Acta Cryst. (2007). E63, i198 [ doi:10.1107/S1600536807058278 ]
The title compound is built from edge-sharing centrosymmetric dimeric [Zr2F12]4- complexes, HF molecules, Rb+ and K+ cations. Rubidium and potassium ions are statistically disordered on one of the metal positions. The ZrIV coordination polyhedron is a monocapped trigonal prism. The two crystallographically independent Rb(K) ions are coordinated by F atoms and HF molecules with coordination numbers 7 and 9, respectively, for the two sites. In addition, the structure is stabilized by strong F-H
F hydrogen bonds.
ZrO2 (6.2 g, 0.05 mol; Reachem(Russia), 99.99% purity) was reacted with RbF (7.8 g, 0.075 mol; Alfa Aesar, 99.7% purity) and KF·2H2O (2.4 g, 0.025 mol; Reachem(Russia), 99.99% purity) in a solution of hydrofluoric acid (40%, 30 ml; Reachem(Russia), 99.99% purity). Upon slow evaporation at room temperature, crystals of Rb5 − xKxZr3F17·0.5H2O (x =2.0 and 2.25) precipitated first (later we will report about their crystal structures), and after they were separated, crystals of (I) precipitated next.
The Rb and K site occupancies were refined together with the refinement of the structural parameters of these atoms, assuming that their positional and thermal parameters were the same. The site-occupancy factors of F8a and F8b atoms were refined by restraining the sum of occupancies to 1.0. Their displacement parameters were constrained to be identical using the EADP instructions. The H atoms were found in a difference Fourier map and refined with Uiso(H) = 1.5Ueq(F). The maximum peak and deepest hole are located 0.79 Å and 0.72 Å, respectively, from Zr and F6.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL (Bruker, 1998); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).
![[Figure 1]](./fi2047fig1thm.gif)
| Fig. 1. A view of the centrosymmetric dimeric [Zr2F12]4− complex, with displacement ellipsoids drawn at the 50% probability level. Symmetry code as in Table 1. |
![[Figure 2]](./fi2047fig2thm.gif)
| Fig. 2. The structure of (I), viewed along the c axis. |
![[Figure 3]](./fi2047fig3thm.gif)
| Fig. 3. (a) The Rb1(K1) and (b) Rb2(K2) coordination polyhedra, with displacement ellipsoids drawn at the 50% probability level. Symmetry codes: ii: 1 − x, 1/2 + y, 1/2 − z; iv: 1 − x, 2 − y, −z; v: 1 − x, −1/2 + y, 1/2 − z; vi: 1 + x, 3/2 − y, −1/2 + z; vii: 1 + x, y, z; ix: x, −1 + y, z; x: 1 + x, −1 + y, z; xii: 1 − x, 1 − y, z. |
| Rb1.58K0.42ZrF6·2HF | F000 = 722 |
| Mr = 396.84 | Dx = 3.425 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1764 reflections |
| a = 7.2427 (5) Å | θ = 2.8–31.3º |
| b = 11.7111 (8) Å | µ = 11.68 mm−1 |
| c = 9.0742 (6) Å | T = 173 (2) K |
| β = 90.413 (2)º | Prism, colourless |
| V = 769.65 (9) Å3 | 0.27 × 0.22 × 0.17 mm |
| Z = 4 |
| Bruker SMART 1000 CCD area-detector diffractometer | 2437 independent reflections |
