Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019048/na6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019048/na6011Isup2.hkl |
Single crystals of PrMo6O12 were obtained by the electrolysis of a melt formed at 1233 K from a mixture of Rb2MoO4, MoO3 and Pr6O11 having the molar ratio 25:15:1. The electrolysis was carried out in air using an alumina crucible. The anode was a platinum foil with a surface area of about 1 cm2 and the cathode a 10-turn spiral platinum made from a 0.4 mm diameter wire. At the end of the run, the electrodes were raised above the melt to allow them to cool rapidly to room temperature. Crystals which grow perpendicularly to the cathode in the form of black needle-shaped square prisms with the needle axis parallel to the tetragonal c axis (maximum dimensions 0.8 x 0.8 x 5 mm) were obtained by applying a constant current of 36 mA for 12 h. Single crystals were separated from the matrix and the cathode by repeated and alternate washings in hot dilute solutions of potassium carbonate and hydrochloric acid.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
PrMo6O12 | Dx = 7.095 Mg m−3 |
Mr = 908.55 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4/m | Cell parameters from 25 reflections |
a = 9.9147 (3) Å | θ = 10.3–31.4° |
c = 8.6508 (6) Å | µ = 14.25 mm−1 |
V = 850.38 (7) Å3 | T = 293 K |
Z = 4 | Parallelepiped, black |
F(000) = 1628 | 0.29 × 0.03 × 0.02 mm |
Enraf-Nonius CAD-4 diffractometer | 1242 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 40.0°, θmin = 2.9° |
θ–2θ scans | h = 0→17 |
Absorption correction: numerical (Coppens, 1970) | k = 0→17 |
Tmin = 0.340, Tmax = 0.768 | l = 0→15 |
1494 measured reflections | 3 standard reflections every 3600 min |
1385 independent reflections | intensity decay: <1% |
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)] = 0.032 | w = 1/[σ2(Fo2) + (0.0281P)2 + 24.9952P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.081 | (Δ/σ)max < 0.001 |
S = 1.18 | Δρmax = 3.40 e Å−3 |
1385 reflections | Δρmin = −2.99 e Å−3 |
50 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00110 (9) |
PrMo6O12 | Z = 4 |
Mr = 908.55 | Mo Kα radiation |
Tetragonal, I4/m | µ = 14.25 mm−1 |
a = 9.9147 (3) Å | T = 293 K |
c = 8.6508 (6) Å | 0.29 × 0.03 × 0.02 mm |
V = 850.38 (7) Å3 |
Enraf-Nonius CAD-4 diffractometer | 1242 reflections with I > 2σ(I) |
Absorption correction: numerical (Coppens, 1970) | Rint = 0.036 |
Tmin = 0.340, Tmax = 0.768 | 3 standard reflections every 3600 min |
1494 measured reflections | intensity decay: <1% |
1385 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0281P)2 + 24.9952P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | Δρmax = 3.40 e Å−3 |
1385 reflections | Δρmin = −2.99 e Å−3 |
50 parameters |
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 | ||
Pr1 | 0.0000 | 0.0000 | −0.20745 (5) | 0.00788 (9) | |
Mo1 | 0.34033 (3) | −0.81670 (3) | −0.34174 (4) | 0.00648 (8) | |
Mo2 | 0.33255 (4) | −0.81617 (4) | 0.0000 | 0.00494 (9) | |
O1 | 0.4568 (3) | −0.1706 (3) | −0.3324 (3) | 0.0066 (4) | |
O2 | 0.1722 (3) | −0.1305 (3) | −0.3329 (3) | 0.0084 (4) | |
O3 | 0.4631 (4) | −0.1626 (4) | 0.0000 | 0.0062 (6) | |
O4 | 0.1229 (4) | 0.1602 (4) | 0.0000 | 0.0065 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pr1 | 0.00901 (11) | 0.00901 (11) | 0.00562 (16) | 0.000 | 0.000 | 0.000 |
Mo1 | 0.00547 (12) | 0.00510 (12) | 0.00887 (14) | −0.00143 (8) | −0.00238 (9) | 0.00218 (9) |
Mo2 | 0.00505 (16) | 0.00513 (16) | 0.00464 (16) | 0.00037 (11) | 0.000 | 0.000 |
O1 | 0.0043 (9) | 0.0096 (10) | 0.0058 (11) | −0.0006 (8) | −0.0002 (8) | −0.0006 (8) |
O2 | 0.0085 (10) | 0.0103 (11) | 0.0062 (11) | −0.0024 (8) | 0.0005 (8) | −0.0016 (9) |
O3 | 0.0060 (13) | 0.0076 (14) | 0.0052 (14) | −0.0010 (11) | 0.000 | 0.000 |
