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ORIGINAL PAPER
Amor Haddad
Introduction
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1134 M. Ayed et al.
POMs, such as Keggin [10–13], Wells-Dawson [14, 15], Silverton [16] and
Lindquist [17] type polyoxoanions serve as the building blocks have been
successfully reported. However, in contrast, the role of Strandberg-type polyoxoa-
nions as the inorganic building units to construct such extended frameworks has not
been so extensively studied. Hence, our current synthetic strategy is to acquire new
extended compounds constructed from Strandberg-type polyoxoanions in the
presence of alkali metal cations. Until very recently, the structures of the Strandberg
type were mainly known by the phosphate groups [18–21]. Analogous structures
have been found are similar for [Se2Mo5O21]4- [22] and [Se2Mo5O21]4- [23–27]. In
the present paper, we successfully prepared the three dimensional (3D) structure
based on Strandberg-type polyoxoanions. The compound is built up of
[Se2Mo5O21]4- clusters as the structural motif covalently which are linked through
K?, NH4? ions and water molecules, hydrogen-bonding interactions form the 3D
supramolecular structure.
Experimental
All chemicals were purchased commercially and used without any further purification.
Qualitative analysis by scanning electron microscopy (SEM) probe was performed
using an apparatus of the type JOEL JSM-5400 (JOEL Ltd, Tokyo, Japan). Infrared
spectrum was recorded at a room temperature on a Nicolet 470 FTIR spectrophotometer
as KBr pellets in the 4,000–400 cm-1 region. UV–Vis spectrum was measured using a
Perkin-Elmer Lambda 19 spectrophotometer in the 180–800 nm range. The TGA-DTA
thermograms were obtained with 4.99 mg. Samples were placed in an open platinum
crucible and heated, under air, from room temperature to 450 °C with 3 °C/min heating
rate; an empty crucible was used as reference.
Chemical Preparation
A suitable transparent single crystal with dimensions 0.2 9 0.1 9 0.1 mm3 was
selected for the structure determination and refinement. The X-ray data collection
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Crystal Structure 1135
was carried out on Enraf-Nonius CAD-4 four circle diffractometer using with
Mo Ka radiation (k = 0.71069 Å). The crystal structure was solved by direct
method using SHELXS-97 [28]. Full-matrix F2 least-squares refinement and
subsequent Fourier synthesis procedures were performed by SHELXL-97 [29]
program included in the WINGX software package [30]. The molybdenum,
selenium and potassium atoms were located and the remaining oxygen atoms were
found from successive difference Fourier maps. Refinement of all atoms, except of
nitrogen atom led to R = 0.053 and wR = 0.134. Moreover the K4–O distances as
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1136 M. Ayed et al.
well as the displacement parameters led us to consider that the position is occupied
simultaneously by potassium K4 and nitrogen. The refinement of the occupancies
factors was then performed leading to 69 and 31 % for N and K4, respectively, and
to an improvement of the agreement factors: R = 0.034 and wR = 0.083; the
corresponding formula is thus K3.31(NH4)0.69[Se2Mo5O21]2H2O. The positions of
the hydrogen atoms attached to oxygen water and nitrogen were determined from a
difference Fourier map and were refined isotropically. The crystal data and structure
solution and refinement details are given in Table 1. The structural figures were
carried out with Diamond 2.1 supplied by Crystal Impact [31].
The asymmetric unit of the crystal structure consists of 3.31 K? cations, 0.69 NH4?
cations two water molecules and one [Se2Mo5O21]4- cluster anion. A projection of
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Crystal Structure 1137
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1138 M. Ayed et al.
Fig. 4 A packing view of compound along the a axis, showing the arrangement of the [Se2Mo5O21]4-
clusters, potassium and ammonium cations and the lattice water molecules in the crystal structure. The
dashed lines denote the hydrogen interactions
The calculated average values of the distortion indices [40] corresponding to the
different angles and distances in SeO3 pyramids and MoO6 octahedra, show that
these groups exhibit a compact assembly of oxygen atoms in which selenium atoms
are slightly displaced from the center of gravity then molybdenum atoms
[DI(OSeO) = 0.007–0.010; DI(SeO) = 0.010–0.016; DI(OMoO) = 0.20–0.21
and DI(MoO) = 0.093–0.117].
