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The La2Mo2O9 (LM) and Pr2Mo2O9 (PM) single crystals are studied using precision X-ray diffraction and high-resolution transmission microscopy at room temperature. The crystal structures are determined in the space group P213. La and Pr atoms, as well as Mo1 and O1 atoms, are located in the vicinity of the threefold axes rather than on the axes as in the high-temperature cubic phase. In both structures studied, the O2 and O3 positions are partially occupied. The coexistence of different configurations of the Mo coordination environment facilitates the oxygen-ion migration in the structure. Based on the X-ray data, the activation energies of O atoms are calculated and the migration paths of oxygen ions in the structures are analysed. The conductivity of PM crystals is close to that of LM crystals. The O2 and O3 atoms are the main contributors to the ion conductivity of LM and PM.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614006623/bp5063sup1.cif
Contains datablocks global, II, III, IV, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614006623/bp5063Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614006623/bp5063IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614006623/bp5063IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614006623/bp5063IVsup5.hkl
Contains datablock IV

CCDC references: 993605; 993606; 993607; 993608

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
(I) top
Crystal data top
La2Mo2O9F(000) = 531
Mr = 613.7Dx = 5.477 Mg m3
Cubic, P213Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac;2ab;3µ = 14.78 mm1
a = 7.1552 (9) ÅT = 293 K
V = 366.32 (8) Å3Sphere, colorless
Z = 20.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
710 reflections with I > 3σ(I)
Radiation source: X-ray tubeRint = 0.022
Graphite monochromatorθmax = 48.9°, θmin = 4.9°
Absorption correction: for a sphere
?
h = 1515
Tmin = 0.776, Tmax = 1.000k = 1515
14670 measured reflectionsl = 1515
767 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.000225F2)
R[F2 > 2σ(F2)] = 0.019(Δ/σ)max = 0.045
wR(F2) = 0.024Δρmax = 0.48 e Å3
S = 1.15Δρmin = 0.76 e Å3
767 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
63 parametersExtinction coefficient: 1690 (80)
0 restraintsAbsolute structure: 312 of Friedel pairs used in the refinement
2 constraintsAbsolute structure parameter: 0.016 (19)
Crystal data top
La2Mo2O9Z = 2
Mr = 613.7Mo Kα radiation
Cubic, P213µ = 14.78 mm1
a = 7.1552 (9) ÅT = 293 K
V = 366.32 (8) Å30.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
767 independent reflections
Absorption correction: for a sphere
?
710 reflections with I > 3σ(I)
Tmin = 0.776, Tmax = 1.000Rint = 0.022
14670 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.024Δρmax = 0.48 e Å3
S = 1.15Δρmin = 0.76 e Å3
767 reflectionsAbsolute structure: 312 of Friedel pairs used in the refinement
63 parametersAbsolute structure parameter: 0.016 (19)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
La10.151 (4)0.135 (4)0.1235 (17)0.0226 (12)0.170 (14)
Mo10.8147 (8)0.8235 (5)0.8696 (16)0.0252 (9)0.191 (10)
O10.686 (2)0.6743 (14)0.6830 (8)0.072 (4)0.3333
O20.8129 (11)0.6583 (8)1.0123 (5)0.079 (2)0.745 (17)
O30.923 (2)0.849 (3)1.0430 (16)0.113 (8)0.323 (16)
Mo20.8303 (5)0.8303 (5)0.8303 (5)0.0279 (9)*0.43 (3)