O4 | 0.0066 (14) | 0.0080 (14) | 0.0050 (14) | 0.0000 (11) | 0.000 | 0.000 |
Pr1—O2 | 2.401 (3) | Mo2—O2xv | 2.064 (3) |
Pr1—O4 | 2.688 (3) | Mo2—O2viii | 2.064 (3) |
Pr1—O1i | 3.312 (3) | Mo2—O4xiii | 2.092 (4) |
Pr1—Mo1ii | 3.5421 (3) | Mo2—Mo1xi | 2.5589 (5) |
Pr1—Pr1iii | 3.5892 (10) | Mo2—Mo1xvi | 2.5589 (5) |
Pr1—Mo1iv | 4.0048 (4) | Mo2—Mo1xvii | 2.9573 (4) |
Pr1—Mo2v | 4.1730 (5) | Mo2—Pr1xiii | 4.1730 (5) |
Pr1—Mo2vi | 4.3575 (5) | Mo2—Pr1xviii | 4.1730 (5) |
Pr1—Pr1vii | 5.0616 (10) | O1—Mo2xix | 2.012 (3) |
Mo1—O3viii | 1.996 (3) | O1—Mo1ix | 2.017 (3) |
Mo1—O1ix | 2.017 (3) | O1—Mo1xx | 2.052 (3) |
Mo1—O1viii | 2.052 (3) | O1—Pr1ii | 3.312 (3) |
Mo1—O2x | 2.085 (3) | O2—Mo2xix | 2.064 (3) |
Mo1—O4ii | 2.101 (3) | O2—Mo1xxi | 2.085 (3) |
Mo1—O2viii | 2.102 (3) | O2—Mo1xx | 2.102 (3) |
Mo1—Mo2xi | 2.5589 (5) | O3—Mo1xx | 1.996 (3) |
Mo1—Mo1xi | 2.7344 (7) | O3—Mo1xxii | 1.996 (3) |
Mo1—Mo1xii | 2.7381 (7) | O3—Mo2xiv | 2.036 (4) |
Mo1—Mo2 | 2.9573 (4) | O4—Mo2v | 2.092 (4) |
Mo1—Pr1ii | 3.5421 (3) | O4—Mo1xxiii | 2.101 (3) |
Mo1—Pr1xiii | 4.0048 (4) | O4—Mo1ii | 2.101 (3) |
Mo2—O1viii | 2.012 (3) | O4—Pr1iii | 2.688 (3) |
Mo2—O3xiv | 2.036 (4) | ||
O2xxiv—Pr1—O2xxv | 126.26 (15) | Mo1xxix—Pr1—Mo2xxx | 171.373 (13) |
O2xxiv—Pr1—O2xxvi | 78.21 (6) | Mo2v—Pr1—Mo2xxx | 79.342 (5) |
O2xxv—Pr1—O2xxvi | 78.21 (6) | Mo2xviii—Pr1—Mo2xxx | 79.342 (5) |
O2xxiv—Pr1—O2 | 78.21 (6) | Mo2xxix—Pr1—Mo2xxx | 129.058 (13) |
O2xxv—Pr1—O2 | 78.21 (6) | O2xxiv—Pr1—Mo2vi | 11.70 (7) |
O2xxvi—Pr1—O2 | 126.26 (15) | O2xxv—Pr1—Mo2vi | 117.02 (7) |
O2xxiv—Pr1—O4 | 164.99 (9) | O2xxvi—Pr1—Mo2vi | 81.61 (7) |
O2xxv—Pr1—O4 | 68.75 (9) | O2—Pr1—Mo2vi | 67.72 (7) |
O2xxvi—Pr1—O4 | 107.80 (11) | O4—Pr1—Mo2vi | 170.18 (8) |
O2—Pr1—O4 | 107.32 (11) | O4xxvii—Pr1—Mo2vi | 106.66 (8) |
O2xxiv—Pr1—O4xxvii | 107.32 (11) | O4xxv—Pr1—Mo2vi | 119.25 (8) |
O2xxv—Pr1—O4xxvii | 107.80 (11) | O4iii—Pr1—Mo2vi | 77.88 (6) |
O2xxvi—Pr1—O4xxvii | 164.99 (9) | O1i—Pr1—Mo2vi | 121.95 (5) |
O2—Pr1—O4xxvii | 68.75 (9) | O1xx—Pr1—Mo2vi | 65.91 (5) |
O4—Pr1—O4xxvii | 63.54 (7) | O1xxviii—Pr1—Mo2vi | 136.11 (5) |
O2xxiv—Pr1—O4xxv | 107.80 (11) | O1ii—Pr1—Mo2vi | 53.15 (5) |
O2xxv—Pr1—O4xxv | 107.32 (11) | Mo1ii—Pr1—Mo2vi | 151.374 (14) |
O2xxvi—Pr1—O4xxv | 68.75 (9) | Mo1xxviii—Pr1—Mo2vi | 42.420 (7) |
O2—Pr1—O4xxv | 164.99 (9) | Mo1xx—Pr1—Mo2vi | 94.934 (9) |
O4—Pr1—O4xxv | 63.54 (7) | Mo1i—Pr1—Mo2vi | 93.069 (9) |
O4xxvii—Pr1—O4xxv | 96.25 (12) | Pr1iii—Pr1—Mo2vi | 125.506 (6) |
O2xxiv—Pr1—O4iii | 68.75 (9) | Mo1iv—Pr1—Mo2vi | 35.318 (8) |
O2xxv—Pr1—O4iii | 164.99 (9) | Mo1v—Pr1—Mo2vi | 118.620 (12) |
O2xxvi—Pr1—O4iii | 107.32 (11) | Mo1xxi—Pr1—Mo2vi | 53.008 (8) |
O2—Pr1—O4iii | 107.80 (11) | Mo1xxix—Pr1—Mo2vi | 105.352 (10) |
O4—Pr1—O4iii | 96.25 (12) | Mo2v—Pr1—Mo2vi | 149.885 (11) |
O4xxvii—Pr1—O4iii | 63.54 (7) | Mo2xviii—Pr1—Mo2vi | 68.563 (5) |
O4xxv—Pr1—O4iii | 63.54 (7) | Mo2xxix—Pr1—Mo2vi | 130.674 (11) |
O2xxiv—Pr1—O1i | 132.08 (9) | Mo2xxx—Pr1—Mo2vi | 81.245 (10) |
O2xxv—Pr1—O1i | 54.82 (9) | O2xxiv—Pr1—Mo2i | 67.72 (7) |
O2xxvi—Pr1—O1i | 132.73 (9) | O2xxv—Pr1—Mo2i | 81.61 (7) |
O2—Pr1—O1i | 54.23 (8) | O2xxvi—Pr1—Mo2i | 11.70 (7) |
O4—Pr1—O1i | 53.65 (9) | O2—Pr1—Mo2i | 117.02 (7) |
O4xxvii—Pr1—O1i | 53.60 (9) | O4—Pr1—Mo2i | 119.25 (8) |
O4xxv—Pr1—O1i | 117.03 (9) | O4xxvii—Pr1—Mo2i | 170.18 (8) |
O4iii—Pr1—O1i | 116.99 (9) | O4xxv—Pr1—Mo2i | 77.88 (6) |
O2xxiv—Pr1—O1xx | 54.82 (9) | O4iii—Pr1—Mo2i | 106.66 (8) |
O2xxv—Pr1—O1xx | 132.08 (9) | O1i—Pr1—Mo2i | 136.11 (5) |
O2xxvi—Pr1—O1xx | 54.23 (8) | O1xx—Pr1—Mo2i | 53.15 (5) |
O2—Pr1—O1xx | 132.73 (9) | O1xxviii—Pr1—Mo2i | 65.91 (5) |
O4—Pr1—O1xx | 116.99 (9) | O1ii—Pr1—Mo2i | 121.95 (5) |
O4xxvii—Pr1—O1xx | 117.03 (9) | Mo1ii—Pr1—Mo2i | 93.069 (9) |
