Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012154/qd0030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012154/qd0030Isup2.hkl |
The title compound was prepared by mixing hot aqueous solutions of K6[H4Co2Mo10O38]·5H2O(0.5 mM per 20 ml) and Y(NO3)3·6H2O(0.5 mM per 20 ml), adjusting the pH to about 2.0 with 3.0 M HNO3. The solution was concentrated to about 20 ml by heating it in a water bath. After a day, monoclinic pale-blue crystals and an unstable colorless by-product were obtained.
Rather low completness of 93.05% for θmax = 27.45° is due to the omission of the off-center reflections. The highest peaks in the difference map are 1.29 Å from Ow15 and 0.91 Å from K2, and the largest hole is 0.79 Å from K2. H atoms were not included in the structure model.
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).
K3[H6CoMo6O24]·KNO3·4H2O | F(000) = 2496 |
Mr = 1315.09 | Dx = 2.959 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 24.191 (3) Å | Cell parameters from 26 reflections |
b = 10.9675 (16) Å | θ = 9.6–10.5° |
c = 11.6115 (15) Å | µ = 3.69 mm−1 |
β = 106.644 (9)° | T = 298 K |
V = 2951.6 (7) Å3 | Monoclinic, pale blue |
Z = 4 | 0.20 × 0.15 × 0.07 mm |
Stoe Stadi-4 diffractometer | 2574 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 1.8° |
ω–2θ scans | h = −31→30 |
Absorption correction: numerical (Stoe & Cie, 1996) | k = 0→14 |
Tmin = 0.463, Tmax = 0.650 | l = 0→15 |
3148 measured reflections | 3 standard reflections every 60 min |
3148 independent reflections | intensity decay: 2.8% |
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)] = 0.042 | H-atom parameters not refined |
wR(F2) = 0.119 | Calculated w = 1/[σ2(Fo2) + (0.053P)2 + 53.7384P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3148 reflections | Δρmax = 1.88 e Å−3 |
206 parameters | Δρmin = −1.60 e Å−3 |
0 restraints |
K3[H6CoMo6O24]·KNO3·4H2O | V = 2951.6 (7) Å3 |
Mr = 1315.09 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.191 (3) Å | µ = 3.69 mm−1 |
b = 10.9675 (16) Å | T = 298 K |
c = 11.6115 (15) Å | 0.20 × 0.15 × 0.07 mm |
β = 106.644 (9)° |
Stoe Stadi-4 diffractometer | 2574 reflections with I > 2σ(I) |
Absorption correction: numerical (Stoe & Cie, 1996) | Rint = 0.000 |
Tmin = 0.463, Tmax = 0.650 | 3 standard reflections every 60 min |
