inorganic compounds
Monopotassium monosodium hexahydrogen α-hexamolybdoplatinate(IV) undecahydrate
aDepartment of Chemistry, Pukyong National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea, and bDepartment of Chemistry, Dongeui University, San 24 Kaya-dong Busanjin-gu, Busan 614-714, Republic of Korea
*Correspondence e-mail: uklee@pknu.ac.kr
The title compound, KNa[H6PtMo6O24]·11H2O, contains a discrete hexamolybdoplatinate(IV) [H6PtMo6O24]2− polyanion (1 symmetry), which has the highest level of protonation. Five O atoms of the central PtO6 octahedron (μ3-atoms, Oc) and one O atom of an outer edge-sharing MoO6 octahedron (O bridging μ2-atom, Ob) are protonated. The polyanions are connected by almost linear O—H⋯O hydrogen bonds between protonated and unprotonated Ob atoms. Further consolidation of the is accomplished by extensive O—H⋯O hydrogen bonding involving the uncoordinated water molecules. The two independent K+ cations are equally disordered about a twofold rotation axis.
Related literature
For other crystal structures containing the [H6PtMo6O24]6− anion, see: Lee & Sasaki (1994); Lee & Joo (2006a,b). For background to the bond-valence method, see: Brown & Altermatt (1985); Brese & O'Keeffe (1991).
Experimental
Crystal data
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Refinement
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Data collection: STADI4 (Stoe & Cie, 1996); cell STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S160053681000228X/wm2298sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681000228X/wm2298Isup2.hkl
Crystals of the title compound were prepared by the reaction of Na2MoO4.2H2O and K2Pt(OH)6 at pH 0.20 as described in a previous report (Lee & Sasaki, 1994).
The Oc and Ob bound H atoms in the polyanion were located in difference Fourier maps and were freely refined except H5. H5 was refined with a distance restraint [O5c–H5 = 0.85 (10) Å]. All water molecules bound H atoms were located in difference Fourier maps and their positional parameters were refined with a distance restraint [O–H = 0.85 (10) Å, but O6w–6HA = 0.75 (10) Å] and an additional angle restraint; these H atoms were refined with an isotropic displacement parameter Uiso = 1.5Ueq(O). O5w bound H atoms were placed in calculated positions. They were included in the
using the riding-motion approximation, with Uiso(H) = 1.5 Ueq(O). K1 and K2 showed very large displacement parameters under consideration of full occupation. of the site occupation factors (s.o.f.) converged at values close to half-occupation. In the final the s.o.f.'s were constrained to 0.5 and reasonable displacement parameters were eventually obtained.In our previous studies we isolated the same polyanion, [H6PtMo6O24]2-, that is present in the title compound, (I), at various pH conditions; 1.60 (II; Lee & Joo, 2006b), 0.70 (III; Lee & Sasaki, 1994) and 0.48 (IV; Lee & Joo, 2006a). Structures (II, III) have the same 1. The polyanions bear an inversion center in these three structures. The current study was carried out to confirm the presence of a highly protonated species that exists at very low pH.
viz. C2/c, whereas the of (IV) is PThe structure of the present crystals contains a crystallographically discrete [H6PMo6O24]2- polyanion (Fig. 1). All atoms in the polyanion are located in general positions and consequently the symmetry of the polyanion is C1. The O atoms of the polyoxometalate were designated as Ot (terminal Mo═O atom), Ob (O bridging µ2-O atom), and Oc (µ3-O atom). The protonated O atoms in the polyanion were identified in difference Fourier maps and by using structural features as observed in the previously determined structures II & IV, viz. bond lengths of Mo–Oc(H) & Mo–Ob(H) units, bond angles of Mo–Oc(H)–Mo & Mo–Ob(H)–Mo units, and distances between Mo···Mo. As a result, the structure of (I) confirms the protonation of atoms O1c(H), O3c(H), O4c(H), O5c(H), O6c(H) and O8b(H).
The different bond-lengths and bond-angles in the [H6PtMo6O24]2- polyanion of protonated and unprotonated O atoms are compared in Table 1. The protonated O atoms of [H6PtMo6O24]2- in the structures (II), (III) and (IV) show the same protonation scheme, viz. four Oc(H) and two Ob(H) atoms are protonated. Therefore, the feature of the three-dimensional hydrogen bonding formation is very similar in the these polyanions, viz. the central PtO2(OH)4 polyhedron forms hydrogen bonds with neighbouring polyanions by four sets of Oc(H)···Ot and Ob(H)···Ot hydrogen bonds.
However, the protonation scheme of the polyanion in (I) is different, consisting of five Oc(H) and one Ob(H) protonated O atoms (Fig. 1). In contrast to the hydrogen bonding scheme in (II-IV), the protonated Oc atoms form various O–H···O hydrogen bonds with water molecules (Ow). Nevertheless, the polyanion is linearly connected by an O8b–H8···O11bi hydrogen bond (Fig.2 and Table 2).
The Na and K ions are coordinated by O atoms as [Na(Ow)5(Ot)]+ in the range 2.371 (7)-2.510 (9) Å, and [K1(Ot)4(Ow)2]+ and [K2(Ot)3(Ow)4]+ in the range 2.59 (1)-3.41 (1) Å. Bond valence sum calculations (BVS; Brown & Altermatt, 1985; Brese & O'Keeffe, 1991) for the K1 and K2 ions reveal a considerable undersaturation in terms of valence units which we ascribe to the disordered character of the metal positions.
For other crystal structures containing the [H6PtMo6O24]6- anion, see: Lee & Sasaki (1994); Lee & Joo (2006a,b). For background to the bond-valence method, see: Brown & Altermatt (1985); Brese & O'Keeffe (1991).
