Acta Cryst.(2002). E58, i119±i120 DOI: 10.1107/S1600536802020950 Paweø E. Tomaszewskiet al. CsAl(MoO4)2
i119
inorganic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
CsAl(MoO4)2
Paweø E. Tomaszewski,* Adam Pietraszko, Mirosøaw MaÎczka and Jerzy Hanuza²
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P. Nr 1410, 50-950 Wrocøaw 2, Poland
² Present address: Department of Bioorganic Chemistry, Faculty of Engineering and Economics, Academy of Economics, Wrocøaw, Poland.
Correspondence e-mail: petomasz@int.pan.wroc.pl
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(Al±O) = 0.002 AÊ
Rfactor = 0.015
wRfactor = 0.043
Data-to-parameter ratio = 13.8
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, caesium aluminium dimolybdate(VI), CsAl(MoO4)2, belongs to the glaserite type family of double molybdates and tungstates. The crystal structure was studied byin situX-ray single-crystal and powder diffraction at room temperature. The temperature dependence of the lattice parameters at low temperatures is also presented.
Comment
Double molybdates and tungstates with the general formula MIMIII(MVIO
4)2, whereMI= alkali metal,MIII= Al, In, Cr, Bi, Fe, RE (rare earths), andMVI= Mo or W, exhibit interesting structural and physicochemical properties, and are used as acousto-optic ®lters, second-harmonic generators and laser crystals. They exhibit ferroelectric, ferroelastic or even ferro-magnetic properties and have been extensively studied for the last 40 years. CsAl(MoO4)2belongs to this family.
The room temperature phase of CsAl(MoO4)2was re®ned in the trigonal space groupP3m1 (No. 164), as for many other double molybdates and tungstates of the glaserite structure (Efremov et al., 1971, Klevtsov et al., 1972, Klevtsova & Klevtsov, 1970, Klevtsovaet al., 1995, Liiet al., 1989, Toma-szewski et al. 2002). The structure consists of [AlMo2O8ÿ]n layers perpendicular to the trigonalc-axis, with the caesium cations between the layers. Each layer is built up from MoO4 tetrahedra and AlO6octahedra; each octahedron shares its six corners with six MoO4tetrahedra.
The additional low-temperature experiments do not show any changes in the powder-diffraction diagram, thus indicating no symmetry changes and the absence of a phase transition. The low-temperature lattice parameters are as follows: a = 5.525 (2), c = 7.966 (3) AÊ at 110 K and a = 5.513 (3), c = 7.954 (4) AÊ at 40 K. The lattice parameterachanges linearly with temperature, while the temperature dependence of the parametercis quadratic.
Received 11 November 2002 Accepted 15 November 2002 Online 22 November 2002
Figure 1
Experimental
Single crystals of CsAl(MoO4)2 were grown by cooling a molten
mixture containing CsAl(MoO4)2and solvent (Cs2Mo2O7) in a 1:1
ratio. The cooling rate was 2 K hÿ1. The resulting single crystals were
colourless and of good optical quality.
Crystal data
CsAl(MoO4)2 Mr= 479.77 Trigonal,P3m1 a= 5.551 (1) AÊ c= 8.037 (2) AÊ V= 214.47 (8) AÊ3 Z= 1
Dx= 3.715 Mg mÿ3
MoKradiation Cell parameters from all
re¯ections = 4.2±29.0 = 7.21 mmÿ1 T= 293 (2) K Plate, colourless 0.200.200.10 mm
Data collection
KUMA Diffraction KM-4 CCD diffractometer
!scans
Absorption correction: numerical (XEMP; Sheldrick, 1991) Tmin= 0.068,Tmax= 0.155 2447 measured re¯ections
249 independent re¯ections 248 re¯ections withI> 2(I) Rint= 0.045
max= 29.0 h=ÿ7!5 k=ÿ7!7 l=ÿ10!10
Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.015 wR(F2) = 0.043 S= 1.37 249 re¯ections 18 parameters
w= 1/[2(F
o2) + (0.017P)2 + 0.22P]
whereP= (Fo2+ 2Fc2)/3 (/)max= 0.027
max= 0.65 e AÊÿ3
min=ÿ0.36 e AÊÿ3
Extinction correction:SHELXL Extinction coef®cient: 0.253 (6)
Table 1
Selected geometric parameters (AÊ,).
CsÐO1i 3.2716 (9)
CsÐO2ii 3.287 (2)
AlÐO2 1.883 (2)
MoÐO1 1.721 (4)
MoÐO2 1.763 (2)
O2ÐAlÐO2iii 88.98 (10)
O1ÐMoÐO2 107.60 (8) O2ÐMoÐO2
iv 111.28 (7)
Symmetry codes: (i) ÿx;1ÿy;1ÿz; (ii) x;y;zÿ1; (iii) ÿy;xÿy;z; (iv) 1ÿy;1xÿy;z.
