Crystal structure and phase transition in (NH4)3WO2F5: from dynamic to static orientational disorder
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520615010835/bp5078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520615010835/bp5078296Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520615010835/bp5078193Ksup3.hkl |
CCDC references: 1404974; 1404975
For both compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.
F4WO2·2(H4N)·F(NH4) | Dx = 2.810 Mg m−3 |
Mr = 370.98 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, Pm3m | Cell parameters from 860 reflections |
Hall symbol: -P 4 2 3 | θ = 3.4–30.0° |
a = 6.0298 (1) Å | µ = 13.24 mm−1 |
V = 219.23 (1) Å3 | T = 296 K |
Z = 1 | Sphere, colorless |
F(000) = 170 | 0.18 × 0.18 × 0.18 mm |
Bruker APEXII CCD diffractometer | 93 independent reflections |
Radiation source: fine-focus sealed tube | 93 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 8.33 pixels mm-1 | θmax = 30.0°, θmin = 3.4° |
ω scans | h = −8→8 |
Absorption correction: multi-scan SADABS 2008/1 | k = −8→8 |
Tmin = 0.199, Tmax = 0.199 | l = −8→8 |
2864 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters not defined |
R[F2 > 2σ(F2)] = 0.016 | w = 1/[σ2(Fo2) + (0.0291P)2 + 0.0078P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.035 | (Δ/σ)max = 0.024 |
S = 1.21 | Δρmax = 0.49 e Å−3 |
93 reflections | Δρmin = −0.63 e Å−3 |
19 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0478 (14) |
Primary atom site location: structure-invariant direct methods |
F4WO2·2(H4N)·F(NH4) | Z = 1 |
Mr = 370.98 | Mo Kα radiation |
Cubic, Pm3m | µ = 13.24 mm−1 |
a = 6.0298 (1) Å | T = 296 K |
V = 219.23 (1) Å3 | 0.18 × 0.18 × 0.18 mm |
Bruker APEXII CCD diffractometer | 93 independent reflections |
Absorption correction: multi-scan SADABS 2008/1 | 93 reflections with I > 2σ(I) |
Tmin = 0.199, Tmax = 0.199 | Rint = 0.020 |
2864 measured reflections |
R[F2 > 2σ(F2)] = 0.016 | 0 restraints |
wR(F2) = 0.035 | H-atom parameters not defined |
S = 1.21 | Δρmax = 0.49 e Å−3 |
93 reflections | Δρmin = −0.63 e Å−3 |
19 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 | Occ. (<1) | |
W1 | 0.02378 (2) | 0.0000 | 0.02378 (2) | 0.04325 (4) | 0.08 |
F3 | 0.5000 | 0.5000 | 0.5000 | 0.0986 (12) | |
N1 | 0.5000 | 0.5000 | 0.0000 | 0.129 (2) | |
F1 | 0.3108 (10) | 0.0000 | 0.0000 | 0.113 (3) | 0.249 (4) |
F2 | 0.2033 (4) | 0.2033 (4) | 0.0997 (9) | 0.1345 (17) | 0.1877 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.04631 (5) | 0.03712 (7) | 0.04631 (5) | 0.000 | 0.00513 (13) | 0.000 |
F3 | 0.0986 (12) | 0.0986 (12) | 0.0986 (12) | 0.000 | 0.000 | 0.000 |
N1 | 0.1118 (19) | 0.1118 (19) | 0.164 (5) | 0.000 | 0.000 | 0.000 |
F1 | 0.048 (2) | 0.145 (4) | 0.145 (4) | 0.000 | 0.000 | 0.000 |
