Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009689/qa0346sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009689/qa0346Isup2.hkl |
The title compound was prepared by mixing a hot aqueous solution of [H2α-PtMo6O24]8− (0.5 mM/20 ml) and Nd(NO3)3·6H2O (0.1 mM/20 ml). The pH was adjusted to 3.2 by adding 3.0 M HNO3. The solution was concentrated to about 20 ml by heating in a water bath. After a day, monoclinic grey crystals were obtained at room temperature.
The largest difference peak lies 2.93 Å from the nearest atom (OW5) and 4.66 Å from the Nd atom. It may represent an additional partially occupied disordered water molecule site.
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Nd2[H2PtMo6O24]·14H2O | F(000) = 3136 |
Mr = 1697.45 | Dx = 3.471 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 21.079 (2) Å | Cell parameters from 28 reflections |
b = 10.324 (4) Å | θ = 10.0–11.4° |
c = 15.8637 (18) Å | µ = 9.78 mm−1 |
β = 109.780 (9)° | T = 298 K |
V = 3248.5 (13) Å3 | Monoclinic, grey |
Z = 4 | 0.12 × 0.08 × 0.06 mm |
Stoe Stadi-4 diffractometer | 2851 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 2.1° |
ω/2θ scans | h = −27→25 |
Absorption correction: numerical (stoe, 1996) ? | k = 0→13 |
Tmin = 0.185, Tmax = 0.340 | l = 0→20 |
3719 measured reflections | 3 standard reflections every 60 min |
3719 independent reflections | intensity decay: 5.0% |
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)] = 0.050 | H-atom parameters not refined |
wR(F2) = 0.120 | Calculated w = 1/[σ2(Fo2) + (0.0476P)2 + 51.4635P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
3719 reflections | Δρmax = 2.68 e Å−3 |
214 parameters | Δρmin = −2.09 e Å−3 |
0 restraints |
Nd2[H2PtMo6O24]·14H2O | V = 3248.5 (13) Å3 |
Mr = 1697.45 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.079 (2) Å | µ = 9.78 mm−1 |
b = 10.324 (4) Å | T = 298 K |
c = 15.8637 (18) Å | 0.12 × 0.08 × 0.06 mm |
β = 109.780 (9)° |
Stoe Stadi-4 diffractometer | 2851 reflections with I > 2σ(I) |
Absorption correction: numerical (stoe, 1996) ? | Rint = 0.000 |
Tmin = 0.185, Tmax = 0.340 | 3 standard reflections every 60 min |
3719 measured reflections | intensity decay: 5.0% |
3719 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters not refined |
S = 1.13 | Δρmax = 2.68 e Å−3 |
3719 reflections | Δρmin = −2.09 e Å−3 |
214 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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 | ||
