Acta Cryst. (2007). E63, i171 [ doi:10.1107/S160053680703615X ]
The title compound is built from edge-sharing centrosymmetric dimeric [Zr2F12]4- complexes, K+ cations and HF molecules. The ZrIV coordination polyhedron is a distorted monocapped octahedron. The K+ ions are coordinated by F atoms and HF molecules with potassium coordination numbers of 7 and 8. In addition, the structure is stabilized by strong F-H
F hydrogen bonds.
ZrO2 (6.2 g, 0.05 mol) was reacted with KHF2 (7.9 g, 0.1 mol) in a solution of hydrofluoric acid (40%, 30 ml). Upon slow evaporation at room temperature, crystals of K2ZrF6 precipitated first, and after they were separated, crystals of (I) precipitated next.
The H1 atom was found in a difference Fourier map and refined with Uiso(H1) = 1.5Ueq(F7). The maximum peak and deepest hole are located 0.51 Å and 0.97 Å, respectively, from Zr and K2.
Data collection: SMART (Bruker, 1998a); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1998b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./mg2031fig1thm.gif)
| Fig. 1. A view of the centrosymmetric dimeric [Zr2F12]4− complex, with displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./mg2031fig2thm.gif)
| Fig. 2. The structure of (I), viewed along the c axis. |
| K2ZrF6·HF | F(000) = 1136 |
| Mr = 303.43 | Dx = 3.093 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1939 reflections |
| a = 13.3641 (5) Å | θ = 3.6–45.0° |
| b = 11.4457 (4) Å | µ = 3.03 mm−1 |
| c = 8.5211 (3) Å | T = 203 K |
| V = 1303.40 (8) Å3 | Prism, colourless |
| Z = 8 | 0.44 × 0.37 × 0.27 mm |
| Bruker SMART 1000 CCD area-detector diffractometer | 5275 independent reflections |
| Radiation source: fine-focus sealed tube | 4834 reflections with I > 2σ(I) |
| graphite | Rint = 0.030 |
| Detector resolution: 8.33 pixels mm-1 | θmax = 45.0°, θmin = 3.1° |
| ω scans | h = −26→23 |
| Absorption correction: gaussian (SADABS in XPREP; Bruker, 2003) | k = −20→22 |
| Tmin = 0.443, Tmax = 0.535 | l = −16→16 |
| 23595 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.030 | Only H-atom coordinates refined |
| wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0278P)2 + 0.8258P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.21 | (Δ/σ)max = 0.003 |
| 5275 reflections | Δρmax = 1.58 e Å−3 |
| 95 parameters | Δρmin = −1.30 e Å−3 |
| 0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0049 (2) |
| K2ZrF6·HF | V = 1303.40 (8) Å3 |
| Mr = 303.43 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 13.3641 (5) Å | µ = 3.03 mm−1 |
| b = 11.4457 (4) Å | T = 203 K |
| c = 8.5211 (3) Å | 0.44 × 0.37 × 0.27 mm |
| Bruker SMART 1000 CCD area-detector diffractometer | 5275 independent reflections |