La20.1784 (19)0.1482 (10)0.1353 (12)0.0395 (10)0.163 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La10.021 (3)0.026 (2)0.0200 (13)0.009 (3)0.0042 (11)0.0013 (8)
Mo10.0224 (9)0.0160 (6)0.037 (2)0.0065 (5)0.0060 (11)0.0008 (7)
O10.127 (9)0.067 (6)0.023 (3)0.057 (5)0.005 (4)0.019 (3)
O20.135 (6)0.065 (3)0.0363 (16)0.027 (3)0.014 (2)0.0010 (15)
O30.099 (10)0.20 (2)0.036 (4)0.027 (12)0.004 (5)0.014 (9)
La20.0208 (14)0.069 (3)0.0292 (11)0.0052 (10)0.0001 (9)0.0221 (16)
Bond lengths (Å) top
La1—La1i0.25 (3)O1—O2xxiv2.725 (15)
La1—La1ii0.25 (3)O1—O33.324 (18)
La1—Mo1iii3.48 (3)O1—O3xix2.725 (18)
La1—Mo1iv3.451 (16)O1—O3i3.328 (19)
La1—O1v2.81 (3)O1—O3xxi2.654 (19)
La1—O1vi2.498 (19)O1—O3ii3.354 (18)
La1—O1iii2.62 (3)O1—O3xxv2.761 (17)
La1—O1vii2.73 (3)O1—Mo21.849 (11)
La1—O1viii2.74 (3)O1—La2xxvi2.922 (19)
La1—O1iv2.47 (2)O1—La2xxvii2.482 (12)
La1—O1ix2.57 (2)O1—La2xxviii2.649 (12)
La1—O1x2.66 (3)O1—La2xxix2.821 (16)
La1—O1xi2.71 (3)O1—La2xxx2.543 (17)
La1—O2xii2.624 (13)O1—La2xxxi2.692 (11)
La1—O2iii2.58 (3)O1—La2xxxii2.858 (15)
La1—O2xiii2.45 (3)O1—La2xxxiii2.442 (13)
La1—O2iv2.66 (2)O1—La2xxxiv2.754 (15)
La1—O2xiv2.57 (3)O2—O2i3.110 (8)
La1—O2xi2.80 (3)O2—O2xx3.198 (8)
La1—O3xv2.68 (3)O2—O2xxi3.027 (9)
La1—O3xii2.88 (2)O2—O2ii3.110 (8)
La1—O3xvi2.60 (3)O2—O2xxxv3.027 (9)
La1—O3xiii2.75 (3)O2—O2xviii3.198 (8)
La1—O3xvii2.68 (3)O2—O31.59 (2)
La1—O3xiv2.72 (3)O2—O3xix2.820 (18)
La1—La20.23 (3)O2—O3i2.768 (17)
La1—La2i0.38 (3)O2—O3xx2.249 (16)
La1—La2ii0.393 (18)O2—O3xxi3.25 (2)
Mo1—Mo1i0.517 (12)O2—O3ii2.837 (13)
Mo1—Mo1ii0.517 (12)O2—Mo21.796 (6)
Mo1—O11.941 (13)O2—La2xxxvi2.523 (9)
Mo1—O1i1.951 (14)O2—La2xxviii2.618 (10)
Mo1—O1ii1.934 (14)O2—La2xxix2.956 (13)
Mo1—O21.562 (9)O2—La2xxxvii2.461 (8)
Mo1—O2i2.071 (10)O2—La2xxxviii2.237 (14)
Mo1—O2ii1.801 (7)O2—La2xxxiii2.768 (11)
Mo1—O2xviii3.388 (13)O3—O3i1.72 (2)
Mo1—O31.472 (17)O3—O3xx3.43 (2)
Mo1—O3xix3.126 (18)O3—O3ii1.72 (2)
Mo1—O3i1.787 (14)O3—O3xviii3.43 (2)
Mo1—O3xx3.310 (19)O3—Mo21.664 (13)
Mo1—O3xxi3.420 (19)O3—Mo2xxxix3.311 (18)
Mo1—O3ii1.634 (13)O3—La2xl2.89 (2)
Mo1—Mo20.307 (11)O3—La2xxxvi2.807 (17)
O1—O1i0.109 (16)O3—La2xli2.91 (2)
O1—O1ii0.109 (16)O3—La2xxxvii2.557 (17)
O1—O22.527 (9)O3—La2xlii2.78 (2)
O1—O2xxii2.675 (11)O3—La2xxxviii2.56 (2)
O1—O2i2.541 (15)La2—La2i0.387 (15)
O1—O2xxiii2.743 (10)La2—La2ii0.387 (15)
O1—O2ii2.599 (11)
Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) x1/2, y+1/2, z+1; (iv) z+1, x1/2, y+1/2; (v) x+1/2, y+1, z1/2; (vi) x+1, y1/2, z+1/2; (vii) z1/2, x+1/2, y+1; (viii) z+1/2, x+1, y1/2; (ix) y+1, z1/2, x+1/2; (x) y1/2, z+1/2, x+1; (xi) y+1/2, z+1, x1/2; (xii) x+1, y1/2, z+3/2; (xiii) z+3/2, x+1, y1/2; (xiv) y1/2, z+3/2, x+1; (xv) x1, y1, z1; (xvi) z1, x1, y1; (xvii) y1, z1, x1; (xviii) y+3/2, z+2, x+1/2; (xix) x1/2, y+3/2, z+2; (xx) z1/2, x+3/2, y+2; (xxi) z+2, x1/2, y+3/2; (xxii) x+3/2, y+1, z1/2; (xxiii) z1/2, x+3/2, y+1; (xxiv) y+1, z1/2, x+3/2; (xxv) y+3/2, z+2, x1/2; (xxvi) x+1/2, y+1, z+1/2; (xxvii) x+1, y+1/2, z+1/2; (xxviii) x+1/2, y+1/2, z+1; (xxix) z+1/2, x+1/2, y+1; (xxx) z+1/2, x+1, y+1/2; (xxxi) z+1, x+1/2, y+1/2; (xxxii) y+1, z+1/2, x+1/2; (xxxiii) y+1/2, z+1/2, x+1; (xxxiv) y+1/2, z+1, x+1/2; (xxxv) y+1/2, z+3/2, x+2; (xxxvi) x+1, y+1/2, z+3/2; (xxxvii) z+1, x+1/2, y+3/2; (xxxviii) y+1, z+1/2, x+3/2; (xxxix) x+1/2, y+3/2, z+2; (xl) x+1, y+1, z+1; (xli) z+1, x+1, y+1; (xlii) y+1, z+1, x+1.