O4xxv—Pr1—O1xx | 53.60 (9) | Mo1xxviii—Pr1—Mo2i | 94.934 (9) |
O4iii—Pr1—O1xx | 53.65 (9) | Mo1xx—Pr1—Mo2i | 151.374 (14) |
O1i—Pr1—O1xx | 168.05 (10) | Mo1i—Pr1—Mo2i | 42.420 (7) |
O2xxiv—Pr1—O1xxviii | 132.73 (9) | Pr1iii—Pr1—Mo2i | 125.506 (6) |
O2xxv—Pr1—O1xxviii | 54.23 (8) | Mo1iv—Pr1—Mo2i | 53.008 (8) |
O2xxvi—Pr1—O1xxviii | 54.82 (9) | Mo1v—Pr1—Mo2i | 105.352 (10) |
O2—Pr1—O1xxviii | 132.08 (9) | Mo1xxi—Pr1—Mo2i | 118.620 (12) |
O4—Pr1—O1xxviii | 53.60 (9) | Mo1xxix—Pr1—Mo2i | 35.318 (7) |
O4xxvii—Pr1—O1xxviii | 116.99 (9) | Mo2v—Pr1—Mo2i | 130.674 (11) |
O4xxv—Pr1—O1xxviii | 53.65 (9) | Mo2xviii—Pr1—Mo2i | 81.245 (10) |
O4iii—Pr1—O1xxviii | 117.03 (9) | Mo2xxix—Pr1—Mo2i | 68.563 (5) |
O1i—Pr1—O1xxviii | 89.380 (10) | Mo2xxx—Pr1—Mo2i | 149.885 (11) |
O1xx—Pr1—O1xxviii | 89.380 (10) | Mo2vi—Pr1—Mo2i | 70.286 (6) |
O2xxiv—Pr1—O1ii | 54.23 (8) | O2xxiv—Pr1—Mo2ii | 117.02 (7) |
O2xxv—Pr1—O1ii | 132.73 (9) | O2xxv—Pr1—Mo2ii | 11.70 (7) |
O2xxvi—Pr1—O1ii | 132.08 (9) | O2xxvi—Pr1—Mo2ii | 67.72 (7) |
O2—Pr1—O1ii | 54.82 (9) | O2—Pr1—Mo2ii | 81.61 (7) |
O4—Pr1—O1ii | 117.03 (9) | O4—Pr1—Mo2ii | 77.88 (6) |
O4xxvii—Pr1—O1ii | 53.65 (9) | O4xxvii—Pr1—Mo2ii | 119.25 (8) |
O4xxv—Pr1—O1ii | 116.99 (9) | O4xxv—Pr1—Mo2ii | 106.66 (8) |
O4iii—Pr1—O1ii | 53.60 (9) | O4iii—Pr1—Mo2ii | 170.18 (8) |
O1i—Pr1—O1ii | 89.380 (10) | O1i—Pr1—Mo2ii | 65.91 (5) |
O1xx—Pr1—O1ii | 89.380 (10) | O1xx—Pr1—Mo2ii | 121.95 (5) |
O1xxviii—Pr1—O1ii | 168.05 (10) | O1xxviii—Pr1—Mo2ii | 53.15 (5) |
O2xxiv—Pr1—Mo1ii | 157.72 (7) | O1ii—Pr1—Mo2ii | 136.11 (5) |
O2xxv—Pr1—Mo1ii | 35.24 (7) | Mo1ii—Pr1—Mo2ii | 42.420 (7) |
O2xxvi—Pr1—Mo1ii | 83.95 (7) | Mo1xxviii—Pr1—Mo2ii | 151.374 (14) |
O2—Pr1—Mo1ii | 102.36 (7) | Mo1xx—Pr1—Mo2ii | 93.069 (9) |
O4—Pr1—Mo1ii | 36.25 (6) | Mo1i—Pr1—Mo2ii | 94.934 (9) |
O4xxvii—Pr1—Mo1ii | 93.30 (9) | Pr1iii—Pr1—Mo2ii | 125.506 (6) |
O4xxv—Pr1—Mo1ii | 77.41 (9) | Mo1iv—Pr1—Mo2ii | 118.620 (12) |
O4iii—Pr1—Mo1ii | 130.24 (6) | Mo1v—Pr1—Mo2ii | 35.318 (8) |
O1i—Pr1—Mo1ii | 55.40 (5) | Mo1xxi—Pr1—Mo2ii | 105.352 (10) |
O1xx—Pr1—Mo1ii | 122.87 (5) | Mo1xxix—Pr1—Mo2ii | 53.008 (8) |
O1xxviii—Pr1—Mo1ii | 34.01 (5) | Mo2v—Pr1—Mo2ii | 68.563 (5) |
O1ii—Pr1—Mo1ii | 143.51 (5) | Mo2xviii—Pr1—Mo2ii | 149.885 (11) |
O2xxiv—Pr1—Mo1xxviii | 35.24 (7) | Mo2xxix—Pr1—Mo2ii | 81.245 (10) |
O2xxv—Pr1—Mo1xxviii | 157.72 (7) | Mo2xxx—Pr1—Mo2ii | 130.674 (11) |
O2xxvi—Pr1—Mo1xxviii | 102.36 (7) | Mo2vi—Pr1—Mo2ii | 108.987 (13) |
O2—Pr1—Mo1xxviii | 83.95 (7) | Mo2i—Pr1—Mo2ii | 70.286 (6) |
O4—Pr1—Mo1xxviii | 130.24 (6) | O2xxiv—Pr1—Mo2xix | 81.61 (7) |
O4xxvii—Pr1—Mo1xxviii | 77.41 (9) | O2xxv—Pr1—Mo2xix | 67.72 (7) |
O4xxv—Pr1—Mo1xxviii | 93.30 (9) | O2xxvi—Pr1—Mo2xix | 117.02 (7) |
O4iii—Pr1—Mo1xxviii | 36.25 (6) | O2—Pr1—Mo2xix | 11.70 (7) |
O1i—Pr1—Mo1xxviii | 122.87 (5) | O4—Pr1—Mo2xix | 106.66 (8) |
O1xx—Pr1—Mo1xxviii | 55.40 (5) | O4xxvii—Pr1—Mo2xix | 77.88 (6) |
O1xxviii—Pr1—Mo1xxviii | 143.51 (5) | O4xxv—Pr1—Mo2xix | 170.18 (8) |
O1ii—Pr1—Mo1xxviii | 34.01 (5) | O4iii—Pr1—Mo2xix | 119.25 (8) |
Mo1ii—Pr1—Mo1xxviii | 166.201 (19) | O1i—Pr1—Mo2xix | 53.15 (5) |
O2xxiv—Pr1—Mo1xx | 102.36 (7) | O1xx—Pr1—Mo2xix | 136.11 (5) |
O2xxv—Pr1—Mo1xx | 83.95 (7) | O1xxviii—Pr1—Mo2xix | 121.95 (5) |
O2xxvi—Pr1—Mo1xx | 157.72 (7) | O1ii—Pr1—Mo2xix | 65.91 (5) |
O2—Pr1—Mo1xx | 35.24 (7) | Mo1ii—Pr1—Mo2xix | 94.934 (9) |
O4—Pr1—Mo1xx | 77.41 (9) | Mo1xxviii—Pr1—Mo2xix | 93.069 (9) |
O4xxvii—Pr1—Mo1xx | 36.25 (6) | Mo1xx—Pr1—Mo2xix | 42.420 (7) |
O4xxv—Pr1—Mo1xx | 130.24 (6) | Mo1i—Pr1—Mo2xix | 151.374 (14) |
O4iii—Pr1—Mo1xx | 93.30 (9) | Pr1iii—Pr1—Mo2xix | 125.506 (6) |
O1i—Pr1—Mo1xx | 34.01 (5) | Mo1iv—Pr1—Mo2xix | 105.352 (10) |
O1xx—Pr1—Mo1xx | 143.51 (5) | Mo1v—Pr1—Mo2xix | 53.008 (8) |