| Radiation source: fine-focus sealed tube | 2223 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.033 |
| Detector resolution: 8.33 pixels mm-1 | θmax = 31.5º |
| T = 173(2) K | θmin = 2.8º |
| ω scans | h = −10→10 |
| Absorption correction: gaussian (SADABS and XPREP; Bruker, 2003) | k = −17→16 |
| Tmin = 0.176, Tmax = 0.444 | l = −13→7 |
| 6082 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.026 | Only H-atom coordinates refined |
| wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0216P)2 + 0.8571P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max = 0.026 |
| 2437 reflections | Δρmax = 0.68 e Å−3 |
| 119 parameters | Δρmin = −0.62 e Å−3 |
| 1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0034 (3) |
| Rb1.58K0.42ZrF6·2HF | V = 769.65 (9) Å3 |
| Mr = 396.84 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 7.2427 (5) Å | µ = 11.68 mm−1 |
| b = 11.7111 (8) Å | T = 173 (2) K |
| c = 9.0742 (6) Å | 0.27 × 0.22 × 0.17 mm |
| β = 90.413 (2)º |
| Bruker SMART 1000 CCD area-detector diffractometer | 2437 independent reflections |
| Absorption correction: gaussian (SADABS and XPREP; Bruker, 2003) | 2223 reflections with I > 2σ(I) |
| Tmin = 0.176, Tmax = 0.444 | Rint = 0.033 |
| 6082 measured reflections |
| R[F2 > 2σ(F2)] = 0.026 | 1 restraint |
| wR(F2) = 0.061 | Only H-atom coordinates refined |
| S = 1.06 | Δρmax = 0.68 e Å−3 |
| 2437 reflections | Δρmin = −0.62 e Å−3 |
| 119 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 > 2sigma(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) | |
| Zr | 0.13506 (2) | 0.979721 (14) | 0.169058 (18) | 0.01248 (4) | |
| Rb1 | 0.85934 (3) | 0.681632 (16) | −0.00920 (2) | 0.01949 (5) | 0.8742 (7) |
| K1 | 0.85934 (3) | 0.681632 (16) | −0.00920 (2) | 0.01949 (5) | 0.1258 |
| Rb2 | 0.63267 (3) | 0.14738 (2) | 0.22385 (2) | 0.02009 (6) | 0.7087 (7) |
| K2 | 0.63267 (3) | 0.14738 (2) | 0.22385 (2) | 0.02009 (6) | 0.2913 |
| F2 | −0.05205 (17) | 1.02431 (10) | 0.31821 (13) | 0.0210 (3) | |
| F1 | 0.05701 (15) | 0.91307 (9) | −0.04199 (12) | 0.0172 (2) | |
| F5 | 0.08382 (18) | 0.81754 (10) | 0.22501 (13) | 0.0232 (3) | |
| F6 | 0.2991 (2) | 0.97382 (11) | 0.36010 (14) | 0.0300 (3) | |
| F3 | 0.25829 (19) | 1.13146 (11) | 0.16978 (18) | 0.0335 (3) | |
| F4 | 0.37882 (18) | 0.92093 (14) | 0.08435 (16) | 0.0360 (4) | |
| F7 | 0.5434 (2) | 0.17326 (12) | 0.52128 (18) | 0.0402 (4) | |
| H1 | 0.593 (5) | 0.121 (3) | 0.560 (4) | 0.060* | |
| F8a | 0.6904 (3) | 0.8804 (2) | 0.1602 (3) | 0.0417 (6) | 0.790 (4) |
| F8b | 0.6467 (11) | 0.8442 (8) | 0.1869 (10) | 0.040 (2) | 0.210 (4) |
| H2 | 0.586 (5) | 0.897 (3) | 0.147 (4) | 0.060* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zr | 0.01345 (7) | 0.01337 (7) | 0.01059 (7) | 0.00168 (6) | −0.00099 (6) | −0.00001 (6) |
| Rb1 | 0.02571 (10) | 0.01514 (8) | 0.01765 (9) | 0.00183 (7) | 0.00263 (7) | 0.00237 (6) |
