ni cubane clusters, most of them isolated, have been
reported. Ni
to form super cubane clusters via corner, edge, or face
sharing.
It is interesting to note that each pair of cubanes in
4 4
F cubane cluster and a large number
Bashkin, J. S.; Wang, S.; Tsai, H.-L.; Vincent, J. B.; Boyd, P. D. W.;
Huffman, J. C.; Folting, K.; Li, Q.; Streib, W. E. J. Am. Chem. Soc.
4 4
O
1
992, 114, 2455. (c) Wemple, M. W.; Adams, D. M.; Folting, K.;
Hendrickson, D. N.; Christou, G. J. Am. Chem. Soc. 1995, 117, 7275.
d) Liu, X.; McAllister, J. A.; de Miranda, M. P.; Mclnnes, E. J. L.;
17
4
4
O cubane clusters were reported to be able
(
1
7
Kilner, C. A.; Halcrow, M. A. Chem.sEur. J. 2004, 10, 1827. (e)
Liu, X.; McAllister, J. A.; de Miranda, M. P.; Whitaker, B. J.; Kilner,
C. A.; Thornton-Pett, M.; Halcrow, M. A. Angew. Chem., Int. Ed.
2002, 41, 756.
Ni
7 3
(TeO )
6
Cl
2
are also condensed into a dimeric unit by
Inorganic Chemistry, Vol. 45, No. 19, 2006 7595

Jiang et al.
Figure 1. View of the structure of Ni7(TeO3)6Cl2 along the b axis. Ni,
Te, O, and Cl atoms are represented by green, purple, red, and yellow circles,
respectively.
Figure 3. 3D network of nickel(II) oxychloride in Ni7(TeO3)6Cl2. Ni, O,
and Cl atoms are represented by green, red, and yellow circles, respectively.
sharing into a novel 2D cluster layer, forming 12-member
polyhedral rings (Figure 2b). Each ring is composed of six
Ni
some extent similar to those of graphite. The intercluster Ni-
1)‚‚‚Ni(1) distance of 2.877(1) Å is the shortest among all
4 3
ClO cubanes; hence, such cubane cluster layers are to
(
Ni‚‚‚Ni separations. The adjacent layer can be viewed as
1
1
generated by moving the former layer by - /
3
a + / b +
3
1
/
3
c. Neighboring layers are interconnected by sharing Ni-
(2) atoms into a 3D network with small long-narrow-shaped
tunnels along the a axis (Figure 3). To the best of our
knowledge, this is the first example of a 3D network based
on cubane clusters. The Te atoms are located at the above
tunnels and connected to the cubanes via Te-O bonds. It
should be pointed out that such stacking of the cluster layers
eliminates the large tunnels along c axis created by 12-
member rings.
Ni
of Ni
5
(SeO
(SeO
3
)
4
Br
2
features a 3D network different from that
previously reported by us. Its 3D structure
12a
5
)
3 4
Cl
2
can be viewed as nickel(II) oxy-bromide layers being bridged
by Se(IV) and additional Ni(II) ions (Figure 4a). The
5 3 4 2
asymmetric unit of Ni (SeO ) Br contains three unique Ni-
(II) ions, two selenite anions, and a bromide anion. Ni(1)
and Ni(3) are in the general position and Ni(2) occupies a
site with -1 symmetry, which is different from that of
Ni
5 3 4 2
(SeO ) Cl which contains five unique Ni(II) ions, four
selenite anions and two chloride anions, all of which are in
1
2a
the general sites. Both Ni(1) and Ni(3) are octahedrally
coordinated by five selenite oxygen atoms and a bromide
anion, whereas Ni(2) is in a distorted octahedral environment
composed of two bromide anions and four oxygen atoms.
The Ni-Br distances (2.676(1)-2.972(2) Å) are significantly
longer than the Ni-O distances (2.007(5)-2.121(5) Å). Each
Figure 2. Two Ni4O3Cl cubane cluster units sharing a Ni2+ ion in
Ni7(TeO3)6Cl2 (a). A 2D layer normal to the c axis based on Ni4O3Cl cubane
cluster units bridged by a pair of oxygen atoms in Ni7(TeO3)6Cl2 (b). Ni,
O, and Cl atoms are represented by green, red, and yellow circles,
respectively.