3148 measured reflections | intensity decay: 2.8% |
3148 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters not refined |
S = 1.09 | Δρmax = 1.88 e Å−3 |
3148 reflections | Δρmin = −1.60 e Å−3 |
206 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 | Occ. (<1) | |
Co | 0.2500 | 0.2500 | 0.5000 | 0.0119 (2) | |
Mo1 | 0.32555 (2) | 0.01247 (5) | 0.63528 (5) | 0.01787 (15) | |
Mo2 | 0.18205 (2) | 0.00614 (5) | 0.55866 (5) | 0.01793 (15) | |
Mo3 | 0.39278 (2) | 0.25481 (6) | 0.57370 (5) | 0.01880 (15) | |
K1 | 0.40533 (10) | −0.2782 (2) | 0.75229 (17) | 0.0452 (5) | |
K2 | 0.44023 (9) | 0.1058 (3) | 0.93029 (17) | 0.0581 (7) | |
OC1 | 0.30999 (18) | 0.1476 (4) | 0.4786 (4) | 0.0151 (9) | |
OC2 | 0.25304 (18) | 0.1449 (4) | 0.6339 (4) | 0.0160 (9) | |
OC3 | 0.18868 (18) | 0.1454 (4) | 0.4153 (4) | 0.0161 (9) | |
OB4 | 0.37415 (19) | 0.1513 (5) | 0.6916 (4) | 0.0201 (10) | |
OB5 | 0.2534 (2) | −0.0570 (4) | 0.5358 (4) | 0.0203 (9) | |
OB6 | 0.36687 (19) | 0.3603 (5) | 0.4337 (4) | 0.0201 (10) | |
OT7 | 0.3702 (2) | −0.0784 (5) | 0.5813 (5) | 0.0278 (11) | |
OT8 | 0.3266 (2) | −0.0486 (5) | 0.7725 (4) | 0.0296 (12) | |
OT9 | 0.1861 (3) | −0.0576 (6) | 0.6960 (5) | 0.0347 (13) | |
OT10 | 0.1362 (2) | −0.0844 (5) | 0.4535 (5) | 0.0338 (13) | |
OT11 | 0.4396 (2) | 0.3517 (6) | 0.6691 (5) | 0.0335 (13) | |
OT12 | 0.4333 (2) | 0.1584 (6) | 0.5137 (5) | 0.0317 (12) | |
OW13 | 0.2329 (3) | 0.2088 (5) | 0.8370 (5) | 0.0430 (16) | |
OW14 | 0.4997 (7) | −0.4083 (14) | 0.833 (2) | 0.093 (7) | 0.50 |
OW15 | 0.4542 (7) | 0.3450 (16) | 0.9294 (14) | 0.061 (4) | 0.50 |
ON16 | 0.5130 (3) | 0.0945 (8) | 1.1686 (6) | 0.063 (2) | |
ON17 | 0.5000 | −0.0728 (10) | 1.2500 | 0.048 (2) | |
N | 0.5000 | 0.0402 (11) | 1.2500 | 0.036 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0128 (5) | 0.0144 (5) | 0.0093 (5) | 0.0000 (4) | 0.0043 (4) | −0.0004 (4) |
Mo1 | 0.0190 (3) | 0.0195 (3) | 0.0155 (3) | 0.0034 (2) | 0.0054 (2) | 0.0041 (2) |
Mo2 | 0.0204 (3) | 0.0179 (3) | 0.0171 (3) | −0.0030 (2) | 0.0080 (2) | 0.0015 (2) |
Mo3 | 0.0138 (3) | 0.0247 (3) | 0.0180 (3) | −0.0001 (2) | 0.00475 (19) | 0.0010 (2) |
K1 | 0.0624 (13) | 0.0454 (12) | 0.0324 (9) | −0.0124 (10) | 0.0208 (9) | −0.0017 (8) |
K2 | 0.0414 (11) | 0.106 (2) | 0.0264 (9) | 0.0040 (12) | 0.0092 (8) | −0.0060 (11) |
