The title compound, K
2[H
6PtMo
6O
24]·6H
2O, containing the hexamolybdoplatinate(IV) polyanion with the highest level of protonation, was isolated at pH 1.60. The anion has the Pt atom at an inversion center and exhibits a local symmetry close to
m. Four O atoms of the central PtO
6 octahedron and two O atoms of the edge-shared MoO
6 octahedron are protonated. One K
+ ion and one O atom of a water molecule are located on twofold axes; the positions of a second K
+ ion and one water molecule, both on general sites, are half-occupied.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (o-O) = 0.005 Å
- H-atom completeness 78%
- Disorder in solvent or counterion
- R factor = 0.033
- wR factor = 0.081
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O16W
| Author Response: Explained in _publ_section_exptl_refinement
|
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
| Author Response: Because H atoms of H2O(O16w) were not included.
|
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
| Author Response: Because H atoms of H2O(O16w) were not included.
|
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
| Author Response: Because H atoms of H2O(O16w) were not included.
|
PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.69 Ratio
| Author Response: Explained in _publ_section_exptl_refinement.
|
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.67 Ratio
| Author Response: Explained in _publ_section_exptl_refinement.
|
PLAT245_ALERT_2_C U(iso) H14B Smaller than U(eq) O14W by ... 0.02 AngSq
| Author Response: Explained in _publ_section_exptl_refinement.
|
PLAT245_ALERT_2_C U(iso) H13 Smaller than U(eq) O13W by ... 0.01 AngSq
| Author Response: Explained in _publ_section_exptl_refinement.
|
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 17.00 Perc.
| Author Response: I think no problem. Explained in the comment.
|
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:H18 K2 Mo6 O30 Pt1
Atom count from the _atom_site data: H14 K2 Mo6 O30 Pt1
ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 2.00
Tmin and Tmax reported: 0.229 0.376
Tmin and Tmax expected: 0.042 0.366
RR = 5.354
Please check that your absorption correction is appropriate.
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum H18 K2 Mo6 O30 Pt
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
H 72.00 56.00 16.00
K 8.00 8.00 0.00
Mo 24.00 24.00 0.00
O 120.00 120.00 0.00
Pt 4.00 4.00 0.00
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
8 ALERT level C = Check and explain