Pt | 0.2500 | 0.7500 | 0.0000 | 0.01014 (15) | |
Nd | 0.60036 (3) | 0.72948 (6) | 0.14767 (4) | 0.01336 (16) | |
Mo1 | 0.30649 (6) | 0.44624 (10) | 0.01866 (7) | 0.0126 (2) | |
Mo2 | 0.34703 (5) | 0.97780 (10) | 0.13068 (7) | 0.0129 (2) | |
Mo3 | 0.40127 (5) | 0.67833 (10) | 0.13165 (7) | 0.0113 (2) | |
OC1 | 0.2395 (4) | 0.8838 (7) | 0.0860 (5) | 0.0121 (17) | |
OC2 | 0.3454 (4) | 0.8169 (8) | 0.0382 (5) | 0.0118 (17) | |
OC3 | 0.2947 (4) | 0.6138 (8) | 0.0905 (5) | 0.0132 (17) | |
OB4 | 0.3758 (5) | 0.8218 (8) | 0.2024 (6) | 0.0151 (18) | |
OB5 | 0.2893 (4) | 1.0649 (8) | 0.0206 (6) | 0.0160 (18) | |
OB6 | 0.3914 (4) | 0.5510 (8) | 0.0425 (5) | 0.0155 (18) | |
OT7 | 0.4784 (4) | 0.7326 (9) | 0.1308 (6) | 0.0193 (19) | |
OT8 | 0.4187 (5) | 0.5889 (9) | 0.2296 (6) | 0.0180 (19) | |
OT9 | 0.3234 (5) | 1.0609 (9) | 0.2080 (6) | 0.0199 (19) | |
OT10 | 0.4230 (5) | 1.0412 (9) | 0.1340 (7) | 0.025 (2) | |
OT11 | 0.3283 (5) | 0.3479 (9) | 0.1091 (6) | 0.023 (2) | |
OT12 | 0.3263 (5) | 0.3598 (9) | −0.0638 (6) | 0.0191 (19) | |
OW1 | 0.6800 (5) | 0.8998 (9) | 0.1321 (7) | 0.026 (2) | |
OW2 | 0.7072 (5) | 0.6308 (11) | 0.2452 (7) | 0.031 (2) | |
OW3 | 0.5420 (5) | 0.7546 (11) | −0.0188 (6) | 0.032 (2) | |
OW4 | 0.5474 (5) | 0.9460 (10) | 0.1262 (8) | 0.035 (3) | |
OW5 | 0.5605 (5) | 0.5054 (10) | 0.0919 (7) | 0.029 (2) | |
OW6 | 0.4049 (7) | 0.8314 (11) | −0.0853 (7) | 0.039 (3) | |
OW7 | 0.1763 (7) | 0.8413 (11) | 0.2088 (8) | 0.041 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.0102 (3) | 0.0104 (3) | 0.0100 (3) | 0.0005 (2) | 0.0036 (2) | −0.0001 (2) |
Nd | 0.0130 (3) | 0.0156 (3) | 0.0127 (3) | 0.0007 (3) | 0.0058 (2) | 0.0006 (2) |
Mo1 | 0.0151 (5) | 0.0113 (5) | 0.0121 (5) | 0.0005 (4) | 0.0057 (4) | −0.0014 (4) |
Mo2 | 0.0128 (5) | 0.0113 (5) | 0.0157 (5) | 0.0005 (4) | 0.0060 (4) | −0.0012 (4) |
Mo3 | 0.0104 (5) | 0.0121 (5) | 0.0115 (5) | 0.0001 (4) | 0.0039 (4) | −0.0008 (4) |
OC1 | 0.019 (5) | 0.006 (4) | 0.012 (4) | 0.001 (3) | 0.005 (3) | 0.000 (3) |
OC2 | 0.011 (4) | 0.013 (4) | 0.009 (4) | −0.002 (3) | −0.001 (3) | 0.002 (3) |
OC3 | 0.014 (4) | 0.016 (4) | 0.011 (4) | 0.001 (3) | 0.007 (3) | −0.001 (3) |
OB4 | 0.019 (5) | 0.013 (4) | 0.016 (4) | 0.004 (4) | 0.009 (4) | 0.002 (3) |
OB5 | 0.013 (4) | 0.012 (4) | 0.025 (5) | −0.001 (4) | 0.009 (4) | 0.003 (4) |
OB6 | 0.012 (4) | 0.018 (4) | 0.013 (4) | −0.001 (4) | −0.001 (3) | −0.008 (3) |
