Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020950/br6069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020950/br6069Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Al-O) = 0.002 Å
- R factor = 0.015
- wR factor = 0.043
- Data-to-parameter ratio = 13.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: Al1 Cs1 Mo2 O8 Atom count from _chemical_formula_moiety:Al1 Cs1 Mo1 O4
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.
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 Paar circulated-gaseous-helium low-temperature attachment.
Data collection: KM-4 CCD Software (Kuma, 1998); cell refinement: KM-4 CCD Software; data reduction: KM4CCD Data Reduction Software (Kuma, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
CsAl(MoO4)2 | Dx = 3.715 Mg m−3 |
Mr = 479.77 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3m1 | Cell parameters from all reflections |
Hall symbol: -P 3 2" | θ = 4.2–29.0° |
a = 5.551 (1) Å | µ = 7.21 mm−1 |
c = 8.037 (2) Å | T = 293 K |
V = 214.47 (8) Å3 | Plate, colourless |
Z = 1 | 0.20 × 0.20 × 0.10 mm |
F(000) = 216 |
Kuma KM-4 CCD diffractometer | 249 independent reflections |
Radiation source: fine-focus sealed tube | 248 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 1024x1024 with blocs 2x2 pixels mm-1 | θmax = 29.0°, θmin = 4.2° |
CCD scans | h = −7→5 |
Absorption correction: numerical as in XEMP by Sheldrick | k = −7→7 |
Tmin = 0.068, Tmax = 0.155 | l = −10→10 |
2447 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.015 | w = 1/[σ2(Fo2) + (0.017P)2 + 0.220P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.043 | (Δ/σ)max = 0.027 |
S = 1.37 | Δρmax = 0.65 e Å−3 |
249 reflections | Δρmin = −0.36 e Å−3 |
18 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.253 (6) |
CsAl(MoO4)2 | Z = 1 |
Mr = 479.77 | Mo Kα radiation |
Trigonal, P3m1 | µ = 7.21 mm−1 |
a = 5.551 (1) Å | T = 293 K |
c = 8.037 (2) Å | 0.20 × 0.20 × 0.10 mm |
V = 214.47 (8) Å3 |
Kuma KM-4 CCD diffractometer | 249 independent reflections |
Absorption correction: numerical as in XEMP by Sheldrick | 248 reflections with I > 2σ(I) |
Tmin = 0.068, Tmax = 0.155 | Rint = 0.045 |
2447 measured reflections |
R[F2 > 2σ(F2)] = 0.015 | 18 parameters |
wR(F2) = 0.043 | 0 restraints |
S = 1.37 | Δρmax = 0.65 e Å−3 |
249 reflections | Δρmin = −0.36 e Å−3 |
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. |
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) |
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) |
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) |
Al—O2ix | 1.883 (2) | O2—Csxiii | 3.287 (2) |
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) |
O1ii—Cs—O2vi | 87.19 (6) | Mo—O2—Al | 161.61 (14) |
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, z+1; (xvii) x+1, y+1, z+1. |
Experimental details
Crystal data | |
Chemical formula | CsAl(MoO4)2 |
Mr | 479.77 |
Crystal system, space group | Trigonal, P3m1 |
Temperature (K) | 293 |
a, c (Å) | 5.551 (1), 8.037 (2) |
V (Å3) | 214.47 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 7.21 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | Numerical as in XEMP by Sheldrick |
Tmin, Tmax | 0.068, 0.155 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2447, 249, 248 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.015, 0.043, 1.37 |
No. of reflections | 249 |
No. of parameters | 18 |
Δρmax, Δρmin (e Å−3) | 0.65, −0.36 |
Computer programs: KM-4 CCD Software (Kuma, 1998), KM-4 CCD Software, KM4CCD Data Reduction Software (Kuma, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1991).
Cs—O1i | 3.2716 (9) | Mo—O1 | 1.721 (4) |
Cs—O2ii | 3.287 (2) | Mo—O2 | 1.763 (2) |
Al—O2 | 1.883 (2) | ||
O2—Al—O2iii | 88.98 (10) | O2—Mo—O2iv | 111.28 (7) |
O1—Mo—O2 | 107.60 (8) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) −y, x−y, z; (iv) −y+1, x−y+1, z. |
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Double molybdates and tungstates with the general formula MIMIII(MVIO4)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.