Data collection: STADI4 (Stoe & Cie, 1996); cell
STADI4 (Stoe & Cie, 1996); data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The structure of the polyanion in compound (I). Displacement ellipsoids are drawn at the 50% probability level for all non-H atoms. The latter are displayed as spheres of arbitrary radius. | |
Fig. 2. Polyhedral view of the Ob–H···Ob contact of the inter-anion hydrogen bond and Oc–H···Owhydrogen bonds shown as dashed lines. [Symmetry codes: (i) x, - y + 1, z - 1/2; (ii) - x + 1, - y + 1, - z + 1; (iii) - x + 3/2, - y + 3/2, - z + 1; (vi) x, - y + 1, z + 1/2.] |
KNa[H6PtMo6O24]·11H2O | F(000) = 5344 |
Mr = 1421.04 | Dx = 3.003 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 20.935 (2) Å | θ = 9.6–10.3° |
b = 18.535 (3) Å | µ = 7.02 mm−1 |
c = 17.775 (3) Å | T = 298 K |
β = 114.30 (2)° | Block, pale yellow |
V = 6286.2 (18) Å3 | 0.38 × 0.25 × 0.25 mm |
Z = 8 |
Stoe Stadi-4 diffractometer | 5972 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 27.5°, θmin = 1.5° |
ω/2–θ scans | h = −2→27 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie 1996) | k = −24→24 |
Tmin = 0.300, Tmax = 0.422 | l = −23→21 |
8235 measured reflections | 3 standard reflections every 60 min |
7237 independent reflections | intensity decay: 3.2% |
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)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0282P)2 + 43.9139P] where P = (Fo2 + 2Fc2)/3 |
7237 reflections | (Δ/σ)max = 0.001 |
490 parameters | Δρmax = 0.96 e Å−3 |
33 restraints | Δρmin = −1.26 e Å−3 |
KNa[H6PtMo6O24]·11H2O | V = 6286.2 (18) Å3 |
Mr = 1421.04 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.935 (2) Å | µ = 7.02 mm−1 |
b = 18.535 (3) Å | T = 298 K |
c = 17.775 (3) Å | 0.38 × 0.25 × 0.25 mm |
β = 114.30 (2)° |
Stoe Stadi-4 diffractometer | 5972 reflections with I > 2σ(I) |
Absorption correction: numerical (X-SHAPE; Stoe & Cie 1996) | Rint = 0.028 |
Tmin = 0.300, Tmax = 0.422 | 3 standard reflections every 60 min |
8235 measured reflections | intensity decay: 3.2% |
7237 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 33 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0282P)2 + 43.9139P] where P = (Fo2 + 2Fc2)/3 |
7237 reflections | Δρmax = 0.96 e Å−3 |
490 parameters | Δρmin = −1.26 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 | Occ. (<1) | |
Pt | 0.755879 (11) | 0.504087 (12) | 0.501298 (14) | 0.01487 (6) | |
Mo1 | 0.60877 (3) | 0.60494 (3) | 0.40899 (4) | 0.02644 (13) | |
Mo2 | 0.64099 (3) | 0.46279 (3) | 0.31418 (3) | 0.02522 (13) | |
Mo3 | 0.78857 (3) | 0.36281 (3) | 0.40922 (4) | 0.02288 (12) | |
Mo4 | 0.90273 (3) | 0.40566 (3) | 0.60119 (4) | 0.02459 (13) | |
Mo5 | 0.86645 (3) | 0.54226 (3) | 0.69946 (3) | 0.02323 (12) | |
Mo6 | 0.71872 (3) | 0.63908 (3) | 0.60625 (4) | 0.02426 (13) | |
K1 | 0.4929 (4) | 0.7725 (2) | 0.2195 (4) | 0.092 (4) | 0.50 |
K2 | 0.5123 (4) | 0.7131 (4) | 0.7936 (5) | 0.114 (3) | 0.50 |
Na | 0.45373 (19) | 0.66261 (18) | 0.4760 (2) | 0.0478 (8) | |
O1C | 0.7062 (2) | 0.5568 (2) | 0.3956 (3) | 0.0209 (9) | |
H1 | 0.726 (4) | 0.583 (4) | 0.381 (5) | 0.02 (2)* | |
O2C | 0.7085 (2) | 0.4197 (2) | 0.4330 (3) | 0.0194 (9) | |
O3C | 0.8374 (2) | 0.4689 (2) | 0.4811 (3) | 0.0189 (9) | |
H3 | 0.866 (4) | 0.501 (4) | 0.471 (5) | 0.03 (2)* | |
O4C | 0.8038 (2) | 0.4515 (2) | 0.6085 (3) | 0.0185 (9) | |
H4 | 0.781 (4) | 0.429 (4) | 0.626 (4) | 0.022 (19)* | |
O5C | 0.8043 (2) | 0.5910 (2) | 0.5715 (3) | 0.0212 (9) | |
H5 | 0.830 (3) | 0.624 (4) | 0.551 (4) | 0.025 (19)* | |
O6C | 0.6747 (2) | 0.5377 (2) | 0.5240 (3) | 0.0215 (9) | |
H6 | 0.654 (4) | 0.509 (5) | 0.542 (5) | 0.04 (2)* | |
O7B | 0.5858 (2) | 0.5080 (3) | 0.3625 (3) | 0.0286 (10) | |
O8B | 0.7364 (2) | 0.4336 (3) | 0.3155 (3) | 0.0265 (10) | |