(II) top
Crystal data top
La2Mo2O9F(000) = 527
Mr = 613.7Dx = 5.444 Mg m3
Cubic, P213Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac;2ab;3µ = 14.78 mm1
a = 7.155 (1) ÅT = 293 K
V = 366.29 (9) Å3Sphere, colorless
Z = 20.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
1281 independent reflections
Radiation source: X-ray tube820 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.059
ω scansθmax = 49.7°, θmin = 4.9°
Absorption correction: for a sphere
(Jana2000; Petricek, Dusek & Palatinus, 2000)
h = 1515
Tmin = 0.614, Tmax = 1.000k = 1515
33307 measured reflectionsl = 1515
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.000225F2)
R[F2 > 2σ(F2)] = 0.021(Δ/σ)max = 0.047
wR(F2) = 0.030Δρmax = 0.57 e Å3
S = 1.08Δρmin = 0.46 e Å3
1281 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
63 parametersExtinction coefficient: 950 (60)
0 restraintsAbsolute structure: 551 of Friedel pairs used in the refinement
2 constraintsAbsolute structure parameter: 0.017 (19)
Crystal data top
La2Mo2O9Z = 2
Mr = 613.7Mo Kα radiation
Cubic, P213µ = 14.78 mm1
a = 7.155 (1) ÅT = 293 K
V = 366.29 (9) Å30.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
1281 independent reflections
Absorption correction: for a sphere
(Jana2000; Petricek, Dusek & Palatinus, 2000)
820 reflections with I > 3σ(I)
Tmin = 0.614, Tmax = 1.000Rint = 0.059
33307 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.030Δρmax = 0.57 e Å3
S = 1.08Δρmin = 0.46 e Å3
1281 reflectionsAbsolute structure: 551 of Friedel pairs used in the refinement
63 parametersAbsolute structure parameter: 0.017 (19)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
La10.8489 (12)0.8639 (10)0.8726 (9)0.0276 (8)0.188 (8)
Mo10.1855 (6)0.1764 (4)0.1315 (13)0.0280 (7)0.203 (8)
O10.3132 (16)0.3243 (14)0.3175 (7)0.075 (3)0.3333
O20.1869 (11)0.3408 (7)0.0120 (5)0.079 (2)0.709 (16)
O30.078 (2)0.150 (3)0.0414 (14)0.108 (7)0.321 (15)
Mo20.1695 (4)0.1695 (4)0.1695 (4)0.0286 (7)*0.39 (2)
La20.8184 (11)0.8529 (9)0.8669 (11)0.0404 (8)0.146 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La10.0277 (17)0.0266 (12)0.0287 (12)0.0117 (10)0.0082 (9)0.0002 (7)
Mo10.0245 (7)0.0189 (5)0.041 (2)0.0059 (4)0.0061 (9)0.0004 (6)
O10.111 (7)0.090 (6)0.023 (2)0.062 (5)0.013 (3)0.010 (3)
O20.142 (5)0.061 (2)0.0356 (14)0.025 (3)0.0119 (19)0.0018 (12)
O30.103 (9)0.187 (18)0.035 (3)0.008 (11)0.000 (5)0.012 (7)
La20.0209 (10)0.0679 (18)0.0323 (10)0.0034 (8)0.0024 (9)0.0217 (11)
Bond lengths (Å) top
La1—La1i0.210 (11)O1—O2ii2.589 (10)
La1—La1ii0.210 (11)O1—O2xxvi2.740 (12)
La1—Mo1iii3.491 (8)O1—O33.315 (16)
La1—Mo1iv3.473 (7)O1—O3xix2.742 (16)
La1—O1v2.796 (14)O1—O3i3.315 (17)
La1—O1vi2.518 (10)O1—O3xxi2.668 (17)
La1—O1iii2.625 (11)O1—O3ii3.340 (16)
La1—O1vii2.716 (13)O1—O3xxvii2.762 (15)
La1—O1viii2.724 (11)O1—Mo21.845 (10)
La1—O1iv2.501 (11)O1—La2xxviii2.947 (14)
La1—O1ix2.589 (13)O1—La2xxix2.455 (10)
La1—O1x2.644 (10)O1—La2xxii2.660 (11)
La1—O1xi2.708 (12)O1—La2xxx2.859 (12)
La1—O2xii2.598 (7)O1—La2xxxi2.520 (14)
La1—O2iii2.609 (9)O1—La2xxxii2.687 (10)
La1—O2xiii2.448 (9)O1—La2xxxiii2.879 (10)
La1—O2iv2.679 (9)O1—La2xxiii2.431 (12)
La1—O2xiv2.554 (8)O1—La2xxxiv2.754 (13)
La1—O2xi2.796 (10)O2—O2i3.100 (7)
La1—O3xv2.692 (19)O2—O2xx3.195 (7)
La1—O3xii2.869 (15)O2—O2xxi3.033 (9)
La1—O3xvi2.626 (19)O2—O2ii3.100 (7)