| K1 | 0.02571 (10) | 0.01514 (8) | 0.01765 (9) | 0.00183 (7) | 0.00263 (7) | 0.00237 (6) |
| Rb2 | 0.01561 (10) | 0.02453 (11) | 0.02013 (11) | 0.00128 (8) | 0.00099 (8) | −0.00070 (8) |
| K2 | 0.01561 (10) | 0.02453 (11) | 0.02013 (11) | 0.00128 (8) | 0.00099 (8) | −0.00070 (8) |
| F2 | 0.0253 (6) | 0.0220 (5) | 0.0156 (5) | 0.0044 (4) | 0.0042 (4) | 0.0006 (4) |
| F1 | 0.0210 (5) | 0.0169 (5) | 0.0138 (5) | 0.0053 (4) | −0.0029 (4) | −0.0029 (4) |
| F5 | 0.0330 (6) | 0.0160 (5) | 0.0207 (6) | 0.0031 (4) | 0.0029 (5) | 0.0033 (4) |
| F6 | 0.0370 (7) | 0.0303 (6) | 0.0226 (6) | 0.0114 (5) | −0.0128 (5) | −0.0042 (5) |
| F3 | 0.0259 (6) | 0.0244 (6) | 0.0501 (8) | −0.0088 (5) | −0.0119 (6) | 0.0105 (6) |
| F4 | 0.0154 (5) | 0.0602 (9) | 0.0324 (7) | 0.0094 (6) | −0.0016 (5) | −0.0153 (6) |
| F7 | 0.0547 (9) | 0.0300 (7) | 0.0359 (8) | 0.0137 (6) | −0.0158 (7) | 0.0032 (6) |
| F8a | 0.0205 (8) | 0.0497 (12) | 0.0547 (13) | 0.0074 (8) | −0.0132 (8) | −0.0072 (10) |
| F8b | 0.027 (4) | 0.052 (5) | 0.040 (4) | 0.015 (3) | −0.012 (3) | −0.002 (3) |
| Zr—F3 | 1.9886 (13) | F1—Zri | 2.1950 (11) |
| Zr—F2 | 1.9919 (12) | F1—K2xii | 2.8860 (11) |
| Zr—F5 | 2.0014 (11) | F1—Rb2xii | 2.8860 (11) |
| Zr—F4 | 2.0497 (13) | F1—Rb1xiv | 3.0806 (11) |
| Zr—F6 | 2.0958 (13) | F1—K1xiv | 3.0806 (11) |
| Zr—F1 | 2.1403 (11) | F5—K2ii | 2.8964 (12) |
| Zr—F1i | 2.1950 (11) | F5—Rb2ii | 2.8964 (12) |
| Zr—Zri | 3.6579 (4) | F5—Rb1iii | 2.9183 (12) |
| Zr—K1ii | 3.8882 (3) | F5—K1iii | 2.9183 (12) |
| Zr—Rb1ii | 3.8882 (3) | F5—Rb1xiv | 3.1054 (13) |
| Zr—K1iii | 4.0207 (3) | F5—K1xiv | 3.1054 (13) |
| Zr—Rb1iii | 4.0207 (3) | F6—K1ii | 3.0156 (13) |
| Rb1—F3iv | 2.7609 (14) | F6—Rb1ii | 3.0156 (13) |
| Rb1—F2v | 2.8829 (12) | F6—K2xv | 3.3969 (15) |
| Rb1—F5vi | 2.9183 (13) | F6—Rb2xv | 3.3969 (15) |
| Rb1—F7ii | 2.9197 (18) | F3—K2xv | 2.7584 (14) |
| Rb1—F2vi | 2.9489 (12) | F3—Rb2xv | 2.7584 (14) |
| Rb1—F6v | 3.0156 (13) | F3—Rb1iv | 2.7609 (14) |
| Rb1—F8b | 3.033 (9) | F3—K1iv | 2.7609 (14) |
| Rb1—F8a | 3.051 (2) | F3—K1ii | 3.2550 (16) |
| Rb1—F1vii | 3.0806 (11) | F3—Rb1ii | 3.2550 (16) |
| Rb1—F5vii | 3.1054 (13) | F4—K2xii | 2.9094 (14) |
| Rb1—F8bviii | 3.164 (9) | F4—Rb2xii | 2.9094 (14) |
| Rb1—F3v | 3.2550 (16) | F4—Rb2xv | 3.4615 (16) |
| Rb2—F3ix | 2.7584 (14) | F7—K2xvi | 2.8621 (16) |
| Rb2—F7 | 2.7964 (17) | F7—Rb2xvi | 2.8621 (16) |
| Rb2—F2x | 2.8278 (12) | F7—Rb1v | 2.9197 (18) |
| Rb2—F7xi | 2.8621 (16) | F7—K1v | 2.9197 (18) |
| Rb2—F1xii | 2.8860 (11) | F7—H1 | 0.79 (4) |
| Rb2—F5v | 2.8964 (12) | F8a—F8b | 0.583 (9) |
| Rb2—F4xii | 2.9094 (14) | F8a—K2xv | 3.207 (2) |
| Rb2—F8bv | 3.176 (9) | F8a—Rb2xv | 3.207 (2) |
| Rb2—F8aix | 3.207 (2) | F8a—Rb1xvii | 3.313 (2) |
| Rb2—F6ix | 3.3969 (15) | F8a—K1xvii | 3.313 (2) |
| Rb2—F4ix | 3.4615 (16) | F8a—H2 | 0.79 (4) |
| Rb2—F8bix | 3.568 (9) | F8b—K1xvii | 3.164 (9) |