The complementary studies on the temperature dependence of lattice parameters were performed on a Siemens D5000 diffrac-tometer, working in ± Bragg±Brentano geometry with Cu K
radiation. The powder diagrams were recorded at temperatures 295, 110 and 40 K in a 2range of 10±55, with a step size of 0.02. The
temperature was set and stabilized by an Anton Paar circulated-gaseous-helium low-temperature attachment.
Data collection:KM-4CCD Software(KUMA Diffraction, 1998); cell re®nement: KM-4CCD Software; data reduction:KM-4 CCD
Data Reduction Software (KUMA Diffraction, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1991); software used to prepare material for publication:SHELXL97 (Sheldrick, 1997).
The ®nancial support of these investigations by KBN under Research grant No. 7 T09A 020 21 is acknowledged. One of us (PET) expresses his sincere appreciation also to the Norpol-Press, MPEC and Budexpol, all establishments in Wrocøaw, for ®nancial support.
References
Efremov, V. A., Trunov, V. K. & Velikodnyi, Yu. A. (1971).Zh. Strukt. Khim.
12, 731±732.
Klevtsov, P. V., Klevtsova, R. F. & Demenev, A. V. (1972).Kristallogra®ya,17, 547±551.
Klevtsova, R. F., Bazarova, Z. G., Glinskaya, L. A., Alekseev, V. I., Arkhincheeva, S. I., Bazarov, B. G. & Klevtsov, P. V. (1995).Zh. Strukt. Khim.36, 891±894.
Klevtsova, R. F. & Klevtsov, P. V. (1970).Kristallogra®ya,15, 953±959. KUMA Diffraction (1998).KM-4CCD Software(Version 1.168) andKM-4
CCD Data Reduction Software (Version 1.168). KUMA Diffraction, Wrocøaw, Poland.
Lii, K. H., Wang, C. C., Chiang, R. K. & Wang, S. L. (1989).J. Solid State Chem.
80, 144±148.
Sheldrick, G. M. (1991).SHELXTL.Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
supporting information
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Acta Cryst. (2002). E58, i119–i120
supporting information
Acta Cryst. (2002). E58, i119–i120 [doi:10.1107/S1600536802020950]
CsAl(MoO
4)
2Pawe
ł
E. Tomaszewski, Adam Pietraszko, Miros
ł
aw M
ą
czka and Jerzy Hanuza
S1. Comment
Double molybdates and tungstates with the general formula MIMIII(MVIO
4)2, where MI = alkali metal, MIII = Al, In, Cr, Bi,
Fe, RE (rare earths) and MVI = Mo or W, exhibit interesting structural and physicochemical properties and are used as
acousto-optic filters, second-harmonic generators and laser crystals. They exhibit ferroelectric, ferroelastic or even
ferromagnetic properties and have been extensively studied for the last 40 years. CsAl(MoO4)2 belongs to this family.
The room temperature phase of CsAl(MoO4)2 was refined in the trigonal space group P3m1 (No. 164), as for many
other double molybdates and tungstates of glaserite structure (Efremov et al., 1971, Klevtsov et al., 1972, Klevtsova &
Klevtsov, 1970, Klevtsova et al., 1995, Lii et al., 1989, Tomaszewski et al. 2002). The structure consists of [AlMo2O8−]n
layers perpendicular to the trigonal c axis, with the caesium cations between the layers. Each layer is built up from MoO4
tetrahedra and AlO6 octahedra sharing its six corners with six MoO4 tetrahedra.
The supplementary low-temperature experiments do not show any changes in the powder-diffraction diagram, thus
indicating no symmetry changes and the absence of a phase transition. The low-temperature lattice parameters are as
follows: a = 5.525 (2), c = 7.966 (3) Å at 110 K and a = 5.513 (3), c = 7.954 (4) Å at 40 K. The lattice parameter a
changes linearly with the temperature, while the temperature dependence of the parameter c is quadratic.
S2. Experimental
Single crystals of CsAl(MoO4)2, were grown by cooling of a molten mixture containing CsAl(MoO4)2 and solvent
(Cs2Mo2O7) in a 1:1 ratio. The cooling rate was 2 °K/h. The hexagonal single crystals obtained were colourless and of
good optical quality.
