Buy article online - an online subscription or single-article purchase is required to access this article.
Dioxotetrafluorotungstates (NH4)2WO2F4 [(I) at 297 K and (II) at 133 K] and Rb2WO2F4 (III) were synthesized in a single-crystal form and their structures were determined by X-ray diffraction. Two independent states of the cis-WO2F4 octahedron are characteristic of static and dynamic disorder in structure (I). Dynamically disordered W2 is displaced from the symmetry axis producing four possible orientations of anion that permits O and F atoms to be identified in separate orientations owing to the inherent differences between W-O and W-F bonding. After the phase transition at lower temperature (201 K), (I) transforms into the twin structure (II) with complete O/F ordering. Structure (III) is characterized by full O/F static disorder without any phase transitions at lower temperature.
Supporting information
For all compounds, data collection: Bruker Smart v5.054 (Bruker, 1998); cell refinement: Bruker SAINT v6.02a (Bruker, 2000); data reduction: Bruker SAINT v6.02a (Bruker, 2000); program(s) used to solve structure: Bruker SHELXTL v5.1 (Bruker, 1998); program(s) used to refine structure: Bruker SHELXTL v5.1 (Bruker, 1998); molecular graphics: Bruker SHELXTL v5.1 (Bruker, 1998); software used to prepare material for publication: Bruker SHELXTL v5.1 (Bruker, 1998).
(I) ammonium dioxotetrafluorotungstate
top
Crystal data top
(F4O2W)·2(H4N) | F(000) = 557 |
Mr = 327.93 | Dx = 3.558 Mg m−3 |
Orthorhombic, Cmcm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2c 2 | Cell parameters from 863 reflections |
a = 5.9410 (4) Å | θ = 2.8–39.0° |
b = 14.4206 (10) Å | µ = 18.77 mm−1 |
c = 7.1456 (5) Å | T = 297 K |
V = 612.18 (7) Å3 | Sphere, colorless |
Z = 4 | 0.26 × 0.26 × 0.26 × 0.13 (radius) mm |
Data collection top
Bruker Smart 1000 CCD diffractometer | 1012 independent reflections |
Radiation source: fine-focus sealed tube | 937 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 8.33 pixels mm-1 | θmax = 39.0°, θmin = 2.8° |
ω scans | h = −10→9 |
Absorption correction: multi-scan SADABS v.2.03; Bruker 1999 | k = −25→20 |
Tmin = 0.089, Tmax = 0.089 | l = −12→12 |
8105 measured reflections | |
Refinement top
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)] = 0.020 | w = 1/[σ2(Fo2) + (0.0203P)2 + 0.6776P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.045 | (Δ/σ)max = 0.045 |
S = 1.13 | Δρmax = 1.58 e Å−3 |
