Abstract
Single crystals of the title compound, K2[Ni(H2O)6][ZrF6]2, were grown by slow evaporation of a 40% aqueous HF solution in which a stoichiometric mixture of NiCl2·6H2O, ZrF4 and KCl was dissolved. The monoclinic structure is isotypic with its K2Cu, K2Zn, Cs2Zn and Cs2Cu analogues. The structure is built up from isolated, slightly elongated octahedral [Ni(H2O)6]2+ complex cations (symmetry 
) and dimeric [Zr2F12]4− complex anions (symmetry ) that are also isolated from each other. The [Zr2F12]4− anion results from the association of two distorted pentagonal–bipyramidal [ZrF7] coordination polyhedra by sharing an equatorial edge passing through an inversion center of the unit cell. Both isolated [Ni(H2O)6]2+ and [Zr2F12]4− complex ions are situated in planes parallel to (010). They are connected by the eight-coordinated K+ ions into a three-dimensional structure. An intricate O—H⋯F hydrogen-bonding network consolidates the structure.
Related literature
For isotypic structures, see: Fischer & Weiss (1973 ▶); Bukvetskii et al. (1993 ▶); Hitchman et al. (2002 ▶). For a review on the stereochemistry of zirconium and hafnium fluorido complexes, see: Davidovich (1998 ▶). For background to distortion indices, see: Momma & Izumi (2008 ▶).
Experimental
Crystal data
K2[Ni(H2O)6][ZrF6]2
M r = 655.45
Monoclinic,
a = 6.6090 (1) Å
b = 10.0398 (1) Å
c = 11.7843 (1) Å
β = 95.897 (1)°
V = 777.79 (2) Å3
Z = 2
Mo Kα radiation
μ = 3.20 mm−1
T = 296 K
0.28 × 0.14 × 0.09 mm
Data collection
Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.613, T max = 0.748
17267 measured reflections
4436 independent reflections
3858 reflections with I > 2σ(I)
R int = 0.028
Refinement
R[F 2 > 2σ(F 2)] = 0.023
wR(F 2) = 0.052
S = 1.06
4436 reflections
131 parameters
All H-atom parameters refined
Δρmax = 0.63 e Å−3
Δρmin = −0.57 e Å−3
Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).
Supplementary Material
Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681005350X/wm2439sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S160053681005350X/wm2439Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H11⋯F1i | 0.79 (3) | 2.94 (2) | 3.3300 (14) | 112.8 (19) |
| O1—H11⋯F2ii | 0.79 (3) | 1.92 (3) | 2.6877 (14) | 164 (2) |
| O1—H12⋯F4iii | 0.82 (3) | 1.82 (3) | 2.6375 (13) | 177 (2) |
| O1—H12⋯F5iv | 0.82 (3) | 2.61 (2) | 3.0526 (13) | 116 (2) |
| O2—H21⋯F1i | 0.78 (2) | 2.59 (2) | 3.0048 (13) | 115 (2) |
| O2—H21⋯F2ii | 0.78 (2) | 1.95 (2) | 2.7227 (13) | 167 (2) |
| O2—H22⋯F4v | 0.82 (2) | 1.92 (2) | 2.7362 (13) | 173 (2) |
| O2—H22⋯F6vi | 0.82 (2) | 2.76 (2) | 3.1924 (14) | 114.9 (17) |
| O3—H31⋯F1vii | 0.80 (3) | 2.86 (3) | 3.2552 (16) | 113.3 (19) |
| O3—H31⋯F5viii | 0.80 (3) | 1.92 (3) | 2.7019 (14) | 168 (2) |
| O3—H32⋯F3iv | 0.80 (3) | 3.00 (2) | 3.4527 (16) | 119 (2) |
| O3—H32⋯F6ix | 0.80 (3) | 1.97 (3) | 2.7427 (15) | 163 (2) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
; (viii) 
; (ix) 
.
Table 2. Comparison of the geometrical characteristics of the coordination polyhedra in isotypic M I 2[M II(H2O)6][ZrF6]2 structures determined from single-crystal data (Å, °, Å3).