O1xxviii—Pr1—Mo1xx | 122.87 (5) | Mo1xxi—Pr1—Mo2xix | 35.318 (8) |
O1ii—Pr1—Mo1xx | 55.40 (5) | Mo1xxix—Pr1—Mo2xix | 118.620 (12) |
Mo1ii—Pr1—Mo1xx | 89.173 (2) | Mo2v—Pr1—Mo2xix | 81.245 (10) |
Mo1xxviii—Pr1—Mo1xx | 89.173 (2) | Mo2xviii—Pr1—Mo2xix | 130.674 (11) |
O2xxiv—Pr1—Mo1i | 83.95 (7) | Mo2xxix—Pr1—Mo2xix | 149.885 (11) |
O2xxv—Pr1—Mo1i | 102.36 (7) | Mo2xxx—Pr1—Mo2xix | 68.563 (5) |
O2xxvi—Pr1—Mo1i | 35.24 (7) | Mo2vi—Pr1—Mo2xix | 70.286 (6) |
O2—Pr1—Mo1i | 157.72 (7) | Mo2i—Pr1—Mo2xix | 108.987 (13) |
O4—Pr1—Mo1i | 93.30 (9) | Mo2ii—Pr1—Mo2xix | 70.286 (6) |
O4xxvii—Pr1—Mo1i | 130.24 (6) | O2xxiv—Pr1—Pr1vii | 63.13 (7) |
O4xxv—Pr1—Mo1i | 36.25 (6) | O2xxv—Pr1—Pr1vii | 63.13 (7) |
O4iii—Pr1—Mo1i | 77.41 (9) | O2xxvi—Pr1—Pr1vii | 63.13 (7) |
O1i—Pr1—Mo1i | 143.51 (5) | O2—Pr1—Pr1vii | 63.13 (7) |
O1xx—Pr1—Mo1i | 34.01 (5) | O4—Pr1—Pr1vii | 131.88 (6) |
O1xxviii—Pr1—Mo1i | 55.40 (5) | O4xxvii—Pr1—Pr1vii | 131.88 (6) |
O1ii—Pr1—Mo1i | 122.87 (5) | O4xxv—Pr1—Pr1vii | 131.88 (6) |
Mo1ii—Pr1—Mo1i | 89.173 (2) | O4iii—Pr1—Pr1vii | 131.88 (6) |
Mo1xxviii—Pr1—Mo1i | 89.173 (2) | O1i—Pr1—Pr1vii | 95.97 (5) |
Mo1xx—Pr1—Mo1i | 166.201 (18) | O1xx—Pr1—Pr1vii | 95.97 (5) |
O2xxiv—Pr1—Pr1iii | 116.87 (7) | O1xxviii—Pr1—Pr1vii | 95.97 (5) |
O2xxv—Pr1—Pr1iii | 116.87 (7) | O1ii—Pr1—Pr1vii | 95.97 (5) |
O2xxvi—Pr1—Pr1iii | 116.87 (7) | Mo1ii—Pr1—Pr1vii | 96.900 (9) |
O2—Pr1—Pr1iii | 116.87 (7) | Mo1xxviii—Pr1—Pr1vii | 96.900 (9) |
O4—Pr1—Pr1iii | 48.12 (6) | Mo1xx—Pr1—Pr1vii | 96.900 (9) |
O4xxvii—Pr1—Pr1iii | 48.12 (6) | Mo1i—Pr1—Pr1vii | 96.900 (9) |
O4xxv—Pr1—Pr1iii | 48.12 (6) | Pr1iii—Pr1—Pr1vii | 180.0 |
O4iii—Pr1—Pr1iii | 48.12 (6) | Mo1iv—Pr1—Pr1vii | 73.137 (8) |
O1i—Pr1—Pr1iii | 84.03 (5) | Mo1v—Pr1—Pr1vii | 73.137 (8) |
O1xx—Pr1—Pr1iii | 84.03 (5) | Mo1xxi—Pr1—Pr1vii | 73.137 (8) |
O1xxviii—Pr1—Pr1iii | 84.03 (5) | Mo1xxix—Pr1—Pr1vii | 73.137 (8) |
O1ii—Pr1—Pr1iii | 84.03 (5) | Mo2v—Pr1—Pr1vii | 115.471 (6) |
Mo1ii—Pr1—Pr1iii | 83.100 (9) | Mo2xviii—Pr1—Pr1vii | 115.471 (7) |
Mo1xxviii—Pr1—Pr1iii | 83.100 (9) | Mo2xxix—Pr1—Pr1vii | 115.471 (6) |
Mo1xx—Pr1—Pr1iii | 83.100 (9) | Mo2xxx—Pr1—Pr1vii | 115.471 (6) |
Mo1i—Pr1—Pr1iii | 83.100 (9) | Mo2vi—Pr1—Pr1vii | 54.494 (6) |
O2xxiv—Pr1—Mo1iv | 24.82 (7) | Mo2i—Pr1—Pr1vii | 54.494 (6) |
O2xxv—Pr1—Mo1iv | 130.20 (8) | Mo2ii—Pr1—Pr1vii | 54.494 (6) |
O2xxvi—Pr1—Mo1iv | 60.94 (7) | Mo2xix—Pr1—Pr1vii | 54.494 (6) |
O2—Pr1—Mo1iv | 102.92 (7) | O3viii—Mo1—O1ix | 89.81 (15) |
O4—Pr1—Mo1iv | 147.52 (8) | O3viii—Mo1—O1viii | 90.58 (11) |
O4xxvii—Pr1—Mo1iv | 119.06 (9) | O1ix—Mo1—O1viii | 88.90 (15) |
O4xxv—Pr1—Mo1iv | 84.35 (8) | O3viii—Mo1—O2x | 88.40 (14) |
O4iii—Pr1—Mo1iv | 62.85 (6) | O1ix—Mo1—O2x | 172.05 (12) |
O1i—Pr1—Mo1iv | 156.88 (5) | O1viii—Mo1—O2x | 83.38 (12) |
O1xx—Pr1—Mo1iv | 30.76 (5) | O3viii—Mo1—O4ii | 95.33 (11) |
O1xxviii—Pr1—Mo1iv | 111.64 (5) | O1ix—Mo1—O4ii | 84.22 (14) |
O1ii—Pr1—Mo1iv | 72.03 (5) | O1viii—Mo1—O4ii | 170.90 (12) |
Mo1ii—Pr1—Mo1iv | 144.458 (10) | O2x—Mo1—O4ii | 103.65 (14) |
Mo1xxviii—Pr1—Mo1iv | 41.927 (10) | O3viii—Mo1—O2viii | 172.24 (14) |
Mo1xx—Pr1—Mo1iv | 125.376 (10) | O1ix—Mo1—O2viii | 82.90 (12) |
Mo1i—Pr1—Mo1iv | 59.386 (10) | O1viii—Mo1—O2viii | 86.63 (11) |
Pr1iii—Pr1—Mo1iv | 106.863 (8) | O2x—Mo1—O2viii | 98.46 (12) |
O2xxiv—Pr1—Mo1v | 130.20 (8) | O4ii—Mo1—O2viii | 86.62 (11) |
O2xxv—Pr1—Mo1v | 24.82 (7) | O3viii—Mo1—Mo2xi | 89.86 (10) |
O2xxvi—Pr1—Mo1v | 102.92 (7) | O1ix—Mo1—Mo2xi | 136.19 (8) |
O2—Pr1—Mo1v | 60.94 (7) | O1viii—Mo1—Mo2xi | 134.91 (9) |
O4—Pr1—Mo1v | 62.85 (6) | O2x—Mo1—Mo2xi | 51.56 (8) |
O4xxvii—Pr1—Mo1v | 84.35 (8) | O4ii—Mo1—Mo2xi | 52.22 (11) |
O4xxv—Pr1—Mo1v | 119.06 (9) | O2viii—Mo1—Mo2xi | 97.23 (8) |
O4iii—Pr1—Mo1v | 147.52 (8) | O3viii—Mo1—Mo1xi | 137.76 (12) |