F2 | 0.1123 (12) | 0.1123 (12) | 0.179 (4) | −0.0585 (15) | −0.0233 (11) | −0.0233 (11) |
W1—W1i | 0.2028 (2) | F1—F1vii | 2.650 (9) |
W1—W1ii | 0.2028 (2) | F1—F1iii | 2.650 (9) |
W1—W1iii | 0.2028 (2) | F1—F1iv | 2.650 (9) |
W1—W1iv | 0.2028 (2) | F2—F2xiii | 2.584 (9) |
W1—W1v | 0.2868 (3) | F2—F2xiv | 2.584 (9) |
W1—W1vi | 0.2868 (3) | F2—F2xv | 2.606 (7) |
W1—W1vii | 0.3512 (4) | F2—F2xvi | 2.606 (7) |
W1—W1viii | 0.3512 (4) | N1—F2vi | 2.600 (4) |
W1—W1ix | 0.3512 (4) | N1—F2xvii | 2.600 (4) |
W1—W1x | 0.3512 (4) | N1—F2xviii | 2.600 (4) |
W1—W1xi | 0.4055 (4) | N1—F2xix | 2.600 (4) |
W1—F1iii | 1.736 (6) | N1—F2xx | 2.600 (4) |
W1—F1 | 1.736 (6) | N1—F2xxi | 2.600 (4) |
W1—F1vii | 1.885 (6) | N1—F2xxii | 2.600 (4) |
W1—F1ix | 1.885 (6) | N1—F2 | 2.600 (4) |
W1—F1xi | 2.022 (6) | N1—F3xxiii | 3.0149 |
W1—F1viii | 2.022 (6) | N1—F1 | 3.223 (2) |
W1—F2 | 1.698 (4) | N1—F1xviii | 3.223 (2) |
W1—F2iv | 1.698 (4) | N1—F1iv | 3.223 (2) |
W1—F2xii | 1.846 (4) | N1—F1xxiv | 3.223 (2) |
W1—F2xiii | 1.846 (4) | N1—F1xxv | 3.223 (2) |
W1—F2viii | 1.983 (4) | N1—F1xxvi | 3.223 (2) |
W1—F2xi | 1.983 (4) | N1—F1xxvii | 3.223 (2) |
F1—F1viii | 2.650 (9) | N1—F1xxviii | 3.223 (2) |
F1viii—W1—F1vii | 85.339 (17) | F2—W1—F2xv | 100.3 (3) |
F1iv—W1—F1vii | 85.339 (17) | F2xxix—W1—F2viii | 88.8 (2) |
F1viii—W1—F1xi | 85.339 (17) | F2xv—W1—F2xi | 88.8 (2) |
F1iv—W1—F1xi | 85.339 (17) | F2ii—W1—F2ix | 82.3 (2) |
F1iii—W1—F1viii | 93.986 (12) | F2iv—W1—F2xii | 93.5 (3) |
F1—W1—F1viii | 93.986 (12) | F2xxix—W1—F2xii | 94.6 (3) |
F1iii—W1—F1iv | 93.986 (12) | F2xv—W1—F2xiii | 94.6 (3) |
F1—W1—F1iv | 93.986 (12) | F2xii—W1—F2viii | 85.7 (2) |
F1iii—W1—F1 | 99.47 (3) | F2xiii—W1—F2xi | 85.7 (2) |
F1iii—W1—F1xi | 89.329 (5) | F2xxx—W1—F2viii | 84.8 (2) |
F1—W1—F1vii | 89.329 (5) | F2xvi—W1—F2xi | 84.8 (2) |
F1xi—W1—F1vii | 81.87 (3) | F2xv—W1—F2xvi | 93.5 (3) |
F1viii—W1—F1iv | 167.65 (4) | F2xii—W1—F2xxx | 167.39 (3) |
F1—W1—F1xi | 171.20 (3) | F2iv—W1—F2viii | 170.97 (3) |
F1iii—W1—F1vii | 171.20 (3) | F2—W1—F2xi | 170.97 (3) |
F2iv—W1—F2xxix | 100.3 (3) |
Symmetry codes: (i) y, −z, x; (ii) z, −x, −y; (iii) y, z, x; (iv) z, x, y; (v) −x, −y, z; (vi) x, y, −z; (vii) −y, −z, −x; (viii) −z, −x, −y; (ix) −y, z, −x; (x) −z, x, y; (xi) −x, −y, −z; (xii) −y, −z, x; (xiii) y, −z, −x; (xiv) −z, x, −y; (xv) z, −x, y; (xvi) −y, z, x; (xvii) −x+1, −y+1, z; (xviii) −x+1, −y+1, −z; (xix) −x+1, y, z; (xx) x, −y+1, −z; (xxi) x, −y+1, z; (xxii) −x+1, y, −z; (xxiii) x, y, z−1; (xxiv) −z+1, −x+1, −y; (xxv) x, y+1, z; (xxvi) −z, −x+1, −y; (xxvii) z+1, x, y; (xxviii) −x+1, −y, −z; (xxix) x, −y, z; (xxx) y, z, −x. |
F4WO2·F·3(H4N) | Dx = 2.878 Mg m−3 |
Mr = 370.98 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, Pa3 | Cell parameters from 868 reflections |