OC1 | 0.017 (2) | 0.016 (2) | 0.0144 (19) | 0.0035 (17) | 0.0081 (16) | −0.0001 (16) |
OC2 | 0.016 (2) | 0.019 (3) | 0.0130 (19) | 0.0013 (17) | 0.0050 (16) | 0.0006 (16) |
OC3 | 0.015 (2) | 0.021 (3) | 0.0120 (19) | −0.0020 (17) | 0.0031 (16) | −0.0025 (16) |
OB4 | 0.018 (2) | 0.026 (3) | 0.015 (2) | 0.0011 (19) | 0.0016 (17) | 0.0006 (18) |
OB5 | 0.026 (2) | 0.016 (2) | 0.019 (2) | 0.001 (2) | 0.0066 (18) | −0.0017 (18) |
OB6 | 0.020 (2) | 0.027 (3) | 0.018 (2) | 0.0028 (19) | 0.0123 (17) | 0.0039 (18) |
OT7 | 0.028 (3) | 0.022 (3) | 0.035 (3) | 0.006 (2) | 0.011 (2) | 0.004 (2) |
OT8 | 0.033 (3) | 0.033 (3) | 0.023 (2) | 0.002 (2) | 0.008 (2) | 0.013 (2) |
OT9 | 0.043 (3) | 0.039 (3) | 0.029 (3) | 0.005 (3) | 0.020 (2) | 0.014 (2) |
OT10 | 0.031 (3) | 0.034 (3) | 0.038 (3) | −0.010 (2) | 0.012 (2) | −0.010 (2) |
OT11 | 0.022 (3) | 0.045 (4) | 0.028 (3) | −0.011 (2) | −0.001 (2) | 0.002 (2) |
OT12 | 0.028 (3) | 0.040 (3) | 0.031 (3) | 0.008 (2) | 0.015 (2) | 0.004 (2) |
OW13 | 0.084 (5) | 0.024 (3) | 0.027 (3) | −0.006 (3) | 0.026 (3) | −0.003 (2) |
OW14 | 0.047 (9) | 0.036 (9) | 0.20 (2) | 0.018 (7) | 0.043 (12) | −0.002 (11) |
OW15 | 0.061 (9) | 0.059 (10) | 0.080 (10) | 0.017 (8) | 0.049 (8) | 0.002 (8) |
ON16 | 0.067 (5) | 0.088 (6) | 0.031 (3) | −0.034 (5) | 0.011 (3) | 0.010 (4) |
ON17 | 0.037 (5) | 0.053 (6) | 0.054 (5) | 0.000 | 0.011 (4) | 0.000 |
N | 0.027 (5) | 0.053 (7) | 0.025 (4) | 0.000 | 0.005 (4) | 0.000 |
Co—OC1 | 1.907 (4) | K1—OT7 | 2.915 (6) |
Co—OC1i | 1.907 (4) | K1—OW14vi | 3.100 (19) |
Co—OC3 | 1.910 (4) | K1—OT12iii | 3.197 (6) |
Co—OC3i | 1.910 (4) | K1—OT8 | 3.205 (6) |
Co—OC2 | 1.919 (4) | K1—OW13vii | 3.207 (8) |
Co—OC2i | 1.919 (4) | K1—Mo3iii | 3.8387 (19) |
Co—Mo1 | 3.3091 (7) | K1—K2ii | 4.480 (3) |
Co—Mo2 | 3.3106 (7) | K2—OW15 | 2.645 (18) |
Co—Mo3 | 3.3123 (7) | K2—OT7iii | 2.781 (6) |
Mo1—OT7 | 1.715 (5) | K2—OB4 | 2.819 (5) |
Mo1—OT8 | 1.721 (5) | K2—ON16 | 2.826 (7) |
Mo1—OB4 | 1.921 (5) | K2—ON16v | 2.859 (10) |
Mo1—OB5 | 1.951 (5) | K2—ON17v | 2.888 (2) |
Mo1—OC2 | 2.274 (4) | K2—OT12vi | 2.996 (6) |
Mo1—OC1 | 2.293 (4) | K2—OT12iii | 3.075 (7) |
Mo1—Mo3 | 3.2994 (9) | K2—Nv | 3.282 (6) |
Mo1—Mo2 | 3.3282 (9) | K2—OT8 | 3.301 (6) |
Mo1—K1 | 3.772 (2) | K2—K2v | 3.700 (5) |
Mo1—K2 | 3.877 (2) | OC3—Mo3i | 2.290 (4) |
Mo2—OT10 | 1.712 (5) | OB6—Mo2i | 1.902 (5) |