| F2—K2xiii | 2.8278 (12) | F8b—Rb1xvii | 3.164 (9) |
| F2—Rb2xiii | 2.8278 (12) | F8b—K2ii | 3.176 (9) |
| F2—Rb1ii | 2.8829 (12) | F8b—Rb2ii | 3.176 (9) |
| F2—K1ii | 2.8829 (12) | F8b—Rb2xv | 3.568 (9) |
| F2—K1iii | 2.9489 (12) | F8b—H2 | 0.84 (4) |
| F2—Rb1iii | 2.9489 (12) | ||
| F3—Zr—F2 | 94.07 (6) | F8bv—Rb2—F6ix | 83.42 (16) |
| F3—Zr—F5 | 158.63 (6) | F8aix—Rb2—F6ix | 64.92 (4) |
| F2—Zr—F5 | 87.03 (5) | F3ix—Rb2—F4ix | 50.53 (4) |
| F3—Zr—F4 | 85.05 (6) | F7—Rb2—F4ix | 108.06 (4) |
| F2—Zr—F4 | 159.22 (5) | F2x—Rb2—F4ix | 98.39 (3) |
| F5—Zr—F4 | 86.46 (6) | F7xi—Rb2—F4ix | 102.15 (4) |
| F3—Zr—F6 | 77.00 (6) | F1xii—Rb2—F4ix | 90.96 (3) |
| F2—Zr—F6 | 80.28 (5) | F5v—Rb2—F4ix | 163.69 (3) |
| F5—Zr—F6 | 82.18 (5) | F4xii—Rb2—F4ix | 55.00 (5) |
| F4—Zr—F6 | 79.30 (6) | F8bv—Rb2—F4ix | 108.15 (15) |
| F3—Zr—F1 | 116.39 (6) | F8aix—Rb2—F4ix | 42.00 (4) |
| F2—Zr—F1 | 121.80 (5) | F6ix—Rb2—F4ix | 45.37 (3) |
| F5—Zr—F1 | 80.36 (5) | F3ix—Rb2—F8bix | 86.82 (13) |
| F4—Zr—F1 | 76.38 (5) | F7—Rb2—F8bix | 101.86 (15) |
| F6—Zr—F1 | 150.76 (5) | F2x—Rb2—F8bix | 59.86 (13) |
| F3—Zr—F1i | 76.90 (5) | F7xi—Rb2—F8bix | 132.56 (15) |
| F2—Zr—F1i | 77.01 (4) | F1xii—Rb2—F8bix | 71.30 (14) |
| F5—Zr—F1i | 123.92 (5) | F5v—Rb2—F8bix | 132.78 (13) |
| F4—Zr—F1i | 122.65 (5) | F4xii—Rb2—F8bix | 68.69 (15) |
| F6—Zr—F1i | 143.78 (5) | F8bv—Rb2—F8bix | 139.89 (13) |
| F1—Zr—F1i | 64.93 (5) | F8aix—Rb2—F8bix | 7.76 (14) |
| F3—Zr—Zri | 97.13 (4) | F6ix—Rb2—F8bix | 57.28 (14) |
| F2—Zr—Zri | 99.99 (4) | F4ix—Rb2—F8bix | 38.61 (13) |
| F5—Zr—Zri | 103.71 (4) | F3ix—Rb2—H1 | 94.1 (7) |
| F4—Zr—Zri | 100.72 (4) | F7—Rb2—H1 | 14.4 (7) |
| F6—Zr—Zri | 174.11 (4) | F2x—Rb2—H1 | 74.3 (7) |
| F1—Zr—Zri | 32.93 (3) | F7xi—Rb2—H1 | 133.4 (7) |
| F1i—Zr—Zri | 32.00 (3) | F1xii—Rb2—H1 | 128.3 (7) |
| F3—Zr—K1ii | 56.76 (5) | F5v—Rb2—H1 | 88.8 (7) |
| F2—Zr—K1ii | 45.93 (4) | F4xii—Rb2—H1 | 157.3 (7) |
| F5—Zr—K1ii | 112.13 (4) | F8bv—Rb2—H1 | 75.9 (7) |
| F4—Zr—K1ii | 119.86 (4) | F8aix—Rb2—H1 | 95.5 (7) |
| F6—Zr—K1ii | 50.27 (4) | F6ix—Rb2—H1 | 60.6 (7) |
| F1—Zr—K1ii | 158.95 (3) | F4ix—Rb2—H1 | 103.5 (7) |
| F1i—Zr—K1ii | 94.13 (3) | F8bix—Rb2—H1 | 89.9 (7) |
| Zri—Zr—K1ii | 126.108 (8) | Zr—F2—K2xiii | 118.67 (5) |
| F3—Zr—Rb1ii | 56.76 (5) | Zr—F2—Rb2xiii | 118.67 (5) |
| F2—Zr—Rb1ii | 45.93 (4) | Zr—F2—Rb1ii | 104.31 (5) |
| F5—Zr—Rb1ii | 112.13 (4) | K2xiii—F2—Rb1ii | 104.05 (4) |
| F4—Zr—Rb1ii | 119.86 (4) | Rb2xiii—F2—Rb1ii | 104.05 (4) |
| F6—Zr—Rb1ii | 50.27 (4) | Zr—F2—K1ii | 104.31 (5) |
| F1—Zr—Rb1ii | 158.95 (3) | K2xiii—F2—K1ii | 104.05 (4) |
| F1i—Zr—Rb1ii | 94.13 (3) | Rb2xiii—F2—K1ii | 104.05 (4) |
| Zri—Zr—Rb1ii | 126.108 (8) | Zr—F2—K1iii | 107.35 (5) |
| K1ii—Zr—Rb1ii | 0.000 (4) | K2xiii—F2—K1iii | 113.54 (4) |
| F3—Zr—K1iii | 130.00 (5) | Rb2xiii—F2—K1iii | 113.54 (4) |
| F2—Zr—K1iii | 44.43 (3) | Rb1ii—F2—K1iii | 108.04 (4) |