(
17) (a) Schroter, M.; Lork, E.; News, R. Z. Anorg. Allg. Chem. 2005, 631,
1609. (b) Shaw, R.; Tidmarsh, I. S.; Laye, R. H.; Breeze, B.; Helliwell,
M.; Brechin, E. K.; Heath, S. L.; Murrie, M.; Ochsenbein, S.; G u¨ del,
H.-U.; McInnes, E. J. L. Chem. Commun. 2004, 1418. (c) Murrie,
M.; Biner, D.; Stoeckli-Evans, H.; G u¨ del, H.-U. Chem. Commun. 2003,
2
30. (d) Cromie, S.; F. Launay, F.; McKee, V.; Chem. Commun. 2001,
sharing a Ni(2) atom (Figure 2a). Along the ab plane, the
1918. (e) Brechin, E. K.; Clegg, W.; Murrie, M.; Parsons, S.; Teat, S.
Ni
4
ClO
3
cubanes are interconnected via O(2)‚‚‚O(2) edge
J.; Winpenny, R. E. P. J. Am. Chem. Soc. 1998, 120, 7366.
7596 Inorganic Chemistry, Vol. 45, No. 19, 2006

3 n 2
New Members in the Nin+1(QO ) X Family
Figure 5. View of the structure of Ni11(TeO3)10Cl2 down the b axis. Ni-
6) atoms are drawn as cyan circles. The other Ni atoms are represented by
(
green circles. Te, O, and Cl atoms are shown as pink, red, and yellow circles,
respectively.
each displaying two orientations. Partially occupation for the
nickel and halide sites have been also reported in a number
Figure 4. View of the structure of Ni5(SeO3)4Br2 down the c-axis (a) and
the 2D nickel(II) oxybromide layer in Ni5(SeO3)4Br2 (b). Ni(1)O5Br and
Ni(3)O5Br octahedra are shaded in green and Ni(2)O4Br2 octahedra are
shaded in cyan.
12b
of nonstoichiometric nickel Te(IV) oxyhalides. All of these
compounds can be considered to be derivatives of the Nin+1
QO family where n >10. It is obvious that disorder or
-
(
3 n 2
) X
nonstoichiometry is very likely for those members with
bromide anion is tridentate as the chloride anion in Ni
7 3 6
(TeO ) -
higher n values.
Cl . Bond-valence calculations indicate nickel and selenium
atoms are 2+ and 4+, respectively. The calculated total bond
2
The coordination geometry around the Ni(1) atom is a
distorted octahedron composed of one chloride and five
oxygen atoms. Ni(2), Ni(3), and Ni(4) are octahedrally
coordinated by six tellurite oxygen atoms, whereas Ni(5) and
Ni(6) are in the square pyramidal geometry composed of
valences are 1.92 (Ni(1)), 1.96 (Ni(2)), 1.87 (Ni(3)), 3.96
15
(Se(1)), and 4.03 (Se(2)).