Mo2—OT9 | 1.718 (5) | OB6—K1ii | 2.690 (5) |
Mo2—OB6i | 1.902 (5) | OT7—K2ii | 2.781 (6) |
Mo2—OB5 | 1.947 (5) | OT10—K1iv | 2.760 (6) |
Mo2—OC2 | 2.274 (4) | OT12—K2vi | 2.996 (6) |
Mo2—OC3 | 2.298 (4) | OT12—K2ii | 3.075 (7) |
Mo2—Mo3i | 3.3045 (9) | OT12—K1ii | 3.197 (6) |
Mo2—Mo3 | 5.7396 (10) | OW13—K1viii | 3.207 (8) |
Mo3—OT11 | 1.709 (5) | OW14—K1vi | 3.100 (19) |
Mo3—OT12 | 1.719 (5) | ON16—N | 1.232 (9) |
Mo3—OB4 | 1.929 (5) | ON16—K1v | 2.786 (8) |
Mo3—OB6 | 1.947 (4) | ON16—K2v | 2.859 (10) |
Mo3—OC3i | 2.290 (4) | N—ON17 | 1.239 (15) |
Mo3—OC1 | 2.312 (4) | ON17—K2iii | 2.888 (2) |
Mo3—K1ii | 3.8387 (19) | ON17—K2v | 2.888 (2) |
K1—OW14 | 2.627 (16) | N—ON16ix | 1.232 (9) |
K1—OB6iii | 2.690 (5) | N—K2iii | 3.282 (6) |
K1—OT10iv | 2.760 (6) | N—K2v | 3.282 (6) |
K1—ON16v | 2.786 (8) | ||
OC1—Co—OC1i | 180.0 | OW14—K1—OB6iii | 89.9 (5) |
OC1—Co—OC3 | 94.97 (19) | OW14—K1—OT10iv | 94.4 (5) |
OC1i—Co—OC3 | 85.03 (19) | OB6iii—K1—OT10iv | 111.92 (17) |
OC1—Co—OC3i | 85.03 (19) | OW14—K1—ON16v | 79.3 (4) |
OC1i—Co—OC3i | 94.97 (19) | OB6iii—K1—ON16v | 110.83 (18) |
OC3—Co—OC3i | 180.0 | OT10iv—K1—ON16v | 136.7 (2) |
OC1—Co—OC2 | 84.14 (18) | OW14—K1—OT7 | 134.9 (5) |
OC1i—Co—OC2 | 95.86 (18) | OB6iii—K1—OT7 | 133.34 (17) |
OC3—Co—OC2 | 84.28 (18) | OT10iv—K1—OT7 | 81.83 (17) |
OC3i—Co—OC2 | 95.72 (18) | ON16v—K1—OT7 | 73.8 (2) |
OC1—Co—OC2i | 95.86 (18) | OW14—K1—OW14vi | 38.4 (9) |
OC1i—Co—OC2i | 84.14 (18) | OB6iii—K1—OW14vi | 123.4 (4) |
OC3—Co—OC2i | 95.72 (18) | OT10iv—K1—OW14vi | 65.9 (4) |
OC3i—Co—OC2i | 84.28 (18) | ON16v—K1—OW14vi | 85.3 (3) |
OC2—Co—OC2i | 180.0 | OT7—K1—OW14vi | 103.1 (4) |
OC1—Co—Mo1 | 42.33 (12) | OW14—K1—OT12iii | 87.6 (5) |
OC1i—Co—Mo1 | 137.67 (12) | OB6iii—K1—OT12iii | 54.60 (14) |
OC3—Co—Mo1 | 90.76 (13) | OT10iv—K1—OT12iii | 166.43 (17) |
OC3i—Co—Mo1 | 89.24 (13) | ON16v—K1—OT12iii | 56.83 (18) |
OC2—Co—Mo1 | 41.84 (13) | OT7—K1—OT12iii | 106.19 (17) |
OC2i—Co—Mo1 | 138.16 (13) | OW14vi—K1—OT12iii | 121.2 (4) |
OC1—Co—Mo2 | 89.56 (13) | OW14—K1—OT8 | 150.9 (5) |
OC1i—Co—Mo2 | 90.44 (13) | OB6iii—K1—OT8 | 81.94 (15) |
OC3—Co—Mo2 | 42.48 (13) | OT10iv—K1—OT8 | 114.55 (17) |
OC3i—Co—Mo2 | 137.52 (13) | ON16v—K1—OT8 | 77.8 (2) |
OC2—Co—Mo2 | 41.80 (13) | OT7—K1—OT8 | 52.86 (14) |
OC2i—Co—Mo2 | 138.20 (13) | OW14vi—K1—OT8 | 153.6 (3) |