4 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
Dipotassium hexahydrogen hexamolybdoplatinate(IV) hexahydrate
top
Crystal data top
K2[H6PtMo6O24]·6H2O | F(000) = 2504 |
Mr = 1347.07 | Dx = 3.356 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 30 reflections |
a = 21.178 (3) Å | θ = 9.5–10.4° |
b = 12.940 (2) Å | µ = 8.38 mm−1 |
c = 10.110 (2) Å | T = 298 K |
β = 105.77 (1)° | Hexagonal block, pale yellow |
V = 2666.3 (8) Å3 | 0.42 × 0.36 × 0.12 mm |
Z = 4 | |
Data collection top
Stoe Stadi-4 diffractometer | 2608 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.010 |
Graphite monochromator | θmax = 27.5°, θmin = 1.9° |
ω/2θ scans | h = −27→26 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996) | k = 0→16 |
Tmin = 0.229, Tmax = 0.376 | l = 0→13 |
3078 measured reflections | 3 standard reflections every 60 min |
3056 independent reflections | intensity decay: 3.2% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0368P)2 + 9.1413P] where P = (Fo2 + 2Fc2)/3 |
3056 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.97 e Å−3 |
8 restraints | Δρmin = −1.27 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Pt | 0.2500 | 0.2500 | 0.0000 | 0.01349 (9) | |
Mo1 | 0.40336 (3) | 0.34274 (4) | 0.06449 (6) | 0.02157 (14) | |
Mo2 | 0.34798 (3) | 0.26249 (4) | 0.32760 (6) | 0.01849 (13) | |
Mo3 | 0.19606 (3) | 0.16989 (4) | 0.26248 (6) | 0.01903 (13) | |
K1 | 0.5000 | 0.62888 (19) | 0.2500 | 0.0426 (6) | |
K2 | 0.4913 (2) | 0.0638 (3) | 0.5596 (5) | 0.0566 (12) | 0.50 |
O1C | 0.3295 (2) | 0.2475 (3) | −0.0723 (5) | 0.0187 (9) | |
O2C | 0.3026 (2) | 0.3565 (3) | 0.1270 (5) | 0.0186 (9) | |
H2 | 0.284 (4) | 0.416 (5) | 0.131 (9) | 0.03 (2)* | |
O3C | 0.2827 (2) | 0.1571 (3) | 0.1616 (4) | 0.0160 (9) | |
H3 | 0.298 (4) | 0.096 (5) | 0.130 (8) | 0.03 (2)* | |
O4B | 0.3522 (3) | 0.4257 (4) | −0.1024 (5) | 0.0261 (11) | |
H4 | 0.361 (7) | 0.486 (7) | −0.103 (14) | 0.11 (5)* | |
O5B | 0.4045 (2) | 0.2459 (3) | 0.2076 (5) | 0.0216 (10) | |
O6B | 0.2581 (2) | 0.2735 (4) | 0.3417 (5) | 0.0231 (10) | |
O7T | 0.4670 (3) | 0.3023 (5) | 0.0061 (6) | 0.0430 (14) | |
O8T | 0.4277 (3) | 0.4548 (4) | 0.1523 (6) | 0.0377 (14) | |
O9T | 0.3787 (3) | 0.3731 (4) | 0.4121 (5) | 0.0281 (11) | |
O10T | 0.3775 (3) | 0.1636 (4) | 0.4370 (5) | 0.0298 (12) | |
O11T | 0.2256 (3) | 0.0603 (4) | 0.3558 (5) | 0.0305 (12) | |
O12T | 0.1295 (3) | 0.2088 (4) | 0.3103 (5) | 0.0313 (12) | |
O13W | 0.5000 | 0.0853 (8) | 0.2500 | 0.064 (3) | |
H13 | 0.477 (5) | 0.120 (7) | 0.273 (12) | 0.05 (3)* | |