S3. Refinement
Complementary studies on thermal dependence of lattice parameters were performed on a Siemens D5000 diffractometer
working in θ–θ Bragg-Brentano geometry with Cu Kα radiation. The powder diagrams were recorded at temperatures
295, 110 and 40 K in a 2θ range of 10–55°, with a step size of 0.02°. The temperature was set and stabilized by an Anton
Figure 1
View of CsAl(MoO4)2, nearly down the c axis
caesium aluminium bimolybdate(VI)
Crystal data
CsAl(MoO4)2 Mr = 479.77 Trigonal, P3m1 Hall symbol: -P 3 2"
a = 5.551 (1) Å
c = 8.037 (2) Å
V = 214.47 (8) Å3 Z = 1
F(000) = 216
Dx = 3.715 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from all reflections
θ = 4.2–29.0°
µ = 7.21 mm−1 T = 293 K Plate, colourless 0.20 × 0.20 × 0.10 mm
Data collection
Kuma KM-4 CCD diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 1024x1024 with blocs 2x2 pixels mm-1
CCD scans
Absorption correction: numerical as in XEMP by Sheldrick
Tmin = 0.068, Tmax = 0.155 2447 measured reflections 249 independent reflections 248 reflections with I > 2σ(I)
Rint = 0.045
θmax = 29.0°, θmin = 4.2° h = −7→5
k = −7→7
l = −10→10
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.015 wR(F2) = 0.043 S = 1.37 249 reflections
18 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
supporting information
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Acta Cryst. (2002). E58, i119–i120
w = 1/[σ2(F
o2) + (0.017P)2 + 0.220P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.027 Δρmax = 0.65 e Å−3
Δρmin = −0.36 e Å−3
Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.253 (6)
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cs 0.0000 0.0000 0.0000 0.02029 (11)
Al 0.0000 0.0000 0.5000 0.0104 (3)
Mo 0.3333 0.6667 0.70401 (4) 0.01026 (11)
O1 0.3333 0.6667 0.9182 (4) 0.0213 (7)
O2 0.1585 (2) 0.3170 (4) 0.6377 (3) 0.0244 (4)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cs 0.02162 (14) 0.02162 (14) 0.0176 (2) 0.01081 (7) 0.000 0.000
Al 0.0084 (5) 0.0084 (5) 0.0145 (8) 0.0042 (2) 0.000 0.000
Mo 0.00938 (13) 0.00938 (13) 0.0120 (2) 0.00469 (6) 0.000 0.000
O1 0.0257 (11) 0.0257 (11) 0.0126 (14) 0.0128 (6) 0.000 0.000
O2 0.0265 (8) 0.0141 (9) 0.0284 (9) 0.0070 (5) −0.0036 (4) −0.0073 (8)
Geometric parameters (Å, º)
Cs—O1i 3.2716 (9) Al—O2xi 1.883 (2)
Cs—O1ii 3.2716 (9) Al—O2vii 1.883 (2)
Cs—O1iii 3.2716 (9) Al—O2xii 1.883 (2)
Cs—O1iv 3.2716 (9) Al—Csxiii 4.0185 (10)
Cs—O1v 3.2716 (9) Mo—O1 1.721 (4)
Cs—O1vi 3.2716 (9) Mo—O2xiv 1.763 (2)
Cs—O2vii 3.287 (2) Mo—O2 1.763 (2)
Cs—O2viii 3.287 (2) Mo—O2xv 1.763 (2)
Cs—O2ix 3.287 (2) Mo—Csxvi 3.9913 (6)
Cs—O2x 3.287 (2) Mo—Csxvii 3.9913 (6)
Cs—O2vi 3.287 (2) Mo—Csxiii 3.9913 (6)
Cs—O2v 3.287 (2) O1—Csxvi 3.2716 (9)
Al—O2 1.883 (2) O1—Csxvii 3.2716 (9)