| Absorption correction: gaussian (SADABS in XPREP; Bruker, 2003) | 4834 reflections with I > 2σ(I) |
| Tmin = 0.443, Tmax = 0.535 | Rint = 0.030 |
| 23595 measured reflections | θmax = 45.0° |
| R[F2 > 2σ(F2)] = 0.030 | Only H-atom coordinates refined |
| wR(F2) = 0.071 | Δρmax = 1.58 e Å−3 |
| S = 1.21 | Δρmin = −1.30 e Å−3 |
| 5275 reflections | Absolute structure: ? |
| 95 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Zr | 0.118901 (5) | 0.040452 (6) | 0.094477 (8) | 0.00846 (1) | |
| K1 | 0.170769 (16) | 0.740441 (15) | 0.84850 (2) | 0.01749 (3) | |
| K2 | 0.106835 (15) | 0.06846 (2) | 0.61088 (3) | 0.01853 (3) | |
| F1 | 0.08118 (5) | −0.02918 (5) | 0.30531 (7) | 0.01728 (10) | |
| F2 | 0.20020 (4) | −0.10800 (5) | 0.07447 (7) | 0.01528 (9) | |
| F3 | 0.04308 (4) | −0.06348 (6) | −0.08217 (8) | 0.02043 (11) | |
| F4 | 0.25374 (5) | 0.09337 (6) | 0.16899 (10) | 0.02846 (15) | |
| F5 | 0.15406 (7) | 0.12846 (7) | −0.09782 (8) | 0.02574 (14) | |
| F6 | 0.08494 (5) | 0.19919 (5) | 0.20043 (8) | 0.02147 (12) | |
| F7 | −0.03330 (6) | 0.18673 (8) | 0.40966 (9) | 0.02981 (17) | |
| H1 | 0.0108 (18) | 0.198 (2) | 0.335 (3) | 0.045* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zr | 0.00841 (2) | 0.00835 (2) | 0.00861 (3) | −0.00061 (2) | −0.00108 (2) | 0.00001 (2) |
| K1 | 0.02166 (7) | 0.01343 (5) | 0.01738 (7) | −0.00241 (5) | 0.00038 (5) | −0.00296 (5) |
| K2 | 0.01207 (6) | 0.02388 (7) | 0.01963 (7) | 0.00100 (5) | −0.00039 (5) | −0.00405 (6) |
| F1 | 0.0187 (2) | 0.0189 (2) | 0.0143 (2) | 0.00307 (17) | 0.00298 (17) | 0.00444 (16) |
| F2 | 0.01427 (19) | 0.01355 (17) | 0.0180 (2) | 0.00254 (15) | −0.00253 (16) | −0.00328 (15) |
| F3 | 0.01218 (19) | 0.0261 (2) | 0.0230 (2) | 0.00429 (18) | −0.00479 (17) | −0.01411 (19) |
| F4 | 0.0159 (2) | 0.0211 (2) | 0.0483 (4) | −0.00098 (19) | −0.0129 (3) | −0.0108 (3) |
| F5 | 0.0333 (3) | 0.0260 (3) | 0.0179 (3) | −0.0053 (3) | 0.0052 (2) | 0.0075 (2) |
| F6 | 0.0268 (3) | 0.01294 (18) | 0.0247 (3) | −0.00303 (18) | 0.0042 (2) | −0.00626 (18) |
| F7 | 0.0254 (3) | 0.0383 (4) | 0.0258 (3) | 0.0039 (3) | 0.0074 (2) | −0.0036 (3) |
| Zr—F5 | 1.9799 (7) | K2—F4xiv | 2.6735 (7) |
| Zr—F4 | 2.0043 (7) | K2—F6x | 2.7822 (7) |
| Zr—F2 | 2.0241 (5) | K2—F1 | 2.8541 (6) |
| Zr—F1 | 2.0290 (6) | K2—F7 | 2.8774 (9) |
| Zr—F6 | 2.0790 (6) | K2—F7v | 3.0867 (10) |
| Zr—F3 | 2.1696 (6) | K2—F3xv | 3.1381 (7) |
| Zr—F3i | 2.1833 (6) | K2—K2v | 3.7657 (4) |
| Zr—K2ii | 3.8740 (2) | K2—Zrxiv | 3.8740 (2) |
| Zr—K1iii | 3.9373 (2) | K2—K1xvi | 4.0997 (3) |
| Zr—K1iv | 4.0823 (2) | F1—K2v | 2.6506 (7) |
| Zr—K2v | 4.1180 (2) | F1—K1iii | 2.7232 (6) |