O14W | 0.6168 (5) | 0.0610 (6) | 0.5963 (9) | 0.068 (2) | |
H14A | 0.626 (7) | 0.131 (7) | 0.575 (13) | 0.098* | |
H14B | 0.587 (5) | 0.086 (8) | 0.616 (12) | 0.050* | |
O15W | 0.4892 (7) | 0.1583 (9) | 0.6918 (13) | 0.055 (4) | 0.50 |
H15A | 0.5064 | 0.2208 | 0.6617 | 0.082* | 0.50 |
H15B | 0.4428 | 0.1713 | 0.6790 | 0.082* | 0.50 |
O16W | 0.3233 (3) | −0.0263 (4) | 0.1255 (6) | 0.0439 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt | 0.01563 (16) | 0.01233 (15) | 0.01243 (16) | −0.00035 (12) | 0.00369 (12) | 0.00013 (11) |
Mo1 | 0.0183 (3) | 0.0239 (3) | 0.0210 (3) | −0.0040 (2) | 0.0028 (2) | 0.0030 (2) |
Mo2 | 0.0229 (3) | 0.0161 (3) | 0.0147 (3) | −0.0011 (2) | 0.0021 (2) | 0.00053 (19) |
Mo3 | 0.0220 (3) | 0.0196 (3) | 0.0166 (3) | −0.0013 (2) | 0.0072 (2) | 0.0029 (2) |
K1 | 0.0304 (13) | 0.0294 (12) | 0.072 (2) | 0.000 | 0.0213 (13) | 0.000 |
K2 | 0.042 (2) | 0.053 (2) | 0.064 (3) | −0.0027 (19) | −0.004 (2) | 0.007 (2) |
O1C | 0.016 (2) | 0.019 (2) | 0.021 (2) | −0.0012 (17) | 0.0055 (18) | 0.0020 (17) |
O2C | 0.021 (2) | 0.0119 (19) | 0.021 (2) | −0.0014 (17) | 0.0015 (19) | −0.0028 (17) |
O3C | 0.021 (2) | 0.014 (2) | 0.012 (2) | −0.0010 (17) | 0.0030 (17) | 0.0017 (16) |
O4B | 0.032 (3) | 0.022 (2) | 0.019 (2) | −0.009 (2) | −0.001 (2) | 0.0025 (19) |
O5B | 0.019 (2) | 0.021 (2) | 0.023 (2) | 0.0008 (18) | 0.0020 (19) | 0.0019 (18) |
O6B | 0.028 (3) | 0.024 (2) | 0.018 (2) | −0.0044 (19) | 0.008 (2) | −0.0049 (18) |
O7T | 0.026 (3) | 0.058 (4) | 0.047 (4) | 0.001 (3) | 0.014 (3) | 0.010 (3) |
O8T | 0.040 (3) | 0.028 (3) | 0.037 (3) | −0.016 (2) | −0.004 (3) | 0.006 (2) |
O9T | 0.030 (3) | 0.022 (2) | 0.027 (3) | −0.002 (2) | −0.002 (2) | −0.004 (2) |
O10T | 0.036 (3) | 0.026 (2) | 0.024 (3) | 0.005 (2) | 0.003 (2) | 0.005 (2) |
O11T | 0.037 (3) | 0.024 (2) | 0.029 (3) | −0.006 (2) | 0.007 (2) | 0.009 (2) |
O12T | 0.030 (3) | 0.038 (3) | 0.028 (3) | −0.001 (2) | 0.012 (2) | 0.000 (2) |
O13W | 0.040 (6) | 0.033 (5) | 0.109 (10) | 0.000 | 0.001 (6) | 0.000 |
O14W | 0.094 (7) | 0.037 (4) | 0.071 (5) | −0.019 (4) | 0.022 (5) | 0.006 (4) |
O15W | 0.056 (9) | 0.048 (7) | 0.050 (8) | 0.017 (6) | −0.004 (7) | 0.002 (6) |
O16W | 0.057 (4) | 0.035 (3) | 0.035 (3) | 0.011 (3) | 0.004 (3) | −0.004 (2) |
Geometric parameters (Å, º) top
Mo1—Mo2 | 3.3503 (10) | Mo3—O12T | 1.688 (5) |
Mo1—Mo3i | 3.4065 (10) | K1—O7Tii | 2.994 (6) |
Mo2—Mo3 | 3.3269 (9) | K1—O7Tiii | 2.994 (6) |
Pt—O1C | 2.010 (4) | K1—O8T | 2.751 (5) |
Pt—O2C | 2.003 (4) | K1—O8Tiv | 2.751 (5) |