OT7 | 0.013 (4) | 0.025 (5) | 0.021 (4) | 0.002 (4) | 0.008 (4) | 0.001 (4) |
OT8 | 0.022 (5) | 0.019 (4) | 0.013 (4) | 0.002 (4) | 0.005 (4) | 0.000 (3) |
OT9 | 0.022 (5) | 0.019 (5) | 0.019 (4) | 0.001 (4) | 0.007 (4) | −0.004 (4) |
OT10 | 0.018 (5) | 0.019 (5) | 0.039 (6) | −0.006 (4) | 0.011 (4) | 0.000 (4) |
OT11 | 0.034 (6) | 0.020 (5) | 0.015 (4) | 0.004 (4) | 0.008 (4) | 0.008 (4) |
OT12 | 0.021 (5) | 0.019 (5) | 0.019 (4) | 0.000 (4) | 0.009 (4) | −0.009 (4) |
OW1 | 0.026 (5) | 0.024 (5) | 0.035 (6) | −0.004 (4) | 0.019 (5) | −0.004 (4) |
OW2 | 0.016 (5) | 0.050 (7) | 0.028 (5) | 0.016 (5) | 0.010 (4) | 0.012 (5) |
OW3 | 0.027 (6) | 0.046 (7) | 0.019 (5) | 0.014 (5) | 0.005 (4) | 0.013 (5) |
OW4 | 0.026 (6) | 0.023 (5) | 0.057 (7) | 0.009 (5) | 0.013 (5) | 0.014 (5) |
OW5 | 0.035 (6) | 0.032 (6) | 0.027 (5) | −0.013 (5) | 0.019 (5) | −0.009 (4) |
OW6 | 0.058 (8) | 0.037 (6) | 0.026 (6) | −0.016 (6) | 0.018 (5) | −0.004 (5) |
OW7 | 0.053 (8) | 0.033 (6) | 0.034 (6) | 0.001 (6) | 0.012 (6) | −0.002 (5) |
Pt—OC3i | 2.002 (8) | Mo1—OC3 | 2.131 (8) |
Pt—OC3 | 2.002 (8) | Mo1—OC1i | 2.384 (8) |
Pt—OC1i | 2.006 (8) | Mo1—Mo3 | 3.2437 (16) |
Pt—OC1 | 2.006 (8) | Mo1—Mo2i | 3.3927 (14) |
Pt—OC2i | 2.015 (8) | Mo2—OT9 | 1.703 (9) |
Pt—OC2 | 2.015 (8) | Mo2—OT10 | 1.715 (9) |
Pt—Mo3 | 3.2511 (11) | Mo2—OB4 | 1.947 (8) |
Pt—Mo1 | 3.3318 (15) | Mo2—OB5 | 1.975 (9) |
Pt—Mo2 | 3.3379 (12) | Mo2—OC2 | 2.209 (8) |
Nd—OB4ii | 2.451 (8) | Mo2—OC1 | 2.345 (9) |
Nd—OW4 | 2.470 (10) | Mo2—Mo3 | 3.2945 (18) |
Nd—OW2 | 2.478 (10) | Mo3—OT7 | 1.723 (9) |
Nd—OT7 | 2.494 (9) | Mo3—OT8 | 1.736 (9) |
Nd—OW1 | 2.501 (10) | Mo3—OB6 | 1.890 (8) |
Nd—OW5 | 2.518 (10) | Mo3—OB4 | 2.037 (8) |
Nd—OW3 | 2.521 (9) | Mo3—OC2 | 2.109 (8) |
Nd—OT12iii | 2.530 (9) | Mo3—OC3 | 2.218 (9) |
Nd—OT8ii | 2.567 (9) | Mo3—Ndii | 3.5521 (12) |
Nd—Mo3ii | 3.5521 (12) | OC1—Mo1i | 2.384 (8) |
Mo1—OT11 | 1.689 (9) | OB4—Ndii | 2.451 (8) |
Mo1—OT12 | 1.747 (8) | OB5—Mo1i | 1.904 (9) |
Mo1—OB5i | 1.904 (9) | OT8—Ndii | 2.567 (9) |
Mo1—OB6 | 2.014 (9) | OT12—Ndiii | 2.530 (9) |
OC3i—Pt—OC3 | 180.0 | OC1i—Mo1—Pt | 36.56 (19) |
OC3i—Pt—OC1i | 97.5 (3) | Mo3—Mo1—Pt | 59.24 (3) |
OC3—Pt—OC1i | 82.5 (3) | OT11—Mo1—Mo2 | 110.0 (3) |
OC3i—Pt—OC1 | 82.5 (3) | OT12—Mo1—Mo2 | 132.2 (3) |
OC3—Pt—OC1 | 97.5 (3) | OB5i—Mo1—Mo2 | 100.9 (3) |
OC1i—Pt—OC1 | 180.0 | OB6—Mo1—Mo2 | 53.1 (2) |
OC3i—Pt—OC2i | 81.1 (3) | OC3—Mo1—Mo2 | 24.6 (2) |
OC3—Pt—OC2i | 98.9 (3) | OC1i—Mo1—Mo2 | 59.68 (19) |