| Zr—K2vi | 4.1364 (3) | F2—K1iv | 2.6214 (6) |
| K1—F2vii | 2.6214 (6) | F2—K2ii | 2.6365 (6) |
| K1—F4viii | 2.6411 (7) | F2—K1iii | 2.8115 (6) |
| K1—F5ix | 2.7079 (8) | F3—Zri | 2.1833 (6) |
| K1—F1x | 2.7232 (6) | F3—K1iv | 2.8805 (7) |
| K1—F2x | 2.8115 (6) | F3—K2vi | 3.1381 (7) |
| K1—F7xi | 2.8284 (8) | F4—K1xvii | 2.6411 (7) |
| K1—F3vii | 2.8805 (7) | F4—K2ii | 2.6735 (7) |
| K1—F7xii | 2.9848 (9) | F4—K1xviii | 3.3629 (9) |
| K1—F4ix | 3.3629 (9) | F5—K2vi | 2.6517 (7) |
| K1—Zrx | 3.9373 (2) | F5—K1xviii | 2.7079 (8) |
| K1—Zrvii | 4.0823 (2) | F6—K2iii | 2.7822 (6) |
| K1—K2xiii | 4.0997 (3) | F7—K1xix | 2.8284 (8) |
| K2—F2xiv | 2.6365 (6) | F7—K1xii | 2.9848 (9) |
| K2—F1v | 2.6506 (7) | F7—K2v | 3.0867 (10) |
| K2—F5xv | 2.6517 (7) | ||
| F5—Zr—F4 | 83.98 (4) | F7xi—K1—Zrvii | 72.45 (2) |
| F5—Zr—F2 | 103.30 (3) | F3vii—K1—Zrvii | 30.543 (12) |
| F4—Zr—F2 | 78.33 (3) | F7xii—K1—Zrvii | 92.234 (18) |
| F5—Zr—F1 | 172.54 (3) | F4ix—K1—Zrvii | 93.154 (13) |
| F4—Zr—F1 | 93.53 (3) | Zrx—K1—Zrvii | 159.923 (6) |
| F2—Zr—F1 | 83.00 (2) | F2vii—K1—K2xiii | 124.870 (15) |
| F5—Zr—F6 | 88.09 (3) | F4viii—K1—K2xiii | 77.459 (17) |
| F4—Zr—F6 | 78.15 (3) | F5ix—K1—K2xiii | 39.595 (15) |
| F2—Zr—F6 | 152.55 (3) | F1x—K1—K2xiii | 79.959 (14) |
| F1—Zr—F6 | 84.52 (3) | F2x—K1—K2xiii | 39.604 (12) |
| F5—Zr—F3 | 79.37 (3) | F7xi—K1—K2xiii | 136.58 (2) |
| F4—Zr—F3 | 143.64 (3) | F3vii—K1—K2xiii | 154.800 (16) |
| F2—Zr—F3 | 74.45 (2) | F7xii—K1—K2xiii | 102.494 (16) |
| F1—Zr—F3 | 106.43 (3) | F4ix—K1—K2xiii | 86.747 (13) |
| F6—Zr—F3 | 132.73 (3) | Zrx—K1—K2xiii | 57.592 (4) |
| F5—Zr—F3i | 97.71 (3) | Zrvii—K1—K2xiii | 141.310 (6) |
| F4—Zr—F3i | 150.48 (3) | F2xiv—K2—F1v | 171.13 (2) |
| F2—Zr—F3i | 129.02 (2) | F2xiv—K2—F5xv | 80.38 (2) |
| F1—Zr—F3i | 81.00 (3) | F1v—K2—F5xv | 90.99 (2) |
| F6—Zr—F3i | 72.48 (3) | F2xiv—K2—F4xiv | 57.253 (19) |
| F3—Zr—F3i | 64.52 (3) | F1v—K2—F4xiv | 119.55 (2) |
| F5—Zr—K2ii | 88.23 (3) | F5xv—K2—F4xiv | 80.80 (3) |
| F4—Zr—K2ii | 40.11 (2) | F2xiv—K2—F6x | 88.34 (2) |
| F2—Zr—K2ii | 39.196 (16) | F1v—K2—F6x | 89.34 (2) |
| F1—Zr—K2ii | 94.399 (18) | F5xv—K2—F6x | 61.36 (2) |
| F6—Zr—K2ii | 118.17 (2) | F4xiv—K2—F6x | 133.22 (2) |
| F3—Zr—K2ii | 106.885 (17) | F2xiv—K2—F1 | 94.437 (19) |
| F3i—Zr—K2ii | 168.149 (19) | F1v—K2—F1 | 93.756 (18) |
| F5—Zr—K1iii | 145.96 (2) | F5xv—K2—F1 | 169.73 (2) |
| F4—Zr—K1iii | 85.09 (2) | F4xiv—K2—F1 | 88.93 (2) |
| F2—Zr—K1iii | 42.802 (17) | F6x—K2—F1 | 127.72 (2) |
| F1—Zr—K1iii | 40.202 (17) | F2xiv—K2—F7 | 119.06 (2) |
| F6—Zr—K1iii | 120.88 (2) | F1v—K2—F7 | 67.88 (2) |
| F3—Zr—K1iii | 90.912 (19) | F5xv—K2—F7 | 126.22 (3) |
| F3i—Zr—K1iii | 107.430 (19) | F4xiv—K2—F7 | 152.86 (3) |