La1—O3xiii2.748 (16)O2—O2xxxv3.033 (9)
La1—O3xvii2.69 (2)O2—O2xviii3.195 (7)
La1—O3xiv2.734 (15)O2—O31.587 (19)
La1—La20.236 (11)O2—O3xix2.823 (17)
La1—La2i0.378 (11)O2—O3i2.749 (16)
La1—La2ii0.390 (10)O2—O3xx2.256 (15)
Mo1—Mo1i0.506 (10)O2—O3xxi3.266 (18)
Mo1—Mo1ii0.506 (10)O2—O3ii2.822 (12)
Mo1—O11.930 (11)O2—Mo21.790 (5)
Mo1—O1i1.937 (12)O2—La2xxxvi2.540 (9)
Mo1—O1ii1.922 (12)O2—La2xxii2.602 (9)
Mo1—O21.561 (8)O2—La2xxx2.984 (10)
Mo1—O2i2.060 (9)O2—La2xxxvii2.474 (7)
Mo1—O2ii1.791 (6)O2—La2xxxviii2.218 (9)
Mo1—O2xviii3.397 (11)O2—La2xxiii2.776 (9)
Mo1—O31.471 (15)O3—O3i1.69 (2)
Mo1—O3xix3.136 (17)O3—O3xx3.44 (2)
Mo1—O3i1.776 (12)O3—O3ii1.69 (2)
Mo1—O3xx3.312 (17)O3—O3xviii3.44 (2)
Mo1—O3xxi3.428 (17)O3—Mo21.652 (12)
Mo1—O3ii1.626 (11)O3—Mo2xxxix3.322 (16)
Mo1—Mo20.299 (9)O3—La2xl2.897 (19)
Mo1—La2xxii3.499 (7)O3—La2xxxvi2.843 (16)
Mo1—La2xxiii3.499 (8)O3—La2xli2.91 (2)
O1—O1i0.099 (14)O3—La2xxxvii2.564 (15)
O1—O1ii0.099 (14)O3—La2xlii2.774 (19)
O1—O22.528 (8)O3—La2xxxviii2.565 (17)
O1—O2xxiv2.689 (10)La2—La2i0.438 (11)
O1—O2i2.531 (12)La2—La2ii0.438 (11)
O1—O2xxv2.748 (8)
Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) x+1/2, y+3/2, z+1; (iv) z+1, x+1/2, y+3/2; (v) x+3/2, y+1, z+1/2; (vi) x+1, y+1/2, z+3/2; (vii) z+1/2, x+3/2, y+1; (viii) z+3/2, x+1, y+1/2; (ix) y+1, z+1/2, x+3/2; (x) y+1/2, z+3/2, x+1; (xi) y+3/2, z+1, x+1/2; (xii) x+1, y+1/2, z+1/2; (xiii) z+1/2, x+1, y+1/2; (xiv) y+1/2, z+1/2, x+1; (xv) x+1, y+1, z+1; (xvi) z+1, x+1, y+1; (xvii) y+1, z+1, x+1; (xviii) y+1/2, z, x1/2; (xix) x+1/2, y+1/2, z; (xx) z+1/2, x+1/2, y; (xxi) z, x+1/2, y+1/2; (xxii) x1/2, y+3/2, z+1; (xxiii) y1/2, z+3/2, x+1; (xxiv) x+1/2, y+1, z+1/2; (xxv) z+1/2, x+1/2, y+1; (xxvi) y+1, z+1/2, x+1/2; (xxvii) y+1/2, z, x+1/2; (xxviii) x+3/2, y+1, z1/2; (xxix) x+1, y1/2, z+3/2; (xxx) z1/2, x+3/2, y+1; (xxxi) z+3/2, x+1, y1/2; (xxxii) z+1, x1/2, y+3/2; (xxxiii) y+1, z1/2, x+3/2; (xxxiv) y+3/2, z+1, x1/2; (xxxv) y1/2, z+1/2, x; (xxxvi) x+1, y1/2, z+1/2; (xxxvii) z+1, x1/2, y+1/2; (xxxviii) y+1, z1/2, x+1/2; (xxxix) x1/2, y+1/2, z; (xl) x1, y1, z1; (xli) z1, x1, y1; (xlii) y1, z1, x1.
(III) top
Crystal data top
Pr2Mo2O9F(000) = 546
Mr = 617.7Dx = 5.729 Mg m3
Cubic, P213Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac;2ab;3µ = 16.92 mm1
a = 7.0849 (11) ÅT = 293 K
V = 355.63 (10) Å3Sphere, colorless
Z = 20.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
512 reflections with I > 3σ(I)
Radiation source: X-ray tubeRint = 0.025
Graphite monochromatorθmax = 48.2°, θmin = 5.0°
Absorption correction: for a sphere
?
h = 1314
Tmin = 0.716, Tmax = 1.000k = 1314
10229 measured reflectionsl = 1414
551 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.000225F2)
R[F2 > 2σ(F2)] = 0.017(Δ/σ)max = 0.047
wR(F2) = 0.022Δρmax = 0.33 e Å3
S = 1.06Δρmin = 0.22 e Å3
551 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
62 parametersExtinction coefficient: 570 (40)
0 restraintsAbsolute structure: 220 of Friedel pairs used in the refinement
2 constraintsAbsolute structure parameter: 0.01 (2)
Crystal data top
Pr2Mo2O9Z = 2
Mr = 617.7Mo Kα radiation
Cubic, P213µ = 16.92 mm1
a = 7.0849 (11) ÅT = 293 K
V = 355.63 (10) Å30.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
551 independent reflections
Absorption correction: for a sphere
?