Mo1—Co—Mo2 | 60.368 (16) | OT12iii—K1—OT8 | 64.94 (15) |
OC1—Co—Mo3 | 42.85 (13) | OW14—K1—OW13vii | 144.1 (4) |
OC1i—Co—Mo3 | 137.15 (13) | OB6iii—K1—OW13vii | 71.10 (14) |
OC3—Co—Mo3 | 137.82 (13) | OT10iv—K1—OW13vii | 66.92 (16) |
OC3i—Co—Mo3 | 42.18 (13) | ON16v—K1—OW13vii | 135.6 (2) |
OC2—Co—Mo3 | 90.29 (13) | OT7—K1—OW13vii | 74.93 (15) |
OC2i—Co—Mo3 | 89.71 (13) | OW14vi—K1—OW13vii | 132.5 (4) |
Mo1—Co—Mo3 | 59.775 (15) | OT12iii—K1—OW13vii | 104.06 (15) |
Mo2—Co—Mo3 | 120.140 (15) | OT8—K1—OW13vii | 58.18 (15) |
OT7—Mo1—OT8 | 105.5 (3) | OW14—K1—Mo1 | 152.9 (4) |
OT7—Mo1—OB4 | 101.3 (2) | OB6iii—K1—Mo1 | 107.99 (12) |
OT8—Mo1—OB4 | 98.5 (2) | OT10iv—K1—Mo1 | 97.33 (14) |
OT7—Mo1—OB5 | 96.2 (2) | ON16v—K1—Mo1 | 75.47 (19) |
OT8—Mo1—OB5 | 99.8 (2) | OT7—K1—Mo1 | 25.89 (10) |
OB4—Mo1—OB5 | 150.2 (2) | OW14vi—K1—Mo1 | 128.6 (4) |
OT7—Mo1—OC2 | 159.1 (2) | OT12iii—K1—Mo1 | 86.68 (12) |
OT8—Mo1—OC2 | 93.6 (2) | OT8—K1—Mo1 | 27.03 (9) |
OB4—Mo1—OC2 | 83.77 (18) | OW13vii—K1—Mo1 | 62.80 (11) |
OB5—Mo1—OC2 | 71.81 (18) | OW14—K1—Mo3iii | 89.5 (5) |
OT7—Mo1—OC1 | 93.6 (2) | OB6iii—K1—Mo3iii | 28.31 (10) |
OT8—Mo1—OC1 | 160.3 (2) | OT10iv—K1—Mo3iii | 140.14 (14) |
OB4—Mo1—OC1 | 72.74 (17) | ON16v—K1—Mo3iii | 82.96 (14) |
OB5—Mo1—OC1 | 82.35 (18) | OT7—K1—Mo3iii | 121.56 (12) |
OC2—Mo1—OC1 | 68.30 (15) | OW14vi—K1—Mo3iii | 127.9 (4) |
OT7—Mo1—Mo3 | 89.27 (18) | OT12iii—K1—Mo3iii | 26.32 (10) |
OT8—Mo1—Mo3 | 129.5 (2) | OT8—K1—Mo3iii | 70.28 (9) |
OB4—Mo1—Mo3 | 31.08 (13) | OW13vii—K1—Mo3iii | 87.25 (11) |
OB5—Mo1—Mo3 | 126.81 (14) | Mo1—K1—Mo3iii | 96.84 (5) |
OC2—Mo1—Mo3 | 84.88 (11) | OW14—K1—K2ii | 100.1 (5) |
OC1—Mo1—Mo3 | 44.47 (11) | OB6iii—K1—K2ii | 170.00 (13) |
OT7—Mo1—Co | 127.15 (17) | OT10iv—K1—K2ii | 67.46 (13) |
OT8—Mo1—Co | 127.28 (19) | ON16v—K1—K2ii | 71.62 (14) |
OB4—Mo1—Co | 74.84 (14) | OT7—K1—K2ii | 37.09 (11) |
OB5—Mo1—Co | 75.38 (14) | OW14vi—K1—K2ii | 66.0 (4) |
OC2—Mo1—Co | 34.27 (11) | OT12iii—K1—K2ii | 125.43 (12) |
OC1—Mo1—Co | 34.06 (10) | OT8—K1—K2ii | 89.28 (11) |
Mo3—Mo1—Co | 60.161 (16) | OW13vii—K1—K2ii | 100.20 (11) |
OT7—Mo1—Mo2 | 127.47 (18) | Mo1—K1—K2ii | 62.75 (5) |
OT8—Mo1—Mo2 | 88.71 (18) | Mo3iii—K1—K2ii | 150.40 (7) |
OB4—Mo1—Mo2 | 126.69 (14) | OW15—K2—OT7iii | 102.2 (3) |
OB5—Mo1—Mo2 | 31.34 (14) | OW15—K2—OB4 | 81.8 (4) |
