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The (isomorphous) structures of Bi14WO24, tetradecabismuth tungsten tetracosaoxide, and Bi14MoO24, tetradecabismuth molybdenum tetracosaoxide, have been solved and refined using neutron powder diffraction data in the space group I4/m. The metal-atom array is fully ordered in terms of composition, and in terms of atomic positions deviates only slightly from a fluorite-type δ-Bi2O3-related parent structure. Three independent O-atom sites (accounting for 70 out of 78 O atoms in the unit cell) are also very close to fluorite-type parent positions. The remaining two O-atom sites, which coordinate W, exhibit partial occupancies and displacive disorder, neither of which could be better modelled by lowering of symmetry. The W site is coordinated by four O atoms in highly distorted tetrahedral coordination, the tetrahedron necessarily being orientationally disordered on that site. Nonetheless, the structure appears to be chemically reasonable.

Supporting information

cif

Crystallographic Information File (CIF)
Contains datablocks global, W, Mo

rtv

Rietveld powder data file (CIF format)
Contains datablock W

rtv

Rietveld powder data file (CIF format)
Contains datablock Mo

Computing details top

For both compounds, program(s) used to refine structure: GSAS.

(W) bismuth tungsten oxide top
Crystal data top
Bi14WO24Neutron radiation
Mr = 3493.57T = 293 K
Tetragonal, I4/mParticle morphology: plate
a = 8.71083 (4) Åyellow
c = 17.32202 (10) Åcylinder, 30 × 15 mm
V = 1314.37 (1) Å3Specimen preparation: Prepared at 1103 K and 101.3 kPa
Z = 2
Data collection top
6Li-doped glass scintillar
diffractometer
Specimen mounting: vanadium can
Radiation source: spallation
Refinement top
Rp = 0.059Profile function: exponential pseudo-Voigt convolution Von Dreele 1990
Rwp = 0.06156 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Bi(1)0.4396 (2)0.2132 (2)0.00.0175 (5)*
Bi(2)0.39520 (17)0.2004 (2)0.32999 (8)0.0145 (3)*
Bi(3)0.00.00.34328 (18)0.0313 (10)*
W(1)0.00.00.00.040 (2)*
O(1)0.00.00.1160 (5)0.03937.5
O(2)0.00.50.1213 (2)0.0241 (7)*
O(3)0.1937 (9)0.0173 (14)0.00.19359.75
O(4)0.6258 (3)0.3194 (2)0.07821 (14)0.0228 (5)*
O(5)0.2541 (3)0.0741 (2)0.25610 (12)0.0233 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O(1)0.050 (4)0.050 (4)0.017 (5)0.00.00.0
O(3)0.042 (5)0.309 (15)0.230 (12)0.047 (6)0.00.0
(Mo) bismuth tungsten oxide top
Crystal data top
Bi14MoO24Neutron radiation
Mr = 3405.66T = 293 K
Tetragonal, I4/mParticle morphology: plate
a = 8.70839 (4) Åyellow
c = 17.31634 (14) Åcylinder, 25 × 8 mm
V = 1313.20 (1) Å3Specimen preparation: Prepared at 1073 K and 101.3 kPa
Z = 2
Data collection top
3He gas and ZnS scintillation counters
diffractometer
Specimen mounting: vanadium can
Radiation source: spallation
Refinement top
Rp = 0.039Profile function: exponential pseudo-Voigt convolution Von Dreele 1990
Rwp = 0.02556 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Bi(1)0.44022 (13)0.21306 (15)0.00.0097 (2)*
Bi(2)0.39542 (11)0.20048 (13)0.32975 (5)0.00794 (11)*
Bi(3)0.00.00.34376 (13)0.0159 (4)*
Mo(1)0.00.00.00.0495 (15)*
O(1)0.00.00.1189 (4)0.02643.5
O(2)0.00.50.12306 (16)0.0176 (4)*
O(3)0.1929 (7)0.0106 (16)0.00.19787.75
O(4)0.62344 (18)0.32173 (17)0.07786 (10)0.0157 (3)*
O(5)0.25313 (15)0.07313 (15)0.25669 (8)0.0108 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O(1)0.034 (2)0.034 (2)0.012 (3)0.00.00.0
O(3)0.048 (5)0.389 (15)0.156 (8)0.024 (7)0.00.0
Structural parameters for the final Rietveld-refined structure of Bi14WO24 top
Space group I4/m (No. 87), a = 8.71083 (4), c = 17.32202 (10)Å; Ueq=1/3ΣiΣjUijai*bj*ai.aj (A°2).
x(a)y(b)z(c)Fraction100Uiso/eq*
Bi(1).43964 (20).21318 (24).01.01.75 (5)
Bi(2).39520 (17).20044 (20).32999 (8)1.01.451 (29)
Bi(3).0.0.34328 (18)1.03.13 (10)
W(1).0.0.01.03.98 (24)
O(1).0.0.1160 (5).53.937
O(2).0.5.12133 (23)1.02.41 (7)
O(3).1937 (9).0173 (14).0.7519.359
O(4).62577 (26).31937 (24).07821 (14)1.02.28 (5)
O(5).25407 (25).07408 (22).25610 (12)1.02.33 (5)
*100U11100U22100U33100U12100U13,U23
O(1)5.0 (4)5.0 (4)1.7 (5)00
O(3)4.2 (5)30.9 (15)23.0 (12)-4.7 (6)0
Structural parameters for the final Rietveld-refined structure of Bi14MoO24 top
Space group I4/m (No. 87), a = 8.70839 (4), c = 17.31634 (14)Å; Ueq=1/3ΣiΣjUijai*bj*ai.aj (A°2).
x(a)y(b)z(c)Fraction100Uiso/eq*
Bi(1).44022 (13).21306 (15).01.0.966 (23)
Bi(2).39542 (11).20048 (13).32975 (5)1.0.794 (11)
Bi(3).0.0.34376 (13)1.01.59 (4)
Mo(1).0.0.01.04.95 (15)
O(1).0.0.1189 (4).52.643
O(2).0.5.12306 (16)1.01.76 (4)
O(3).1929 (7)-.0106 (16).0.7519.787
O(4).62344 (18).32173 (17).07786 (10)1.01.571 (27)
O(5).25313 (15).07313 (15).25669 (8)1.01.083 (21)
*100U11100U22100U33100U12100U13,U23
O(1)3.35 (21)3.35 (21)1.23 (27)00
O(3)4.8 (5)38.9 (15)15.6 (8)2.4 (7)0
 
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