| K2[Ni(H2O)6][ZrF6]2a | K2[Cu(H2O)6][ZrF6]2b | K2[Zn(H2O)6][ZrF6]2c | Cs2[Zn(H2O)6][ZrF6]2d | |
|---|---|---|---|---|
| Space group | P21/n | P21/c | P21/c | P21/n |
| a | 6.6090 (1) | 6.631 (6) | 6.631 (1) | 6.970 (1) |
| b | 10.0398 (1) | 9.981 (10) | 10.071 (1) | 10.515 (2) |
| c | 11.7843 (1) | 12.921 (12) | 12.952 (1) | 11.803 (2) |
| β | 95.897 (1) | 114.20 (15) | 114.96 (2) | 93.56 (3) |
| V | 777.786 (16) | 780.01 (1) | 784.16 (2) | 863.4 (3) |
| Ni—O1 = 2.0548 (10) (2×) | Cu—O1 = 1.966 (4) (2×) | Zn—O1 = 2.0856 (2) (2×) | Zn—O3 = 2.096 (6) (2×) | |
| Distances MII—O | Ni—O3 = 2.0570 (11) (2×) | Cu—O2 = 2.025 (6) (2×) | Zn—O2 = 2.0940 (1) (2×) | Zn—O1 = 2.099 (5) (2×) |
| Ni—O2 = 2.0781 (9) (2×) | Cu—O3 = 2.327 (5) (2×) | Zn—O3 = 2.1185 (2) (2×) | Zn—O2 = 2.105 (5) (2×) | |
| Average MII—O bond length | 2.063 | 2.106 | 2.099 | 2.100 |
| Polyhedral volume | 11.684 | 12.335 | 12.318 | 12.341 |
| Distortion index (bond length) | 0.00483 | 0.06089 | 0.00607 | 0.00156 |
| Quadratic elongation | 1.0013 | 1.0124 | 1.0011 | 1.0006 |
| Zr—F6 = 1.9718 (9) | Zr—F3 = 1.968 (5) | Zr—F3 = 1.9727 (3) | Zr—F3 = 1.962 (5) | |
| Zr—F5 = 2.0006 (8) | Zr—F1 = 2.004 (5) | Zr—F1 = 2.0018 (3) | Zr—F6 = 1.977 (5) | |
| Zr—F3 = 2.0293 (9) | Zr—F5 = 2.029 (4) | Zr—F5 = 2.0277 (3) | Zr—F5 = 2.037 (5) | |
| Distances Zr—F (Å) | Zr—F2 = 2.0554 (8) | Zr—F6 = 2.059 (4) | Zr—F6 = 2.0570 (3) | Zr—F4 = 2.067 (4) |
| Zr—F1 = 2.0708 (8) | Zr—F2 = 2.063 (4) | Zr—F2 = 2.0668 (4) | Zr—F2 = 2.069 (4) | |
| Zr—F4 = 2.1468 (9) | Zr—F4 = 2.156 (5) | Zr—F4 = 2.1501 (4) | Zr—F1 = 2.156 (4) | |
| Zr—F4 = 2.1614 (8) | Zr—F4 = 2.160 (4) | Zr—F4 = 2.1628 (4) | Zr—F1 = 2.180 (4) | |
| Average Zr—F bond length | 2.062 | 2.063 | 2.063 | 2.064 |
| Polyhedral volume | 13.669 | 13.674 | 13.675 | 13.692 |
| Distortion index (bond length) | 0.02662 | 0.02650 | 0.02654 | 0.02985 |
| K—F5 = 2.6496 (10) | K—F1 = 2.668 (5) | K—F1 = 2.6506 (3) | Cs—F6 = 2.911 (5) | |
| K—F3 = 2.7366 (9) | K—F6 = 2.750 (6) | K—F2 = 2.7395 (4) | Cs—F4 = 3.046 (4) | |
| K—F6 = 2.7603 (11) | K—F3 = 2.756 (5) | K—F5 = 2.7633 (2) | Cs—F2 = 3.057 (4) | |
| Distances K—F/O | K—F2 = 2.7658 (9) | K—F5 = 2.767 (5) | K—F6 = 2.7739 (2) | Cs—F3 = 3.065 (5) |
| K—F1 = 2.7895 (9) | K—F2 = 2.799 (5) | K—F3 = 2.8094 (2) | Cs—F3 = 3.102 (5) | |
| K—O2 = 2.8927 (10) | K—O3 = 2.942 (5) | K—O1 = 2.8968 (3) | Cs—O2 = 3.218 (5) | |
| K—O1 = 3.1012 (10) | K—O1 = 2.980 (5) | K—O2 = 3.0873 (5) | Cs—O1 = 3.236 (5) | |
| K—F6 = 3.1684 (12) | K—F3 = 3.1307 (7) | K—F3 = 3.1707 (7) | Cs—F5 = 3.228 (6) | |
| Average MI—F/O bond length | 2.858 | 2.849 | 2.861 | 3.118 |
| Polyhedral volume | 38.458 | 38.158 | 38.569 | 48.130 |
| Distortion index (bond length) | 0.05146 | 0.04429 | 0.04984 | 0.02627 |
supplementary crystallographic information
Comment
The existence of the title compound K2[Ni(H2O)6][ZrF6]2 as member of the large family of zirconium fluorido complexes with general formula MI2[MII(H2O)6][ZrF6]2 where MI = K, Rb, Cs or NH4 and MII = Co, Ni, Cu or Zn, has already been mentioned by Davidovich (1998). The monoclinic structure of the title compound is isotypic with those of K2[Cu(H2O)6][ZrF6]2 (Fischer & Weiss, 1973), K2[Zn(H2O)6][ZrF6]2 (Bukvetskii et al., 1993) and Cs2[Zn(H2O)6][ZrF6]2 (Hitchman et al., 2002). In the title structure the Ni2+ cation (site symmetry 1) is coordinated by six water molecules with two Ni—O distances slightly longer (2.0781 (9) Å) than the four others (2x 2.0548 (10) Å and 2x 2.0570 (11) Å). The Zr4+ cation is 7-coordinated by the fluoride ions but rather than being isolated anions, the fluoridozirconate(IV) ions form centrosymmetric [Zr2F12]4- dimers. Thus the structure is built up from isolated and slightly elongated octahedral [Ni(H2O)6]2+ complex cations and dimeric [Zr2F12]4- complex anions, also isolated from each other. The [ZrF7] coordination polyhedron is a distorted pentagonal bipyramid (symmetry 1) and the centrosymmetric [Zr2F12]4- complex anion results from the association of two pentagonal bipyramids by sharing an equatorial edge F1—F1 passing through an inversion center of the unit cell corresponding to either the 2 b or 2 c Wyckoff positions. Both isolated [Ni(H2O)6]2+ and [Zr2F12]4- complex ions lying in planes parallel to (010) are connected by the 8-coordinated K+ ions (Fig. 1) and an intricate O—H···F hydrogen bonds network (Fig. 2 and Table 1) to form the three-dimensional structure.