OC2—Mo1—Mo2 | 42.96 (11) | OT7iii—K2—OB4 | 111.27 (16) |
OC1—Mo1—Mo2 | 83.09 (11) | OW15—K2—ON16 | 90.2 (4) |
Mo3—Mo1—Mo2 | 120.00 (2) | OT7iii—K2—ON16 | 72.47 (19) |
Co—Mo1—Mo2 | 59.839 (15) | OB4—K2—ON16 | 171.7 (2) |
OT7—Mo1—K1 | 47.93 (17) | OW15—K2—ON16v | 134.0 (3) |
OT8—Mo1—K1 | 57.8 (2) | OT7iii—K2—ON16v | 123.5 (2) |
OB4—Mo1—K1 | 110.31 (14) | OB4—K2—ON16v | 85.37 (18) |
OB5—Mo1—K1 | 99.32 (15) | ON16—K2—ON16v | 98.8 (2) |
OC2—Mo1—K1 | 148.93 (11) | OW15—K2—ON17v | 91.8 (4) |
OC1—Mo1—K1 | 141.52 (11) | OT7iii—K2—ON17v | 164.9 (3) |
Mo3—Mo1—K1 | 121.71 (4) | OB4—K2—ON17v | 64.54 (12) |
Co—Mo1—K1 | 172.88 (3) | ON16—K2—ON17v | 113.81 (18) |
Mo2—Mo1—K1 | 117.74 (4) | ON16v—K2—ON17v | 43.5 (3) |
OT7—Mo1—K2 | 96.32 (18) | OW15—K2—OT12vi | 71.7 (3) |
OT8—Mo1—K2 | 57.85 (19) | OT7iii—K2—OT12vi | 130.72 (16) |
OB4—Mo1—K2 | 43.64 (14) | OB4—K2—OT12vi | 115.82 (16) |
OB5—Mo1—K2 | 156.71 (14) | ON16—K2—OT12vi | 58.99 (18) |
OC2—Mo1—K2 | 101.12 (11) | ON16v—K2—OT12vi | 74.81 (19) |
OC1—Mo1—K2 | 116.34 (12) | ON17v—K2—OT12vi | 59.28 (13) |
Mo3—Mo1—K2 | 72.93 (5) | OW15—K2—OT12iii | 162.6 (4) |
Co—Mo1—K2 | 111.69 (5) | OT7iii—K2—OT12iii | 66.50 (16) |
Mo2—Mo1—K2 | 132.00 (4) | OB4—K2—OT12iii | 114.19 (17) |
K1—Mo1—K2 | 75.06 (6) | ON16—K2—OT12iii | 74.0 (2) |
OT10—Mo2—OT9 | 106.2 (3) | ON16v—K2—OT12iii | 57.71 (18) |
OT10—Mo2—OB6i | 101.3 (2) | ON17v—K2—OT12iii | 101.2 (3) |
OT9—Mo2—OB6i | 98.1 (2) | OT12vi—K2—OT12iii | 104.90 (15) |
OT10—Mo2—OB5 | 96.6 (2) | OW15—K2—Nv | 113.7 (3) |
OT9—Mo2—OB5 | 99.5 (2) | OT7iii—K2—Nv | 143.9 (2) |
OB6i—Mo2—OB5 | 150.3 (2) | OB4—K2—Nv | 71.86 (13) |
OT10—Mo2—OC2 | 157.8 (2) | ON16—K2—Nv | 109.8 (2) |
OT9—Mo2—OC2 | 94.6 (2) | ON16v—K2—Nv | 21.8 (2) |
OB6i—Mo2—OC2 | 82.98 (18) | ON17v—K2—Nv | 22.0 (3) |
OB5—Mo2—OC2 | 71.89 (18) | OT12vi—K2—Nv | 67.86 (14) |
OT10—Mo2—OC3 | 92.0 (2) | OT12iii—K2—Nv | 79.3 (2) |
OT9—Mo2—OC3 | 161.0 (2) | OW15—K2—OT8 | 126.4 (4) |
OB6i—Mo2—OC3 | 72.26 (17) | OT7iii—K2—OT8 | 74.58 (15) |
OB5—Mo2—OC3 | 83.63 (17) | OB4—K2—OT8 | 52.95 (14) |
OC2—Mo2—OC3 | 68.38 (15) | ON16—K2—OT8 | 135.0 (2) |
OT10—Mo2—Mo3i | 88.4 (2) | ON16v—K2—OT8 | 75.21 (19) |
OT9—Mo2—Mo3i | 129.2 (2) | ON17v—K2—OT8 | 92.47 (16) |
OB6i—Mo2—Mo3i | 31.23 (13) | OT12vi—K2—OT8 | 148.78 (17) |
OB5—Mo2—Mo3i | 127.42 (14) | OT12iii—K2—OT8 | 65.13 (15) |