| K2ii—Zr—K1iii | 63.310 (5) | F6x—K2—F7 | 69.22 (2) |
| F5—Zr—K1iv | 87.86 (2) | F1—K2—F7 | 64.05 (2) |
| F4—Zr—K1iv | 105.32 (2) | F2xiv—K2—F7v | 117.85 (2) |
| F2—Zr—K1iv | 32.804 (16) | F1v—K2—F7v | 63.44 (2) |
| F1—Zr—K1iv | 99.579 (17) | F5xv—K2—F7v | 111.96 (2) |
| F6—Zr—K1iv | 174.36 (2) | F4xiv—K2—F7v | 64.96 (2) |
| F3—Zr—K1iv | 42.430 (17) | F6x—K2—F7v | 152.45 (2) |
| F3i—Zr—K1iv | 104.196 (17) | F1—K2—F7v | 62.582 (19) |
| K2ii—Zr—K1iv | 65.620 (5) | F7—K2—F7v | 101.78 (2) |
| K1iii—Zr—K1iv | 64.248 (3) | F2xiv—K2—F3xv | 116.502 (18) |
| F5—Zr—K2v | 146.34 (3) | F1v—K2—F3xv | 55.698 (17) |
| F4—Zr—K2v | 123.85 (3) | F5xv—K2—F3xv | 53.77 (2) |
| F2—Zr—K2v | 100.980 (17) | F4xiv—K2—F3xv | 72.63 (2) |
| F1—Zr—K2v | 32.783 (18) | F6x—K2—F3xv | 101.703 (19) |
| F6—Zr—K2v | 80.783 (19) | F1—K2—F3xv | 122.639 (18) |
| F3—Zr—K2v | 85.118 (18) | F7—K2—F3xv | 123.12 (2) |
| F3i—Zr—K2v | 48.660 (19) | F7v—K2—F3xv | 60.360 (19) |
| K2ii—Zr—K2v | 125.009 (5) | F2xiv—K2—K2v | 138.945 (17) |
| K1iii—Zr—K2v | 63.039 (5) | F1v—K2—K2v | 49.139 (14) |
| K1iv—Zr—K2v | 100.533 (5) | F5xv—K2—K2v | 139.29 (2) |
| F5—Zr—K2vi | 31.28 (2) | F4xiv—K2—K2v | 109.46 (2) |
| F4—Zr—K2vi | 109.10 (3) | F6x—K2—K2v | 117.109 (18) |
| F2—Zr—K2vi | 90.120 (17) | F1—K2—K2v | 44.617 (13) |
| F1—Zr—K2vi | 154.536 (18) | F7—K2—K2v | 53.362 (19) |
| F6—Zr—K2vi | 110.88 (2) | F7v—K2—K2v | 48.418 (16) |
| F3—Zr—K2vi | 48.175 (19) | F3xv—K2—K2v | 90.694 (14) |
| F3i—Zr—K2vi | 84.499 (17) | F2xiv—K2—Zrxiv | 29.024 (12) |
| K2ii—Zr—K2vi | 95.611 (5) | F1v—K2—Zrxiv | 148.434 (15) |
| K1iii—Zr—K2vi | 128.158 (5) | F5xv—K2—Zrxiv | 83.797 (19) |
| K1iv—Zr—K2vi | 63.915 (5) | F4xiv—K2—Zrxiv | 28.880 (14) |
| K2v—Zr—K2vi | 127.033 (4) | F6x—K2—Zrxiv | 114.644 (16) |
| F2vii—K1—F4viii | 83.77 (2) | F1—K2—Zrxiv | 87.405 (13) |
| F2vii—K1—F5ix | 93.40 (2) | F7—K2—Zrxiv | 138.215 (17) |
| F4viii—K1—F5ix | 96.23 (2) | F7v—K2—Zrxiv | 89.697 (17) |
| F2vii—K1—F1x | 138.84 (2) | F3xv—K2—Zrxiv | 97.590 (12) |
| F4viii—K1—F1x | 136.82 (2) | K2v—K2—Zrxiv | 124.431 (9) |
| F5ix—K1—F1x | 89.00 (2) | F2xiv—K2—K1xvi | 42.828 (13) |
| F2vii—K1—F2x | 161.06 (2) | F1v—K2—K1xvi | 129.466 (15) |
| F4viii—K1—F2x | 81.60 (2) | F5xv—K2—K1xvi | 40.607 (18) |
| F5ix—K1—F2x | 76.358 (19) | F4xiv—K2—K1xvi | 74.689 (18) |
| F1x—K1—F2x | 58.032 (17) | F6x—K2—K1xvi | 58.790 (16) |
| F2vii—K1—F7xi | 72.91 (2) | F1—K2—K1xvi | 136.521 (14) |
| F4viii—K1—F7xi | 145.75 (3) | F7—K2—K1xvi | 122.70 (2) |
| F5ix—K1—F7xi | 109.61 (2) | F7v—K2—K1xvi | 135.492 (17) |
| F1x—K1—F7xi | 67.66 (2) | F3xv—K2—K1xvi | 90.930 (13) |
| F2x—K1—F7xi | 125.37 (2) | K2v—K2—K1xvi | 175.841 (10) |