1012 reflections | Δρmin = −1.52 e Å−3 |
41 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0201 (3) |
Special details top
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) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
W1 | 0.0000 | 0.10388 (3) | 0.2500 | 0.00515 (10) | 0.1431 (6) |
W2 | 0.02077 (6) | 0.109663 (14) | 0.23099 (4) | 0.01958 (7) | 0.2142 (2) |
N1 | 0.5000 | 0.27480 (19) | 0.2500 | 0.0318 (5) | |
N2 | 0.0000 | 0.4420 (2) | 0.2500 | 0.0308 (5) | |
F1 | 0.0000 | 0.24802 (14) | 0.2500 | 0.0534 (7) | |
O1 | 0.0000 | −0.01325 (15) | 0.2500 | 0.0329 (5) | |
F2 | 0.22685 (19) | 0.12096 (9) | 0.06646 (15) | 0.0364 (2) | 0.75 |
O2 | 0.22685 (19) | 0.12096 (9) | 0.06646 (15) | 0.0364 (2) | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
W1 | 0.0114 (2) | 0.00007 (16) | 0.00398 (16) | 0.000 | 0.000 | 0.000 |
W2 | 0.01619 (14) | 0.02899 (9) | 0.01358 (13) | 0.00032 (7) | 0.00311 (10) | −0.00168 (6) |
N1 | 0.0306 (11) | 0.0266 (10) | 0.0381 (11) | 0.000 | 0.000 | 0.000 |
N2 | 0.0278 (10) | 0.0334 (12) | 0.0313 (10) | 0.000 | 0.000 | 0.000 |
F1 | 0.0458 (12) | 0.0179 (8) | 0.097 (2) | 0.000 | 0.000 | 0.000 |
O1 | 0.0383 (11) | 0.0168 (8) | 0.0435 (11) | 0.000 | 0.000 | 0.000 |
F2 | 0.0265 (4) | 0.0568 (6) | 0.0260 (4) | −0.0044 (4) | 0.0101 (3) | −0.0030 (4) |
O2 | 0.0265 (4) | 0.0568 (6) | 0.0260 (4) | −0.0044 (4) | 0.0101 (3) | −0.0030 (4) |
Geometric parameters (Å, º) top
W1—W2i | 0.2015 (4) | N1—F2ix | 3.046 (2) |
W1—W2ii | 0.2015 (4) | N1—F2x | 3.046 (2) |
W1—W2iii | 0.2015 (4) | N1—O1xi | 3.056 (4) |
W1—O1 | 1.689 (2) | N2—F1 | 2.798 (3) |
W1—O2i | 1.8966 (11) | N2—O2xii | 2.9278 (14) |
W1—F2i | 1.8966 (11) | N2—O2vii | 2.9278 (14) |
W1—O2ii | 1.8966 (11) | N2—F2viii | 2.9278 (14) |
W1—F2ii | 1.8966 (11) | N2—O2xiii | 2.9278 (14) |
W1—F1 | 2.079 (2) | N2—O1xi | 3.0397 (8) |
W2—W2i | 0.2467 (7) | N2—O1xiv | 3.0397 (8) |
W2—W2ii | 0.2717 (5) | N2—F2xv | 3.318 (3) |
W2—W2iii | 0.3670 (6) | N2—F2xvi | 3.318 (3) |
W2—O2 | 1.7052 (11) | N2—F2xvii | 3.318 (3) |
W2—O1 | 1.782 (2) | F1—O2i | 2.6256 (19) |
W2—F2i | 1.8902 (11) | F1—F2i | 2.6256 (19) |
W2—F2ii | 1.9027 (11) | F1—F2 | 2.6256 (19) |
W2—F1 | 2.004 (2) | F1—O2iii | 2.6256 (19) |
W2—F2iii | 2.0701 (11) | O1—O2ii | 2.6986 (19) |
N1—F1 | 2.9955 (5) | O1—F2ii | 2.6986 (19) |
N1—F1iv | 2.9955 (5) | O1—O2i | 2.6986 (19) |
N1—F2v | 3.0314 (18) | O1—O2iii | 2.6986 (19) |
N1—F2vi | 3.0314 (18) | F2—O2ii | 2.623 (2) |
N1—F2vii | 3.0314 (18) | F2—F2ii | 2.623 (2) |