H8 | 0.747 (3) | 0.435 (4) | 0.277 (4) | 0.016 (17)* | |
O9B | 0.8324 (2) | 0.3398 (2) | 0.5227 (3) | 0.0264 (10) | |
O10B | 0.9231 (2) | 0.5009 (3) | 0.6477 (3) | 0.0279 (10) | |
O11B | 0.7729 (2) | 0.5689 (3) | 0.6895 (3) | 0.0258 (10) | |
O12B | 0.6770 (3) | 0.6662 (3) | 0.4900 (3) | 0.0310 (11) | |
O13T | 0.5397 (3) | 0.6145 (3) | 0.4351 (4) | 0.0463 (15) | |
O14T | 0.5911 (3) | 0.6567 (3) | 0.3234 (3) | 0.0448 (14) | |
O15T | 0.6253 (3) | 0.5154 (4) | 0.2295 (3) | 0.0504 (16) | |
O16T | 0.5949 (3) | 0.3850 (3) | 0.2793 (4) | 0.0476 (15) | |
O17T | 0.7403 (3) | 0.2868 (3) | 0.3706 (4) | 0.0409 (13) | |
O18T | 0.8564 (3) | 0.3585 (3) | 0.3792 (3) | 0.0365 (12) | |
O19T | 0.9696 (3) | 0.3948 (3) | 0.5710 (4) | 0.0408 (13) | |
O20T | 0.9220 (3) | 0.3524 (3) | 0.6861 (3) | 0.0433 (14) | |
O21T | 0.8880 (3) | 0.4880 (3) | 0.7839 (3) | 0.0403 (13) | |
O22T | 0.9118 (3) | 0.6211 (3) | 0.7340 (3) | 0.0398 (13) | |
O23T | 0.7642 (3) | 0.7167 (3) | 0.6445 (4) | 0.0423 (14) | |
O24T | 0.6480 (3) | 0.6418 (3) | 0.6303 (3) | 0.0419 (14) | |
O1W | 0.3734 (4) | 0.6928 (4) | 0.5338 (6) | 0.072 (2) | |
H1A | 0.357 (7) | 0.658 (5) | 0.547 (8) | 0.108* | |
H1B | 0.349 (6) | 0.727 (5) | 0.518 (9) | 0.108* | |
O2W | 0.5059 (4) | 0.5835 (6) | 0.5945 (5) | 0.089 (3) | |
H2A | 0.478 (6) | 0.607 (9) | 0.604 (9) | 0.133* | |
H2B | 0.541 (5) | 0.582 (8) | 0.636 (7) | 0.133* | |
O3W | 0.4069 (5) | 0.7211 (5) | 0.3363 (5) | 0.075 (2) | |
H3A | 0.394 (7) | 0.761 (5) | 0.306 (8) | 0.113* | |
H3B | 0.380 (7) | 0.692 (6) | 0.309 (8) | 0.113* | |
O4W | 0.6004 (9) | 0.7658 (7) | 0.6985 (7) | 0.151 (6) | |
H4A | 0.624 (11) | 0.729 (7) | 0.714 (14) | 0.227* | |
H4B | 0.624 (11) | 0.802 (8) | 0.726 (13) | 0.227* | |
O5W | 0.3899 (4) | 0.5535 (5) | 0.4228 (4) | 0.085 (3) | |
H5A | 0.4118 | 0.5270 | 0.3935 | 0.128* | |
H5B | 0.3427 | 0.5653 | 0.3859 | 0.128* | |
O6W | 0.5264 (4) | 0.7653 (4) | 0.5274 (6) | 0.071 (2) | |
H6A | 0.538 (7) | 0.755 (7) | 0.586 (5) | 0.106* | |
H6B | 0.501 (6) | 0.803 (5) | 0.526 (8) | 0.106* | |
O7W | 0.8968 (3) | 0.5657 (3) | 0.4306 (3) | 0.0335 (12) | |
H7A | 0.909 (4) | 0.560 (5) | 0.385 (4) | 0.050* | |
H7B | 0.929 (4) | 0.582 (5) | 0.465 (5) | 0.050* | |
O8W | 0.7388 (4) | 0.3605 (4) | 0.6632 (4) | 0.0536 (18) | |
H8A | 0.757 (6) | 0.335 (6) | 0.645 (7) | 0.080* | |
H8B | 0.749 (6) | 0.367 (6) | 0.711 (5) | 0.080* | |
O9W | 0.8666 (4) | 0.6922 (3) | 0.5311 (6) | 0.068 (2) | |
H9A | 0.904 (4) | 0.694 (7) | 0.537 (8) | 0.102* | |
H9B | 0.844 (6) | 0.723 (6) | 0.529 (9) | 0.102* | |
O10W | 0.7273 (3) | 0.8572 (3) | 0.6648 (3) | 0.0384 (13) | |
H10A | 0.729 (5) | 0.819 (4) | 0.639 (6) | 0.058* | |
H10B | 0.682 (4) | 0.870 (5) | 0.639 (6) | 0.058* | |
O11W | 0.9966 (3) | 0.5975 (5) | 0.5839 (4) | 0.065 (2) | |
H11A | 1.040 (4) | 0.599 (7) | 0.601 (7) | 0.098* | |
H11B | 0.982 (6) | 0.581 (7) | 0.613 (7) | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.01848 (11) | 0.01434 (11) | 0.01480 (10) | −0.00019 (9) | 0.00989 (8) | −0.00024 (8) |
Mo1 | 0.0277 (3) | 0.0272 (3) | 0.0253 (3) | 0.0088 (2) | 0.0118 (2) | 0.0026 (2) |
Mo2 | 0.0240 (3) | 0.0335 (3) | 0.0178 (3) | 0.0001 (2) | 0.0084 (2) | −0.0043 (2) |
Mo3 | 0.0284 (3) | 0.0189 (3) | 0.0263 (3) | 0.0011 (2) | 0.0163 (2) | −0.0031 (2) |
Mo4 | 0.0230 (3) | 0.0280 (3) | 0.0255 (3) | 0.0061 (2) | 0.0128 (2) | 0.0037 (2) |
Mo5 | 0.0232 (3) | 0.0303 (3) | 0.0176 (3) | −0.0037 (2) | 0.0098 (2) | −0.0032 (2) |
Mo6 | 0.0325 (3) | 0.0199 (3) | 0.0252 (3) | 0.0021 (2) | 0.0168 (2) | −0.0031 (2) |
K1 | 0.041 (4) | 0.039 (2) | 0.183 (10) | −0.008 (2) | 0.035 (6) | −0.025 (3) |
K2 | 0.079 (4) | 0.102 (5) | 0.174 (8) | −0.040 (4) | 0.067 (6) | −0.056 (5) |
Na | 0.055 (2) | 0.0396 (18) | 0.064 (2) | −0.0055 (16) | 0.0407 (18) | −0.0080 (17) |