Hall symbol: -P 2ac 2ab | θ = 1.7–33.0° |
a = 11.9635 (7) Å | µ = 13.56 mm−1 |
V = 1712.28 (17) Å3 | T = 193 K |
Z = 8 | Sphere, colorless |
F(000) = 1360 | 0.18 × 0.18 × 0.18 mm |
Bruker APEXII CCD diffractometer | 1134 independent reflections |
Radiation source: fine-focus sealed tube | 696 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 8.33 pixels mm-1 | θmax = 33.0°, θmin = 1.7° |
φ and ω scans | h = −18→18 |
Absorption correction: multi-scan SADABS 2008/1 | k = −16→18 |
Tmin = 0.194, Tmax = 0.194 | l = −18→18 |
27085 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters not defined |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.031P)2 + 14.1528P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.101 | (Δ/σ)max < 0.001 |
S = 0.98 | Δρmax = 1.90 e Å−3 |
1079 reflections | Δρmin = −1.32 e Å−3 |
38 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00054 (7) |
Primary atom site location: structure-invariant direct methods |
F4WO2·F·3(H4N) | Z = 8 |
Mr = 370.98 | Mo Kα radiation |
Cubic, Pa3 | µ = 13.56 mm−1 |
a = 11.9635 (7) Å | T = 193 K |
V = 1712.28 (17) Å3 | 0.18 × 0.18 × 0.18 mm |
Bruker APEXII CCD diffractometer | 1134 independent reflections |
Absorption correction: multi-scan SADABS 2008/1 | 696 reflections with I > 2σ(I) |
Tmin = 0.194, Tmax = 0.194 | Rint = 0.033 |
27085 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters not defined |
S = 0.98 | w = 1/[σ2(Fo2) + (0.031P)2 + 14.1528P] where P = (Fo2 + 2Fc2)/3 |
1079 reflections | Δρmax = 1.90 e Å−3 |
38 parameters | Δρmin = −1.32 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 | ||
W1 | 0.5000 | 0.0000 | 0.5000 | 0.02738 (16) | |
W2 | 0.5000 | 0.5000 | 0.5000 | 0.04546 (18) | |
N1 | 0.5152 (6) | 0.2579 (5) | 0.2331 (7) | 0.059 (2) | |
F3 | 0.2445 (4) | 0.2445 (4) | 0.2445 (4) | 0.0514 (19) | |
F1 | 0.4455 (3) | 0.1082 (3) | 0.3996 (3) | 0.0398 (8) | |
F2 | 0.4786 (5) | 0.3465 (3) | 0.5179 (5) | 0.0697 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.02738 (16) | 0.02738 (16) | 0.02738 (16) | −0.00399 (10) | 0.00399 (10) | 0.00399 (10) |
W2 | 0.04546 (18) | 0.04546 (18) | 0.04546 (18) | 0.00152 (16) | 0.00152 (16) | 0.00152 (16) |
N1 | 0.078 (5) | 0.037 (4) | 0.063 (5) | −0.019 (4) | −0.009 (4) | 0.022 (3) |
F3 | 0.0514 (19) | 0.0514 (19) | 0.0514 (19) | −0.002 (2) | −0.002 (2) | −0.002 (2) |
F1 | 0.0450 (19) | 0.0366 (18) | 0.0379 (19) | 0.0029 (16) | −0.0047 (16) | 0.0123 (15) |
F2 | 0.099 (5) | 0.0236 (16) | 0.086 (4) | −0.015 (2) | −0.010 (3) | 0.009 (2) |
W1—F1 | 1.882 (3) | N1—F1 | 2.806 (7) |
W1—F1i | 1.882 (3) | N1—F2xii | 2.894 (11) |
W1—F1ii | 1.882 (3) | N1—F1xiii | 2.946 (8) |
W1—F1iii | 1.882 (3) | N1—F2viii | 2.969 (10) |
W1—F1iv | 1.882 (3) | F1—F1iii | 2.634 (6) |