A careful examination of the geometry of the [Zr2F12]4- complex anion in isotypic structures, refined from single-crystal data, shows this anion being quasi unvarying for all the members (Table 2). The distortion index (bond length) (Momma & Izumi, 2008) is the same for all the K compounds (0.0265) and is only very slightly higher (0.02985) for the Cs analogue. It is also worth noting that the higher the index of distortion of the [MII(H2O)6] cationic polyhedron, the lower the index of distortion of the counter cation K+ (0.04429). This observation is obvious because water molecules are only shared between K+ and M2+ ions.
Experimental
Single crystals of the title compound were obtained by reacting a mixture of NiCl2.6H2O, ZrF4 and KCl in the molar ratio 1:2:2 with a 40% aqueous HF boiling solution in a platinum crucible. Then the solution was poured out into a PTFE beaker and slowly evaporated to dryness using a sand bath. Green single-crystals of the title compound were extracted from the dry residue.
Refinement
The highest residual peak in the final difference Fourier map was located 0.60 Å from the Zr atom and the deepest hole was located 0.86 Å from the same atom. H atom parameter were fefined freely.
Figures
Fig. 1.
View of the polyhedral linkage inK2[Ni(H2O)6][ZrF6]2. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) x, y + 1, z; (ii) x - 1, y + 1, z; (iii) -x, -y + 1, -z + 1; (iv) -x, -y, -z; (v) -x, -y - 1, -z; (vi) -x - 1/2, y + 1/2, -z + 1/2; (vii) -x + 1/2, y + 1/2, -z + 1/2; (viii) x + 1/2, -y + 3/2, z - 1/2; (x) x + 1, y + 1, z; (xi) -x + 1/2, y - 1/2, -z + 1/2; (xii) x, y - 1, z; (xiii) x - 1, y - 1, z; (xiv) x + 1, y - 1, z; (xv) x - 1, y, z; (xvi) x - 1/2, -y + 3/2, z + 1/2; (xvii) -x - 1/2, y - 1/2, -z + 1/2.
Fig. 2.
Projection of the crystal structure of K2[Ni(H2O)6][ZrF6]2 along [100] showing the hydrogen-bonding interactions.