| F5—Zr—K1iii | 43.60 (4) | K1ii—F2—K1iii | 108.04 (4) |
| F4—Zr—K1iii | 123.24 (5) | Zr—F2—Rb1iii | 107.35 (5) |
| F6—Zr—K1iii | 70.46 (4) | K2xiii—F2—Rb1iii | 113.54 (4) |
| F1—Zr—K1iii | 110.42 (3) | Rb2xiii—F2—Rb1iii | 113.54 (4) |
| F1i—Zr—K1iii | 109.51 (3) | Rb1ii—F2—Rb1iii | 108.04 (4) |
| Zri—Zr—K1iii | 113.868 (8) | K1ii—F2—Rb1iii | 108.04 (4) |
| K1ii—Zr—K1iii | 73.249 (7) | Zr—F1—Zri | 115.07 (5) |
| Rb1ii—Zr—K1iii | 73.249 (7) | Zr—F1—K2xii | 113.54 (4) |
| F3—Zr—Rb1iii | 130.00 (5) | Zri—F1—K2xii | 109.46 (4) |
| F2—Zr—Rb1iii | 44.43 (3) | Zr—F1—Rb2xii | 113.54 (4) |
| F5—Zr—Rb1iii | 43.60 (4) | Zri—F1—Rb2xii | 109.46 (4) |
| F4—Zr—Rb1iii | 123.24 (5) | Zr—F1—Rb1xiv | 110.76 (4) |
| F6—Zr—Rb1iii | 70.46 (4) | Zri—F1—Rb1xiv | 105.12 (4) |
| F1—Zr—Rb1iii | 110.42 (3) | K2xii—F1—Rb1xiv | 101.76 (3) |
| F1i—Zr—Rb1iii | 109.51 (3) | Rb2xii—F1—Rb1xiv | 101.76 (3) |
| Zri—Zr—Rb1iii | 113.868 (8) | Zr—F1—K1xiv | 110.76 (4) |
| K1ii—Zr—Rb1iii | 73.249 (7) | Zri—F1—K1xiv | 105.12 (4) |
| Rb1ii—Zr—Rb1iii | 73.249 (7) | K2xii—F1—K1xiv | 101.76 (3) |
| F3iv—Rb1—F2v | 165.97 (4) | Rb2xii—F1—K1xiv | 101.76 (3) |
| F3iv—Rb1—F5vi | 74.50 (4) | Zr—F5—K2ii | 124.13 (6) |
| F2v—Rb1—F5vi | 103.22 (3) | Zr—F5—Rb2ii | 124.13 (6) |
| F3iv—Rb1—F7ii | 72.69 (4) | Zr—F5—Rb1iii | 108.18 (5) |
| F2v—Rb1—F7ii | 118.71 (4) | K2ii—F5—Rb1iii | 105.57 (4) |
| F5vi—Rb1—F7ii | 122.10 (4) | Rb2ii—F5—Rb1iii | 105.57 (4) |
| F3iv—Rb1—F2vi | 115.83 (4) | Zr—F5—K1iii | 108.18 (5) |
| F2v—Rb1—F2vi | 71.96 (4) | K2ii—F5—K1iii | 105.57 (4) |
| F5vi—Rb1—F2vi | 55.89 (3) | Rb2ii—F5—K1iii | 105.57 (4) |
| F7ii—Rb1—F2vi | 100.01 (4) | Zr—F5—Rb1xiv | 114.20 (5) |
| F3iv—Rb1—F6v | 139.43 (4) | K2ii—F5—Rb1xiv | 97.13 (3) |
| F2v—Rb1—F6v | 53.04 (4) | Rb2ii—F5—Rb1xiv | 97.13 (3) |
| F5vi—Rb1—F6v | 126.13 (4) | Rb1iii—F5—Rb1xiv | 105.98 (4) |
| F7ii—Rb1—F6v | 66.82 (4) | K1iii—F5—Rb1xiv | 105.98 (4) |
| F2vi—Rb1—F6v | 70.32 (3) | Zr—F5—K1xiv | 114.20 (5) |
| F3iv—Rb1—F8b | 69.88 (18) | K2ii—F5—K1xiv | 97.13 (3) |
| F2v—Rb1—F8b | 107.10 (17) | Rb2ii—F5—K1xiv | 97.13 (3) |
| F5vi—Rb1—F8b | 140.44 (18) | Rb1iii—F5—K1xiv | 105.98 (4) |
| F7ii—Rb1—F8b | 62.08 (17) | K1iii—F5—K1xiv | 105.98 (4) |
| F2vi—Rb1—F8b | 159.74 (18) | Zr—F6—K1ii | 97.42 (5) |
| F6v—Rb1—F8b | 92.68 (18) | Zr—F6—Rb1ii | 97.42 (5) |
| F3iv—Rb1—F8a | 62.45 (6) | Zr—F6—K2xv | 94.57 (5) |
| F2v—Rb1—F8a | 112.27 (5) | K1ii—F6—K2xv | 87.38 (3) |
| F5vi—Rb1—F8a | 129.92 (5) | Rb1ii—F6—K2xv | 87.38 (3) |
| F7ii—Rb1—F8a | 68.92 (5) | Zr—F6—Rb2xv | 94.57 (5) |
| F2vi—Rb1—F8a | 168.91 (5) | K1ii—F6—Rb2xv | 87.38 (3) |
| F6v—Rb1—F8a | 103.56 (5) | Rb1ii—F6—Rb2xv | 87.38 (3) |
| F3iv—Rb1—F1vii | 52.65 (3) | Zr—F3—K2xv | 120.10 (6) |
| F2v—Rb1—F1vii | 113.39 (3) | Zr—F3—Rb2xv | 120.10 (6) |
| F5vi—Rb1—F1vii | 69.83 (3) | Zr—F3—Rb1iv | 124.75 (6) |
| F7ii—Rb1—F1vii | 119.39 (4) | K2xv—F3—Rb1iv | 109.85 (4) |