Al—O2vi 1.883 (2) O1—Csxiii 3.2716 (9)
O1i—Cs—O1ii 180.0 O1vi—Cs—O2vi 50.78 (7)
O1i—Cs—O1iii 63.93 (4) O2vii—Cs—O2vi 47.35 (6)
O1ii—Cs—O1iii 116.07 (4) O2viii—Cs—O2vi 132.65 (6)
O1i—Cs—O1iv 116.07 (4) O2ix—Cs—O2vi 47.35 (6)
O1ii—Cs—O1iv 63.93 (4) O2x—Cs—O2vi 132.65 (6)
O1iii—Cs—O1iv 180.0 O1i—Cs—O2v 87.19 (6)
O1i—Cs—O1v 63.93 (4) O1ii—Cs—O2v 92.81 (6)
O1ii—Cs—O1v 116.07 (4) O1iii—Cs—O2v 92.81 (6)
O1iii—Cs—O1v 116.07 (4) O1iv—Cs—O2v 87.19 (6)
O1iv—Cs—O1v 63.93 (4) O1v—Cs—O2v 50.78 (7)
O1i—Cs—O1vi 116.07 (4) O1vi—Cs—O2v 129.22 (7)
O1ii—Cs—O1vi 63.93 (4) O2vii—Cs—O2v 132.65 (6)
O1iii—Cs—O1vi 63.93 (4) O2viii—Cs—O2v 47.35 (6)
O1iv—Cs—O1vi 116.07 (4) O2ix—Cs—O2v 132.65 (6)
O1v—Cs—O1vi 180.0 O2x—Cs—O2v 47.35 (6)
O1i—Cs—O2vii 92.81 (6) O2vi—Cs—O2v 180.0
O1ii—Cs—O2vii 87.19 (6) O2—Al—O2vi 180.0
O1iii—Cs—O2vii 129.22 (7) O2—Al—O2ix 91.02 (10)
O1iv—Cs—O2vii 50.78 (7) O2vi—Al—O2ix 88.98 (10)
O1v—Cs—O2vii 87.19 (6) O2—Al—O2xi 88.98 (10)
O1vi—Cs—O2vii 92.81 (6) O2vi—Al—O2xi 91.02 (10)
O1i—Cs—O2viii 87.19 (6) O2ix—Al—O2xi 180.0
O1ii—Cs—O2viii 92.81 (6) O2—Al—O2vii 91.02 (10)
O1iii—Cs—O2viii 50.78 (7) O2vi—Al—O2vii 88.98 (10)
O1iv—Cs—O2viii 129.22 (7) O2ix—Al—O2vii 88.98 (10)
O1v—Cs—O2viii 92.81 (6) O2xi—Al—O2vii 91.02 (10)
O1vi—Cs—O2viii 87.19 (6) O2—Al—O2xii 88.98 (10)
O2vii—Cs—O2viii 180.0 O2vi—Al—O2xii 91.02 (10)
O1i—Cs—O2ix 50.78 (7) O2ix—Al—O2xii 91.02 (10)
O1ii—Cs—O2ix 129.22 (7) O2xi—Al—O2xii 88.98 (10)
O1iii—Cs—O2ix 87.19 (6) O2vii—Al—O2xii 180.0
O1iv—Cs—O2ix 92.81 (6) O1—Mo—O2xiv 107.60 (8)
O1v—Cs—O2ix 87.19 (6) O1—Mo—O2 107.60 (8)
O1vi—Cs—O2ix 92.81 (6) O2xiv—Mo—O2 111.28 (7)
O2vii—Cs—O2ix 47.35 (6) O1—Mo—O2xv 107.60 (8)
O2viii—Cs—O2ix 132.65 (6) O2xiv—Mo—O2xv 111.28 (7)
O1i—Cs—O2x 129.22 (7) O2—Mo—O2xv 111.28 (7)
O1ii—Cs—O2x 50.78 (7) Csxvi—Mo—Csxvii 88.117 (14)
O1iii—Cs—O2x 92.81 (6) Csxvi—Mo—Csxiii 88.117 (14)
O1iv—Cs—O2x 87.19 (6) Csxvii—Mo—Csxiii 88.117 (14)
O1v—Cs—O2x 92.81 (6) Mo—O1—Csxvi 101.59 (6)
O1vi—Cs—O2x 87.19 (6) Mo—O1—Csxvii 101.59 (6)
O2vii—Cs—O2x 132.65 (6) Csxvi—O1—Csxvii 116.07 (4)
O2viii—Cs—O2x 47.35 (6) Mo—O1—Csxiii 101.59 (6)
O2ix—Cs—O2x 180.0 Csxvi—O1—Csxiii 116.07 (4)
O1i—Cs—O2vi 92.81 (6) Csxvii—O1—Csxiii 116.07 (4)
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Acta Cryst. (2002). E58, i119–i120
O1iii—Cs—O2vi 87.19 (6) Mo—O2—Csxiii 100.03 (9)
O1iv—Cs—O2vi 92.81 (6) Al—O2—Csxiii 98.36 (8)
O1v—Cs—O2vi 129.22 (7)
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y−1, z−1; (iii) x−1, y−1, z−1; (iv) −x+1, −y+1, −z+1; (v) x, y, z−1; (vi) −x, −y, −z+1; (vii) y, −x+y, −z+1; (viii) −y, x−y, z−1; (ix) x−y, x, −z+1; (x) −x+y, −x, z−1; (xi) −x+y, −x, z; (xii) −y, x−y, z; (xiii) x, y, z+1; (xiv) −x+y, −x+1, z; (xv) −y+1, x−y+1, z; (xvi) x, y+1,