Ni(1)O Br and Ni(3)O Br octahedra are interconnected via
5
5
edge-sharing (O‚‚‚O) into a 1D chain and neighboring chains
are further interconnected via corner-sharing (Br) into a 2D
architecture (Figure 4b). The Ni‚‚‚Ni distances between Ni-
five oxygen atoms (two oxygen atoms of the Ni(6)O
5
polyhedron are only 50% occupied). The Ni-Cl distance of
2.482(2) Å is significantly longer than those of the Ni-O
bonds (1.910(2)-2.366(9) Å). All of Te atoms are in a
(II) ions bridged by a pair of oxygen atoms fall in the range
of 3.034(1)-3.243(1) Å, whereas the Ni‚‚‚Ni separation
between two nickel(II) ions bridged by a pair of bromide
anions is 5.333(1) Å. The above 2D nickel oxybromide layers
are further interconnected by Ni(2) and Se(IV) atoms into a
condensed 3D network (Figure 4a). Ni(2) atoms are edge
sharing (Br-O) with Ni(1) and Ni(3) with Ni‚‚‚Ni separa-
tions of 3.289(1) and 3.415(1) Å. Such a 3D network can
also be viewed as a pillared layered structure in which Ni-
ψ-TeO
Te(IV) occupying the pyramidal site. One oxygen atom of
the Te(5)O group is distorted over two orientations as
mentioned earlier. Te-O distances are in the range of 1.659-
(9)-1.960(4) Å. It should be mentioned that Te(4) also forms
a very weak Te-O bond with a greatly elongated distance
3
trigonal pyramidal geometry with the lone pair of
3
(Te(4)-O(13) 2.445(5) Å). Unlike those in Ni
and Ni (SeO Br , the halide anions in Ni11(TeO
unidentate.
The interconnection of above NiO
7
(TeO
)10Cl
3 2
3
)
6
Cl
are
2
5
3
)
4
2
(
2) and selenite groups act as pillars (Figure 4a). This type
of structure is different from that of Ni (SeO Cl whose
D network can also be considered to be formed by the
interconnection of nickel(II) octahedra via corner, edge, and
5
3
)
4
2
5
Cl, NiO
6
, and NiO
5
3
polyhedra via corner and edge sharing leads to a complex
3D network of nickel oxychloride (Figure 6a). The Te(IV)
atoms are located at the voids of the network and also
connect with the framework through Ni-O-Te bridges
(Figure 5). The Ni‚‚‚Ni separations between two edge-sharing
nickel(II) coordination octahedra are in the range of 2.983-
(1)-3.305(1) Å, and those between corner-sharing ones range
from 3.377(1) to 3.495(1) Å. The 3D nickel oxychloride
network can also be considered as a pillared layered
face sharing with Se4 ions capping the cavities.
The structure of Ni11(TeO features a very compli-
cated 3D network (Figure 5). There are six unique nickel-
II) ions, five tellurite groups and one chloride anion in the
asymmetric unit of Ni11(TeO : all of them occupy the
+
12a
3 2
)10Cl
(
3 2
)10Cl
general sites. The Ni(6) site is only 50% occupied, and the
three tellurite oxygens (O(4), O(5) and O(15)) are disordered,
Inorganic Chemistry, Vol. 45, No. 19, 2006 7597

Jiang et al.
Figure 6. View of the 3D network structure of nickel(II) oxychloride in
Ni11(TeO3)10Cl2 down the b axis (a) and a (002) nickel(II) oxide layer
composed of Ni(2), Ni(3), Ni(4), and Ni(5) atoms (b). The Ni(2), Ni(3),
Ni(4), and Ni(5) polyhedra are shaded in green, whereas those of Ni(1)
and Ni(6) are shaded in blue and cyan, respectively.
architecture based on the nickel oxide layers composed of
Ni(2), Ni(3), Ni(4), and Ni(5) (Figure 6b). Ni(6)O
are attached on both sides of the above nickel oxide layer;
each pair of Ni(1)O Cl octahedra form a dimeric unit via
5
polyhedra
Figure 7. ø vs T and 1/ø vs T plots for Ni7(TeO3)6Cl2 (a), Ni5(SeO3)4Br2
(
b), and Ni11(TeO3)10Cl2 (c). The red line represents the linear fit of data
5
according to the Curie-Weiss Law.
edge sharing (O(14)-O(14)), and they act as pillars between
the two neighboring nickel oxide layers.
c
remains almost unchanged below T (22.5 K) and that the
Magnetic Properties. Ni
Weiss Law in the temperature range of 25-300 K; below
5 K, a large deviation was observed (Figure 7a). The
7
(TeO
3
)
6
Cl
2
obeys the Curie-
molar susceptibility increases slightly with increasing mag-
netic field (see Supporting Information). Ni (SeO Br obeys
the Curie-Weiss Law in the temperature range of 50-300K;
5
)
3 4
2
2
existence of a maximum of molar susceptibility at 22.5 K is
indicative of long-range magnetic ordering at low temper-
below 50 K a significant deviation was observed (Figure 7b).