OC1i—Pt—OC2i | 83.6 (3) | Mo3—Mo1—Mo2 | 28.81 (2) |
OC1—Pt—OC2i | 96.4 (3) | Pt—Mo1—Mo2 | 30.607 (19) |
OC3i—Pt—OC2 | 98.9 (3) | OT9—Mo2—OT10 | 106.5 (5) |
OC3—Pt—OC2 | 81.1 (3) | OT9—Mo2—OB4 | 96.0 (4) |
OC1i—Pt—OC2 | 96.4 (3) | OT10—Mo2—OB4 | 101.2 (4) |
OC1—Pt—OC2 | 83.6 (3) | OT9—Mo2—OB5 | 99.4 (4) |
OC2i—Pt—OC2 | 180.0 | OT10—Mo2—OB5 | 98.2 (4) |
OC3i—Pt—Mo3 | 137.9 (2) | OB4—Mo2—OB5 | 150.5 (4) |
OC3—Pt—Mo3 | 42.1 (2) | OT9—Mo2—OC2 | 156.1 (4) |
OC1i—Pt—Mo3 | 88.3 (2) | OT10—Mo2—OC2 | 96.4 (4) |
OC1—Pt—Mo3 | 91.7 (2) | OB4—Mo2—OC2 | 72.4 (3) |
OC2i—Pt—Mo3 | 141.0 (2) | OB5—Mo2—OC2 | 83.6 (3) |
OC2—Pt—Mo3 | 39.0 (2) | OT9—Mo2—OC1 | 86.4 (4) |
OC3i—Pt—Mo1 | 142.4 (2) | OT10—Mo2—OC1 | 164.8 (4) |
OC3—Pt—Mo1 | 37.6 (2) | OB4—Mo2—OC1 | 85.0 (3) |
OC1i—Pt—Mo1 | 45.1 (2) | OB5—Mo2—OC1 | 71.2 (3) |
OC1—Pt—Mo1 | 134.9 (2) | OC2—Mo2—OC1 | 72.1 (3) |
OC2i—Pt—Mo1 | 89.7 (2) | OT9—Mo2—Mo3 | 130.9 (3) |
OC2—Pt—Mo1 | 90.3 (2) | OT10—Mo2—Mo3 | 92.2 (3) |
Mo3—Pt—Mo1 | 59.03 (3) | OB4—Mo2—Mo3 | 35.1 (2) |
OC3i—Pt—Mo2 | 89.5 (2) | OB5—Mo2—Mo3 | 122.7 (3) |
OC3—Pt—Mo2 | 90.5 (2) | OC2—Mo2—Mo3 | 39.2 (2) |
OC1i—Pt—Mo2 | 136.2 (2) | OC1—Mo2—Mo3 | 84.93 (19) |
OC1—Pt—Mo2 | 43.8 (2) | OT9—Mo2—Pt | 122.4 (3) |
OC2i—Pt—Mo2 | 140.1 (2) | OT10—Mo2—Pt | 131.1 (3) |
OC2—Pt—Mo2 | 39.9 (2) | OB4—Mo2—Pt | 77.6 (3) |
Mo3—Pt—Mo2 | 59.98 (3) | OB5—Mo2—Pt | 73.0 (3) |
Mo1—Pt—Mo2 | 118.85 (3) | OC2—Mo2—Pt | 35.8 (2) |
Mo1—Pt—Mo2i | 61.15 (3) | OC1—Mo2—Pt | 36.30 (19) |
OB4ii—Nd—OW4 | 73.5 (3) | Mo3—Mo2—Pt | 58.70 (3) |
OB4ii—Nd—OW2 | 73.1 (3) | OT9—Mo2—Mo1 | 130.9 (3) |
OW4—Nd—OW2 | 137.0 (4) | OT10—Mo2—Mo1 | 114.4 (3) |
OB4ii—Nd—OT7 | 88.0 (3) | OB4—Mo2—Mo1 | 51.3 (3) |
OW4—Nd—OT7 | 64.6 (3) | OB5—Mo2—Mo1 | 100.3 (3) |
OW2—Nd—OT7 | 139.3 (3) | OC2—Mo2—Mo1 | 26.9 (2) |
OB4ii—Nd—OW1 | 84.2 (3) | OC1—Mo2—Mo1 | 58.90 (19) |
OW4—Nd—OW1 | 68.7 (3) | Mo3—Mo2—Mo1 | 28.32 (3) |
OW2—Nd—OW1 | 81.5 (4) | Pt—Mo2—Mo1 | 30.545 (16) |
OT7—Nd—OW1 | 133.1 (3) | OT7—Mo3—OT8 | 105.4 (4) |
OB4ii—Nd—OW5 | 129.2 (3) | OT7—Mo3—OB6 | 94.9 (4) |
OW4—Nd—OW5 | 134.5 (4) | OT8—Mo3—OB6 | 103.7 (4) |
OW2—Nd—OW5 | 88.1 (4) | OT7—Mo3—OB4 | 101.1 (4) |
OT7—Nd—OW5 | 76.4 (3) | OT8—Mo3—OB4 | 84.8 (4) |
OW1—Nd—OW5 | 140.1 (3) | OB6—Mo3—OB4 | 159.2 (4) |
OB4ii—Nd—OW3 | 147.5 (3) | OT7—Mo3—OC2 | 94.4 (4) |
OW4—Nd—OW3 | 74.0 (4) | OT8—Mo3—OC2 | 152.7 (4) |
OW2—Nd—OW3 | 135.6 (3) | OB6—Mo3—OC2 | 92.9 (3) |
OT7—Nd—OW3 | 76.5 (3) | OB4—Mo3—OC2 | 72.9 (3) |