512 reflections with I > 3σ(I)
Tmin = 0.716, Tmax = 1.000Rint = 0.025
10229 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.022Δρmax = 0.33 e Å3
S = 1.06Δρmin = 0.22 e Å3
551 reflectionsAbsolute structure: 220 of Friedel pairs used in the refinement
62 parametersAbsolute structure parameter: 0.01 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pr10.1352 (9)0.1615 (13)0.1327 (17)0.0437 (11)0.285 (19)
Mo10.8154 (9)0.8262 (7)0.8837 (16)0.0294 (10)0.132 (8)
O10.693 (3)0.6724 (17)0.6853 (11)0.089 (5)0.3333
O20.8117 (12)0.6565 (9)1.0136 (6)0.083 (3)0.722 (19)
O30.920 (3)0.849 (4)1.0458 (19)0.178 (15)0.40 (2)
Mo20.8294 (5)0.8294 (5)0.8294 (5)0.0379 (6)*0.60 (2)
Pr20.115 (7)0.188 (4)0.172 (10)0.045 (4)0.049 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pr10.0420 (16)0.053 (2)0.0358 (18)0.0206 (9)0.0115 (12)0.0199 (18)
Mo10.0273 (14)0.0219 (11)0.039 (3)0.0081 (9)0.0063 (13)0.0054 (13)
O10.163 (13)0.072 (8)0.030 (4)0.065 (8)0.005 (6)0.017 (5)
O20.130 (6)0.070 (3)0.048 (2)0.024 (4)0.015 (2)0.005 (2)
O30.143 (15)0.34 (4)0.049 (5)0.022 (18)0.012 (7)0.050 (13)
Pr20.065 (8)0.035 (3)0.036 (9)0.023 (4)0.022 (7)0.014 (4)
Bond lengths (Å) top
Pr1—Pr1i0.277 (14)O1—O2ii2.590 (13)
Pr1—Pr1ii0.277 (14)O1—O2xxviii2.717 (19)
Pr1—Mo1iii3.432 (13)O1—O33.27 (2)
Pr1—O1iv2.63 (2)O1—O3xix2.72 (2)
Pr1—O1v2.563 (16)O1—O3i3.27 (2)
Pr1—O1vi2.725 (15)O1—O3xxi2.59 (2)
Pr1—O1vii2.88 (2)O1—O3ii3.32 (2)
Pr1—O1viii2.511 (13)O1—O3xxix3.45 (3)
Pr1—O1iii2.518 (16)O1—O3xxx2.76 (2)
Pr1—O1ix2.68 (2)O1—Mo21.794 (14)
Pr1—O1x2.764 (15)O1—Pr2xxii2.40 (5)
Pr1—O1xi2.471 (14)O1—Pr2xxxi2.87 (7)
Pr1—O2xii2.535 (13)O1—Pr2xxxii2.80 (4)
Pr1—O2vi2.777 (12)O1—Pr2xxiv2.23 (5)
Pr1—O2xiii2.502 (8)O1—Pr2xxxiii2.99 (7)
Pr1—O2iii2.538 (13)O1—Pr2xxxiv2.84 (4)
Pr1—O2xiv2.341 (10)O1—Pr2xxxv2.29 (5)
Pr1—O2xi2.724 (11)O1—Pr2xxxvi2.82 (7)
Pr1—O3xv2.76 (3)O1—Pr2xxxvii2.96 (4)
Pr1—O3xii2.67 (2)O2—O2i3.107 (9)
Pr1—O3xvi2.71 (3)O2—O2xx3.159 (9)
Pr1—O3xiii2.79 (2)O2—O2xxi2.992 (10)
Pr1—O3xvii2.66 (3)O2—O2ii3.107 (9)
Pr1—O3xiv2.60 (2)O2—O2xxxviii2.992 (10)
Pr1—Mo2v3.493 (12)O2—O2xviii3.159 (9)
Pr1—Pr20.36 (6)O2—O31.58 (3)
Pr1—Pr2i0.57 (5)O2—O3xix2.81 (2)
Pr1—Pr2ii0.40 (3)O2—O3i2.76 (2)
Mo1—Mo1i0.637 (13)O2—O3xx2.19 (2)
Mo1—Mo1ii0.637 (13)O2—O3xxi3.23 (3)
Mo1—O11.980 (15)O2—O3ii2.849 (16)
Mo1—O1i1.997 (17)O2—Mo21.794 (7)
Mo1—O1ii1.964 (18)O2—Pr2xxiii2.30 (7)
Mo1—O21.514 (10)O2—Pr2xxxii3.10 (4)
Mo1—O2i2.138 (11)O2—Pr2xxiv2.59 (5)
Mo1—O2ii1.814 (9)O2—Pr2xxv2.14 (3)
Mo1—O2xviii3.244 (14)O2—Pr2xxxix2.63 (5)
Mo1—O31.376 (19)O2—Pr2xxxvi2.65 (6)
Mo1—O3xix3.11 (2)O3—O3i1.73 (3)
Mo1—O3i1.779 (16)O3—O3xx3.35 (3)
Mo1—O3xx3.21 (2)O3—O3ii1.73 (3)
Mo1—O3xxi3.46 (2)O3—O3xviii3.35 (3)
Mo1—O3ii1.595 (15)O3—Mo21.668 (15)