Crystal data
| K2[Ni(H2O)6][ZrF6]2 | F(000) = 628 |
| Mr = 655.45 | Dx = 2.799 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 7940 reflections |
| a = 6.6090 (1) Å | θ = 3.7–38.7° |
| b = 10.0398 (1) Å | µ = 3.20 mm−1 |
| c = 11.7843 (1) Å | T = 296 K |
| β = 95.897 (1)° | Block, green |
| V = 777.79 (2) Å3 | 0.28 × 0.14 × 0.09 mm |
| Z = 2 |
Data collection
| Bruker APEXII CCD diffractometer | 4436 independent reflections |
| Radiation source: fine-focus sealed tube | 3858 reflections with I > 2σ(I) |
| graphite | Rint = 0.028 |
| Detector resolution: 8.3333 pixels mm-1 | θmax = 38.8°, θmin = 4.2° |
| ω and φ scans | h = −11→11 |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | k = −17→12 |
| Tmin = 0.613, Tmax = 0.748 | l = −18→20 |
| 17267 measured reflections |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.023 | All H-atom parameters refined |
| wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.0182P)2 + 0.3179P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max = 0.032 |
| 4436 reflections | Δρmax = 0.63 e Å−3 |
| 131 parameters | Δρmin = −0.57 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 constraints | Extinction coefficient: 0.0068 (4) |
| Primary atom site location: structure-invariant direct methods |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| Zr | −0.462200 (17) | 0.984514 (11) | 0.350424 (9) | 0.01376 (3) | |
| Ni | 0.0000 | 0.0000 | 0.0000 | 0.01508 (4) | |
| K | 0.47534 (5) | 0.71630 (3) | 0.08423 (3) | 0.02839 (7) | |
| O1 | 0.21314 (15) | −0.11683 (10) | −0.06747 (9) | 0.02154 (17) | |
| O2 | −0.23852 (15) | −0.12500 (10) | −0.05901 (9) | 0.02039 (17) | |
| O3 | −0.04437 (19) | −0.88871 (12) | −0.14701 (9) | 0.0293 (2) | |
| F1 | 0.53736 (16) | 0.11314 (9) | 0.49592 (7) | 0.0300 (2) | |
| F2 | −0.53154 (14) | 0.78950 (8) | 0.31006 (7) | 0.02440 (16) | |
| F3 | −0.17901 (13) | 0.93040 (11) | 0.39692 (9) | 0.0346 (2) | |
| F4 | −0.46635 (13) | 0.97177 (8) | 0.17481 (7) | 0.02228 (15) | |
| F5 | −0.35001 (14) | 0.16232 (8) | 0.30407 (8) | 0.02609 (17) | |
| F6 | −0.75507 (12) | 0.03609 (11) | 0.31945 (8) | 0.02759 (18) | |
| H11 | 0.159 (4) | −0.169 (3) | −0.111 (2) | 0.044 (6)* | |
| H12 | 0.289 (4) | −0.072 (3) | −0.103 (2) | 0.044 (6)* | |
| H21 | −0.196 (3) | −0.178 (2) | −0.099 (2) | 0.041 (6)* | |
| H22 | −0.327 (3) | −0.084 (2) | −0.0981 (19) | 0.038 (6)* | |
| H31 | 0.028 (4) | −0.829 (3) | −0.163 (2) | 0.046 (7)* | |
| H32 | −0.086 (4) | −0.925 (3) | −0.205 (2) | 0.048 (7)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zr | 0.01662 (5) | 0.01302 (5) | 0.01144 (5) | −0.00068 (3) | 0.00044 (3) | 0.00045 (3) |
| Ni | 0.01666 (9) | 0.01442 (9) | 0.01395 (9) | −0.00119 (6) | 0.00064 (7) | −0.00028 (6) |