N1—F2viii | 3.0314 (18) | F2—O2i | 2.695 (2) |
N1—F2 | 3.046 (2) | F2—F2i | 2.695 (2) |
N1—F2ii | 3.046 (2) | | |
| | | |
O1—W1—O2i | 97.46 (4) | O1—W2—F2ii | 94.11 (4) |
O1—W1—F2i | 97.46 (4) | O2i—W2—F2ii | 165.14 (6) |
O1—W1—O2ii | 97.46 (4) | F2i—W2—F2ii | 165.14 (6) |
F2i—W1—O2ii | 165.08 (8) | F2—W2—F1 | 89.76 (5) |
O1—W1—F2ii | 97.46 (4) | O1—W2—F1 | 168.84 (2) |
O2i—W1—F2ii | 165.08 (8) | O2i—W2—F1 | 84.75 (4) |
O1—W1—O2iii | 97.46 (4) | F2i—W2—F1 | 84.75 (4) |
O2i—W1—O2iii | 87.50 (7) | O2ii—W2—F1 | 84.42 (4) |
F2i—W1—O2iii | 87.50 (7) | F2ii—W2—F1 | 84.42 (4) |
O2ii—W1—O2iii | 90.57 (7) | F1—W2—O2iii | 80.24 (4) |
F2ii—W1—O2iii | 90.57 (7) | F2—W2—O2iii | 169.98 (8) |
O1—W1—F2iii | 97.46 (4) | O1—W2—O2iii | 88.61 (4) |
O1—W1—F1 | 180.0 | O1—W2—F2i | 94.55 (4) |
O2i—W1—F1 | 82.54 (4) | F2—W2—O1 | 101.38 (5) |
F2i—W1—F1 | 82.54 (4) | O2i—W2—O2iii | 82.82 (7) |
O2ii—W1—F1 | 82.54 (4) | F2i—W2—O2iii | 82.82 (7) |
F2ii—W1—F1 | 82.54 (4) | O2ii—W2—O2iii | 85.34 (7) |
F2—W2—O2i | 96.99 (7) | F2ii—W2—O2iii | 85.34 (7) |
O1—W2—O2i | 94.55 (4) | F2—W2—F2iii | 169.98 (8) |
F2—W2—O2ii | 93.11 (8) | O1—W2—F2iii | 88.61 (4) |
O1—W2—O2ii | 94.11 (4) | O2i—W2—F2iii | 82.82 (7) |
O2i—W2—O2ii | 165.14 (6) | F2i—W2—F2iii | 82.82 (7) |
F2i—W2—O2ii | 165.14 (6) | O2ii—W2—F2iii | 85.34 (7) |
F2—W2—F2ii | 93.11 (8) | F2ii—W2—F2iii | 85.34 (7) |
Symmetry codes: (i) −x, y, z; (ii) x, y, −z+1/2; (iii) −x, y, −z+1/2; (iv) x+1, y, z; (v) x+1/2, −y+1/2, z+1/2; (vi) x+1/2, −y+1/2, −z; (vii) −x+1/2, −y+1/2, −z; (viii) −x+1/2, −y+1/2, z+1/2; (ix) −x+1, y, z; (x) −x+1, y, −z+1/2; (xi) x+1/2, y+1/2, z; (xii) x−1/2, −y+1/2, −z; (xiii) x−1/2, −y+1/2, z+1/2; (xiv) x−1/2, y+1/2, z; (xv) −x+1/2, y+1/2, −z+1/2; (xvi) −x+1/2, y+1/2, z; (xvii) x−1/2, y+1/2, −z+1/2. |
(II) ammonium dioxotetrafluorotungstate
top
Crystal data top
(F4O2W)·2(H4N) | Z = 4 |
Mr = 327.93 | F(000) = 592 |
Triclinic, P1 | Dx = 3.645 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9013 (4) Å | Cell parameters from 1019 reflections |
b = 14.1993 (9) Å | θ = 1.4–39.4° |
c = 7.7162 (5) Å | µ = 19.36 mm−1 |
α = 90.022 (2)° | T = 133 K |
β = 112.466 (2)° | Sphere, colorless |
γ = 89.999 (2)° | 0.26 × 0.26 × 0.25 × 0.13 (radius) mm |
V = 597.50 (7) Å3 | |
Data collection top
Bruker Smart 1000 CCD diffractometer | 6355 independent reflections |
Radiation source: fine-focus sealed tube | 6066 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 8.33 pixels mm-1 | θmax = 39.4°, θmin = 1.4° |