O1C | 0.026 (2) | 0.020 (2) | 0.019 (2) | 0.0016 (19) | 0.0117 (19) | 0.0037 (18) |
O2C | 0.023 (2) | 0.020 (2) | 0.016 (2) | −0.0006 (17) | 0.0089 (17) | −0.0009 (17) |
O3C | 0.021 (2) | 0.018 (2) | 0.024 (2) | −0.0002 (17) | 0.0147 (18) | −0.0002 (18) |
O4C | 0.023 (2) | 0.020 (2) | 0.019 (2) | 0.0016 (18) | 0.0142 (18) | 0.0068 (18) |
O5C | 0.027 (2) | 0.018 (2) | 0.024 (2) | −0.0026 (18) | 0.0154 (19) | −0.0044 (18) |
O6C | 0.026 (2) | 0.021 (2) | 0.025 (2) | 0.0018 (19) | 0.0172 (19) | −0.0008 (19) |
O7B | 0.022 (2) | 0.037 (3) | 0.027 (2) | 0.000 (2) | 0.0098 (19) | −0.003 (2) |
O8B | 0.029 (2) | 0.036 (3) | 0.020 (2) | 0.002 (2) | 0.015 (2) | −0.002 (2) |
O9B | 0.035 (3) | 0.017 (2) | 0.029 (2) | 0.0049 (19) | 0.016 (2) | 0.0032 (19) |
O10B | 0.020 (2) | 0.038 (3) | 0.026 (2) | −0.009 (2) | 0.0107 (18) | −0.005 (2) |
O11B | 0.032 (2) | 0.030 (3) | 0.022 (2) | 0.002 (2) | 0.017 (2) | 0.0037 (19) |
O12B | 0.041 (3) | 0.022 (2) | 0.032 (3) | 0.007 (2) | 0.017 (2) | 0.006 (2) |
O13T | 0.039 (3) | 0.054 (4) | 0.052 (4) | 0.012 (3) | 0.025 (3) | −0.008 (3) |
O14T | 0.048 (3) | 0.042 (3) | 0.035 (3) | 0.010 (3) | 0.008 (3) | 0.012 (3) |
O15T | 0.047 (3) | 0.081 (5) | 0.025 (3) | 0.026 (3) | 0.017 (3) | 0.015 (3) |
O16T | 0.034 (3) | 0.059 (4) | 0.048 (3) | −0.015 (3) | 0.016 (3) | −0.029 (3) |
O17T | 0.055 (4) | 0.024 (3) | 0.047 (3) | −0.008 (2) | 0.024 (3) | −0.012 (2) |
O18T | 0.038 (3) | 0.042 (3) | 0.036 (3) | 0.008 (2) | 0.022 (2) | −0.001 (2) |
O19T | 0.030 (3) | 0.047 (3) | 0.055 (3) | 0.006 (2) | 0.027 (3) | −0.005 (3) |
O20T | 0.044 (3) | 0.049 (4) | 0.031 (3) | 0.011 (3) | 0.010 (2) | 0.015 (3) |
O21T | 0.038 (3) | 0.060 (4) | 0.023 (2) | 0.010 (3) | 0.013 (2) | 0.012 (3) |
O22T | 0.038 (3) | 0.044 (3) | 0.037 (3) | −0.018 (3) | 0.015 (2) | −0.016 (3) |
O23T | 0.064 (4) | 0.020 (3) | 0.046 (3) | −0.008 (3) | 0.025 (3) | −0.009 (2) |
O24T | 0.042 (3) | 0.054 (4) | 0.037 (3) | 0.012 (3) | 0.025 (3) | −0.001 (3) |
O1W | 0.085 (5) | 0.031 (4) | 0.139 (7) | 0.015 (4) | 0.086 (6) | 0.021 (4) |
O2W | 0.040 (4) | 0.134 (9) | 0.067 (5) | −0.022 (5) | −0.005 (4) | 0.044 (6) |
O3W | 0.091 (6) | 0.064 (5) | 0.063 (5) | 0.017 (5) | 0.025 (5) | 0.004 (4) |
O4W | 0.278 (19) | 0.086 (8) | 0.088 (8) | 0.070 (10) | 0.074 (10) | −0.009 (6) |
O5W | 0.113 (6) | 0.110 (7) | 0.058 (4) | −0.082 (5) | 0.062 (5) | −0.047 (4) |
O6W | 0.066 (5) | 0.045 (4) | 0.106 (6) | 0.000 (4) | 0.041 (5) | −0.011 (4) |
O7W | 0.033 (3) | 0.040 (3) | 0.034 (3) | −0.012 (2) | 0.020 (2) | −0.003 (2) |
O8W | 0.077 (5) | 0.052 (4) | 0.047 (4) | −0.028 (4) | 0.041 (4) | −0.012 (3) |
O9W | 0.074 (5) | 0.030 (3) | 0.140 (7) | 0.012 (3) | 0.084 (6) | 0.022 (4) |
O10W | 0.049 (3) | 0.034 (3) | 0.037 (3) | −0.002 (3) | 0.024 (3) | −0.003 (2) |
O11W | 0.033 (3) | 0.113 (7) | 0.042 (4) | −0.021 (4) | 0.006 (3) | 0.020 (4) |
Mo1—Mo2 | 3.3426 (9) | Mo4—O20T | 1.707 (5) |
Mo1—Mo6 | 3.3690 (12) | Mo5—O4C | 2.328 (5) |
Mo2—Mo3 | 3.3968 (10) | Mo5—O5C | 2.290 (5) |
Mo3—Mo4 | 3.3577 (12) | Mo5—O10B | 1.935 (5) |
Mo4—Mo5 | 3.3363 (9) | Mo5—O11B | 1.956 (4) |
Mo5—Mo6 | 3.3635 (10) | Mo5—O21T | 1.705 (5) |
Pt—O1C | 1.989 (4) | Mo5—O22T | 1.713 (5) |
Pt—O2C | 1.978 (4) | Mo6—O5C | 2.302 (4) |
Pt—O3C | 1.993 (4) | Mo6—O6C | 2.326 (5) |
Pt—O4C | 2.003 (4) | Mo6—O11B | 1.946 (5) |
Pt—O5C | 2.034 (4) | Mo6—O12B | 1.949 (5) |
Pt—O6C | 2.001 (4) | Mo6—O23T | 1.704 (5) |
Mo1—O1C | 2.327 (5) | Mo6—O24T | 1.702 (5) |
Mo1—O6C | 2.306 (5) | K1—O14Ti | 2.678 (8) |
Mo1—O7B | 1.954 (5) | K1—O14T | 3.020 (8) |
Mo1—O12B | 1.927 (5) | K1—O22Tii | 2.682 (9) |
Mo1—O13T | 1.701 (5) | K1—O22Tiii | 2.683 (8) |
Mo1—O14T | 1.706 (5) | K1—O9Wii | 3.368 (12) |
Mo2—O1C | 2.317 (5) | K1—O3W | 3.396 (14) |
Mo2—O2C | 2.154 (4) | K1—O3Wi | 2.831 (14) |
Mo2—O7B | 1.894 (5) | K2—O16Tiv | 2.594 (10) |