BVS calculations [41] revealed that all the molybdenum atoms have valence
sums ranging from 5.858 to 5.9319, with an average value of 5.908, close to the
ideal value of 6 for MoVI. The calculated average value of selenium (?IV), oxygen
(-II) and potassium (?I) atoms are, respectively, 4.060, 1.970 and 0.964.
The K? ions occupy four crystallographically distinct sites. As often occurs for
alkali ions, the environment of this site consists of a wide range of cation–oxygen
distances, thus it is very difficult to distinguish between bonding and non-bonding
interactions. A simple criterion is to consider all distances which are shorter than the
shortest distance between K? and its nearest cation. Assuming this criterion, the K2
and K3 are linked to nine oxygen atom with K1–O ranging from 2.702(6) to
3.209(5) Å and K3–O ranging from 2.712(5) to 3.325(5) Å with an average value of
2.940(5) and 2.977(5) Å respectively. The environment of K1 consists of eight
atoms oxygen with K1–O distances scattering from 2.688(6) to 3.005(5) Å. The K4
and N atoms are statistically distributed and have partial occupancies of 0.31 and
0.69 respectively. K4 is surrounded by seven oxygen atoms with an average value of
2.991(4) Å (Fig. 3).
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Crystal Structure 1139
Fig. 5 The two curves corresponding to the DTA and TGA analysis in argon of
K3.31(NH4)0.69[Se2Mo5O21]2H2O
The arrangement of the [Se2Mo5O21]4- clusters, K? cations NH4? and the lattice
water molecules in the crystal structure along the a axis is displayed in Fig. 4, which
shows extensive hydrogen bonding. As listed in Table 2, OW–HO, OW–HOW,
N–HN–O and N–HN–OW hydrogen bonds between the solvent water molecules and the
clusters have interatomic OO distances ranging from 2.888 to 3.160 Å and NO
distances varying between 2.845 and 3.082 Å. These hydrogen bonds hold the
components together into a 3D network and make the crystal structure of 1 more stable.
Thermal Analysis
The two curves corresponding to the DTA and TGA analysis in argon of
K3.31(NH4)0.69[Se2Mo5O21]2H2O are given in Fig. 5. The DTA curve shows that
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1140 M. Ayed et al.
Spectroscopic Characterization
Vibrational Spectrum
As shown in Fig. 6, the strong band at 905 cm-1 in the IR spectrum of the tittle
compound is due to the stretching vibration of the Mo–Ot groups of [Se2Mo5O21]4-
clusters, those at 851–835, 634 cm-1 can be attributed to m (Mo–(l-O)) and m (Mo–
O–Mo). The bands around 758 and 455 cm-1 can be assigned to the vibrations of
the selenite groups. The compound also possesses an intense band at 1625, 1455 and
1385 cm-1 are attributed to the bending vibration of water and ammonium
molecules. The symmetric and asymmetric O–H and N–H stretchings appear
respectively around 3388, 3507 and 3220 cm-1.
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Crystal Structure 1141
charge transfers from terminal oxygen to molybdenum center, where electrons are
promoted from the low-energy electronic states, mainly comprised of oxygen 2p
orbitals, to the high-energy states, which are mainly comprised of metal d orbitals
[44, 45].
Conclusion
It is important to remark that few Strandberg-type anions with selenite groups have
been previously described. In this paper we described the chemical preparation and
crystal structure for a new selenomolybdate K3.31(NH4)0.69[Se2Mo5O21]2H2O. This
compound crystallizes in the monoclinic system, space group P21/n and the main
geometrical feature of this structure is the existence of [Se2Mo5O21]4- anionic
clusters, these groups are linked via ionic bonds or hydrogen bonds to form 3D
frameworks.
Supplementary Material
CCDC 849017 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [Or from the Cambridge Crystallographic Data Centre (CCDC),
12 Union Road, Cambridge CB2 1EZ, UK; Fax: ?44(0)1223-336033; email:
deposit@ccdc.cam.ac.uk].
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1142 M. Ayed et al.
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