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c Indian Academy of Sciences.
Abstract. The structure of plate/shelf like disodium ditungstate (Na2 W2 O7 ) synthesized by new method in the pro-
cess of ultrasonic spray pyrolysis using acidified aqueous solutions of tungsten (VI) oxide clusters as a precursor was
refined down to the R-factor of 8·9%. X-ray diffraction analysis undoubtedly confirmed formation of orthorhom-
bic Na2 W2 O7 and refinement of the diffraction data showed that Na2 W2 O7 powder belongs to the base-centred
orthorhombic type of structure with 64 space group, Cmca. The structure of Na2 W2 O7 can be described as infinite
chains formed from tetrahedral (WO4 ) and octahedral (WO6 ) building units joined together. It was found that the
basic units of the precursor complexes exist in the structure of Na2 W2 O7 . Scanning electron microscopy confirmed
formation of plate/shelf like Na2 W2 O7 particles with an average thickness of about 1·2 μm.
Keywords. Inorganic materials; disodium ditungstate; crystal structure; scanning electron microscopy; X-ray
diffraction.
149
150 Dragana J Jovanović et al
Table 1. Structure of Na2 W2 O7 (space group: Cmca. Unit cell dimensions: a = 7·22192(11) Å, b =
11·91559(17) Å, c = 14·74755(23) Å. Cell content: 8 Na2 W2 O7 ).
Atom Position X(σ (X)) Y(σ (Y)) Z(σ (Z)) B(σ (B))
Octahedron <O–W–O
W–O 5 – 1 – 5 77·1(3)◦
1 – 5 = 1 – 5 2·428(9) Å 5–1–6 92·5(4)◦
1 – 6 = 1 – 6 1·751(10) Å 5 – 1 – 6 166·9(5)◦
1 – 8 = 1 – 8 1·876(4) Å 5–1–8 80·6(5)◦
5 – 1 – 8 79·9(5)◦
O – O mean 2·96 Å 6 – 1 – 6 98·9(4)◦
6–1–8 90·7(6)◦ Figure 3. Octahedron as a structural unit of precursor complexes
6 – 1 – 8 105·6(7)◦ (A) and schematic presentation of structure of Na2 W2 O7 solid (B).
8 – 1 – 8 155·0(6)◦
Tetrahedron <O–W–O
W–O 5 – 2 – 5 118·9(4)◦ The W (1) — O distances in the disodium ditungstate
2 – 5 = 2 – 5 1·818(10) Å 5–2–7 113·7(3)◦ within each WO6 octahedron were found to be 2·428, 1·751
2–7 1·705(16) Å 5–2–9 106·6(4)◦ and 1·876 Å. For a tetrahedron, the W (2) — O distances
2–9 1·91(2) Å 7–2–9 93·7(9)◦ were found to be 1·818, 1·705 and 1·910 Å (see table 2).
O – O mean 2·93 Å The obtained values are in reasonable agreement with data
reported by Okada et al (1975) (2·252, 1·725 and 1·921 Å
Na – O (octahedral arrangement); Na(3) – O mean 2·48 Å; Na(4) – for W (1) — O and 1·807, 1·759 and 1·762 Å for W (2) —
O mean 2·41 Å O, respectively), although as can be seen a small deviation in
interatomic distances exist. The slight differences in values
for bond angles are also present.
The WO6 octahedral building unit of the precursor com-
plexes is shown in figure 3A, while the structure of Na2 W2 O7
is shown in figure 3B. The structure of Na2 W2 O7 can be
described as infinite chains formed from WO6 octahedra
sharing corners within the chains (Baes and Mesmer 1976).
WO4 tetrahedra are bridging adjacent WO6 units.
It is clear that geometrically the same building units (octa-
hedrons) exist in the precursor clusters and synthesized solid.
Of course, there is a difference in bond lengths. However,
Na2 W2 O7 also contains tetrahedral units. During the course
of synthesis at elevated temperature termination of the weak
octahedral bonds in precursor species (dashed lines in figure 3A)
may lead to the formation of tetrahedral building units.
Acknowledgement