Ž.
Inorganic Chemistry Communications 3 2000 379–382
www.elsevier.nlrlocaterinoche
Hydrothermal synthesis and crystal structure of a novel one-dimensional
ž/wx
tritungstate: C H N W O
2102 310
Bangbo Yan, Yan Xu
)
, Ngoh K. Goh, Lian S. Chia
DiÕision of Chemistry, School of Science, Nanyang Technological UniÕersity, 469 Bukit Timah Road, Singapore 259756, Singapore
Received 21 February 2000
Abstract
Ž.wx
Ethylenediammonium tritungstate, C H N W O , has been hydrothermally synthesized and structurally characterized. The
2102 310
structure of title compound consists of infinite chains running parallel to the b axis, that are made up of distorted WO octahedra linked
6
through shared corners and edges. The ethylenediammonium ions occupy interstrand region providing space-filling and charge-compensa-
tion to anionic tritungstate matrix. q 2000 Elsevier Science S.A. All rights reserved.
Keywords: Hydrothermal synthesis; Tungstate; Crystal structures; Polyanions compounds
1. Introduction
Recent years have witnessed a considerable achieve-
ment in the crystal engineering of novel organicrinorganic
hybrid materials due to their applications in catalysis,
sorption, energy storage, molecular electronics, optical ma-
wx
terials and ceramics 1–4 . A promising synthetic route
takes advantage of a low-temperature soft approach, hy-
drothermal method, and the structure-directing function of
organoamines. Recent developments in this area have

2
.
1.11 mol in the mole ratio 1:3.5:555 was heated at 1908C
and autogenous pressure conditions for 62 h. Needle-shape
Ž.wx
colorless crystals of C H N W O 1 were isolated
2102 310
Ž
and recovered yield: 0.37 g, 48% based on Na WO P
24
. w
2H O . The CHN elemental analysis of 1 gave observed
2
Ž.x Ž. Ž.
calculated in wt% C, 3.02 3.10 ; H, 1.29 1.30 ;N,
Ž.
3.61 3.62 which confirmed an empirical formula of
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C H N W O for 1.
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2.2. Thermal analysis
Ž.
Thermogravimetric analysis TGA was performed us-
ing a Sateram TG-DTGrDSC thermogravimetric analyzer
on powder specimen of 1 at a heating rate of 58C min
y1
in
N stream.
2
2.3. Infrared studies

wx
using the SHELXTL-97 package 14 . Non-hydrogen atoms
were refined with anisotropic temperature factors. Hydro-
gen atoms were placed at calculated positions and refined
using the riding model of SHELXTL program with a fixed
˚
C–H bond length of 0.97 A and a N–H bond length of
˚
0.90 A. Final refinement was based on 1917 reflections
w Ž.x Ž.
I)2s I for 134 parameters and converged to RwR
12
Ž.
s0.0281 0.0634 . Atomic coordinates, bond lengths and
angles and thermal parameters are presented in supplemen-
tary crystallographic data.
3. Results and Discussion
The title compound is initially isolated from the hy-
drothermal reaction of WO , en, NaOH and H O in
32
polycrystalline form. Replacement of NaOH with LiOH
produces the same crystalline phase with similar product
quality and morphology. The reaction is then rationalized
by using Na WO as W
6q
source instead of WO that
24 3
gives rise to monophasic product of compound 1 contain-
ing large single crystals. TGA shows a weight loss of ca.
7.9% in the temperature range 300–4808C indicating the

6 20 2 10 2 3 10
()
B. Yan, et al.rInorganic Chemistry Communications 3 2000 379–382 381
Fig. 3. Comparison of the one-dimensional chains adopted by the anions
Ž.Ž .wxŽ.Ž .wxwxŽ.
in: a C H N W O 1; b C H N Mo O 15 ; and c an
2102 310 2102 310
wxwx
open framework solid K W O 16 .
2310
Ž
X
.
clinic one-dimensional solid WO 2,2 -bipy , are summa-
3
rized in a footnote
1
.
Ž.wx
The structure of C H N W O 1 consists of infi-
2102 310
nite puckered chains of W O
4y
separated by interstrand
620
2q
Ž
2q
.
ethylenediammonium ions, C H N enH , as shown

W 3 show one short-three intermediate-two long bond
length pattern. enH
2q
cations occupy interstrand regions
2
of the W O
4y
chains and exhibit strong hydrogen bond
620
network to terminal and bridging oxo groups of the anionic
chains of W O
4y
.
620
1
Ž
X
.
Crystal data for the monoclinic WO 2,2 -bipy phase. chemical
3
formula, C H N O W, M s 388.03, monoclinic space group Cc with
10 823 w
˚
Ž. Ž. Ž .
unit cell dimensions as14.323 3 , bs9.608 2 , cs7.2922 15 A,
b
s
˚
3 y3
Ž. Ž.

wxwx
2y
phase, K W O 16 , in which W O anions are orga-
2310 310
nized into a three dimensional covalent framework struc-
Ž
ture through corner- and edge-shared WO octahedra Fig.
6
Ž
3c .
Ž.wx
The one-dimensional tritungstate C H N W O 1
2102 310
reported in this paper provides novel examples to the
hydrothermal cooperate assembly of tungsten oxide com-
posite materials. The strong solvating effect of water in
combination with the structure-directing role of
organoamines under the hydrothermal autogenous condi-
tions evidently provides the conducive environment for the
rearrangement of tungstenoxoanions, and construction of
novel solid architecture from molecular precursors. It opens
up the possibility of applying this method for assembling
other low-dimensional and open-framework tungsten oxide
materials with potentially interesting or useful properties.
4. Conclusion
Ž.
The successful synthesis of compound C H N
2102
wx
WO 1 illustrates the power of hydrothermal synthesis

wx
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