O1i—Pr1—Mo1v | 30.76 (5) | O1ix—Mo1—Mo1xi | 131.32 (9) |
O1xx—Pr1—Mo1v | 156.88 (5) | O1viii—Mo1—Mo1xi | 82.35 (8) |
O1xxviii—Pr1—Mo1v | 72.03 (5) | O2x—Mo1—Mo1xi | 49.50 (8) |
O1ii—Pr1—Mo1v | 111.64 (5) | O4ii—Mo1—Mo1xi | 97.74 (10) |
Mo1ii—Pr1—Mo1v | 41.927 (10) | O2viii—Mo1—Mo1xi | 48.96 (9) |
Mo1xxviii—Pr1—Mo1v | 144.458 (10) | Mo2xi—Mo1—Mo1xi | 67.837 (14) |
Mo1xx—Pr1—Mo1v | 59.386 (10) | O3viii—Mo1—Mo1xii | 46.69 (8) |
Mo1i—Pr1—Mo1v | 125.376 (10) | O1ix—Mo1—Mo1xii | 92.30 (8) |
Pr1iii—Pr1—Mo1v | 106.863 (8) | O1viii—Mo1—Mo1xii | 137.23 (8) |
Mo1iv—Pr1—Mo1v | 146.274 (16) | O2x—Mo1—Mo1xii | 92.11 (8) |
O2xxiv—Pr1—Mo1xxi | 60.94 (7) | O4ii—Mo1—Mo1xii | 49.34 (7) |
O2xxv—Pr1—Mo1xxi | 102.92 (7) | O2viii—Mo1—Mo1xii | 135.94 (8) |
O2xxvi—Pr1—Mo1xxi | 130.20 (8) | Mo2xi—Mo1—Mo1xii | 57.654 (10) |
O2—Pr1—Mo1xxi | 24.82 (7) | Mo1xi—Mo1—Mo1xii | 125.483 (14) |
O4—Pr1—Mo1xxi | 119.06 (9) | O3viii—Mo1—Mo2 | 133.36 (8) |
O4xxvii—Pr1—Mo1xxi | 62.85 (6) | O1ix—Mo1—Mo2 | 89.20 (8) |
O4xxv—Pr1—Mo1xxi | 147.52 (8) | O1viii—Mo1—Mo2 | 42.78 (8) |
O4iii—Pr1—Mo1xxi | 84.35 (8) | O2x—Mo1—Mo2 | 86.41 (8) |
O1i—Pr1—Mo1xxi | 72.03 (5) | O4ii—Mo1—Mo2 | 130.88 (8) |
O1xx—Pr1—Mo1xxi | 111.64 (5) | O2viii—Mo1—Mo2 | 44.27 (8) |
O1xxviii—Pr1—Mo1xxi | 156.88 (5) | Mo2xi—Mo1—Mo2 | 121.095 (13) |
O1ii—Pr1—Mo1xxi | 30.76 (5) | Mo1xi—Mo1—Mo2 | 53.257 (15) |
Mo1ii—Pr1—Mo1xxi | 125.376 (10) | Mo1xii—Mo1—Mo2 | 178.501 (11) |
Mo1xxviii—Pr1—Mo1xxi | 59.386 (10) | O3viii—Mo1—Pr1ii | 137.22 (10) |
Mo1xx—Pr1—Mo1xxi | 41.927 (10) | O1ix—Mo1—Pr1ii | 66.73 (9) |
Mo1i—Pr1—Mo1xxi | 144.458 (10) | O1viii—Mo1—Pr1ii | 122.38 (8) |
Pr1iii—Pr1—Mo1xxi | 106.863 (8) | O2x—Mo1—Pr1ii | 119.24 (9) |
Mo1iv—Pr1—Mo1xxi | 85.173 (5) | O4ii—Mo1—Pr1ii | 49.16 (8) |
Mo1v—Pr1—Mo1xxi | 85.173 (5) | O2viii—Mo1—Pr1ii | 41.23 (8) |
O2xxiv—Pr1—Mo1xxix | 102.92 (7) | Mo2xi—Mo1—Pr1ii | 84.680 (13) |
O2xxv—Pr1—Mo1xxix | 60.94 (7) | Mo1xi—Mo1—Pr1ii | 78.127 (14) |
O2xxvi—Pr1—Mo1xxix | 24.82 (7) | Mo1xii—Mo1—Pr1ii | 96.900 (9) |
O2—Pr1—Mo1xxix | 130.20 (8) | Mo2—Mo1—Pr1ii | 83.684 (14) |
O4—Pr1—Mo1xxix | 84.35 (8) | O3viii—Mo1—Pr1xiii | 81.74 (11) |
O4xxvii—Pr1—Mo1xxix | 147.52 (8) | O1ix—Mo1—Pr1xiii | 143.15 (8) |
O4xxv—Pr1—Mo1xxix | 62.85 (6) | O1viii—Mo1—Pr1xiii | 55.63 (8) |
O4iii—Pr1—Mo1xxix | 119.06 (9) | O2x—Mo1—Pr1xiii | 28.90 (8) |
O1i—Pr1—Mo1xxix | 111.64 (5) | O4ii—Mo1—Pr1xiii | 132.09 (11) |
O1xx—Pr1—Mo1xxix | 72.03 (5) | O2viii—Mo1—Pr1xiii | 102.53 (9) |
O1xxviii—Pr1—Mo1xxix | 30.76 (5) | Mo2xi—Mo1—Pr1xiii | 79.889 (13) |
O1ii—Pr1—Mo1xxix | 156.88 (5) | Mo1xi—Mo1—Pr1xiii | 59.946 (12) |
Mo1ii—Pr1—Mo1xxix | 59.386 (10) | Mo1xii—Mo1—Pr1xiii | 106.863 (8) |
Mo1xxviii—Pr1—Mo1xxix | 125.376 (10) | Mo2—Mo1—Pr1xiii | 71.870 (13) |
Mo1xx—Pr1—Mo1xxix | 144.458 (10) | Pr1ii—Mo1—Pr1xiii | 138.073 (10) |
Mo1i—Pr1—Mo1xxix | 41.927 (10) | O1viii—Mo2—O1xv | 92.21 (16) |
Pr1iii—Pr1—Mo1xxix | 106.863 (8) | O1viii—Mo2—O3xiv | 86.78 (12) |
Mo1iv—Pr1—Mo1xxix | 85.173 (4) | O1xv—Mo2—O3xiv | 86.78 (12) |
Mo1v—Pr1—Mo1xxix | 85.173 (5) | O1viii—Mo2—O2xv | 170.62 (13) |
Mo1xxi—Pr1—Mo1xxix | 146.274 (16) | O1xv—Mo2—O2xv | 88.70 (12) |
O2xxiv—Pr1—Mo2v | 158.52 (7) | O3xiv—Mo2—O2xv | 83.95 (12) |
O2xxv—Pr1—Mo2v | 57.19 (7) | O1viii—Mo2—O2viii | 88.70 (12) |
O2xxvi—Pr1—Mo2v | 121.39 (7) | O1xv—Mo2—O2viii | 170.62 (13) |
O2—Pr1—Mo2v | 82.41 (7) | O3xiv—Mo2—O2viii | 83.95 (12) |
O4—Pr1—Mo2v | 25.42 (8) | O2xv—Mo2—O2viii | 88.89 (17) |
O4xxvii—Pr1—Mo2v | 56.23 (9) | O1viii—Mo2—O4xiii | 84.66 (12) |
O4xxv—Pr1—Mo2v | 88.95 (8) | O1xv—Mo2—O4xiii | 84.66 (12) |
O4iii—Pr1—Mo2v | 109.21 (6) | O3xiv—Mo2—O4xiii | 167.64 (16) |
O1i—Pr1—Mo2v | 28.31 (5) | O2xv—Mo2—O4xiii | 104.72 (12) |
O1xx—Pr1—Mo2v | 142.27 (5) | O2viii—Mo2—O4xiii | 104.72 (12) |