| K | 0.03371 (15) | 0.02741 (14) | 0.02299 (14) | −0.00580 (11) | −0.00224 (11) | 0.00113 (10) |
| O1 | 0.0229 (4) | 0.0194 (4) | 0.0230 (5) | −0.0021 (3) | 0.0058 (4) | −0.0031 (3) |
| O2 | 0.0207 (4) | 0.0186 (4) | 0.0213 (4) | −0.0003 (3) | −0.0007 (3) | −0.0024 (3) |
| O3 | 0.0407 (6) | 0.0279 (5) | 0.0175 (5) | −0.0127 (4) | −0.0053 (4) | 0.0056 (4) |
| F1 | 0.0579 (6) | 0.0175 (4) | 0.0158 (4) | −0.0105 (4) | 0.0091 (4) | −0.0021 (3) |
| F2 | 0.0394 (5) | 0.0162 (3) | 0.0173 (4) | −0.0029 (3) | 0.0014 (3) | −0.0013 (3) |
| F3 | 0.0216 (4) | 0.0442 (6) | 0.0365 (5) | 0.0060 (4) | −0.0048 (3) | 0.0052 (4) |
| F4 | 0.0280 (4) | 0.0239 (4) | 0.0152 (3) | −0.0041 (3) | 0.0037 (3) | −0.0007 (3) |
| F5 | 0.0367 (4) | 0.0181 (4) | 0.0247 (4) | −0.0067 (3) | 0.0091 (3) | 0.0002 (3) |
| F6 | 0.0193 (4) | 0.0350 (5) | 0.0280 (5) | 0.0055 (3) | 0.0004 (3) | −0.0062 (3) |
Geometric parameters (Å, °)
| Zr—F3 | 1.9717 (9) | K—F3xi | 3.1685 (12) |
| Zr—F6i | 2.0006 (8) | O1—Kxii | 2.8929 (11) |
| Zr—F5i | 2.0293 (8) | O1—H11 | 0.79 (3) |
| Zr—F2 | 2.0554 (8) | O1—H12 | 0.82 (3) |
| Zr—F4 | 2.0708 (8) | O2—Kxiii | 3.1015 (11) |
| Zr—F1ii | 2.1467 (8) | O2—H21 | 0.78 (2) |
| Zr—F1iii | 2.1614 (8) | O2—H22 | 0.82 (2) |
| Ni—O1iv | 2.0548 (10) | O3—Nixii | 2.0570 (11) |
| Ni—O1 | 2.0548 (10) | O3—H31 | 0.80 (3) |
| Ni—O3v | 2.0570 (11) | O3—H32 | 0.80 (3) |
| Ni—O3i | 2.0570 (11) | F1—Zrxiv | 2.1467 (8) |
| Ni—O2iv | 2.0781 (9) | F1—Zriii | 2.1614 (8) |
| Ni—O2 | 2.0781 (9) | F2—Kxv | 2.7658 (9) |
| K—F6vi | 2.6497 (9) | F3—Kxvi | 2.7603 (10) |
| K—F5vii | 2.7365 (10) | F3—Kvii | 3.1685 (12) |
| K—F3viii | 2.7603 (10) | F4—Kxv | 2.7896 (9) |
| K—F2ix | 2.7658 (9) | F5—Zrxii | 2.0293 (8) |
| K—F4ix | 2.7896 (9) | F5—Kxi | 2.7365 (10) |
| K—O1i | 2.8929 (11) | F6—Zrxii | 2.0006 (8) |
| K—O2x | 3.1015 (11) | F6—Kxvii | 2.6497 (9) |
| F3—Zr—F6i | 174.24 (4) | F5vii—K—F2ix | 72.14 (3) |
| F3—Zr—F5i | 87.40 (4) | F3viii—K—F2ix | 150.45 (3) |
| F6i—Zr—F5i | 95.54 (4) | F6vi—K—F4ix | 121.62 (3) |
| F3—Zr—F2 | 89.11 (4) | F5vii—K—F4ix | 85.15 (3) |
| F6i—Zr—F2 | 90.90 (4) | F3viii—K—F4ix | 145.26 (3) |
| F5i—Zr—F2 | 148.71 (3) | F2ix—K—F4ix | 53.33 (2) |
| F3—Zr—F4 | 100.10 (4) | F6vi—K—O1i | 109.85 (3) |
| F6i—Zr—F4 | 85.44 (4) | F5vii—K—O1i | 150.10 (3) |
| F5i—Zr—F4 | 75.70 (3) | F3viii—K—O1i | 70.50 (3) |
| F2—Zr—F4 | 74.34 (3) | F2ix—K—O1i | 111.88 (3) |
| F3—Zr—F1ii | 91.31 (4) | F4ix—K—O1i | 75.79 (3) |
| F6i—Zr—F1ii | 84.80 (4) | F6vi—K—O2x | 167.54 (3) |
| F5i—Zr—F1ii | 73.52 (3) | F5vii—K—O2x | 77.96 (3) |
| F2—Zr—F1ii | 137.67 (3) | F3viii—K—O2x | 92.00 (3) |
| F4—Zr—F1ii | 146.55 (3) | F2ix—K—O2x | 117.28 (3) |