OW1—Nd—OW3 | 86.0 (4) | OT7—Mo3—OC3 | 163.5 (4) |
OW5—Nd—OW3 | 74.9 (4) | OT8—Mo3—OC3 | 89.5 (4) |
OB4ii—Nd—OT12iii | 133.7 (3) | OB6—Mo3—OC3 | 74.1 (3) |
OW4—Nd—OT12iii | 125.8 (3) | OB4—Mo3—OC3 | 87.2 (3) |
OW2—Nd—OT12iii | 65.8 (3) | OC2—Mo3—OC3 | 74.2 (3) |
OT7—Nd—OT12iii | 137.7 (3) | OT7—Mo3—Mo1 | 129.9 (3) |
OW1—Nd—OT12iii | 69.8 (3) | OT8—Mo3—Mo1 | 90.4 (3) |
OW5—Nd—OT12iii | 70.8 (3) | OB6—Mo3—Mo1 | 35.0 (3) |
OW3—Nd—OT12iii | 69.8 (3) | OB4—Mo3—Mo1 | 127.9 (3) |
OB4ii—Nd—OT8ii | 61.1 (3) | OC2—Mo3—Mo1 | 91.1 (2) |
OW4—Nd—OT8ii | 115.9 (3) | OC3—Mo3—Mo1 | 40.8 (2) |
OW2—Nd—OT8ii | 68.7 (3) | OT7—Mo3—Pt | 130.0 (3) |
OT7—Nd—OT8ii | 70.6 (3) | OT8—Mo3—Pt | 124.1 (3) |
OW1—Nd—OT8ii | 139.1 (3) | OB6—Mo3—Pt | 80.9 (3) |
OW5—Nd—OT8ii | 68.1 (3) | OB4—Mo3—Pt | 78.7 (3) |
OW3—Nd—OT8ii | 135.0 (3) | OC2—Mo3—Pt | 37.0 (2) |
OT12iii—Nd—OT8ii | 118.2 (3) | OC3—Mo3—Pt | 37.3 (2) |
OB4ii—Nd—Mo3ii | 33.8 (2) | Mo1—Mo3—Pt | 61.73 (3) |
OW4—Nd—Mo3ii | 96.7 (3) | OT7—Mo3—Mo2 | 91.2 (3) |
OW2—Nd—Mo3ii | 68.5 (2) | OT8—Mo3—Mo2 | 118.1 (3) |
OT7—Nd—Mo3ii | 75.8 (2) | OB6—Mo3—Mo2 | 134.3 (3) |
OW1—Nd—Mo3ii | 115.6 (2) | OB4—Mo3—Mo2 | 33.3 (2) |
OW5—Nd—Mo3ii | 95.5 (2) | OC2—Mo3—Mo2 | 41.4 (2) |
OW3—Nd—Mo3ii | 152.1 (3) | OC3—Mo3—Mo2 | 88.0 (2) |
OT12iii—Nd—Mo3ii | 132.5 (2) | Mo1—Mo3—Mo2 | 122.87 (5) |
OT8ii—Nd—Mo3ii | 27.4 (2) | Pt—Mo3—Mo2 | 61.32 (3) |
OT11—Mo1—OT12 | 105.3 (5) | OT7—Mo3—Ndii | 106.4 (3) |
OT11—Mo1—OB5i | 101.3 (4) | OT8—Mo3—Ndii | 42.8 (3) |
OT12—Mo1—OB5i | 102.7 (4) | OB6—Mo3—Ndii | 143.7 (3) |
OT11—Mo1—OB6 | 101.2 (4) | OB4—Mo3—Ndii | 42.0 (2) |
OT12—Mo1—OB6 | 89.6 (4) | OC2—Mo3—Ndii | 113.8 (2) |
OB5i—Mo1—OB6 | 150.5 (4) | OC3—Mo3—Ndii | 89.3 (2) |
OT11—Mo1—OC3 | 94.6 (4) | Mo1—Mo3—Ndii | 116.41 (4) |
OT12—Mo1—OC3 | 156.2 (4) | Pt—Mo3—Ndii | 105.35 (3) |
OB5i—Mo1—OC3 | 85.5 (4) | Mo2—Mo3—Ndii | 75.29 (3) |
OB6—Mo1—OC3 | 73.8 (3) | Pt—OC1—Mo2 | 99.9 (3) |
OT11—Mo1—OC1i | 164.4 (4) | Pt—OC1—Mo1i | 98.4 (3) |
OT12—Mo1—OC1i | 89.9 (4) | Mo2—OC1—Mo1i | 91.7 (3) |
OB5i—Mo1—OC1i | 71.4 (3) | Pt—OC2—Mo3 | 104.0 (4) |
OB6—Mo1—OC1i | 82.0 (3) | Pt—OC2—Mo2 | 104.3 (4) |
OC3—Mo1—OC1i | 71.4 (3) | Mo3—OC2—Mo2 | 99.4 (3) |
OT11—Mo1—Mo3 | 92.0 (3) | Pt—OC3—Mo1 | 107.4 (4) |
OT12—Mo1—Mo3 | 122.2 (3) | Pt—OC3—Mo3 | 100.6 (4) |
OB5i—Mo1—Mo3 | 127.8 (3) | Mo1—OC3—Mo3 | 96.4 (3) |
OB6—Mo1—Mo3 | 32.6 (2) | Mo2—OB4—Mo3 | 111.6 (4) |
OC3—Mo1—Mo3 | 42.8 (2) | Mo2—OB4—Ndii | 144.1 (4) |