Pt—O3C | 1.995 (4) | K1—O15Wv | 2.813 (13) |
Pt—O3Ci | 1.995 (4) | K1—O15Wvi | 2.813 (13) |
Pt—O2Ci | 2.003 (4) | K1—O12Tvii | 2.837 (5) |
Pt—O1Ci | 2.010 (4) | K1—O12Tviii | 2.837 (5) |
Mo1—O1C | 2.169 (4) | K2—O10T | 2.719 (7) |
Mo1—O2C | 2.391 (5) | K2—O7Tiv | 3.325 (8) |
Mo1—O4B | 2.044 (5) | K2—O13W | 3.198 (5) |
Mo1—O5B | 1.909 (5) | K2—O13Wix | 2.696 (9) |
Mo1—O7T | 1.696 (6) | K2—O14W | 2.583 (11) |
Mo1—O8T | 1.706 (5) | K2—O14Wix | 2.894 (10) |
Mo2—O2C | 2.336 (5) | K2—O15W | 1.820 (14) |
Mo2—O3C | 2.308 (4) | K2—O15Wx | 2.723 (14) |
Mo2—O5B | 1.934 (5) | O2C—H2 | 0.86 (7) |
Mo2—O6B | 1.953 (5) | O3C—H3 | 0.93 (6) |
Mo2—O9T | 1.702 (5) | O4B—H4 | 0.81 (8) |
Mo2—O10T | 1.695 (5) | O13W—H13 | 0.75 (7) |
Mo3—O1Ci | 2.137 (4) | O14W—H14A | 0.96 (8) |
Mo3—O3C | 2.335 (5) | O14W—H14B | 0.78 (7) |
Mo3—O4Bi | 2.073 (5) | O15W—H15A | 0.9700 |
Mo3—O6B | 1.895 (5) | O15W—H15B | 0.9700 |
Mo3—O11T | 1.724 (5) | | |
| | | |
Mo3i—O1C—Mo1 | 104.58 (18) | O6B—Mo2—O2C | 81.16 (18) |
Mo2—O2C—Mo1 | 90.27 (16) | O3C—Mo2—O2C | 69.69 (15) |
Mo2—O3C—Mo3 | 91.55 (15) | O12T—Mo3—O11T | 107.2 (3) |
Mo1—O4B—Mo3i | 111.7 (2) | O12T—Mo3—O6B | 101.8 (2) |
Mo1—O5B—Mo2 | 121.3 (2) | O11T—Mo3—O6B | 104.1 (2) |
Mo3—O6B—Mo2 | 119.7 (2) | O12T—Mo3—O4Bi | 97.4 (2) |
Pt—O1C—Mo3i | 106.7 (2) | O11T—Mo3—O4Bi | 88.0 (2) |
Pt—O1C—Mo1 | 106.8 (2) | O6B—Mo3—O4Bi | 152.9 (2) |
Pt—O2C—Mo2 | 102.93 (18) | O12T—Mo3—O1Ci | 94.7 (2) |
Pt—O2C—Mo1 | 99.22 (18) | O11T—Mo3—O1Ci | 150.4 (2) |
Pt—O3C—Mo2 | 104.20 (17) | O6B—Mo3—O1Ci | 90.18 (19) |
Pt—O3C—Mo3 | 100.13 (19) | O4Bi—Mo3—O1Ci | 69.25 (18) |
H14A—O14W—H14B | 83 (10) | O12T—Mo3—O3C | 164.5 (2) |
O15Wx—O15W—H15B | 104.1 | O11T—Mo3—O3C | 88.2 (2) |
H15A—O15W—H15B | 105.5 | O6B—Mo3—O3C | 72.43 (18) |
Mo3—Mo2—Mo1 | 118.87 (2) | O4Bi—Mo3—O3C | 84.05 (19) |
Mo2—Mo1—Mo3i | 119.88 (2) | O1Ci—Mo3—O3C | 71.31 (16) |
O3C—Pt—O3Ci | 180.0 (3) | O8T—K1—O8Tiv | 70.1 (2) |
O3C—Pt—O2Ci | 96.84 (18) | O8T—K1—O15Wv | 151.9 (3) |
O3Ci—Pt—O2Ci | 83.16 (18) | O8Tiv—K1—O15Wv | 136.1 (3) |
O3C—Pt—O2C | 83.16 (18) | O8T—K1—O15Wvi | 136.1 (3) |
O3Ci—Pt—O2C | 96.84 (18) | O8Tiv—K1—O15Wvi | 151.9 (3) |
O2Ci—Pt—O2C | 180.0 (4) | O15Wv—K1—O15Wvi | 23.4 (5) |
O3C—Pt—O1C | 98.60 (18) | O8T—K1—O12Tvii | 141.86 (18) |
O3Ci—Pt—O1C | 81.40 (18) | O8Tiv—K1—O12Tvii | 79.05 (17) |
O2Ci—Pt—O1C | 97.51 (19) | O15Wv—K1—O12Tvii | 65.1 (3) |
O2C—Pt—O1C | 82.49 (19) | O8T—K1—O7Tii | 99.85 (18) |
O3C—Pt—O1Ci | 81.40 (18) | O8Tiv—K1—O7Tii | 108.43 (18) |
O3Ci—Pt—O1Ci | 98.60 (18) | O15Wv—K1—O7Tii | 82.2 (3) |