B
At 300 K, the effective magnetic moment (µeff) is 7.0 µ ,
2
+
ature. At 300 K, the effective magnetic moment (µeff) is 8.40
which corresponds to five isolated Ni (S ) 1, g ) 2.21)
+
µ
B
, which corresponds to seven isolated Ni2 (S ) 1, g )
ions. It decreases continuously upon cooling and reaches 1.37
2
.24) ions. It decreases continuously upon cooling and
reaches 1.85 µ at 2.0 K. A linear fit of the magnetic data in
the range of 100-300 K gave a Weiss constant of -10.4
2) K, indicating significant antiferromagnetic interactions
B
µ at 2.0 K. The linear fit of the magnetic data in the range
of 100-300 K gave a Weiss constant of -74.4 (2) K,
B
indicating very strong antiferromagnetic interactions between
2+
(
Ni ions. It is expected that the magnetic interactions should
be dominated by the magnetic interactions between Ni(II)
polyhedra sharing O-O or O-Br edges (Ni‚‚‚Ni ) 3.034-
between magnetic centers. As mentioned earlier, the Ni‚‚‚
Ni separations between Ni(II) ions within a cubane-like
cluster unit are 3.302(1) and 3.044(1) Å, respectively. The
intercluster Ni(1)‚‚‚Ni(1) distance is 2.877(1) Å. ZFC and
FC measurements indicate that the maximum of susceptibility
3 2
(1)-3.415(1) Å). Ni11(TeO )10Cl obeys the Curie-Weiss
Law in the temperature range of 12-300 K; below 12 K a
significant deviation was observed (Figure 7c). The existence
7598 Inorganic Chemistry, Vol. 45, No. 19, 2006

3 n 2
New Members in the Nin+1(QO ) X Family
Cl, Br, I) are isostructural and feature a layered structure
built up of corner-connected [Ni ] entities. They are
5
17 2
O X
new compounds having a 2D S ) 1 quantum spin system
with antiferromagnetic superexchange interaction. The transi-
tion temperature increases with the interlayer distances: 23,
9
2
8, and 30 K for X ) Cl, Br, and I, respectively. On the
other hand, the corresponding selenite compounds, Ni
SeO (X) Cl, Br), form two types of 3D networks.
Ni (SeO Br is pillar layered, and the packing of Ni (SeO
Cl is more condensed with shorter Ni‚‚‚Ni distances. Both
5
-
(
3 4 2
) X
5
3
)
4
2
5
3 4
) -
2
compounds exhibit strong antiferromagnetic interactions
between nickel(II) ions with Weiss constants of -143(2) and
12a
-
74.4 (2) K for X ) Cl and Br, respectively. The structure
of Ni (TeO Cl features a novel 3D cluster network based
on Ni ClO cubane-like clusters. The structure of Ni11(TeO
Cl features a condensed 3D network based on NiO Cl, NiO
and NiO polyhedra interconnected via corner and edge
7
)
3 6
2
Figure 8. TGA curves for Ni7(TeO3)6Cl2, Ni5(SeO3)4Br2, and Ni11(TeO3)10-
Cl2.
4
3
3 10
) -
6
,
2
5
5
of a maximum of molar susceptibility at 12.0 K is indicative
of long-range magnetic ordering at low temperature. At 300
sharing, as well as with O-Te-O bridges. Several tellurite
oxygen atoms are disordered. The three nonstoichiometric
K, the effective magnetic moment (µeff) is 9.9 µ
B
, which
compounds, [Ni30Te32
O
90Br2.64][Ni3.39Br12.14], [Ni30Te32
90
O -
corresponds to eleven isolated Ni2 (S ) 1, g ) 2.11) ions.