| F2vii—K1—F3vii | 54.737 (17) | Zrxiv—K2—K1xvi | 59.097 (4) |
| F4viii—K1—F3vii | 77.52 (2) | Zr—F1—K2v | 122.73 (3) |
| F5ix—K1—F3vii | 147.81 (2) | Zr—F1—K1iii | 111.05 (2) |
| F1x—K1—F3vii | 117.33 (2) | K2v—F1—K1iii | 103.28 (2) |
| F2x—K1—F3vii | 132.321 (18) | Zr—F1—K2 | 128.62 (3) |
| F7xi—K1—F3vii | 68.60 (2) | K2v—F1—K2 | 86.244 (18) |
| F2vii—K1—F7xii | 116.68 (2) | K1iii—F1—K2 | 99.88 (2) |
| F4viii—K1—F7xii | 66.87 (2) | Zr—F2—K1iv | 122.47 (3) |
| F5ix—K1—F7xii | 142.08 (2) | Zr—F2—K2ii | 111.78 (2) |
| F1x—K1—F7xii | 82.98 (2) | K1iv—F2—K2ii | 110.29 (2) |
| F2x—K1—F7xii | 67.95 (2) | Zr—F2—K1iii | 107.91 (2) |
| F7xi—K1—F7xii | 101.41 (3) | K1iv—F2—K1iii | 103.432 (19) |
| F3vii—K1—F7xii | 64.47 (2) | K2ii—F2—K1iii | 97.567 (19) |
| F2vii—K1—F4ix | 71.922 (18) | Zr—F3—Zri | 115.48 (3) |
| F4viii—K1—F4ix | 135.74 (3) | Zr—F3—K1iv | 107.03 (2) |
| F5ix—K1—F4ix | 50.694 (19) | Zri—F3—K1iv | 132.19 (3) |
| F1x—K1—F4ix | 78.296 (19) | Zr—F3—K2vi | 100.81 (2) |
| F2x—K1—F4ix | 111.259 (18) | Zri—F3—K2vi | 99.85 (2) |
| F7xi—K1—F4ix | 59.63 (2) | K1iv—F3—K2vi | 92.473 (18) |
| F3vii—K1—F4ix | 113.649 (19) | Zr—F4—K1xvii | 138.12 (3) |
| F7xii—K1—F4ix | 157.36 (2) | Zr—F4—K2ii | 111.01 (3) |
| F2vii—K1—Zrx | 166.072 (14) | K1xvii—F4—K2ii | 109.88 (2) |
| F4viii—K1—Zrx | 109.69 (2) | Zr—F4—K1xviii | 99.42 (3) |
| F5ix—K1—Zrx | 81.870 (17) | K1xvii—F4—K1xviii | 89.73 (2) |
| F1x—K1—Zrx | 28.747 (13) | K2ii—F4—K1xviii | 89.27 (2) |
| F2x—K1—Zrx | 29.286 (11) | Zr—F5—K2vi | 125.91 (4) |
| F7xi—K1—Zrx | 96.241 (19) | Zr—F5—K1xviii | 125.86 (4) |
| F3vii—K1—Zrx | 130.140 (14) | K2vi—F5—K1xviii | 99.80 (2) |
| F7xii—K1—Zrx | 73.412 (18) | Zr—F6—K2iii | 133.89 (3) |
| F4ix—K1—Zrx | 95.194 (13) | K1xix—F7—K2 | 95.21 (2) |
| F2vii—K1—Zrvii | 24.729 (12) | K1xix—F7—K1xii | 94.38 (3) |
| F4viii—K1—Zrvii | 75.902 (18) | K2—F7—K1xii | 166.20 (3) |
| F5ix—K1—Zrvii | 117.271 (17) | K1xix—F7—K2v | 92.30 (2) |
| F1x—K1—Zrvii | 137.870 (15) | K2—F7—K2v | 78.22 (2) |
| F2x—K1—Zrvii | 154.647 (13) | K1xii—F7—K2v | 91.52 (2) |
| Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, −y, z−1/2; (iii) x, −y+1/2, z−1/2; (iv) x, y−1, z−1; (v) −x, −y, −z+1; (vi) x, y, z−1; (vii) x, y+1, z+1; (viii) −x+1/2, −y+1, z+1/2; (ix) −x+1/2, y+1/2, z+1; (x) x, −y+1/2, z+1/2; (xi) −x, y+1/2, −z+3/2; (xii) −x, −y+1, −z+1; (xiii) −x+1/2, y+1/2, z; (xiv) −x+1/2, −y, z+1/2; (xv) x, y, z+1; (xvi) −x+1/2, y−1/2, z; (xvii) −x+1/2, −y+1, z−1/2; (xviii) −x+1/2, y−1/2, z−1; (xix) −x, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| F7—H1···F6 | 0.87 (2) | 1.52 (2) | 2.3865 (10) | 172 (2) |
| Zr—F5 | 1.9799 (7) | K1—F2v | 2.8115 (6) |
| Zr—F4 | 2.0043 (7) | K1—F7vi | 2.8284 (8) |