Mo2—O8B | 2.060 (5) | K2—O16Tv | 2.763 (8) |
Mo2—O15T | 1.708 (6) | K2—O20Tvi | 2.878 (9) |
Mo2—O16T | 1.703 (6) | K2—O20Tvii | 3.305 (10) |
Mo3—O2C | 2.163 (4) | K2—O1Wviii | 3.039 (13) |
Mo3—O3C | 2.338 (4) | K2—O2Wviii | 3.239 (14) |
Mo3—O8B | 2.047 (5) | K2—O4W | 3.13 (2) |
Mo3—O9B | 1.889 (5) | K2—O4Wviii | 2.61 (2) |
Mo3—O17T | 1.705 (5) | Na—O13T | 2.374 (6) |
Mo3—O18T | 1.712 (5) | Na—O1W | 2.371 (7) |
Mo4—O3C | 2.323 (4) | Na—O2W | 2.425 (9) |
Mo4—O4C | 2.291 (4) | Na—O3W | 2.510 (9) |
Mo4—O9B | 1.979 (5) | Na—O5W | 2.393 (7) |
Mo4—O10B | 1.921 (5) | Na—O6W | 2.373 (9) |
Mo4—O19T | 1.706 (5) | ||
Mo2—Mo1—Mo6 | 118.66 (2) | O12B—Mo6—O5C | 82.81 (18) |
Mo1—Mo2—Mo3 | 120.68 (3) | O24T—Mo6—O6C | 91.2 (2) |
Mo4—Mo3—Mo2 | 119.85 (3) | O23T—Mo6—O6C | 160.8 (2) |
Mo5—Mo4—Mo3 | 119.43 (2) | O11B—Mo6—O6C | 83.89 (18) |
Mo4—Mo5—Mo6 | 120.55 (3) | O12B—Mo6—O6C | 69.74 (18) |
Mo5—Mo6—Mo1 | 120.55 (3) | O5C—Mo6—O6C | 70.70 (15) |
O2C—Pt—O1C | 82.75 (18) | Pt—O1C—Mo2 | 99.52 (19) |
O2C—Pt—O3C | 83.14 (17) | Pt—O1C—Mo1 | 103.37 (19) |
O1C—Pt—O3C | 98.28 (18) | Pt—O2C—Mo2 | 105.61 (19) |
O2C—Pt—O6C | 96.73 (18) | Pt—O2C—Mo3 | 105.81 (18) |
O1C—Pt—O6C | 83.14 (19) | Pt—O3C—Mo4 | 102.91 (17) |
O3C—Pt—O6C | 178.53 (18) | Pt—O3C—Mo3 | 99.17 (17) |
O2C—Pt—O4C | 97.30 (17) | Pt—O4C—Mo4 | 103.71 (18) |
O1C—Pt—O4C | 178.52 (18) | Pt—O4C—Mo5 | 103.15 (18) |
O3C—Pt—O4C | 83.19 (17) | Pt—O5C—Mo5 | 103.48 (19) |
O6C—Pt—O4C | 95.39 (18) | Pt—O5C—Mo6 | 102.98 (18) |
O2C—Pt—O5C | 179.86 (18) | Pt—O6C—Mo1 | 103.74 (19) |
O1C—Pt—O5C | 97.20 (19) | Pt—O6C—Mo6 | 103.20 (19) |
O3C—Pt—O5C | 97.00 (17) | Mo2—O1C—Mo1 | 92.06 (17) |
O6C—Pt—O5C | 83.13 (18) | Mo2—O2C—Mo3 | 103.72 (16) |
O4C—Pt—O5C | 82.74 (18) | Mo4—O3C—Mo3 | 92.16 (16) |
O13T—Mo1—O14T | 106.8 (3) | Mo4—O4C—Mo5 | 92.48 (16) |
O13T—Mo1—O12B | 100.7 (3) | Mo5—O5C—Mo6 | 94.18 (16) |
O14T—Mo1—O12B | 99.0 (3) | Mo1—O6C—Mo6 | 93.33 (17) |
O13T—Mo1—O7B | 97.1 (3) | Mo2—O7B—Mo1 | 120.6 (2) |
O14T—Mo1—O7B | 102.4 (3) | Mo3—O8B—Mo2 | 111.6 (2) |
O12B—Mo1—O7B | 146.8 (2) | Mo3—O9B—Mo4 | 120.5 (2) |
O13T—Mo1—O6C | 94.6 (2) | Mo4—O10B—Mo5 | 119.8 (2) |
O14T—Mo1—O6C | 157.8 (2) | Mo6—O11B—Mo5 | 119.1 (2) |
O12B—Mo1—O6C | 70.55 (18) | Mo1—O12B—Mo6 | 120.7 (2) |
O7B—Mo1—O6C | 80.28 (18) | H1A—O1W—H1B | 118 (10) |
O13T—Mo1—O1C | 161.4 (2) | H2A—O2W—H2B | 107 (10) |
O14T—Mo1—O1C | 90.1 (2) | H3A—O3W—H3B | 103 (10) |
O12B—Mo1—O1C | 83.76 (19) | H4A—O4W—H4B | 110 (10) |
O7B—Mo1—O1C | 71.17 (18) | H5A—O5W—H5B | 109.5 |
O6C—Mo1—O1C | 69.71 (15) | H6A—O6W—H6B | 93 (8) |
O16T—Mo2—O15T | 106.7 (3) | H7A—O7W—H7B | 106 (7) |
O16T—Mo2—O7B | 100.3 (2) | H8A—O8W—H8B | 126 (10) |
O15T—Mo2—O7B | 102.4 (2) | H9A—O9W—H9B | 126 (10) |
O16T—Mo2—O8B | 100.5 (2) | H10A—O10W—H10B | 103 (7) |
O15T—Mo2—O8B | 89.7 (2) | H11A—O11W—H11B | 117 (10) |
O7B—Mo2—O8B | 151.67 (19) | O14Ti—K1—O22Tii | 104.4 (4) |
O16T—Mo2—O2C | 95.1 (2) | O14Ti—K1—O22Tiii | 174.0 (4) |
O15T—Mo2—O2C | 152.4 (2) | O22Tii—K1—O22Tiii | 81.4 (3) |
O7B—Mo2—O2C | 89.79 (18) | O14Ti—K1—O3Wi | 97.1 (3) |
O8B—Mo2—O2C | 69.47 (17) | O22Tii—K1—O3Wi | 150.6 (4) |
O16T—Mo2—O1C | 164.6 (2) | O22Tiii—K1—O3Wi | 77.9 (3) |
O15T—Mo2—O1C | 88.4 (3) | O14Ti—K1—O14T | 78.8 (3) |
O7B—Mo2—O1C | 72.37 (18) | O22Tii—K1—O14T | 139.7 (3) |
O8B—Mo2—O1C | 82.60 (18) | O22Tiii—K1—O14T | 95.8 (3) |
O2C—Mo2—O1C | 71.70 (16) | O3Wi—K1—O14T | 63.8 (3) |
O17T—Mo3—O18T | 105.4 (3) | O14Ti—K1—O9Wii | 73.6 (2) |
O17T—Mo3—O9B | 100.9 (2) | O22Tii—K1—O9Wii | 71.6 (2) |
O18T—Mo3—O9B | 102.8 (2) | O22Tiii—K1—O9Wii | 110.1 (3) |
O17T—Mo3—O8B | 99.9 (2) | O3Wi—K1—O9Wii | 96.2 (3) |
O18T—Mo3—O8B | 90.6 (2) | O14T—K1—O9Wii | 143.5 (2) |
O9B—Mo3—O8B | 151.14 (19) | O14Ti—K1—O3W | 59.9 (3) |
O17T—Mo3—O2C | 95.9 (2) | O22Tii—K1—O3W | 68.4 (3) |
O18T—Mo3—O2C | 153.2 (2) | O22Tiii—K1—O3W | 122.2 (3) |