Mo1—Mo20.398 (12)O3—Mo2xl3.29 (2)
Mo1—Pr2xxii3.40 (6)O3—Pr2xli2.91 (5)
Mo1—Pr2xxiii3.33 (7)O3—Pr2xxiii2.32 (6)
Mo1—Pr2xxiv3.33 (5)O3—Pr2xlii2.79 (6)
Mo1—Pr2xxv3.38 (4)O3—Pr2xxv2.59 (5)
O1—O1i0.18 (2)O3—Pr2xliii3.01 (6)
O1—O1ii0.18 (2)O3—Pr2xxxix2.82 (6)
O1—O22.477 (11)Mo2—Pr2xxii3.34 (5)
O1—O2xxvi2.629 (13)Mo2—Pr2xxiv3.34 (5)
O1—O2i2.488 (19)Mo2—Pr2xxxv3.34 (5)
O1—O2xxvii2.736 (13)Pr2—Pr2i0.66 (7)
O1—O2xxi3.482 (16)Pr2—Pr2ii0.66 (7)
Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) z+1, x1/2, y+1/2; (iv) x+1/2, y+1, z1/2; (v) x+1, y1/2, z+1/2; (vi) x1/2, y+1/2, z+1; (vii) z1/2, x+1/2, y+1; (viii) z+1/2, x+1, y1/2; (ix) y+1, z1/2, x+1/2; (x) y1/2, z+1/2, x+1; (xi) y+1/2, z+1, x1/2; (xii) x+1, y1/2, z+3/2; (xiii) z+3/2, x+1, y1/2; (xiv) y1/2, z+3/2, x+1; (xv) x1, y1, z1; (xvi) z1, x1, y1; (xvii) y1, z1, x1; (xviii) y+3/2, z+2, x+1/2; (xix) x1/2, y+3/2, z+2; (xx) z1/2, x+3/2, y+2; (xxi) z+2, x1/2, y+3/2; (xxii) x+1/2, y+1, z+1/2; (xxiii) x+1, y+1/2, z+3/2; (xxiv) z+1/2, x+1/2, y+1; (xxv) z+1, x+1/2, y+3/2; (xxvi) x+3/2, y+1, z1/2; (xxvii) z1/2, x+3/2, y+1; (xxviii) y+1, z1/2, x+3/2; (xxix) y+2, z1/2, x+3/2; (xxx) y+3/2, z+2, x1/2; (xxxi) x+1, y+1/2, z+1/2; (xxxii) x+1/2, y+1/2, z+1; (xxxiii) z+1/2, x+1, y+1/2; (xxxiv) z+1, x+1/2, y+1/2; (xxxv) y+1, z+1/2, x+1/2; (xxxvi) y+1/2, z+1/2, x+1; (xxxvii) y+1/2, z+1, x+1/2; (xxxviii) y+1/2, z+3/2, x+2; (xxxix) y+1, z+1/2, x+3/2; (xl) x+1/2, y+3/2, z+2; (xli) x+1, y+1, z+1; (xlii) z+1, x+1, y+1; (xliii) y+1, z+1, x+1.
(IV) top
Crystal data top
Pr2Mo2O9F(000) = 543
Mr = 617.7Dx = 5.686 Mg m3
Cubic, P213Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac;2ab;3µ = 16.82 mm1
a = 7.0992 (18) ÅT = 293 K
V = 357.79 (16) Å3Sphere, colorless
Z = 20.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
592 reflections with I > 3σ(I)
Radiation source: X-ray tubeRint = 0.025
Graphite monochromatorθmax = 48.8°, θmin = 5.0°
Absorption correction: for a sphere
?
h = 1414
Tmin = 0.662, Tmax = 1.000k = 1314
11700 measured reflectionsl = 1413
634 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.000225F2)
R[F2 > 2σ(F2)] = 0.019(Δ/σ)max = 0.046
wR(F2) = 0.025Δρmax = 0.48 e Å3
S = 1.22Δρmin = 0.43 e Å3
634 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
63 parametersExtinction coefficient: 860 (70)
0 restraintsAbsolute structure: 255 of Friedel pairs used in the refinement
2 constraintsAbsolute structure parameter: 0.02 (2)
Crystal data top
Pr2Mo2O9Z = 2
Mr = 617.7Mo Kα radiation
Cubic, P213µ = 16.82 mm1
a = 7.0992 (18) ÅT = 293 K
V = 357.79 (16) Å30.30 × 0.30 × 0.30 × 0.15 (radius) mm
Data collection top
Oxford Diffraction CCD
diffractometer
634 independent reflections
Absorption correction: for a sphere
?