O1xxviii—Pr1—Mo2v | 68.08 (5) | O1viii—Mo2—Mo1xi | 87.76 (8) |
O1ii—Pr1—Mo2v | 106.49 (5) | O1xv—Mo2—Mo1xi | 137.06 (9) |
Mo1ii—Pr1—Mo2v | 37.630 (8) | O3xiv—Mo2—Mo1xi | 136.00 (8) |
Mo1xxviii—Pr1—Mo2v | 133.523 (12) | O2xv—Mo2—Mo1xi | 97.92 (8) |
Mo1xx—Pr1—Mo2v | 56.160 (8) | O2viii—Mo2—Mo1xi | 52.29 (9) |
Mo1i—Pr1—Mo2v | 116.972 (10) | O4xiii—Mo2—Mo1xi | 52.56 (9) |
Pr1iii—Pr1—Mo2v | 64.529 (7) | O1viii—Mo2—Mo1xvi | 137.06 (9) |
Mo1iv—Pr1—Mo2v | 171.373 (13) | O1xv—Mo2—Mo1xvi | 87.76 (8) |
Mo1v—Pr1—Mo2v | 42.338 (6) | O3xiv—Mo2—Mo1xvi | 136.00 (7) |
Mo1xxi—Pr1—Mo2v | 97.713 (8) | O2xv—Mo2—Mo1xvi | 52.29 (9) |
Mo1xxix—Pr1—Mo2v | 96.621 (8) | O2viii—Mo2—Mo1xvi | 97.92 (8) |
O2xxiv—Pr1—Mo2xviii | 57.19 (7) | O4xiii—Mo2—Mo1xvi | 52.56 (9) |
O2xxv—Pr1—Mo2xviii | 158.52 (7) | Mo1xi—Mo2—Mo1xvi | 64.692 (19) |
O2xxvi—Pr1—Mo2xviii | 82.41 (7) | O1viii—Mo2—Mo1 | 43.84 (8) |
O2—Pr1—Mo2xviii | 121.39 (7) | O1xv—Mo2—Mo1 | 136.02 (8) |
O4—Pr1—Mo2xviii | 109.21 (6) | O3xiv—Mo2—Mo1 | 88.502 (11) |
O4xxvii—Pr1—Mo2xviii | 88.95 (8) | O2xv—Mo2—Mo1 | 134.16 (9) |
O4xxv—Pr1—Mo2xviii | 56.23 (9) | O2viii—Mo2—Mo1 | 45.30 (9) |
O4iii—Pr1—Mo2xviii | 25.42 (8) | O4xiii—Mo2—Mo1 | 91.474 (11) |
O1i—Pr1—Mo2xviii | 142.27 (5) | Mo1xi—Mo2—Mo1 | 58.905 (13) |
O1xx—Pr1—Mo2xviii | 28.31 (5) | Mo1xvi—Mo2—Mo1 | 123.590 (15) |
O1xxviii—Pr1—Mo2xviii | 106.49 (5) | O1viii—Mo2—Mo1xvii | 136.02 (8) |
O1ii—Pr1—Mo2xviii | 68.08 (5) | O1xv—Mo2—Mo1xvii | 43.84 (8) |
Mo1ii—Pr1—Mo2xviii | 133.523 (12) | O3xiv—Mo2—Mo1xvii | 88.502 (11) |
Mo1xxviii—Pr1—Mo2xviii | 37.630 (8) | O2xv—Mo2—Mo1xvii | 45.30 (9) |
Mo1xx—Pr1—Mo2xviii | 116.972 (10) | O2viii—Mo2—Mo1xvii | 134.16 (9) |
Mo1i—Pr1—Mo2xviii | 56.160 (8) | O4xiii—Mo2—Mo1xvii | 91.474 (11) |
Pr1iii—Pr1—Mo2xviii | 64.529 (6) | Mo1xi—Mo2—Mo1xvii | 123.590 (15) |
Mo1iv—Pr1—Mo2xviii | 42.338 (6) | Mo1xvi—Mo2—Mo1xvii | 58.905 (13) |
Mo1v—Pr1—Mo2xviii | 171.373 (13) | Mo1—Mo2—Mo1xvii | 177.00 (2) |
Mo1xxi—Pr1—Mo2xviii | 96.621 (8) | O1viii—Mo2—Pr1xiii | 51.33 (9) |
Mo1xxix—Pr1—Mo2xviii | 97.713 (8) | O1xv—Mo2—Pr1xiii | 89.71 (8) |
Mo2v—Pr1—Mo2xviii | 129.058 (13) | O3xiv—Mo2—Pr1xiii | 137.80 (9) |
O2xxiv—Pr1—Mo2xxix | 121.39 (7) | O2xv—Mo2—Pr1xiii | 138.03 (9) |
O2xxv—Pr1—Mo2xxix | 82.41 (7) | O2viii—Mo2—Pr1xiii | 98.12 (9) |
O2xxvi—Pr1—Mo2xxix | 57.19 (7) | O4xiii—Mo2—Pr1xiii | 33.48 (7) |
O2—Pr1—Mo2xxix | 158.52 (7) | Mo1xi—Mo2—Pr1xiii | 57.690 (10) |
O4—Pr1—Mo2xxix | 56.23 (9) | Mo1xvi—Mo2—Pr1xiii | 85.738 (14) |
O4xxvii—Pr1—Mo2xxix | 109.21 (6) | Mo1—Mo2—Pr1xiii | 65.791 (10) |
O4xxv—Pr1—Mo2xxix | 25.42 (8) | Mo1xvii—Mo2—Pr1xiii | 116.727 (14) |
O4iii—Pr1—Mo2xxix | 88.95 (8) | O1viii—Mo2—Pr1xviii | 89.71 (9) |
O1i—Pr1—Mo2xxix | 106.49 (5) | O1xv—Mo2—Pr1xviii | 51.33 (9) |
O1xx—Pr1—Mo2xxix | 68.08 (5) | O3xiv—Mo2—Pr1xviii | 137.80 (9) |
O1xxviii—Pr1—Mo2xxix | 28.31 (5) | O2xv—Mo2—Pr1xviii | 98.12 (9) |
O1ii—Pr1—Mo2xxix | 142.27 (5) | O2viii—Mo2—Pr1xviii | 138.03 (9) |
Mo1ii—Pr1—Mo2xxix | 56.160 (8) | O4xiii—Mo2—Pr1xviii | 33.48 (7) |
Mo1xxviii—Pr1—Mo2xxix | 116.972 (10) | Mo1xi—Mo2—Pr1xviii | 85.738 (14) |
Mo1xx—Pr1—Mo2xxix | 133.523 (12) | Mo1xvi—Mo2—Pr1xviii | 57.690 (10) |
Mo1i—Pr1—Mo2xxix | 37.630 (8) | Mo1—Mo2—Pr1xviii | 116.727 (14) |
Pr1iii—Pr1—Mo2xxix | 64.529 (6) | Mo1xvii—Mo2—Pr1xviii | 65.791 (10) |
Mo1iv—Pr1—Mo2xxix | 96.621 (8) | Pr1xiii—Mo2—Pr1xviii | 50.942 (13) |
Mo1v—Pr1—Mo2xxix | 97.713 (8) | Mo2xix—O1—Mo1ix | 131.55 (15) |
Mo1xxi—Pr1—Mo2xxix | 171.373 (13) | Mo2xix—O1—Mo1xx | 93.38 (12) |
Mo1xxix—Pr1—Mo2xxix | 42.338 (6) | Mo1ix—O1—Mo1xx | 135.07 (15) |
Mo2v—Pr1—Mo2xxix | 79.342 (5) | Mo2xix—O1—Pr1ii | 100.35 (11) |
Mo2xviii—Pr1—Mo2xxix | 79.342 (5) | Mo1ix—O1—Pr1ii | 79.26 (9) |
O2xxiv—Pr1—Mo2xxx | 82.41 (7) | Mo1xx—O1—Pr1ii | 93.62 (10) |
O2xxv—Pr1—Mo2xxx | 121.39 (7) | Mo2xix—O2—Mo1xxi | 76.14 (11) |