ω scans | h = −9→10 |
Absorption correction: multi-scan SADABS v.2.03; Bruker 1999 | k = −25→25 |
Tmin = 0.086, Tmax = 0.086 | l = −13→12 |
15611 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters not defined |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.P)2 + 17.957P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.092 | (Δ/σ)max = 0.027 |
S = 1.06 | Δρmax = 10.21 e Å−3 |
6355 reflections | Δρmin = −7.78 e Å−3 |
165 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00027 (10) |
Primary atom site location: structure-invariant direct methods | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
W1 | 0.62509 (3) | 0.118066 (15) | 0.21307 (2) | 0.00468 (3) | |
W2 | 0.41301 (3) | 0.382878 (15) | 0.78691 (2) | 0.00510 (3) | |
N1 | 0.7310 (8) | 0.3639 (3) | 0.4445 (6) | 0.0081 (8) | |
N2 | 0.9588 (8) | 0.1236 (4) | 0.8872 (7) | 0.0109 (8) | |
N3 | 0.2855 (8) | 0.1360 (3) | 0.5537 (7) | 0.0081 (8) | |
N4 | 0.0741 (9) | 0.3764 (4) | 0.1145 (7) | 0.0111 (8) | |
O1 | 0.5008 (7) | 0.1123 (4) | −0.0296 (5) | 0.0115 (7) | |
O2 | 0.8673 (7) | 0.0355 (3) | 0.2679 (6) | 0.0105 (7) | |
O3 | 0.5313 (7) | 0.3883 (3) | 1.0289 (5) | 0.0101 (6) | |
O4 | 0.5998 (6) | 0.4641 (3) | 0.7321 (5) | 0.0082 (6) | |
F1 | 0.7293 (7) | 0.1486 (3) | 0.4929 (5) | 0.0121 (7) | |
F2 | 0.8345 (6) | 0.2233 (2) | 0.2278 (5) | 0.0087 (6) | |
F3 | 0.3709 (6) | 0.2106 (2) | 0.2138 (5) | 0.0108 (6) | |
F4 | 0.4036 (6) | 0.0316 (2) | 0.2592 (5) | 0.0118 (6) | |
F5 | 0.2371 (7) | 0.3521 (3) | 0.5071 (5) | 0.0128 (7) | |
F6 | 0.1421 (6) | 0.4678 (3) | 0.7396 (5) | 0.0119 (7) | |
F7 | 0.1562 (6) | 0.2882 (2) | 0.7857 (6) | 0.0112 (7) | |
F8 | 0.6074 (6) | 0.2770 (2) | 0.7713 (5) | 0.0095 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
W1 | 0.00575 (5) | 0.00573 (5) | 0.00226 (5) | −0.00412 (6) | 0.00118 (4) | −0.00104 (6) |
W2 | 0.00601 (5) | 0.00393 (5) | 0.00440 (6) | 0.00096 (6) | 0.00091 (4) | −0.00117 (6) |
N1 | 0.0101 (13) | 0.0087 (16) | 0.0063 (13) | −0.0008 (11) | 0.0041 (11) | 0.0001 (11) |
N2 | 0.0106 (14) | 0.0081 (16) | 0.0121 (15) | 0.0001 (15) | 0.0022 (12) | 0.0023 (15) |
N3 | 0.0061 (13) | 0.0077 (16) | 0.0101 (15) | 0.0009 (11) | 0.0026 (11) | 0.0003 (12) |
N4 | 0.0112 (14) | 0.0087 (17) | 0.0124 (16) | 0.0021 (15) | 0.0035 (12) | 0.0010 (15) |
O1 | 0.0141 (12) | 0.0160 (15) | 0.0052 (11) | −0.0049 (15) | 0.0045 (9) | −0.0039 (13) |
O2 | 0.0102 (13) | 0.0076 (13) | 0.0136 (15) | −0.0008 (11) | 0.0044 (11) | −0.0016 (12) |