OC1i—Mo1—Mo3 | 82.6 (2) | Mo3—OB4—Ndii | 104.2 (3) |
OT11—Mo1—Pt | 128.8 (3) | Mo1i—OB5—Mo2 | 122.0 (4) |
OT12—Mo1—Pt | 125.6 (3) | Mo3—OB6—Mo1 | 112.4 (4) |
OB5i—Mo1—Pt | 73.8 (3) | Mo3—OT7—Nd | 159.3 (5) |
OB6—Mo1—Pt | 77.2 (2) | Mo3—OT8—Ndii | 109.8 (4) |
OC3—Mo1—Pt | 35.0 (2) | Mo1—OT12—Ndiii | 157.4 (5) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | Nd2[H2PtMo6O24]·14H2O |
Mr | 1697.45 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 21.079 (2), 10.324 (4), 15.8637 (18) |
β (°) | 109.780 (9) |
V (Å3) | 3248.5 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.78 |
Crystal size (mm) | 0.12 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Stoe Stadi-4 diffractometer |
Absorption correction | Numerical (Stoe, 1996) |
Tmin, Tmax | 0.185, 0.340 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3719, 3719, 2851 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.120, 1.13 |
No. of reflections | 3719 |
No. of parameters | 214 |
H-atom treatment | H-atom parameters not refined |
Calculated w = 1/[σ2(Fo2) + (0.0476P)2 + 51.4635P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.68, −2.09 |
Computer programs: STADI4 (Stoe & Cie, 1996), STADI4, X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
Pt—OC3 | 2.002 (8) | Mo1—OB6 | 2.014 (9) |
Pt—OC1 | 2.006 (8) | Mo1—OC3 | 2.131 (8) |
Pt—OC2 | 2.015 (8) | Mo1—OC1iii | 2.384 (8) |
Pt—Mo3 | 3.2511 (11) | Mo1—Mo3 | 3.2437 (16) |
Pt—Mo1 | 3.3318 (15) | Mo1—Mo2iii | 3.3927 (14) |
Pt—Mo2 | 3.3379 (12) | Mo2—OT9 | 1.703 (9) |
Nd—OB4i | 2.451 (8) | Mo2—OT10 | 1.715 (9) |
Nd—OW4 | 2.470 (10) | Mo2—OB4 | 1.947 (8) |
Nd—OW2 | 2.478 (10) | Mo2—OB5 | 1.975 (9) |
Nd—OT7 | 2.494 (9) | Mo2—OC2 | 2.209 (8) |
Nd—OW1 | 2.501 (10) | Mo2—OC1 | 2.345 (9) |
Nd—OW5 | 2.518 (10) | Mo2—Mo3 | 3.2945 (18) |
Nd—OW3 | 2.521 (9) | Mo3—OT7 | 1.723 (9) |
Nd—OT12ii | 2.530 (9) | Mo3—OT8 | 1.736 (9) |
Nd—OT8i | 2.567 (9) | Mo3—OB6 | 1.890 (8) |
Nd—Mo3i | 3.5521 (12) | Mo3—OB4 | 2.037 (8) |
Mo1—OT11 | 1.689 (9) | Mo3—OC2 | 2.109 (8) |
Mo1—OT12 | 1.747 (8) | Mo3—OC3 | 2.218 (9) |
Mo1—OB5iii | 1.904 (9) | ||
OC3—Pt—OC1 | 97.5 (3) | Mo3—Pt—Mo2 | 59.98 (3) |
OC3—Pt—OC2 | 81.1 (3) | Mo1—Pt—Mo2 | 118.85 (3) |
OC1—Pt—OC2 | 83.6 (3) | Mo1—Pt—Mo2iii | 61.15 (3) |
Mo3—Pt—Mo1 | 59.03 (3) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1/2, −y+3/2, −z. |