| F2vi—Rb1—F1vii | 124.42 (3) | Rb2xv—F3—Rb1iv | 109.85 (4) |
| F6v—Rb1—F1vii | 158.76 (3) | Zr—F3—K1iv | 124.75 (6) |
| F8b—Rb1—F1vii | 75.10 (18) | K2xv—F3—K1iv | 109.85 (4) |
| F8a—Rb1—F1vii | 64.26 (5) | Rb2xv—F3—K1iv | 109.85 (4) |
| F3iv—Rb1—F5vii | 96.48 (4) | Zr—F3—K1ii | 92.52 (5) |
| F2v—Rb1—F5vii | 70.57 (3) | K2xv—F3—K1ii | 94.77 (4) |
| F5vi—Rb1—F5vii | 105.77 (4) | Rb2xv—F3—K1ii | 94.77 (4) |
| F7ii—Rb1—F5vii | 124.11 (4) | Rb1iv—F3—K1ii | 105.93 (4) |
| F2vi—Rb1—F5vii | 131.90 (3) | K1iv—F3—K1ii | 105.93 (4) |
| F6v—Rb1—F5vii | 107.80 (3) | Zr—F3—Rb1ii | 92.52 (5) |
| F8b—Rb1—F5vii | 62.77 (16) | K2xv—F3—Rb1ii | 94.77 (4) |
| F8a—Rb1—F5vii | 58.27 (4) | Rb2xv—F3—Rb1ii | 94.77 (4) |
| F1vii—Rb1—F5vii | 51.23 (3) | Rb1iv—F3—Rb1ii | 105.93 (4) |
| F3iv—Rb1—F8bviii | 57.94 (17) | K1iv—F3—Rb1ii | 105.93 (4) |
| F2v—Rb1—F8bviii | 133.92 (18) | Zr—F4—K2xii | 115.73 (6) |
| F5vi—Rb1—F8bviii | 63.29 (16) | Zr—F4—Rb2xii | 115.73 (6) |
| F7ii—Rb1—F8bviii | 58.94 (16) | Zr—F4—Rb2xv | 93.56 (5) |
| F2vi—Rb1—F8bviii | 64.24 (18) | K2xii—F4—Rb2xv | 125.00 (5) |
| F6v—Rb1—F8bviii | 97.44 (16) | Rb2xii—F4—Rb2xv | 125.00 (5) |
| F8b—Rb1—F8bviii | 109.0 (2) | Rb2—F7—K2xvi | 130.29 (6) |
| F8a—Rb1—F8bviii | 108.51 (18) | Rb2—F7—Rb2xvi | 130.29 (6) |
| F1vii—Rb1—F8bviii | 102.92 (16) | Rb2—F7—Rb1v | 101.85 (5) |
| F5vii—Rb1—F8bviii | 153.48 (17) | K2xvi—F7—Rb1v | 102.74 (5) |
| F3iv—Rb1—F3v | 124.10 (4) | Rb2xvi—F7—Rb1v | 102.74 (5) |
| F2v—Rb1—F3v | 56.27 (3) | Rb2—F7—K1v | 101.85 (5) |
| F5vi—Rb1—F3v | 159.03 (4) | K2xvi—F7—K1v | 102.74 (5) |
| F7ii—Rb1—F3v | 76.19 (4) | Rb2xvi—F7—K1v | 102.74 (5) |
| F2vi—Rb1—F3v | 114.48 (3) | Rb2—F7—H1 | 104 (3) |
| F6v—Rb1—F3v | 47.68 (3) | K2xvi—F7—H1 | 100 (3) |
| F8b—Rb1—F3v | 54.60 (18) | Rb2xvi—F7—H1 | 100 (3) |
| F8a—Rb1—F3v | 63.41 (5) | Rb1v—F7—H1 | 120 (3) |
| F1vii—Rb1—F3v | 112.03 (3) | K1v—F7—H1 | 120 (3) |
| F5vii—Rb1—F3v | 65.43 (3) | F8b—F8a—Rb1 | 82.8 (9) |
| F8bviii—Rb1—F3v | 132.73 (15) | F8b—F8a—K2xv | 124.3 (9) |
| F3ix—Rb2—F7 | 86.85 (5) | Rb1—F8a—K2xv | 152.61 (8) |
| F3ix—Rb2—F2x | 144.10 (4) | F8b—F8a—Rb2xv | 124.3 (9) |
| F7—Rb2—F2x | 87.41 (4) | Rb1—F8a—Rb2xv | 152.61 (8) |
| F3ix—Rb2—F7xi | 73.63 (5) | F8b—F8a—Rb1xvii | 70.3 (9) |
| F7—Rb2—F7xi | 119.18 (4) | Rb1—F8a—Rb1xvii | 98.15 (6) |
| F2x—Rb2—F7xi | 138.31 (4) | K2xv—F8a—Rb1xvii | 95.66 (6) |
| F3ix—Rb2—F1xii | 130.57 (4) | Rb2xv—F8a—Rb1xvii | 95.66 (6) |
| F7—Rb2—F1xii | 139.90 (4) | F8b—F8a—K1xvii | 70.3 (9) |
| F2x—Rb2—F1xii | 54.38 (3) | Rb1—F8a—K1xvii | 98.15 (6) |
| F7xi—Rb2—F1xii | 89.20 (4) | K2xv—F8a—K1xvii | 95.66 (6) |
| F3ix—Rb2—F5v | 140.34 (4) | Rb2xv—F8a—K1xvii | 95.66 (6) |
| F7—Rb2—F5v | 86.53 (4) | F8b—F8a—H2 | 74 (3) |
| F2x—Rb2—F5v | 74.46 (4) | Rb1—F8a—H2 | 120 (3) |
| F7xi—Rb2—F5v | 75.80 (4) | K2xv—F8a—H2 | 70 (3) |
| F1xii—Rb2—F5v | 72.92 (3) | Rb2xv—F8a—H2 | 70 (3) |