O3 | 0.0120 (12) | 0.0091 (13) | 0.0073 (12) | −0.0009 (13) | 0.0016 (10) | −0.0041 (13) |
O4 | 0.0091 (11) | 0.0065 (12) | 0.0118 (13) | 0.0031 (10) | 0.0071 (10) | −0.0009 (11) |
F1 | 0.0125 (12) | 0.0138 (13) | 0.0077 (12) | −0.0007 (11) | 0.0013 (10) | −0.0017 (11) |
F2 | 0.0089 (10) | 0.0051 (10) | 0.0144 (12) | −0.0042 (9) | 0.0068 (9) | −0.0026 (10) |
F3 | 0.0116 (12) | 0.0115 (13) | 0.0098 (12) | 0.0058 (10) | 0.0045 (10) | 0.0036 (10) |
F4 | 0.0134 (11) | 0.0089 (12) | 0.0174 (13) | −0.0059 (10) | 0.0107 (10) | −0.0034 (10) |
F5 | 0.0168 (13) | 0.0168 (14) | 0.0031 (10) | −0.0015 (12) | 0.0020 (10) | −0.0032 (10) |
F6 | 0.0087 (11) | 0.0093 (12) | 0.0150 (14) | 0.0041 (10) | 0.0016 (11) | −0.0013 (11) |
F7 | 0.0093 (11) | 0.0087 (12) | 0.0161 (14) | −0.0018 (10) | 0.0053 (10) | 0.0038 (11) |
F8 | 0.0110 (11) | 0.0051 (11) | 0.0152 (13) | 0.0028 (9) | 0.0080 (10) | −0.0016 (10) |
Geometric parameters (Å, º) top
W1—O1 | 1.732 (3) | N3—F5 | 3.090 (6) |
W1—O2 | 1.770 (4) | N3—O2v | 3.097 (6) |
W1—F2 | 1.915 (3) | N3—F2viii | 3.136 (5) |
W1—F4 | 1.923 (4) | N3—F1viii | 3.138 (6) |
W1—F3 | 1.996 (4) | N4—F5 | 2.828 (6) |
W1—F1 | 2.053 (4) | N4—F3 | 2.859 (6) |
W2—O3 | 1.727 (4) | N4—F2viii | 2.904 (6) |
W2—O4 | 1.755 (4) | N4—O4iii | 2.914 (6) |
W2—F6 | 1.923 (4) | N4—F6ix | 2.981 (7) |
W2—F8 | 1.923 (3) | N4—O3x | 3.018 (6) |
W2—F7 | 2.024 (4) | N4—O3ii | 3.018 (7) |
W2—F5 | 2.053 (3) | N4—F7ii | 3.030 (7) |
N1—F2 | 2.816 (6) | N4—F8x | 3.319 (6) |
N1—F5i | 2.842 (6) | N4—F6ii | 3.332 (7) |
N1—O4 | 2.976 (6) | N4—O4x | 3.432 (6) |
N1—O3ii | 2.984 (6) | N4—W2x | 3.752 (4) |
N1—F6i | 3.004 (5) | O1—F3 | 2.676 (6) |
N1—F6iii | 3.017 (6) | O1—F2 | 2.705 (5) |
N1—F7i | 3.056 (5) | O1—O2 | 2.709 (5) |
N1—F1 | 3.081 (6) | O1—F4 | 2.754 (6) |
N1—F3 | 3.087 (5) | O2—F2 | 2.683 (5) |
N1—O4iii | 3.099 (6) | O2—F1 | 2.708 (6) |
N1—F8 | 3.134 (6) | O2—F4 | 2.712 (6) |
N1—F5 | 3.136 (6) | O3—F7 | 2.696 (5) |
N2—F1 | 2.840 (6) | O3—O4 | 2.697 (6) |
N2—F7i | 2.852 (6) | O3—F8 | 2.708 (6) |
N2—F8 | 2.903 (6) | O3—F6 | 2.759 (5) |
N2—O2iv | 2.920 (7) | O4—F8 | 2.672 (5) |
N2—F4v | 2.976 (6) | O4—F5 | 2.699 (5) |
N2—O1vi | 3.011 (7) | O4—F6 | 2.724 (6) |
N2—O1vii | 3.017 (6) | F1—F3 | 2.532 (5) |
N2—F3vii | 3.018 (5) | F1—F2 | 2.583 (5) |
N2—F2vi | 3.304 (7) | F1—F4 | 2.656 (5) |
N3—F8 | 2.827 (5) | F2—F3 | 2.702 (5) |
N3—F1 | 2.837 (6) | F3—F4 | 2.564 (5) |
N3—O2viii | 2.971 (6) | F5—F7 | 2.541 (6) |