W1—F1v | 1.882 (3) | F1—F1i | 2.634 (6) |
W2—F2 | 1.867 (4) | F1—F1ii | 2.688 (6) |
W2—F2vi | 1.867 (4) | F1—F1iv | 2.688 (6) |
W2—F2vii | 1.867 (4) | F2—F2viii | 2.632 (8) |
W2—F2viii | 1.867 (4) | F2—F2x | 2.632 (8) |
W2—F2ix | 1.867 (4) | F2—F2vii | 2.648 (8) |
W2—F2x | 1.867 (4) | F2—F2ix | 2.648 (8) |
N1—F3xi | 2.760 (8) | ||
F1—W1—F1i | 88.83 (16) | F2vi—W2—F2vii | 89.6 (3) |
F1—W1—F1iii | 88.83 (16) | F2—W2—F2viii | 89.6 (3) |
F1i—W1—F1iv | 88.83 (16) | F2vi—W2—F2ix | 89.6 (3) |
F1iv—W1—F1v | 88.83 (16) | F2vii—W2—F2ix | 89.6 (3) |
F1ii—W1—F1v | 88.83 (16) | F2—W2—F2x | 89.6 (3) |
F1ii—W1—F1iii | 88.83 (16) | F2viii—W2—F2x | 89.6 (3) |
F1—W1—F1ii | 91.17 (16) | F2—W2—F2vii | 90.4 (3) |
F1i—W1—F1iii | 91.17 (16) | F2vi—W2—F2viii | 90.4 (3) |
F1—W1—F1iv | 91.17 (16) | F2vii—W2—F2viii | 90.4 (3) |
F1ii—W1—F1iv | 91.17 (16) | F2—W2—F2ix | 90.4 (3) |
F1i—W1—F1v | 91.17 (16) | F2vi—W2—F2x | 90.4 (3) |
F1iii—W1—F1v | 91.17 (16) | F2ix—W2—F2x | 90.4 (3) |
F1i—W1—F1ii | 180.00 (17) | F2—W2—F2vi | 179.999 (1) |
F1iii—W1—F1iv | 180.00 (17) | F2viii—W2—F2ix | 180.000 (1) |
F1—W1—F1v | 179.999 (1) | F2vii—W2—F2x | 180.0 |
Symmetry codes: (i) −y+1/2, z−1/2, x; (ii) y+1/2, −z+1/2, −x+1; (iii) z, −x+1/2, y+1/2; (iv) −z+1, x−1/2, −y+1/2; (v) −x+1, −y, −z+1; (vi) −x+1, −y+1, −z+1; (vii) −y+1, −z+1, −x+1; (viii) z, x, y; (ix) −z+1, −x+1, −y+1; (x) y, z, x; (xi) x+1/2, y, −z+1/2; (xii) x, −y+1/2, z−1/2; (xiii) y+1/2, z, −x+1/2. |
Experimental details
For all structures: Mr = 370.98. Experiments were carried out with Mo Kα radiation using a Bruker APEXII CCD diffractometer. Absorption was corrected for by multi-scan methods, SADABS 2008/1. H-atom parameters were not defined.
(296K) | (193K) | |
Crystal data | ||
Chemical formula | F4WO2·2(H4N)·F(NH4) | F4WO2·F·3(H4N) |
Crystal system, space group | Cubic, Pm3m | Cubic, Pa3 |
Temperature (K) | 296 | 193 |
a (Å) | 6.0298 (1) | 11.9635 (7) |
V (Å3) | 219.23 (1) | 1712.28 (17) |
Z | 1 | 8 |
Dx (Mg m−3) | 2.810 | 2.878 |
µ (mm−1) | 13.24 | 13.56 |
Crystal size (mm) | 0.18 × 0.18 × 0.18 | 0.18 × 0.18 × 0.18 |
Data collection | ||
Tmin, Tmax | 0.199, 0.199 | 0.194, 0.194 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2864, 93, 93 | 27085, 1134, 696 |
Rint | 0.020 | 0.033 |
(sin θ/λ)max (Å−1) | 0.704 | 0.766 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.016, 0.035, 1.21 | 0.037, 0.101, 0.98 |
No. of reflections | 93 | 1079 |
No. of parameters | 19 | 38 |
w = 1/[σ2(Fo2) + (0.0291P)2 + 0.0078P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.031P)2 + 14.1528P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.49, −0.63 | 1.90, −1.32 |
Computer programs: Bruker APEX2, Bruker SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Bruker SHELXTL.