| Zr—F2 | 2.0241 (5) | K1—F3ii | 2.8805 (7) |
| Zr—F1 | 2.0290 (6) | K1—F7vii | 2.9848 (9) |
| Zr—F6 | 2.0790 (6) | K2—F2viii | 2.6365 (6) |
| Zr—F3 | 2.1696 (6) | K2—F1ix | 2.6506 (7) |
| Zr—F3i | 2.1833 (6) | K2—F5x | 2.6517 (7) |
| K1—F2ii | 2.6214 (6) | K2—F4viii | 2.6735 (7) |
| K1—F4iii | 2.6411 (7) | K2—F6v | 2.7822 (7) |
| K1—F5iv | 2.7079 (8) | K2—F1 | 2.8541 (6) |
| K1—F1v | 2.7232 (6) | K2—F7 | 2.8774 (9) |
| Symmetry codes: (i) −x, −y, −z; (ii) x, y+1, z+1; (iii) −x+1/2, −y+1, z+1/2; (iv) −x+1/2, y+1/2, z+1; (v) x, −y+1/2, z+1/2; (vi) −x, y+1/2, −z+3/2; (vii) −x, −y+1, −z+1; (viii) −x+1/2, −y, z+1/2; (ix) −x, −y, −z+1; (x) x, y, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| F7—H1···F6 | 0.87 (2) | 1.52 (2) | 2.3865 (10) | 172 (2) |
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 (1998a). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1998b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2003). SAINT (Version 6.45) and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.
Serezhkin, V. N., Mikhailov, Yu. N. & Buslaev, Yu. A. (1997). Zh. Neorg. Khim. 42, 2036–2077.
Tkachev, V. V., Davidovich, R. L., Logvinova, V. B. & Atovmyan, L. O. (1993). Koord. Khim. 19, 698–700.
The title compound, (I), is isostructural to K2Rb2(ZrF6)2.2H2O, (II), if hydrogen atoms are neglected (Tkachev et al., 1993). The asymmetric unit contains one crystallographically independent Zr atom, six fluorine atoms, two potassium cations and one hydrogen fluoride molecule. The Zr atoms are coordinated by seven F atoms in a distorted monocapped octahedral 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 3.6810 (2) Å. Parallel to the ac plane, layers of K1 atoms and HF molecules alternate with layers of K2 atoms and [Zr2F12]4− complexes (Fig. 2).
The coordination numbers (CN) of potassium atoms were calculated by the method of intersecting spheres (Serezhkin et al., 1997) with use of the program package TOPOS (Blatov, 2004). For K1, the CN is 8 (K1–F, 2.6214 (6)–2.9848 (9) Å) and for K2, the CN is 7 (K2–F, 2.6365 (6)–2.8774 (9) Å).
The HF molecule is coordinated to both potassium atoms and is involved as a donor in the strong hydrogen bond (2.3865 (10) Å) with the F6 atom (Fig. 2). Unlike the structure of (II), where the water molecule forms two hydrogen bonds with an F6 atom (2.88 Å) and a bridging F3 atom (2.74 Å) (Tkachev et al., 1993), in (I) there is only one hydrogen bond, resulting in a lengthened Zr–F6 bond (2.0790 (6) Å) and nearly equal Zr–F3 and Zr–F3i bridging bonds (2.1696 (6) and 2.1833 (6) Å). In (II), the corresponding bonds are 2.046, 2.188, and 2.199 Å, respectively (Tkachev et al., 1993).