N3—O1vi | 2.991 (6) | F5—F8 | 2.582 (5) |
N3—F4 | 3.010 (6) | F5—F6 | 2.646 (6) |
N3—F4v | 3.015 (6) | F6—F7 | 2.573 (5) |
N3—F3 | 3.045 (7) | F7—F8 | 2.712 (5) |
N3—F7 | 3.081 (6) | | |
| | | |
O1—W1—O2 | 101.4 (2) | O3—W2—F6 | 98.07 (18) |
O1—W1—F2 | 95.62 (18) | O4—W2—F6 | 95.48 (17) |
O2—W1—F2 | 93.36 (16) | O3—W2—F8 | 95.64 (18) |
O1—W1—F4 | 97.64 (18) | O4—W2—F8 | 93.09 (17) |
O2—W1—F4 | 94.40 (17) | F6—W2—F8 | 162.04 (15) |
F2—W1—F4 | 163.00 (16) | O3—W2—F7 | 91.56 (18) |
O1—W1—F3 | 91.48 (18) | O4—W2—F7 | 166.87 (17) |
O2—W1—F3 | 167.00 (18) | F6—W2—F7 | 81.33 (15) |
F2—W1—F3 | 87.39 (15) | F8—W2—F7 | 86.77 (16) |
F4—W1—F3 | 81.69 (15) | O3—W2—F5 | 168.29 (18) |
O1—W1—F1 | 168.51 (18) | O4—W2—F5 | 89.89 (17) |
O2—W1—F1 | 89.88 (17) | F6—W2—F5 | 83.35 (16) |
F2—W1—F1 | 81.15 (15) | F8—W2—F5 | 80.91 (16) |
F4—W1—F1 | 83.76 (15) | F7—W2—F5 | 77.12 (16) |
F3—W1—F1 | 77.40 (15) | O3—W2—O4 | 101.51 (19) |
Symmetry codes: (i) x+1, y, z; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y, −z+1; (v) −x+1, −y, −z+1; (vi) x, y, z+1; (vii) x+1, y, z+1; (viii) x−1, y, z; (ix) −x, −y+1, −z+1; (x) x−1, y, z−1. |
(III) rubidium tungsten oxide fluoride
top
Crystal data top
(F4O2W)·2Rb | Dx = 5.059 Mg m−3 |
Mr = 462.79 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3m1 | Cell parameters from 876 reflections |
Hall symbol: -P 3 2" | θ = 3.9–31.4° |
a = 6.0056 (3) Å | µ = 34.94 mm−1 |
c = 4.8636 (5) Å | T = 297 K |
V = 151.92 (2) Å3 | Plate, colorless |
Z = 1 | 0.12 × 0.12 × 0.03 mm |
F(000) = 200 | |
Data collection top
Bruker Smart 1000 CCD diffractometer | 216 independent reflections |
Radiation source: fine-focus sealed tube | 208 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 8.33 pixels mm-1 | θmax = 31.4°, θmin = 3.9° |
ω scans | h = −8→5 |
Absorption correction: integration SADABS v.2.03; Bruker 1999 | k = −8→8 |
Tmin = 0.011, Tmax = 0.183 | l = −6→7 |
1232 measured reflections | |
Refinement top
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)] = 0.020 | w = 1/[σ2(Fo2) + (0.013P)2 + 0.656P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.95 e Å−3 |
216 reflections | Δρmin = −1.90 e Å−3 |
13 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.169 (3) |
Special details top
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) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
W | 0.0000 | 0.0000 | 0.0000 | 0.02998 (8) | |
Rb | 0.6667 | 0.3333 | 0.68686 (12) | 0.02856 (12) | |
