ARTICLE
DOI: 10.1002/zaac.200801330
Solvothermal Synthesis, Crystal Structure and Properties of the
First Organic-templated Holmium Sulfate [C N H ] [Ho (SO ) ·2H O]
2
2
10 3
2
4 6
2
Wanli Zhou,[a,b,c] Qi Chen, Dunru Zhu, and Yan Xu*
[c]
[a]
[a,c]
Keywords: Solvothermal synthesis; Template synthesis; Organometallic compounds; Holmium sulfate; Lanthanides
Abstract. The first organic amine-templated holmium sulfate
[Ho (SO ·2H O] (1) has been synthesized solvo-
thermally and has been structurally characterized by single-crystal
X-ray diffraction studies, IR spectroscopic, thermogravimetric
analyses of compound 1 showed a novel inorganic layer con-
structed from the zigzag and helical [ϪHoϪOϪSϪOϪ] chains,
groups to form
[C
2
N
2
H
10
]
3
2
4
)
6
2
n
2
Ϫ
both of the chains are connected by μ-2 SO
4
10-membered rings. The solvent plays an important role during the
(TG) and inductivity coupled plasma (ICP) measurements. Crystal
formation of 1.
Introduction
[La
2
(H
2
O)
2
(C
2
H
10
N
2
)(SO
4
)
6
]·4H
2
O, [La
2
(H
2
O)
2 4 12 2
(C H N )-
(SO ) ] [18], [La (SO ) ][C N H ] [19] [NC H ] [(UO ) -
4
4
2
4 4
3
2
12
4
12 2
2 6
Over the past years, solid state materials with transition
metals have been studied intensively due to their wide appli-
cations such as precursors for oxides and catalysis [1Ϫ3],
their ion exchanging [4, 5] and their magnetic properties
(
H O) (SO ) [20] and [Sm(en)(OH)(SO )] [21]. But unfor-
2
2
4 7
4
tunately, the compounds with organic ammonium tem-
plated holmium sulfate are much less developed. Until now,
no organic templated holmium sulfates have been reported.
More recently, solid-state inorganic materials with helical
chains or pores have aroused interest because of their desir-
able applications in enantiotopic selective separation and
catalysis. Therefore, it was of great interest to synthesize the
organic-templated holmium sulfates with helical chains, in
order to explore their properties. We have tried to synthesize
the organic templated holmium sulfate hydrothermally, but
the final product did not include the organic amine. In this
work, we used isopropyl alcohol as solvent and the first
ethylene diammonium templated holmium sulfate
[
6]. Solid inorganic materials, mostly with phosphates and
silicates, have been well reported. Nowadays, great efforts
are made to obtain new inorganic framework materials with
different compositions and structures. Sulfate ions can ef-
fectively be used to construct solid state materials with new
topological structures and interesting properties [7Ϫ9].
Compared with other transition metals such as iron, cobalt
and vanadium, the rare-earth elements not only adopt more
flexible coordination numbers (from 8 to 12), in addition to
it, the bond lengths and angles of solid-state compounds
with rare-earth elements have a greater variety. Therefore,
it is possible to form inorganic materials with novel topo-
logical frameworks [10Ϫ14]. One of the strategies used in
the preparations of solid state sulfate materials is to employ
a special organic amine as structure-directing agent (SDA)
by using the hydrothermal synthesis method. Successful ex-
[
C N H ] [Ho (SO ) ·2H O] (1) with a novel structure
2 2 10 3 2 4 6 2
was successfully prepared. Structural analysis showed that
the layered inorganic framework in 1 is constructed from
zigzag and helical [ϪHoϪOϪSϪOϪ] chains.
n
amples include the formation of [(C H N )La(SO ) ]·H O Experimental Section
4
16
3
4 3
2
[
15Ϫ17],
[La (H O) (C H N ) (SO ) ]·5H O
[17],
2
2
4
6
14 2 2
4 5
2
All chemicals purchased were of reagent grade and used without
further purification. The crystalline products were characterized by
thermal analyses, single crystal X-ray diffraction and IR spec-
troscopy. The elemental analysis for Ho was performed with a Lee-
man inductivity coupled plasma (ICP) spectrometer, whereas the
C, H, and N analyses were performed with a Perkin-Elemer 2400
elemental analyzer. IR spectra were recorded with a Nicolet Impact
*
Prof. Dr. Y. Xu
E-Mail: yanxu@njut.edu.cn
[a] College of Chemistry and Chemical Engineering
State Key Laboratory of Materials-oriented Chemical
Engineering
Nanjing University of Technology
Nanjing 210009, P. R. China
410 FTIR spectrometer using KBr pellets. Thermogravimetric
analyses were carried out in nitrogen atmosphere with a Diamond
thermogravimetric analyzer from 50 °C to 1100 °C at a heating rate
of 10 °C /min.
[
[
b] Department of Chemistry
Tonghua Normal University
Tonghua 134002, P. R. China
c] Institute of Functionalized Chemistry Materials
Faculty of Chemistry and Chemical Engineering
Liaoning Normal University
Compound 1 was synthesized under solvothermal conditions.
2 3
Ho O (0.2115 g) was dissolved in a mixture of isopropyl alcohol
Dalian Liaoning, 116029, P.R. China
(5.1633 g), ethylenediamine (en) (0.4508 g) and sulfuric acid
572
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 635, 572Ϫ576
Zhou, Wanli