O2xxvi—Pr1—Mo2xxx | 158.52 (7) | Mo2xix—O2—Mo1xx | 90.43 (12) |
O2—Pr1—Mo2xxx | 57.19 (7) | Mo1xxi—O2—Mo1xx | 81.54 (12) |
O4—Pr1—Mo2xxx | 88.95 (8) | Mo2xix—O2—Pr1 | 154.66 (16) |
O4xxvii—Pr1—Mo2xxx | 25.42 (8) | Mo1xxi—O2—Pr1 | 126.28 (14) |
O4xxv—Pr1—Mo2xxx | 109.21 (6) | Mo1xx—O2—Pr1 | 103.54 (12) |
O4iii—Pr1—Mo2xxx | 56.23 (9) | Mo1xx—O3—Mo1xxii | 86.62 (16) |
O1i—Pr1—Mo2xxx | 68.08 (5) | Mo1xx—O3—Mo2xiv | 136.48 (8) |
O1xx—Pr1—Mo2xxx | 106.49 (5) | Mo1xxii—O3—Mo2xiv | 136.48 (8) |
O1xxviii—Pr1—Mo2xxx | 142.27 (5) | Mo2v—O4—Mo1xxiii | 75.22 (13) |
O1ii—Pr1—Mo2xxx | 28.31 (5) | Mo2v—O4—Mo1ii | 75.22 (13) |
Mo1ii—Pr1—Mo2xxx | 116.972 (10) | Mo1xxiii—O4—Mo1ii | 81.31 (15) |
Mo1xxviii—Pr1—Mo2xxx | 56.160 (8) | Mo2v—O4—Pr1 | 121.11 (12) |
Mo1xx—Pr1—Mo2xxx | 37.630 (8) | Mo1xxiii—O4—Pr1 | 161.8 (2) |
Mo1i—Pr1—Mo2xxx | 133.523 (12) | Mo1ii—O4—Pr1 | 94.59 (4) |
Pr1iii—Pr1—Mo2xxx | 64.529 (6) | Mo2v—O4—Pr1iii | 121.11 (12) |
Mo1iv—Pr1—Mo2xxx | 97.713 (8) | Mo1xxiii—O4—Pr1iii | 94.59 (4) |
Mo1v—Pr1—Mo2xxx | 96.621 (8) | Mo1ii—O4—Pr1iii | 161.8 (2) |
Mo1xxi—Pr1—Mo2xxx | 42.338 (6) | Pr1—O4—Pr1iii | 83.75 (12) |
Symmetry codes: (i) y+1/2, −x+1/2, −z−1/2; (ii) −x+1/2, −y−1/2, −z−1/2; (iii) −x, −y, −z; (iv) −x, −y−1, z; (v) x, y+1, z; (vi) x−1/2, y+1/2, z−1/2; (vii) −x, −y, −z−1; (viii) y+1/2, −x−1/2, −z−1/2; (ix) −x+1, −y−1, z; (x) −y, x−1, z; (xi) −x+1/2, −y−3/2, −z−1/2; (xii) x, y, −z−1; (xiii) x, y−1, z; (xiv) −x+1, −y−1, −z; (xv) y+1/2, −x−1/2, z+1/2; (xvi) −x+1/2, −y−3/2, z+1/2; (xvii) x, y, −z; (xviii) −x, −y−1, −z; (xix) −y−1/2, x−1/2, z−1/2; (xx) −y−1/2, x−1/2, −z−1/2; (xxi) y+1, −x, z; (xxii) −y−1/2, x−1/2, z+1/2; (xxiii) −x+1/2, −y−1/2, z+1/2; (xxiv) y, −x, z; (xxv) −y, x, z; (xxvi) −x, −y, z; (xxvii) y, −x, −z; (xxviii) x−1/2, y+1/2, −z−1/2; (xxix) −y−1, x, z; (xxx) y+1, −x, −z. |
Experimental details
Crystal data | |
Chemical formula | PrMo6O12 |
Mr | 908.55 |
Crystal system, space group | Tetragonal, I4/m |
Temperature (K) | 293 |
a, c (Å) | 9.9147 (3), 8.6508 (6) |
V (Å3) | 850.38 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 14.25 |
Crystal size (mm) | 0.29 × 0.03 × 0.02 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Numerical (Coppens, 1970) |
Tmin, Tmax | 0.340, 0.768 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1494, 1385, 1242 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.904 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.081, 1.18 |
No. of reflections | 1385 |
No. of parameters | 50 |
w = 1/[σ2(Fo2) + (0.0281P)2 + 24.9952P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 3.40, −2.99 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1989), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Pr1—O2 | 2.401 (3) | Mo1—Mo2v | 2.5589 (5) |
Pr1—O4 | 2.688 (3) | Mo1—Mo1v | 2.7344 (7) |
Mo1—O3i | 1.996 (3) | Mo1—Mo1vi | 2.7381 (7) |
Mo1—O1ii | 2.017 (3) | Mo1—Mo2 | 2.9573 (4) |
Mo1—O1i | 2.052 (3) | Mo2—O1i | 2.012 (3) |
Mo1—O2iii | 2.085 (3) | Mo2—O3vii | 2.036 (4) |
Mo1—O4iv | 2.101 (3) | Mo2—O2viii | 2.064 (3) |
Mo1—O2i | 2.102 (3) | Mo2—O4ix | 2.092 (4) |
Symmetry codes: (i) y+1/2, −x−1/2, −z−1/2; (ii) −x+1, −y−1, z; (iii) −y, x−1, z; (iv) −x+1/2, −y−1/2, −z−1/2; (v) −x+1/2, −y−3/2, −z−1/2; (vi) x, y, −z−1; (vii) −x+1, −y−1, −z; (viii) y+1/2, −x−1/2, z+1/2; (ix) x, y−1, z. |