O9B—Mo3—O2C | 88.67 (18) | O3Wi—K1—O3W | 140.8 (4) |
O8B—Mo3—O2C | 69.52 (17) | O14T—K1—O3W | 80.0 (2) |
O17T—Mo3—O3C | 165.5 (2) | O9Wii—K1—O3W | 105.4 (3) |
O18T—Mo3—O3C | 88.7 (2) | O16Tiv—K2—O4Wviii | 157.2 (4) |
O9B—Mo3—O3C | 72.29 (18) | O16Tiv—K2—O16Tv | 86.4 (3) |
O8B—Mo3—O3C | 82.70 (18) | O4Wviii—K2—O16Tv | 72.2 (3) |
O2C—Mo3—O3C | 71.54 (15) | O16Tiv—K2—O20Tvi | 109.7 (3) |
O19T—Mo4—O20T | 106.5 (3) | O4Wviii—K2—O20Tvi | 93.1 (3) |
O19T—Mo4—O10B | 100.3 (2) | O16Tv—K2—O20Tvi | 154.7 (4) |
O20T—Mo4—O10B | 102.8 (3) | O16Tiv—K2—O1Wviii | 74.5 (3) |
O19T—Mo4—O9B | 100.0 (2) | O4Wviii—K2—O1Wviii | 110.2 (4) |
O20T—Mo4—O9B | 95.9 (2) | O16Tv—K2—O1Wviii | 122.8 (3) |
O10B—Mo4—O9B | 147.10 (19) | O20Tvi—K2—O1Wviii | 81.2 (2) |
O19T—Mo4—O4C | 160.1 (2) | O16Tiv—K2—O4W | 66.4 (3) |
O20T—Mo4—O4C | 93.1 (2) | O4Wviii—K2—O4W | 131.3 (5) |
O10B—Mo4—O4C | 71.40 (17) | O16Tv—K2—O4W | 119.9 (4) |
O9B—Mo4—O4C | 80.87 (17) | O20Tvi—K2—O4W | 55.2 (3) |
O19T—Mo4—O3C | 91.1 (2) | O1Wviii—K2—O4W | 100.9 (3) |
O20T—Mo4—O3C | 160.0 (2) | O16Tiv—K2—O2Wviii | 78.0 (3) |
O10B—Mo4—O3C | 82.77 (18) | O4Wviii—K2—O2Wviii | 84.7 (3) |
O9B—Mo4—O3C | 71.18 (17) | O16Tv—K2—O2Wviii | 61.4 (2) |
O4C—Mo4—O3C | 70.19 (14) | O20Tvi—K2—O2Wviii | 139.4 (3) |
O21T—Mo5—O22T | 106.3 (3) | O1Wviii—K2—O2Wviii | 62.0 (2) |
O21T—Mo5—O10B | 101.2 (2) | O4W—K2—O2Wviii | 143.9 (4) |
O22T—Mo5—O10B | 98.7 (2) | O16Tiv—K2—O20Tvii | 137.5 (3) |
O21T—Mo5—O11B | 96.9 (2) | O4Wviii—K2—O20Tvii | 54.8 (3) |
O22T—Mo5—O11B | 101.8 (2) | O16Tv—K2—O20Tvii | 94.7 (3) |
O10B—Mo5—O11B | 147.60 (19) | O20Tvi—K2—O20Tvii | 60.1 (3) |
O21T—Mo5—O5C | 160.5 (2) | O1Wviii—K2—O20Tvii | 134.9 (3) |
O22T—Mo5—O5C | 91.4 (2) | O4W—K2—O20Tvii | 76.6 (3) |
O10B—Mo5—O5C | 83.82 (18) | O2Wviii—K2—O20Tvii | 138.6 (3) |
O11B—Mo5—O5C | 70.87 (17) | O1W—Na—O6W | 95.8 (3) |
O21T—Mo5—O4C | 93.1 (2) | O1W—Na—O13T | 169.6 (3) |
O22T—Mo5—O4C | 159.4 (2) | O6W—Na—O13T | 88.4 (3) |
O10B—Mo5—O4C | 70.36 (17) | O1W—Na—O5W | 89.5 (3) |
O11B—Mo5—O4C | 82.08 (18) | O6W—Na—O5W | 174.4 (3) |
O5C—Mo5—O4C | 70.60 (15) | O13T—Na—O5W | 86.1 (3) |
O24T—Mo6—O23T | 106.0 (3) | O1W—Na—O2W | 85.0 (3) |
O24T—Mo6—O11B | 97.1 (2) | O6W—Na—O2W | 99.4 (4) |
O23T—Mo6—O11B | 101.9 (2) | O13T—Na—O2W | 85.0 (3) |
O24T—Mo6—O12B | 101.6 (2) | O5W—Na—O2W | 79.1 (3) |
O23T—Mo6—O12B | 97.9 (2) | O1W—Na—O3W | 105.6 (3) |
O11B—Mo6—O12B | 147.71 (19) | O6W—Na—O3W | 87.8 (3) |
O24T—Mo6—O5C | 158.8 (2) | O13T—Na—O3W | 84.0 (3) |
O23T—Mo6—O5C | 93.7 (2) | O5W—Na—O3W | 92.7 (3) |
O11B—Mo6—O5C | 70.77 (17) | O2W—Na—O3W | 166.7 (4) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+3/2, −y+3/2, −z+1; (iv) x, −y+1, z+1/2; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, y+1/2, −z+3/2; (vii) x−1/2, y+1/2, z; (viii) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1C—H1···O10Wiii | 0.74 (7) | 1.89 (7) | 2.620 (7) | 174 (8) |
O3C—H3···O7W | 0.91 (8) | 1.66 (8) | 2.547 (7) | 163 (7) |
O4C—H4···O8W | 0.79 (7) | 1.82 (8) | 2.594 (8) | 166 (7) |
O5C—H5···O9W | 0.97 (6) | 1.60 (6) | 2.551 (8) | 165 (7) |
O6C—H6···O5Wv | 0.83 (8) | 1.75 (9) | 2.576 (8) | 179 (9) |
O8B—H8···O11Bix | 0.80 (7) | 1.85 (7) | 2.648 (6) | 175 (7) |
O1W—H1A···O2Cv | 0.81 (8) | 2.12 (8) | 2.909 (8) | 166 (13) |
O1W—H1B···O9Bvii | 0.79 (8) | 2.13 (9) | 2.838 (8) | 150 (14) |
O2W—H2B···O24T | 0.80 (8) | 2.54 (14) | 2.978 (9) | 116 (13) |
O3W—H3A···O18Tvii | 0.88 (8) | 2.54 (14) | 2.975 (10) | 111 (11) |
O4W—H4B···O20Tvi | 0.85 (10) | 2.3 (2) | 2.792 (12) | 113 (19) |
O4W—H4A···O24T | 0.82 (10) | 2.39 (19) | 2.957 (12) | 127 (20) |
O5W—H5B···O8Wv | 0.96 | 2.08 | 2.958 (13) | 151 |
O5W—H5A···O15Ti | 0.96 | 2.01 | 2.687 (8) | 126 |
O6W—H6B···O19Tvii | 0.88 (8) | 2.09 (9) | 2.921 (9) | 158 (12) |