| F3—Zr—F1iii | 86.30 (4) | F4ix—K—O2x | 70.61 (3) |
| F6i—Zr—F1iii | 88.22 (4) | O1i—K—O2x | 74.11 (3) |
| F5i—Zr—F1iii | 138.27 (3) | F6vi—K—F3xi | 66.39 (3) |
| F2—Zr—F1iii | 72.35 (3) | F5vii—K—F3xi | 55.25 (2) |
| F4—Zr—F1iii | 145.96 (3) | F3viii—K—F3xi | 72.07 (3) |
| F1ii—Zr—F1iii | 65.45 (4) | F2ix—K—F3xi | 102.83 (3) |
| F3—Zr—Zrxviii | 88.57 (3) | F4ix—K—F3xi | 139.92 (3) |
| F6i—Zr—Zrxviii | 85.86 (3) | O1i—K—F3xi | 142.29 (3) |
| F5i—Zr—Zrxviii | 106.09 (3) | O2x—K—F3xi | 103.01 (3) |
| F2—Zr—Zrxviii | 104.90 (2) | F6vi—K—Zrxi | 89.24 (2) |
| F4—Zr—Zrxviii | 171.25 (2) | F5vii—K—Zrxi | 28.097 (18) |
| F1ii—Zr—Zrxviii | 32.85 (2) | F3viii—K—Zrxi | 93.88 (2) |
| F1iii—Zr—Zrxviii | 32.60 (2) | F2ix—K—Zrxi | 93.56 (2) |
| F3—Zr—Kvii | 51.84 (3) | F4ix—K—Zrxi | 112.72 (2) |
| F6i—Zr—Kvii | 129.16 (3) | O1i—K—Zrxi | 151.51 (2) |
| F5i—Zr—Kvii | 39.43 (3) | O2x—K—Zrxi | 83.09 (2) |
| F2—Zr—Kvii | 139.29 (3) | F3xi—K—Zrxi | 29.294 (16) |
| F4—Zr—Kvii | 99.03 (2) | F6vi—K—Zrix | 97.85 (2) |
| F1ii—Zr—Kvii | 63.98 (3) | F5vii—K—Zrix | 75.428 (19) |
| F1iii—Zr—Kvii | 110.72 (3) | F3viii—K—Zrix | 163.11 (2) |
| Zrxviii—Zr—Kvii | 87.200 (6) | F2ix—K—Zrix | 26.431 (17) |
| F3—Zr—Kxv | 92.84 (3) | F4ix—K—Zrix | 27.023 (17) |
| F6i—Zr—Kxv | 90.62 (3) | O1i—K—Zrix | 95.67 (2) |
| F5i—Zr—Kxv | 112.37 (3) | O2x—K—Zrix | 93.42 (2) |
| F2—Zr—Kxv | 36.80 (2) | F3xi—K—Zrix | 121.99 (2) |
| F4—Zr—Kxv | 37.74 (2) | Zrxi—K—Zrix | 102.640 (7) |
| F1ii—Zr—Kxv | 172.94 (3) | F6vi—K—Zrxvii | 20.660 (19) |
| F1iii—Zr—Kxv | 109.12 (2) | F5vii—K—Zrxvii | 120.27 (2) |
| Zrxviii—Zr—Kxv | 141.547 (7) | F3viii—K—Zrxvii | 67.44 (2) |
| Kvii—Zr—Kxv | 123.004 (4) | F2ix—K—Zrxvii | 83.04 (2) |
| F3—Zr—Kvi | 148.57 (3) | F4ix—K—Zrxvii | 121.05 (2) |
| F6i—Zr—Kvi | 27.86 (3) | O1i—K—Zrxvii | 89.46 (2) |
| F5i—Zr—Kvi | 83.54 (3) | O2x—K—Zrxvii | 157.34 (2) |
| F2—Zr—Kvi | 113.62 (3) | F3xi—K—Zrxvii | 80.348 (18) |
| F4—Zr—Kvi | 106.63 (3) | Zrxi—K—Zrxvii | 106.804 (8) |
| F1ii—Zr—Kvi | 57.25 (3) | Zrix—K—Zrxvii | 103.843 (7) |
| F1iii—Zr—Kvi | 80.80 (3) | F6vi—K—Zrviii | 65.81 (2) |
| Zrxviii—Zr—Kvi | 65.435 (5) | F5vii—K—Zrviii | 137.16 (2) |
| Kvii—Zr—Kvi | 106.804 (8) | F3viii—K—Zrviii | 20.89 (2) |
| Kxv—Zr—Kvi | 118.448 (4) | F2ix—K—Zrviii | 131.81 (2) |
| F3—Zr—Kxvi | 29.95 (3) | F4ix—K—Zrviii | 137.38 (2) |
| F6i—Zr—Kxvi | 144.59 (3) | O1i—K—Zrviii | 63.49 (2) |
| F5i—Zr—Kxvi | 110.23 (3) | O2x—K—Zrviii | 107.49 (2) |
| F2—Zr—Kxvi | 79.65 (3) | F3xi—K—Zrviii | 82.684 (18) |
| F4—Zr—Kxvi | 123.50 (3) | Zrxi—K—Zrviii | 109.132 (8) |
| F1ii—Zr—Kxvi | 79.97 (3) | Zrix—K—Zrviii | 143.549 (10) |
| F1iii—Zr—Kxvi | 56.37 (3) | Zrxvii—K—Zrviii | 50.252 (5) |
| Zrxviii—Zr—Kxvi | 64.313 (5) | Ni—O1—Kxii | 118.84 (4) |