Compounds which crystallize in the hollandite-type structure have been the subject of numerous researches because of the possibility of one-dimensional ionic conductivity through the tunnel on the one hand, and on the other hand, that of their use as host materials for the storage of radioactive wastes. From the crystallographic point of view, these phases frequently exhibit complex commensurate or incommensurate superstructures due to partial occupation and ordering of the A cation within the four-sided tunnels. Reduced molybdenum oxides which crystallize with a hollandite-type structure are in addition characterized by a clustering of the Mo atoms which results in the formation of tetrameric molybdenum Mo4 clusters in K2Mo8O16 (Torardy & Calabrese, 1984) and Ba1.14Mo8O16 (Torardy & McCarley, 1981) synthesized by solid-state reaction, and Mo3 triangles in La1.16Mo8O16 (Leligny et al., 1992) and NdMo6O12 (Tortelier et al., 1998) obtained by fused-salt electrolysis. While in K2Mo8O16 all square-prismatic sites are occupied, a partial occupation and disorder of the large cations occur in the Ba compound. For La1.16Mo8O16, a one-dimensional incommensurate modulated structure with a modulation wavevector of q* = 0.608c* was determined. We report here the single-crystal structure determination of a new reduced ternary oxide of molybdenum which adopts the hollandite-type structure, namely PrMo6O12.
PrMo6O12 crystallizes in a hollandite-type structure with a tripled c axis due to the ordering of the cations in the tunnels. The Mo–O framework of PrMo6O12 consists of double-rutile chains of edge-sharing MoO6 octahedra with each octahedron sharing four edges with four other neighboring octahedra. Within each chain, the Mo atoms that are displaced from the centre of their octahedral oxygen environment, form infinite metallic chains based on Mo3 triangular clusters, as shown in Fig. 1. These double strings which run parallel to the c axis are then linked together by sharing sp2-type O-atom corners to form large square tunnels of 2 × 2 octahedra in cross-section in which the Pr3+ ions are located (Fig. 2a) as well as smaller sized channels similar to those found in the rutile-type structure. The Mo—Mo distances within the Mo3 triangles are 2.5589 (5) Å for the two diagonal bonds Mo1—Mo2, and 2.7381 (7) Å for the Mo1—Mo1 bond parallel to the c axis. The shortest distance between triangles is 2.7344 (7) Å and corresponds to the diagonal bond Mo1—Mo1. The other two intertriangle Mo1—Mo2 distances that are parallel to the c axis are 2.9573 (4) Å and thus are only weakly bonding.
As previously observed in the other hollandite-related reduced molybdenum oxides, the O atoms can be divided into two different types: O1 and O3 which interconnect the double chains and are linked in trigonal planar-like coordination to three Mo atoms, and O2 and O4 that bridge three Mo atoms of the same double chain and are also bonded to one (O2) or two Pr atoms (O4). The Mo—O bond lengths vary from 1.996 (3) to 2.052 (3) Å for the O atoms of the former type, and from 2.064 (3) to 2.102 (3) Å for those of the second type. From the Mo—O bond lengths, the valences of the two crystallographically independent Mo atoms calculated by using the relationship of Brown & Wu (1976) [s = (dMo—O /1.882)-6.0] are +3.53 (3) and +3.64 (3), respectively. This yields an average value of +3.57 (3), in reasonably good agreement with the expected value of +3.5. The Pr3+ ions occupy, in an ordered way, two out of the three possible square-prismatic sites formed by the intrachain O atoms (Fig. 2 b). In order to minimize Pr3+–Pr3+ Coulomb repulsions, the Pr3+ ions of two consecutive sites are shifted away from one another along the [001] direction. Consequently, each Pr3+ ion is displaced by 0.368 Å from the center of its tetragonal prismatic site and thus has four nearest O atoms at 2.401 (3) Å and four furthest ones at 2.688 (3) Å. The average Pr—O bond distance is 2.54 Å that is slightly larger than the value of 2.51 Å expected from the sum of the ionic radii of Pr3+ (CN8) and O2- (CN4) (Shannon & Prewitt, 1969). The distance between two close Pr3+ ions is 3.589 (1) Å.