+
Cl2.69][Ni3.10Cl11.52], and [Ni30Te32O90Cl2.67][Ni4.48Cl15.78] are
It decreases continuously upon cooling and reaches 1.73 µ
at 2.0 K. The linear fit of the magnetic data in the range of
00-300 K gave Weiss constant of -63.1 (2) K, indicating
B
formed at relatively lower temperatures (above 800 K). All
three compounds contain covalently bonded, cationic entities
1
5+
of approximate composition [Ni30Te32
90 3
O X ]
(X ) Br, Cl),
2+
very strong antiferromagnetic interactions between Ni ions.
It is expected that the magnetic interactions should be
dominated by the magnetic interactions between edge- or
corner-sharing Ni(II) polyhedra (Ni‚‚‚Ni ) 2.983(1)-3.495-
which form an infinite porous network enclosing large
12b
cavities that contain different guests of anionic clusters.
Conclusion
(1) Å).
TGA Analysis. TGA analyses under an oxygen atmo-
In summary, we have prepared three new compounds in
sphere indicate that Ni
7
(TeO
3
)
6
Cl
2
, Ni
5
(SeO
3
)
4
Br
2
, and
the family of Nin+1(QO ) X (Q ) Te, Se; X ) halide). Their
3 n
2
Ni11(TeO are stable up to 700, 500, and 750 °C,
3
)
10Cl
2
structures are closely related to the n value, as well as to the
Q and X elements. When n is small, the structures are
ordered, and nonstoichiometric compounds will be isolated
if n is larger (i.e., n > 10). The structures of selenite
compounds are usually different from those of the corre-
sponding tellurite ones. It is very interesting that the structure
respectively (Figure 8). Then, all of them exhibit one main
step of weight loss (in the temperature ranges of 700-1100,
5
00-750, and 800-1050 °C for Ni
Br , and Ni11(TeO , respectively), which corresponds
to the release of QO and halogen. The final residues are
7 3 6 2 5 3 4
(TeO ) Cl , Ni (SeO ) -
2
3 2
)10Cl
2
found to be mainly NiO on the basis of XRD powder studies.
The observed total weight losses at 1300 °C are 61.3 and
of Ni
7
(TeO )
3 6
Cl
2
features a novel 3D cluster network based
on Ni
4
ClO
3
cubane-like clusters. Such an extended open
6
6.0% for Ni
These values are very close to the calculated ones (61.1 and
6.8%, respectively). For Ni (TeO Cl , the observed total
5 3 4 2 3 2
(SeO ) Br and Ni11(TeO )10Cl , respectively.
framework based on cubane clusters provides an important
addition to the family of cubane compounds. Future efforts
will be devoted to the exploration of other missing members
in this family.
6
7
3
)
6
2
weight loss of 56.2% is significantly smaller than the
calculated value of 65.9%; hence, decomposition is incom-
plete at 1300 °C, as also indicated by the slope of the TGA
Acknowledgment. This work was supported by National
curves. Ni
Br , which may be the result of the Ni-Br bond being
weaker than the Ni-Cl bond. The higher thermal stability
of Ni (TeO Cl than that of Ni11(TeO could be
attributed to the fact that the chloride ion bridges with three
nickel(II) ions in Ni (TeO Cl whereas it forms one Ni-
Cl bond in Ni11(TeO
It is interesting to compare the structures and physical
properties of compounds in this family. Ni (TeO (X)
7
(TeO
3
)
6
Cl
2
is thermally more stable than Ni
5
(SeO
3
)
4
-
Natural Science Foundation of China (No. 20573113 and
2
2
0521101) and NSF of Fujian Province (No. E0420003).
Supporting Information Available: X-ray crystallographic files
7
3
)
6
2
3 2
)10Cl
in CIF format and simulated and experimental XRD powder patterns
for Ni (TeO Cl , Ni (SeO Br , Ni11(TeO , and NiO. This
7
3
)
6
2
5
3
)
4
2
3 2
)10Cl
7
3
)
6
2
material is available free of charge via the Internet at http://
pubs.acs.org.
3 2
)10Cl .
5
3
)
4
X
2
IC060356X
Inorganic Chemistry, Vol. 45, No. 19, 2006 7599