| Kvii—Zr—Kxvi | 70.868 (8) | Ni—O1—H11 | 110.3 (17) |
| Kxv—Zr—Kxvi | 100.955 (4) | Kxii—O1—H11 | 102.4 (18) |
| Kvi—Zr—Kxvi | 129.748 (5) | Ni—O1—H12 | 111.2 (17) |
| O1iv—Ni—O1 | 180.00 (7) | Kxii—O1—H12 | 106.2 (17) |
| O1iv—Ni—O3v | 91.62 (5) | H11—O1—H12 | 107 (2) |
| O1—Ni—O3v | 88.38 (5) | Ni—O2—Kxiii | 127.74 (4) |
| O1iv—Ni—O3i | 88.38 (5) | Ni—O2—H21 | 107.6 (17) |
| O1—Ni—O3i | 91.62 (5) | Kxiii—O2—H21 | 105.2 (17) |
| O3v—Ni—O3i | 180.0 | Ni—O2—H22 | 111.1 (16) |
| O1iv—Ni—O2iv | 93.00 (4) | Kxiii—O2—H22 | 97.1 (15) |
| O1—Ni—O2iv | 87.00 (4) | H21—O2—H22 | 106 (2) |
| O3v—Ni—O2iv | 90.50 (4) | Nixii—O3—H31 | 124.4 (17) |
| O3i—Ni—O2iv | 89.50 (4) | Nixii—O3—H32 | 118.5 (19) |
| O1iv—Ni—O2 | 87.00 (4) | H31—O3—H32 | 108 (2) |
| O1—Ni—O2 | 93.00 (4) | Zrxiv—F1—Zriii | 114.55 (4) |
| O3v—Ni—O2 | 89.50 (4) | Zr—F2—Kxv | 116.77 (3) |
| O3i—Ni—O2 | 90.50 (4) | Zr—F3—Kxvi | 129.16 (5) |
| O2iv—Ni—O2 | 180.00 (5) | Zr—F3—Kvii | 98.87 (4) |
| F6vi—K—F5vii | 99.70 (3) | Kxvi—F3—Kvii | 107.93 (3) |
| F6vi—K—F3viii | 78.70 (3) | Zr—F4—Kxv | 115.24 (3) |
| F5vii—K—F3viii | 121.39 (3) | Zrxii—F5—Kxi | 112.48 (4) |
| F6vi—K—F2ix | 72.85 (3) | Zrxii—F6—Kxvii | 131.48 (4) |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y+1, z; (iii) −x, −y+1, −z+1; (iv) −x, −y, −z; (v) −x, −y−1, −z; (vi) −x−1/2, y+1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+1/2; (viii) x+1/2, −y+3/2, z−1/2; (ix) x+1, y, z; (x) x+1, y+1, z; (xi) −x+1/2, y−1/2, −z+1/2; (xii) x, y−1, z; (xiii) x−1, y−1, z; (xiv) x+1, y−1, z; (xv) x−1, y, z; (xvi) x−1/2, −y+3/2, z+1/2; (xvii) −x−1/2, y−1/2, −z+1/2; (xviii) −x−1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H11···F1xi | 0.79 (3) | 2.94 (2) | 3.3300 (14) | 112.8 (19) |
| O1—H11···F2xix | 0.79 (3) | 1.92 (3) | 2.6877 (14) | 164 (2) |
| O1—H12···F4xx | 0.82 (3) | 1.82 (3) | 2.6375 (13) | 177 (2) |
| O1—H12···F5iv | 0.82 (3) | 2.61 (2) | 3.0526 (13) | 116 (2) |
| O2—H21···F1xi | 0.78 (2) | 2.59 (2) | 3.0048 (13) | 115 (2) |
| O2—H21···F2xix | 0.78 (2) | 1.95 (2) | 2.7227 (13) | 167 (2) |
| O2—H22···F4xxi | 0.82 (2) | 1.92 (2) | 2.7362 (13) | 173 (2) |
| O2—H22···F6xxii | 0.82 (2) | 2.76 (2) | 3.1924 (14) | 114.9 (17) |
| O3—H31···F1xxiii | 0.80 (3) | 2.86 (3) | 3.2552 (16) | 113.3 (19) |
| O3—H31···F5xxiv | 0.80 (3) | 1.92 (3) | 2.7019 (14) | 168 (2) |
| O3—H32···F3iv | 0.80 (3) | 3.00 (2) | 3.4527 (16) | 119 (2) |
| O3—H32···F6xxv | 0.80 (3) | 1.97 (3) | 2.7427 (15) | 163 (2) |
Symmetry codes: (xi) −x+1/2, y−1/2, −z+1/2; (xix) x+1/2, −y+1/2, z−1/2; (xx) −x, −y+1, −z; (iv) −x, −y, −z; (xxi) −x−1, −y+1, −z; (xxii) −x−1, −y, −z; (xxiii) x−1/2, −y−1/2, z−1/2; (xxiv) x+1/2, −y−1/2, z−1/2; (xxv) −x−1, −y−1, −z.