| F3ix—Rb2—F4xii | 77.83 (4) | Rb1xvii—F8a—H2 | 123 (3) |
| F7—Rb2—F4xii | 162.24 (5) | K1xvii—F8a—H2 | 123 (3) |
| F2x—Rb2—F4xii | 99.69 (4) | F8a—F8b—Rb1 | 86.2 (9) |
| F7xi—Rb2—F4xii | 65.15 (4) | F8a—F8b—K1xvii | 99.7 (10) |
| F1xii—Rb2—F4xii | 53.12 (3) | Rb1—F8b—K1xvii | 101.8 (2) |
| F5v—Rb2—F4xii | 111.01 (4) | F8a—F8b—Rb1xvii | 99.7 (10) |
| F3ix—Rb2—F8bv | 57.80 (15) | Rb1—F8b—Rb1xvii | 101.8 (2) |
| F7—Rb2—F8bv | 61.51 (17) | F8a—F8b—K2ii | 169.4 (11) |
| F2x—Rb2—F8bv | 143.82 (16) | Rb1—F8b—K2ii | 91.2 (2) |
| F7xi—Rb2—F8bv | 59.32 (17) | K1xvii—F8b—K2ii | 90.9 (2) |
| F1xii—Rb2—F8bv | 145.50 (16) | Rb1xvii—F8b—K2ii | 90.9 (2) |
| F5v—Rb2—F8bv | 84.96 (15) | F8a—F8b—Rb2ii | 169.4 (11) |
| F4xii—Rb2—F8bv | 115.52 (16) | Rb1—F8b—Rb2ii | 91.2 (2) |
| F3ix—Rb2—F8aix | 91.79 (5) | K1xvii—F8b—Rb2ii | 90.9 (2) |
| F7—Rb2—F8aix | 108.11 (5) | Rb1xvii—F8b—Rb2ii | 90.9 (2) |
| F2x—Rb2—F8aix | 56.75 (4) | F8a—F8b—Rb2xv | 47.9 (9) |
| F7xi—Rb2—F8aix | 128.97 (5) | Rb1—F8b—Rb2xv | 134.0 (3) |
| F1xii—Rb2—F8aix | 63.57 (4) | K1xvii—F8b—Rb2xv | 91.6 (2) |
| F5v—Rb2—F8aix | 127.33 (4) | Rb1xvii—F8b—Rb2xv | 91.6 (2) |
| F4xii—Rb2—F8aix | 64.00 (5) | K2ii—F8b—Rb2xv | 132.8 (3) |
| F8bv—Rb2—F8aix | 146.87 (16) | Rb2ii—F8b—Rb2xv | 132.8 (3) |
| F3ix—Rb2—F6ix | 47.43 (4) | F8a—F8b—H2 | 65 (3) |
| F7—Rb2—F6ix | 62.84 (4) | Rb1—F8b—H2 | 118 (3) |
| F2x—Rb2—F6ix | 99.19 (3) | K1xvii—F8b—H2 | 134 (3) |
| F7xi—Rb2—F6ix | 120.99 (4) | Rb1xvii—F8b—H2 | 134 (3) |
| F1xii—Rb2—F6ix | 128.33 (3) | K2ii—F8b—H2 | 108 (3) |
| F5v—Rb2—F6ix | 149.16 (3) | Rb2ii—F8b—H2 | 108 (3) |
| F4xii—Rb2—F6ix | 99.78 (4) | Rb2xv—F8b—H2 | 45 (3) |
| Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, −y+3/2, z+1/2; (iv) −x+1, −y+2, −z; (v) −x+1, y−1/2, −z+1/2; (vi) x+1, −y+3/2, z−1/2; (vii) x+1, y, z; (viii) x, −y+3/2, z−1/2; (ix) x, y−1, z; (x) x+1, y−1, z; (xi) x, −y+1/2, z−1/2; (xii) −x+1, −y+1, −z; (xiii) x−1, y+1, z; (xiv) x−1, y, z; (xv) x, y+1, z; (xvi) x, −y+1/2, z+1/2; (xvii) x, −y+3/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| F7—H1···F6xviii | 0.79 (4) | 1.54 (4) | 2.326 (2) | 176 (4) |
| F8a—H2···F4 | 0.79 (4) | 1.62 (4) | 2.402 (2) | 168 (4) |
| F8b—H2···F4 | 0.84 (4) | 1.62 (4) | 2.326 (8) | 139 (4) |
| Symmetry codes: (xviii) −x+1, −y+1, −z+1. |
| Zr—F3 | 1.9886 (13) | Zr—F6 | 2.0958 (13) |
| Zr—F2 | 1.9919 (12) | Zr—F1 | 2.1403 (11) |
| Zr—F5 | 2.0014 (11) | Zr—F1i | 2.1950 (11) |
| Zr—F4 | 2.0497 (13) | Zr—Zri | 3.6579 (4) |
| Symmetry codes: (i) −x, −y+2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| F7—H1···F6ii | 0.79 (4) | 1.54 (4) | 2.326 (2) | 176 (4) |
| F8a—H2···F4 | 0.79 (4) | 1.62 (4) | 2.402 (2) | 168 (4) |
| F8b—H2···F4 | 0.84 (4) | 1.62 (4) | 2.326 (8) | 139 (4) |
| Symmetry codes: (ii) −x+1, −y+1, −z+1. |
The authors thank the Russian Foundation for Basic Research (project No. 05–03–33298) for financial support.