Crystallograpic studies of the hexamolybdoplatinate(IV) polyanions [H6α-PtMo6O24]2− (Lee, 1994), [H4.5α-PtMo6O24]3.5−, [H4β-PtMo6O24]4− and [H3.5α-PtMo6O24]4.5− (Lee & Sasaki, 1994; Joo et al., 1994) have been reported previously. The behaviour of gradual protonation of the polyanion and geometric isomerism in Anderson-type heteropolyanions was only found in this polyanion system. The [H6α-PtMo6O24]2−, [H4.5α-PtMo6O24]3.5−, [H4β-PtMo6O24]4− and [H3.5α-PtMo6O24]4.5− polyanion species were isolated at pH 0.7, 2.5, 5.4 and 6.4, respectively. It seems that the [H2α-PtMo6O24]6− species were isolated above pH 8.0, from the process of protonation in this polyanion system. However, it was isolated at pH 3.2 by using Nd3+ as the counter-ion.
The present polyanion, [H2α-PtMo6O24]6−, has the Pt atom on an inversion centre and has close to 3 m symmetry. The O atoms in the anion can be divided into three groups, Ot, Ob and Oc, where Ot represents a terminal O atom bound to one Mo atom, Ob represents a bridging O atom bound to two Mo atoms and Oc represents a central O atom coordinated to both the Pt and the two Mo atoms. The position of the H atoms, as expected, could not be observed even in the electron-density difference maps. The attached positions of the H atoms were determined from the unusually long Mo—O distances. It was concluded that the H atoms of the polyanion are bound to the Oc1 atoms from the Mo1—Oc1 (2.384 Å) and Mo2—Oc1 (2.345 Å) distances, which are longer than the Mo1—Oc3 (2.131 Å), Mo2—Oc2 (2.209 Å), Mo3—Oc2 (2.109 Å) and Mo3—Oc3 (2.218 Å) distances. The average bond-distance elongation of Mo—Oc by protonation is about 0.197 Å. This value agrees well with those of the same family of polyanions. The H atom of Oc1 does not contribute to the interanion hydrogen bond. The Mo—Ot bond distances of the Ot atoms coordinated to Nd3+ show elongation.
The Nd3+ cation achieves tricapped trigonal prismatic coordination, with Ob4, Ot7 and Ot8 forming one base triangle, OW1, OW3 and Ot12 forming the other, and OW2, OW4 and OW5 capping the side faces. The bond distances between Nd and OW(1—5) atoms are in the range of 2.451–2.521 Å. The average Nd—O distance is 2.50 Å, which agrees with the typical lanthanide–O bond distance. Of the seven independent water molecules in the crystal structure, five are bonded to the Nd3+ ion. The remaining two water molecules in the unit cell only fill the empty space like zeolitic water. The [H2α-PtMo6O24]6− polyanion forms infinite three-dimensional networks with surrounding polyanions via six Nd3+ ions.