Table 2 Comparison of the geometrical characteristics of the coordination polyhedra in isotypic MI2[MII(H2O)6][ZrF6]2 structures determined from single-crystal data (Å, °, Å3)
| K2[Ni(H2O)6][ZrF6]2a | K2[Cu(H2O)6][ZrF6]2b | K2[Zn(H2O)6][ZrF6]2c | Cs2[Zn(H2O)6][ZrF6]2d | |
| Space group | P21/n | P21/c | P21/c | P21/n |
| a | 6.6090 (1) | 6.631 (6) | 6.631 (1) | 6.970 (1) |
| b | 10.0398 (1) | 9.981 (10) | 10.071 (1) | 10.515 (2) |
| c | 11.7843 (1) | 12.921 (12) | 12.952 (1) | 11.803 (2) |
| β | 95.897 (1) | 114.20 (15) | 114.96 (2) | 93.56 (3) |
| V | 777.786 (16) | 780.01 (1) | 784.16 (2) | 863.4 (3) |
| Ni—O1 = 2.0548 (10) (2×) | Cu—O1 = 1.966 (4) (2×) | Zn—O1 = 2.0856 (2) (2×) | Zn—O3 = 2.096 (6) (2×) | |
| Distances MII—O | Ni—O3 = 2.0570 (11) (2×) | Cu—O2 = 2.025 (6) (2×) | Zn—O2 = 2.0940 (1) (2×) | Zn—O1 = 2.099 (5) (2×) |
| Ni—O2 = 2.0781 (9) (2×) | Cu—O3 = 2.327 (5) (2×) | Zn—O3 = 2.1185 (2) (2×) | Zn—O2 = 2.105 (5) (2×) | |
| Average MII—O bond length | 2.063 | 2.106 | 2.099 | 2.100 |
| Polyhedral volume | 11.684 | 12.335 | 12.318 | 12.341 |
| Distortion index (bond length) | 0.00483 | 0.06089 | 0.00607 | 0.00156 |
| Quadratic elongation | 1.0013 | 1.0124 | 1.0011 | 1.0006 |
| Zr—F6 = 1.9718 (9) | Zr—F3 = 1.968 (5) | Zr—F3 = 1.9727 (3) | Zr—F3 = 1.962 (5) | |
| Zr—F5 = 2.0006 (8) | Zr—F1 = 2.004 (5) | Zr—F1 = 2.0018 (3) | Zr—F6 = 1.977 (5) | |
| Zr—F3 = 2.0293 (9) | Zr—F5 = 2.029 (4) | Zr—F5 = 2.0277 (3) | Zr—F5 = 2.037 (5) | |
| Distances Zr—F (Å) | Zr—F2 = 2.0554 (8) | Zr—F6 = 2.059 (4) | Zr—F6 = 2.0570 (3) | Zr—F4 = 2.067 (4) |
| Zr—F1 = 2.0708 (8) | Zr—F2 = 2.063 (4) | Zr—F2 = 2.0668 (4) | Zr—F2 = 2.069 (4) | |
| Zr—F4 = 2.1468 (9) | Zr—F4 = 2.156 (5) | Zr—F4 = 2.1501 (4) | Zr—F1 = 2.156 (4) | |
| Zr—F4 = 2.1614 (8) | Zr—F4 = 2.160 (4) | Zr—F4 = 2.1628 (4) | Zr—F1 = 2.180 (4) | |
| Average Zr—F bond length | 2.062 | 2.063 | 2.063 | 2.064 |
| Polyhedral volume | 13.669 | 13.674 | 13.675 | 13.692 |
| Distortion index (bond length) | 0.02662 | 0.02650 | 0.02654 | 0.02985 |
| K—F5 = 2.6496 (10) | K—F1 = 2.668 (5) | K—F1 = 2.6506 (3) | Cs—F6 = 2.911 (5) | |
| K—F3 = 2.7366 (9) | K—F6 = 2.750 (6) | K—F2 = 2.7395 (4) | Cs—F4 = 3.046 (4) | |
| K—F6 = 2.7603 (11) | K—F3 = 2.756 (5) | K—F5 = 2.7633 (2) | Cs—F2 = 3.057 (4) | |
| Distances K—F/O | K—F2 = 2.7658 (9) | K—F5 = 2.767 (5) | K—F6 = 2.7739 (2) | Cs—F3 = 3.065 (5) |
| K—F1 = 2.7895 (9) | K—F2 = 2.799 (5) | K—F3 = 2.8094 (2) | Cs—F3 = 3.102 (5) | |
| K—O2 = 2.8927 (10) | K—O3 = 2.942 (5) | K—O1 = 2.8968 (3) | Cs—O2 = 3.218 (5) | |
| K—O1 = 3.1012 (10) | K—O1 = 2.980 (5) | K—O2 = 3.0873 (5) | Cs—O1 = 3.236 (5) | |
| K—F6 = 3.1684 (12) | K—F3 = 3.1307 (7) | K—F3 = 3.1707 (7) | Cs—F5 = 3.228 (6) | |
| Average MI—F/O bond length | 2.858 | 2.849 | 2.861 | 3.118 |
| Polyhedral volume | 38.458 | 38.158 | 38.569 | 48.130 |
| Distortion index (bond length) | 0.05146 | 0.04429 | 0.04984 | 0.02627 |
Notes: (a) this work; (b) Fischer & Weiss (1973); (c) Bukvetskii et al. (1993); (d) Hitchman et al. (2002).
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2439).
References
- Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
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- Bukvetskii, B. V., Gerasimenko, A. V., Davidovich, R. L., Kaidalova, T. A. & Teplukhina, L. V. (1993). Koord. Khim. 19, 526–528.
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- Hitchman, M. A., Yablokov, Yu. V., Petrashen, V. E., Augustyniak-Jublokov, M. A., Stratemeier, H., Riley, M. J., Lukaszewicz, K., Tomaszewski, P. E. & Pietraszko, A. (2002). Inorg. Chem. 41, 229–238. [DOI] [PubMed]
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681005350X/wm2439sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S160053681005350X/wm2439Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report