592 reflections with I > 3σ(I)
Tmin = 0.662, Tmax = 1.000Rint = 0.025
11700 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.025Δρmax = 0.48 e Å3
S = 1.22Δρmin = 0.43 e Å3
634 reflectionsAbsolute structure: 255 of Friedel pairs used in the refinement
63 parametersAbsolute structure parameter: 0.02 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pr10.1353 (10)0.1600 (13)0.1317 (10)0.0414 (11)0.274 (13)
Mo10.8147 (7)0.8254 (6)0.8852 (12)0.0238 (9)0.123 (6)
O10.694 (3)0.6716 (17)0.6845 (10)0.084 (5)0.3333
O20.8122 (12)0.6571 (10)1.0131 (7)0.077 (3)0.72 (2)
O30.913 (3)0.851 (4)1.047 (2)0.171 (17)0.39 (2)
Mo20.8301 (3)0.8301 (3)0.8301 (3)0.0336 (5)*0.630 (18)
Pr20.129 (4)0.186 (3)0.162 (4)0.046 (4)0.059 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pr10.0363 (15)0.053 (2)0.035 (2)0.0193 (9)0.0132 (12)0.0222 (13)
Mo10.0221 (12)0.0169 (10)0.032 (2)0.0091 (8)0.0049 (11)0.0043 (10)
O10.159 (13)0.070 (7)0.023 (4)0.064 (8)0.001 (6)0.018 (4)
O20.120 (7)0.066 (3)0.046 (2)0.026 (4)0.015 (2)0.004 (2)
O30.110 (13)0.35 (5)0.050 (6)0.002 (17)0.012 (7)0.049 (15)
Pr20.073 (7)0.030 (4)0.034 (7)0.020 (3)0.037 (4)0.013 (4)
Bond lengths (Å) top
Pr1—Pr1i0.267 (12)O1—O33.27 (2)
Pr1—Pr1ii0.267 (12)O1—O3xix2.76 (2)
Pr1—Mo1iii3.429 (9)O1—O3i3.26 (3)
Pr1—O1iv2.65 (2)O1—O3xxvi2.61 (2)
Pr1—O1v2.552 (13)O1—O3ii3.32 (2)
Pr1—O1vi2.723 (15)O1—O3xxviii3.42 (4)
Pr1—O1vii2.90 (2)O1—O3xxix2.79 (2)
Pr1—O1viii2.512 (13)O1—Mo21.808 (14)
Pr1—O1iii2.516 (13)O1—Pr2xxx2.51 (3)
Pr1—O1ix2.694 (19)O1—Pr2xxxi2.77 (3)
Pr1—O1x2.753 (14)O1—Pr2xxxii2.80 (3)
Pr1—O1xi2.482 (14)O1—Pr2xxii2.33 (3)
Pr1—O2xii2.549 (9)O1—Pr2xxxiii2.90 (3)
Pr1—O2vi2.775 (11)O1—Pr2xxxiv2.84 (3)
Pr1—O2xiii2.510 (9)O1—Pr2xxxv2.38 (3)
Pr1—O2iii2.546 (10)O1—Pr2xxxvi2.71 (3)
Pr1—O2xiv2.360 (11)O1—Pr2xxxvii2.97 (3)
Pr1—O2xi2.731 (10)O2—O2i3.104 (9)
Pr1—O3xv2.76 (3)O2—O2xx3.168 (9)
Pr1—O3xii2.68 (2)O2—O2xxvi2.999 (10)
Pr1—O3xvi2.72 (3)O2—O2ii3.104 (9)
Pr1—O3xiii2.79 (2)O2—O2xxxviii2.999 (10)
Pr1—O3xvii2.66 (3)O2—O2xviii3.168 (9)
Pr1—O3xiv2.60 (2)O2—O31.58 (3)
Pr1—Pr20.29 (3)O2—O3xix2.86 (2)
Pr1—Pr2i0.48 (3)O2—O3i2.72 (2)
Pr1—Pr2ii0.36 (2)O2—O3xx2.17 (2)
Mo1—Mo1i0.661 (10)O2—O3xxvi3.27 (3)
Mo1—Mo1ii0.661 (10)O2—O3ii2.873 (17)
Mo1—O11.989 (14)O2—Mo21.792 (6)
Mo1—O1i2.006 (15)O2—Pr2xxi2.35 (3)
Mo1—O1ii1.968 (17)O2—Pr2xxxii3.03 (3)
Mo1—O21.501 (9)O2—Pr2xxii2.69 (3)
Mo1—O2i2.149 (9)O2—Pr2xxiii2.15 (2)
Mo1—O2ii1.816 (8)O2—Pr2xxxix2.54 (3)
Mo1—O2xviii3.247 (12)O2—Pr2xxxvi2.64 (3)
Mo1—O31.360 (19)O3—O3i1.74 (3)
Mo1—O3xix3.15 (2)O3—O3xx3.29 (3)
Mo1—O3i1.782 (17)O3—O3ii1.74 (3)
Mo1—O3xx3.16 (2)O3—O3xviii3.29 (3)
Mo1—O3ii1.610 (17)O3—Mo21.659 (16)
Mo1—Mo20.408 (9)O3—Mo2xl3.48 (2)
Mo1—Pr2xxi3.39 (3)O3—Mo2xli3.34 (2)
Mo1—Pr2xxii3.44 (3)O3—Pr2xlii2.94 (4)
Mo1—Pr2xxiii3.35 (3)O3—Pr2xxi2.39 (3)
O1—O1i0.20 (2)O3—Pr2xliii2.82 (4)
O1—O1ii0.20 (2)O3—Pr2xxiii2.52 (3)
O1—O22.481 (11)O3—Pr2xliv2.99 (4)
O1—O2xxiv2.632 (13)O3—Pr2xxxix2.75 (3)