O2Ci—Pt—O1Ci | 82.49 (19) | O15Wvi—K1—O7Tii | 63.4 (3) |
O2C—Pt—O1Ci | 97.51 (19) | O15Wv—K1—O7Tiii | 63.4 (3) |
O1C—Pt—O1Ci | 180.00 (9) | O15Wvi—K1—O7Tiii | 82.2 (3) |
O7T—Mo1—O8T | 106.7 (3) | O15W—K2—O14W | 97.7 (6) |
O7T—Mo1—O5B | 102.3 (3) | K2ix—K2—O14W | 75.0 (3) |
O8T—Mo1—O5B | 102.9 (2) | O15W—K2—O13Wix | 88.1 (5) |
O7T—Mo1—O4B | 99.6 (3) | O14W—K2—O13Wix | 91.1 (2) |
O8T—Mo1—O4B | 90.0 (2) | O15W—K2—O10T | 79.7 (5) |
O5B—Mo1—O4B | 149.9 (2) | O14W—K2—O10T | 145.4 (3) |
O7T—Mo1—O1C | 96.1 (2) | O13Wix—K2—O10T | 123.1 (2) |
O8T—Mo1—O1C | 151.5 (2) | O15W—K2—O15Wx | 18.0 (5) |
O5B—Mo1—O1C | 88.19 (18) | O14W—K2—O15Wx | 89.0 (4) |
O4B—Mo1—O1C | 69.13 (18) | O13Wix—K2—O15Wx | 72.5 (3) |
O7T—Mo1—O2C | 165.1 (2) | O10T—K2—O15Wx | 95.8 (4) |
O8T—Mo1—O2C | 87.9 (2) | O15W—K2—O14Wix | 127.0 (6) |
O5B—Mo1—O2C | 71.16 (18) | O14W—K2—O14Wix | 134.5 (2) |
O4B—Mo1—O2C | 82.45 (19) | O15W—K2—O13W | 132.8 (5) |
O1C—Mo1—O2C | 70.74 (16) | O14W—K2—O13W | 79.1 (2) |
O10T—Mo2—O9T | 106.5 (2) | O13Wix—K2—O13W | 138.60 (18) |
O10T—Mo2—O5B | 98.3 (2) | O10T—K2—O13W | 78.00 (18) |
O9T—Mo2—O5B | 101.0 (2) | O15Wx—K2—O13W | 146.1 (4) |
O10T—Mo2—O6B | 101.6 (2) | O14Wix—K2—O13W | 76.3 (2) |
O9T—Mo2—O6B | 98.6 (2) | O15W—K2—O7Tiv | 65.4 (5) |
O5B—Mo2—O6B | 146.69 (19) | K2ix—K2—O7Tiv | 120.6 (3) |
O10T—Mo2—O3C | 94.0 (2) | O14W—K2—O7Tiv | 73.9 (2) |
O9T—Mo2—O3C | 159.0 (2) | O13Wix—K2—O7Tiv | 146.8 (2) |
O5B—Mo2—O3C | 80.14 (18) | O10T—K2—O7Tiv | 73.66 (18) |
O6B—Mo2—O3C | 72.11 (18) | O15Wx—K2—O7Tiv | 77.6 (3) |
O10T—Mo2—O2C | 162.0 (2) | O14Wix—K2—O7Tiv | 128.5 (2) |
O9T—Mo2—O2C | 90.5 (2) | O13W—K2—O7Tiv | 68.6 (2) |
O5B—Mo2—O2C | 72.04 (18) | | |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x+1, −y+1, −z; (iii) x, −y+1, z+1/2; (iv) −x+1, y, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) x, −y+1, z−1/2; (vii) x+1/2, y+1/2, z; (viii) −x+1/2, y+1/2, −z+1/2; (ix) −x+1, −y, −z+1; (x) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2C—H2···O11Tviii | 0.86 (7) | 1.89 (7) | 2.720 (6) | 160 (8) |
O4B—H4···O9Tvi | 0.81 (8) | 1.86 (9) | 2.659 (7) | 174 (14) |
O13W—H13···O5B | 0.75 (7) | 2.21 (8) | 2.850 (9) | 144 (11) |
O14W—H14A···O1Civ | 0.96 (8) | 1.79 (9) | 2.707 (8) | 159 (12) |
O15W—H15B···O12Txi | 0.97 | 2.20 | 3.041 (15) | 144 |
O15W—H15B···O10T | 0.97 | 2.46 | 2.988 (14) | 114 |
O15W—H15A···O7Tiv | 0.97 | 2.20 | 3.056 (16) | 147 |
Symmetry codes: (iv) −x+1, y, −z+1/2; (vi) x, −y+1, z−1/2; (viii) −x+1/2, y+1/2, −z+1/2; (xi) −x+1/2, −y+1/2, −z+1. |