O6W—H6A···O4W | 0.98 (8) | 1.90 (10) | 2.788 (15) | 148 (12) |
O7W—H7B···O11W | 0.75 (7) | 2.03 (7) | 2.730 (9) | 155 (9) |
O7W—H7A···O21Tix | 0.96 (7) | 1.88 (7) | 2.727 (7) | 146 (7) |
O8W—H8B···O10Wx | 0.80 (7) | 2.05 (8) | 2.840 (8) | 167 (12) |
O8W—H8A···O17Txi | 0.76 (7) | 2.27 (10) | 2.867 (9) | 136 (12) |
O9W—H9B···O12Biii | 0.73 (8) | 2.09 (10) | 2.752 (8) | 150 (14) |
O9W—H9A···O6Wiii | 0.75 (8) | 2.32 (11) | 2.937 (10) | 141 (13) |
O10W—H10B···O7Wiii | 0.90 (7) | 1.99 (7) | 2.835 (8) | 155 (9) |
O10W—H10A···O23T | 0.85 (7) | 2.02 (7) | 2.782 (8) | 149 (9) |
O11W—H11B···O10B | 0.77 (8) | 2.18 (9) | 2.880 (8) | 153 (14) |
O11W—H11A···O18Txii | 0.84 (7) | 2.18 (8) | 2.983 (8) | 159 (12) |
Symmetry codes: (i) −x+1, y, −z+1/2; (iii) −x+3/2, −y+3/2, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, y+1/2, −z+3/2; (vii) x−1/2, y+1/2, z; (ix) x, −y+1, z−1/2; (x) −x+3/2, y−1/2, −z+3/2; (xi) −x+3/2, −y+1/2, −z+1; (xii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | KNa[H6PtMo6O24]·11H2O |
Mr | 1421.04 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 20.935 (2), 18.535 (3), 17.775 (3) |
β (°) | 114.30 (2) |
V (Å3) | 6286.2 (18) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 7.02 |
Crystal size (mm) | 0.38 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Stoe Stadi-4 |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie 1996) |
Tmin, Tmax | 0.300, 0.422 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8235, 7237, 5972 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.082, 1.14 |
No. of reflections | 7237 |
No. of parameters | 490 |
No. of restraints | 33 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0282P)2 + 43.9139P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.96, −1.26 |
Computer programs: STADI4 (Stoe & Cie, 1996), X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
Pt—O1C | 1.989 (4) | Mo3—O3C | 2.338 (4) |
Pt—O2C | 1.978 (4) | Mo3—O8B | 2.047 (5) |
Pt—O3C | 1.993 (4) | Mo3—O9B | 1.889 (5) |
Pt—O4C | 2.003 (4) | Mo4—O3C | 2.323 (4) |
Pt—O5C | 2.034 (4) | Mo4—O4C | 2.291 (4) |
Pt—O6C | 2.001 (4) | Mo4—O9B | 1.979 (5) |
Mo1—O1C | 2.327 (5) | Mo4—O10B | 1.921 (5) |
Mo1—O6C | 2.306 (5) | Mo5—O4C | 2.328 (5) |
Mo1—O7B | 1.954 (5) | Mo5—O5C | 2.290 (5) |
Mo1—O12B | 1.927 (5) | Mo5—O10B | 1.935 (5) |
Mo2—O1C | 2.317 (5) | Mo5—O11B | 1.956 (4) |
Mo2—O2C | 2.154 (4) | Mo6—O5C | 2.302 (4) |
Mo2—O7B | 1.894 (5) | Mo6—O6C | 2.326 (5) |
Mo2—O8B | 2.060 (5) | Mo6—O11B | 1.946 (5) |
Mo3—O2C | 2.163 (4) | Mo6—O12B | 1.949 (5) |
Mo2—O1C—Mo1 | 92.06 (17) | Mo2—O7B—Mo1 | 120.6 (2) |
Mo2—O2C—Mo3 | 103.72 (16) | Mo3—O8B—Mo2 | 111.6 (2) |
Mo4—O3C—Mo3 | 92.16 (16) | Mo3—O9B—Mo4 | 120.5 (2) |
Mo4—O4C—Mo5 | 92.48 (16) | Mo4—O10B—Mo5 | 119.8 (2) |
Mo5—O5C—Mo6 | 94.18 (16) | Mo6—O11B—Mo5 | 119.1 (2) |
Mo1—O6C—Mo6 | 93.33 (17) | Mo1—O12B—Mo6 | 120.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1C—H1···O10Wi | 0.74 (7) | 1.89 (7) | 2.620 (7) | 174 (8) |
O3C—H3···O7W | 0.91 (8) | 1.66 (8) | 2.547 (7) | 163 (7) |
O4C—H4···O8W | 0.79 (7) | 1.82 (8) | 2.594 (8) | 166 (7) |
O5C—H5···O9W | 0.97 (6) | 1.60 (6) | 2.551 (8) | 165 (7) |
O6C—H6···O5Wii | 0.83 (8) | 1.75 (9) | 2.576 (8) | 179 (9) |
O8B—H8···O11Biii | 0.80 (7) | 1.85 (7) | 2.648 (6) | 175 (7) |
O1W—H1A···O2Cii | 0.81 (8) | 2.12 (8) | 2.909 (8) | 166 (13) |
O1W—H1B···O9Biv | 0.79 (8) | 2.13 (9) | 2.838 (8) | 150 (14) |
O2W—H2B···O24T | 0.80 (8) | 2.54 (14) | 2.978 (9) | 116 (13) |
O3W—H3A···O18Tiv | 0.88 (8) | 2.54 (14) | 2.975 (10) | 111 (11) |
O4W—H4B···O20Tv | 0.85 (10) | 2.3 (2) | 2.792 (12) | 113 (19) |
O4W—H4A···O24T | 0.82 (10) | 2.39 (19) | 2.957 (12) | 127 (20) |
O5W—H5B···O8Wii | 0.96 | 2.08 | 2.958 (13) | 150.8 |
O5W—H5A···O15Tvi | 0.96 | 2.01 | 2.687 (8) | 126.1 |
O6W—H6B···O19Tiv | 0.88 (8) | 2.09 (9) | 2.921 (9) | 158 (12) |