O1—O2i2.483 (19)Mo2—Pr2xxx3.47 (3)
O1—O2xxv2.747 (13)Mo2—Pr2xxii3.47 (3)
O1—O2xxvi3.478 (17)Mo2—Pr2xxxv3.47 (3)
O1—O2ii2.602 (13)Pr2—Pr2i0.50 (4)
O1—O2xxvii2.735 (19)Pr2—Pr2ii0.50 (4)
Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) z+1, x1/2, y+1/2; (iv) x+1/2, y+1, z1/2; (v) x+1, y1/2, z+1/2; (vi) x1/2, y+1/2, z+1; (vii) z1/2, x+1/2, y+1; (viii) z+1/2, x+1, y1/2; (ix) y+1, z1/2, x+1/2; (x) y1/2, z+1/2, x+1; (xi) y+1/2, z+1, x1/2; (xii) x+1, y1/2, z+3/2; (xiii) z+3/2, x+1, y1/2; (xiv) y1/2, z+3/2, x+1; (xv) x1, y1, z1; (xvi) z1, x1, y1; (xvii) y1, z1, x1; (xviii) y+3/2, z+2, x+1/2; (xix) x1/2, y+3/2, z+2; (xx) z1/2, x+3/2, y+2; (xxi) x+1, y+1/2, z+3/2; (xxii) z+1/2, x+1/2, y+1; (xxiii) z+1, x+1/2, y+3/2; (xxiv) x+3/2, y+1, z1/2; (xxv) z1/2, x+3/2, y+1; (xxvi) z+2, x1/2, y+3/2; (xxvii) y+1, z1/2, x+3/2; (xxviii) y+2, z1/2, x+3/2; (xxix) y+3/2, z+2, x1/2; (xxx) x+1/2, y+1, z+1/2; (xxxi) x+1, y+1/2, z+1/2; (xxxii) x+1/2, y+1/2, z+1; (xxxiii) z+1/2, x+1, y+1/2; (xxxiv) z+1, x+1/2, y+1/2; (xxxv) y+1, z+1/2, x+1/2; (xxxvi) y+1/2, z+1/2, x+1; (xxxvii) y+1/2, z+1, x+1/2; (xxxviii) y+1/2, z+3/2, x+2; (xxxix) y+1, z+1/2, x+3/2; (xl) x+3/2, y+2, z+1/2; (xli) x+1/2, y+3/2, z+2; (xlii) x+1, y+1, z+1; (xliii) z+1, x+1, y+1; (xliv) y+1, z+1, x+1.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaLa2Mo2O9La2Mo2O9Pr2Mo2O9Pr2Mo2O9
Mr613.7613.7617.7617.7
Crystal system, space groupCubic, P213Cubic, P213Cubic, P213Cubic, P213
Temperature (K)293293293293
a (Å)7.1552 (9) 7.155 (1) 7.0849 (11) 7.0992 (18)
V3)366.32 (8)366.29 (9)355.63 (10)357.79 (16)
Z2222
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)14.7814.7816.9216.82
Crystal size (mm)0.30 × 0.30 × 0.30 × 0.15 (radius)0.30 × 0.30 × 0.30 × 0.15 (radius)0.30 × 0.30 × 0.30 × 0.15 (radius)0.30 × 0.30 × 0.30 × 0.15 (radius)
Data collection
DiffractometerOxford Diffraction CCD
diffractometer
Oxford Diffraction CCD
diffractometer
Oxford Diffraction CCD
diffractometer
Oxford Diffraction CCD
diffractometer
Absorption correctionFor a sphereFor a sphere
(Jana2000; Petricek, Dusek & Palatinus, 2000)
For a sphereFor a sphere
Tmin, Tmax0.776, 1.0000.614, 1.0000.716, 1.0000.662, 1.000
No. of measured, independent and
observed [I > 3σ(I)] reflections
14670, 767, 710 33307, 1281, 820 10229, 551, 512 11700, 634, 592
Rint0.0220.0590.0250.025
(sin θ/λ)max1)1.0601.0741.0491.059
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.024, 1.15 0.021, 0.030, 1.08 0.017, 0.022, 1.06 0.019, 0.025, 1.22
No. of reflections7671281551634
No. of parameters63636263
Δρmax, Δρmin (e Å3)0.48, 0.760.57, 0.460.33, 0.220.48, 0.43
Absolute structure312 of Friedel pairs used in the refinement551 of Friedel pairs used in the refinement220 of Friedel pairs used in the refinement255 of Friedel pairs used in the refinement
Absolute structure parameter0.016 (19)0.017 (19)0.01 (2)0.02 (2)

 

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