Blatov, V. A. (2004). Crystallogr. Rev. 10, 249–318.
Bruker (1998). SMART (Version 5.054) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2003). SAINT (Version 6.45) and SADABS (Version 2.10). Bruker AXS Inc., Madison, Wisconsin, USA.
Gerasimenko, A. V., Didenko, N. A. & Kavun, V. Y. (2007). Acta Cryst. E63, i171–?.
Gerasimenko, A. V., Kavun, V. Ya., Didenko, N. A., Slobodyuk, A. B., Uvarov, N. F. & Sergienko, V. I. (2007). Russ. J. Inorg. Chem. 52, 713–726.
Gerasimenko, A. V., Tkachenko, I. A., Kavun, V. Ya., Didenko, N. A. & Sergienko, V. I. (2006). Russ. J. Inorg. Chem. 51, 9–22.
Kavun, V. Ya., Didenko, N. A., Gerasimenko, A. V., Slobodyuk, A. B., Tkachenko, I. A., Uvarov, N. F. & Sergienko, V. I. (2006). Russ. J. Inorg. Chem. 51, 513–520.
Serezhkin, V. N., Mikhailov, Yu. N. & Buslaev, Yu. A. (1997). Zh. Neorg. Khim. 42, 2036–2077.
This work is a continuation of the study of the structure and physicochemical properties of zirconium fluoride complexes with homo- and heteroatomic cations (Gerasimenko et al., 2006, 2007a, 2007b; Kavun et al., 2006) and deals with synthesis and crystal structure of rubidium–potassium hexafluoridozirconate(IV) di(hydrogen fluoride), Rb2 − xKxZrF6·2HF (I) where x=0.4171. The asymmetric unit contains one Zr atom, six fluorine atoms, two sites of rubidium and potassium cations and two hydrogen fluoride molecules. The Zr atoms are coordinated by seven F atoms in a slightly distorted monocapped trigonal prism geometry. Two Zr-centred polyhedra are linked by double F bridges to form a centrosymmetric dimeric [Zr2F12]4− complex (Fig. 1) with a Zr···Zri distance of 3.6579 (4) Å. Along to the c direction, Zr- polyhedra pack up in columns (Fig. 2).
In this structure, there are two sites in which the outer-sphere rubidium and potassium cations are located. In each site the rubidium cations are statistically substituted by the potassium cations. According to the performed refinement, Rb/K site occupancy factors are equal to 0.8742 (7)/0.1258 for the Rb1/K1 site and 0.7087 (7)/0.2913 for the Rb2/K2 site. The coordination numbers (CN) of these sites were calculated by the method of intersecting spheres (Serezhkin et al., 1997) with use of the program package TOPOS (Blatov, 2004). For the first site (Fig. 3a), the CN is 9 (Rb1(K1)–F, 2.7609 (14) – 3.1054 (13) Å) and for the second site (Fig. 3 b), the CN is 7 (Rb2(K2)–F, 2.7584 (14) – 2.9094 (14) Å).
The HF molecules are involved as donors in strong hydrogen bonds (2.326 (2), 2.402 (2) and 2.326 (8) Å) with the F6ii and F4 atoms (Fig. 2). The F8 atom of HF molecule is split on two sites: F8a and F8b (Fig. 2, 3). The refined occupancy of the F8a and F8b sites are 0.790 (4) and 0.210 (4), respectively. Unfortunately, we did not manage to split the position of H2 atom, therefore, the angle of the hydrogen bond F8b–H2···F4 equal to139(4)° is unusual for strong hydrogen bonds.