O6W—H6A···O4W | 0.98 (8) | 1.90 (10) | 2.788 (15) | 148 (12) |
O7W—H7B···O11W | 0.75 (7) | 2.03 (7) | 2.730 (9) | 155 (9) |
O7W—H7A···O21Tiii | 0.96 (7) | 1.88 (7) | 2.727 (7) | 146 (7) |
O8W—H8B···O10Wvii | 0.80 (7) | 2.05 (8) | 2.840 (8) | 167 (12) |
O8W—H8A···O17Tviii | 0.76 (7) | 2.27 (10) | 2.867 (9) | 136 (12) |
O9W—H9B···O12Bi | 0.73 (8) | 2.09 (10) | 2.752 (8) | 150 (14) |
O9W—H9A···O6Wi | 0.75 (8) | 2.32 (11) | 2.937 (10) | 141 (13) |
O10W—H10B···O7Wi | 0.90 (7) | 1.99 (7) | 2.835 (8) | 155 (9) |
O10W—H10A···O23T | 0.85 (7) | 2.02 (7) | 2.782 (8) | 149 (9) |
O11W—H11B···O10B | 0.77 (8) | 2.18 (9) | 2.880 (8) | 153 (14) |
O11W—H11A···O18Tix | 0.84 (7) | 2.18 (8) | 2.983 (8) | 159 (12) |
Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1, z−1/2; (iv) x−1/2, y+1/2, z; (v) −x+3/2, y+1/2, −z+3/2; (vi) −x+1, y, −z+1/2; (vii) −x+3/2, y−1/2, −z+3/2; (viii) −x+3/2, −y+1/2, −z+1; (ix) −x+2, −y+1, −z+1. |
Acknowledgements
This work was supported by the Pukyong National University Research Fund in 2008 (PK–2008–018).
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In our previous studies we isolated the same polyanion, [H6PtMo6O24]2-, that is present in the title compound, (I), at various pH conditions; 1.60 (II; Lee & Joo, 2006b), 0.70 (III; Lee & Sasaki, 1994) and 0.48 (IV; Lee & Joo, 2006a). Structures (II, III) have the same space group, viz. C2/c, whereas the space group of (IV) is P1. The polyanions bear an inversion center in these three structures. The current study was carried out to confirm the presence of a highly protonated species that exists at very low pH.
The structure of the present crystals contains a crystallographically discrete [H6PMo6O24]2- polyanion (Fig. 1). All atoms in the polyanion are located in general positions and consequently the symmetry of the polyanion is C1. The O atoms of the polyoxometalate were designated as Ot (terminal Mo═O atom), Ob (O bridging µ2-O atom), and Oc (µ3-O atom). The protonated O atoms in the polyanion were identified in difference Fourier maps and by using structural features as observed in the previously determined structures II & IV, viz. bond lengths of Mo–Oc(H) & Mo–Ob(H) units, bond angles of Mo–Oc(H)–Mo & Mo–Ob(H)–Mo units, and distances between Mo···Mo. As a result, the structure of (I) confirms the protonation of atoms O1c(H), O3c(H), O4c(H), O5c(H), O6c(H) and O8b(H).
The different bond-lengths and bond-angles in the [H6PtMo6O24]2- polyanion of protonated and unprotonated O atoms are compared in Table 1. The protonated O atoms of [H6PtMo6O24]2- in the structures (II), (III) and (IV) show the same protonation scheme, viz. four Oc(H) and two Ob(H) atoms are protonated. Therefore, the feature of the three-dimensional hydrogen bonding formation is very similar in the these polyanions, viz. the central PtO2(OH)4 polyhedron forms hydrogen bonds with neighbouring polyanions by four sets of Oc(H)···Ot and Ob(H)···Ot hydrogen bonds.
However, the protonation scheme of the polyanion in (I) is different, consisting of five Oc(H) and one Ob(H) protonated O atoms (Fig. 1). In contrast to the hydrogen bonding scheme in (II-IV), the protonated Oc atoms form various O–H···O hydrogen bonds with water molecules (Ow). Nevertheless, the polyanion is linearly connected by an O8b–H8···O11bi hydrogen bond (Fig.2 and Table 2).
The Na and K ions are coordinated by O atoms as [Na(Ow)5(Ot)]+ in the range 2.371 (7)-2.510 (9) Å, and [K1(Ot)4(Ow)2]+ and [K2(Ot)3(Ow)4]+ in the range 2.59 (1)-3.41 (1) Å. Bond valence sum calculations (BVS; Brown & Altermatt, 1985; Brese & O'Keeffe, 1991) for the K1 and K2 ions reveal a considerable undersaturation in terms of valence units which we ascribe to the disordered character of the metal positions.