F | 0.3003 (4) | 0.1501 (2) | 0.2177 (4) | 0.0293 (5) | 0.67 |
O | 0.3003 (4) | 0.1501 (2) | 0.2177 (4) | 0.0293 (5) | 0.33 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
W | 0.02882 (10) | 0.02882 (10) | 0.03229 (16) | 0.01441 (5) | 0.000 | 0.000 |
Rb | 0.02559 (15) | 0.02559 (15) | 0.0345 (3) | 0.01279 (8) | 0.000 | 0.000 |
F | 0.0223 (9) | 0.0294 (7) | 0.0339 (10) | 0.0111 (5) | −0.0077 (8) | −0.0038 (4) |
O | 0.0223 (9) | 0.0294 (7) | 0.0339 (10) | 0.0111 (5) | −0.0077 (8) | −0.0038 (4) |
Geometric parameters (Å, º) top
W—Fi | 1.887 (2) | Rb—Fvi | 3.0434 (4) |
W—F | 1.887 (2) | Rb—Fxv | 3.0434 (4) |
W—Fii | 1.887 (2) | Rb—Fxvi | 3.0434 (4) |
W—Fiii | 1.887 (2) | Rb—Fxvii | 3.0434 (4) |
W—Fiv | 1.887 (2) | Rb—Fviii | 3.0434 (4) |
W—Fv | 1.887 (2) | Rb—Oxiv | 3.0434 (4) |
W—Oi | 1.887 (2) | Rb—Ovi | 3.0434 (4) |
W—O | 1.887 (2) | Rb—Oxv | 3.0434 (4) |
W—Oii | 1.887 (2) | Rb—Oxvi | 3.0434 (4) |
W—Oiii | 1.887 (2) | Rb—Oxvii | 3.0434 (4) |
W—Oiv | 1.887 (2) | Rb—Oviii | 3.0434 (4) |
W—Ov | 1.887 (2) | Rb—Fxviii | 3.209 (2) |
W—Rbvi | 3.7871 (3) | Rb—Fxix | 3.209 (2) |
W—Rbvii | 3.7871 (3) | Rb—Fxx | 3.209 (2) |
W—Rbviii | 3.7871 (3) | Rb—Oxviii | 3.209 (2) |
W—Rbix | 3.7871 (3) | Rb—Oxix | 3.209 (2) |
W—Rbx | 3.7871 (3) | Rb—Oxx | 3.209 (2) |
W—Rbxi | 3.7871 (3) | F—Fii | 2.631 (4) |
Rb—Fxii | 2.973 (2) | F—Fiv | 2.631 (4) |
Rb—F | 2.973 (2) | F—Fiii | 2.705 (4) |
Rb—Fxiii | 2.973 (2) | F—Fv | 2.705 (4) |
Rb—Oxii | 2.973 (2) | F—Rbvi | 3.0434 (4) |
Rb—O | 2.973 (2) | F—Rbviii | 3.0434 (4) |
Rb—Oxiii | 2.973 (2) | F—Fxv | 3.159 (4) |
Rb—Fxiv | 3.0434 (4) | F—Fxvii | 3.159 (4) |
| | | |
Fi—W—F | 180.00 (11) | Fii—W—Fiv | 91.59 (9) |
Fi—W—Fii | 91.59 (9) | Fiii—W—Fiv | 180.00 (3) |
F—W—Fii | 88.41 (9) | Fi—W—Fv | 88.41 (9) |
Fi—W—Fiii | 88.41 (9) | F—W—Fv | 91.59 (9) |
F—W—Fiii | 91.59 (9) | Fii—W—Fv | 180.00 (12) |
Fii—W—Fiii | 88.41 (9) | Fiii—W—Fv | 91.59 (9) |
Fi—W—Fiv | 91.59 (9) | Fiv—W—Fv | 88.41 (9) |
F—W—Fiv | 88.41 (9) | | |
Symmetry codes: (i) −x, −y, −z; (ii) y, −x+y, −z; (iii) −x+y, −x, z; (iv) x−y, x, −z; (v) −y, x−y, z; (vi) −x+1, −y, −z+1; (vii) x−1, y, z−1; (viii) −x+1, −y+1, −z+1; (ix) x−1, y−1, z−1; (x) −x, −y, −z+1; (xi) x, y, z−1; (xii) −y+1, x−y, z; (xiii) −x+y+1, −x+1, z; (xiv) y+1, −x+y+1, −z+1; (xv) x−y, x, −z+1; (xvi) x−y+1, x, −z+1; (xvii) y, −x+y, −z+1; (xviii) −y+1, x−y, z+1; (xix) −x+y+1, −x+1, z+1; (xx) x, y, z+1. |
Subscribe to Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.