OC2—Mo2—Mo3i | 84.28 (11) | Nv—K2—OT8 | 81.04 (15) |
OC3—Mo2—Mo3i | 43.82 (11) | OW15—K2—K2v | 122.6 (4) |
OT10—Mo2—Co | 125.5 (2) | OT7iii—K2—K2v | 101.35 (15) |
OT9—Mo2—Co | 128.3 (2) | OB4—K2—K2v | 133.88 (15) |
OB6i—Mo2—Co | 74.89 (14) | ON16—K2—K2v | 49.8 (2) |
OB5—Mo2—Co | 75.38 (14) | ON16v—K2—K2v | 49.00 (15) |
OC2—Mo2—Co | 34.23 (10) | ON17v—K2—K2v | 75.38 (15) |
OC3—Mo2—Co | 34.15 (10) | OT12vi—K2—K2v | 53.42 (13) |
Mo3i—Mo2—Co | 60.095 (16) | OT12iii—K2—K2v | 51.48 (12) |
OT10—Mo2—Mo1 | 127.98 (19) | Nv—K2—K2v | 62.68 (12) |
OT9—Mo2—Mo1 | 89.0 (2) | OT8—K2—K2v | 110.05 (16) |
OB6i—Mo2—Mo1 | 125.93 (15) | OW15—K2—Mo1 | 108.6 (4) |
OB5—Mo2—Mo1 | 31.41 (13) | OT7iii—K2—Mo1 | 96.76 (12) |
OC2—Mo2—Mo1 | 42.96 (11) | OB4—K2—Mo1 | 28.05 (10) |
OC3—Mo2—Mo1 | 84.03 (11) | ON16—K2—Mo1 | 160.2 (2) |
Mo3i—Mo2—Mo1 | 119.88 (2) | ON16v—K2—Mo1 | 72.98 (15) |
Co—Mo2—Mo1 | 59.793 (14) | ON17v—K2—Mo1 | 72.93 (7) |
OT10—Mo2—Mo3 | 133.27 (19) | OT12vi—K2—Mo1 | 132.09 (11) |
OT9—Mo2—Mo3 | 110.5 (2) | OT12iii—K2—Mo1 | 86.54 (12) |
OB6i—Mo2—Mo3 | 101.04 (14) | Nv—K2—Mo1 | 69.03 (5) |
OB5—Mo2—Mo3 | 50.14 (14) | OT8—K2—Mo1 | 26.20 (9) |
OC2—Mo2—Mo3 | 26.32 (11) | K2v—K2—Mo1 | 119.51 (12) |
OC3—Mo2—Mo3 | 57.37 (10) | Co—OC1—Mo1 | 103.61 (17) |
Mo3i—Mo2—Mo3 | 90.033 (18) | Co—OC1—Mo3 | 103.03 (19) |
Co—Mo2—Mo3 | 29.938 (8) | Mo1—OC1—Mo3 | 91.53 (15) |
Mo1—Mo2—Mo3 | 29.858 (13) | Co—OC2—Mo2 | 103.97 (18) |
OT11—Mo3—OT12 | 107.3 (3) | Co—OC2—Mo1 | 103.89 (18) |
OT11—Mo3—OB4 | 98.7 (2) | Mo2—OC2—Mo1 | 94.08 (17) |
OT12—Mo3—OB4 | 101.6 (2) | Co—OC3—Mo3i | 103.76 (19) |
OT11—Mo3—OB6 | 99.6 (2) | Co—OC3—Mo2 | 103.37 (17) |
OT12—Mo3—OB6 | 96.4 (2) | Mo3i—OC3—Mo2 | 92.15 (15) |
OB4—Mo3—OB6 | 149.06 (19) | Mo1—OB4—Mo3 | 118.0 (2) |
OT11—Mo3—OC3i | 95.0 (2) | Mo1—OB4—K2 | 108.3 (2) |
OT12—Mo3—OC3i | 156.4 (2) | Mo3—OB4—K2 | 128.3 (2) |
OB4—Mo3—OC3i | 82.07 (18) | Mo2—OB5—Mo1 | 117.3 (2) |
OB6—Mo3—OC3i | 71.71 (17) | Mo2i—OB6—Mo3 | 118.3 (2) |
OT11—Mo3—OC1 | 161.5 (2) | Mo2i—OB6—K1ii | 130.8 (2) |
OT12—Mo3—OC1 | 90.6 (2) | Mo3—OB6—K1ii | 110.7 (2) |
OB4—Mo3—OC1 | 72.15 (17) | Mo1—OT7—K2ii | 148.7 (3) |
OB6—Mo3—OC1 | 82.85 (18) | Mo1—OT7—K1 | 106.2 (2) |
OC3i—Mo3—OC1 | 68.18 (15) | K2ii—OT7—K1 | 103.70 (18) |
OT11—Mo3—Mo1 | 129.53 (19) | Mo1—OT8—K1 | 95.2 (2) |
OT12—Mo3—Mo1 | 88.0 (2) | Mo1—OT8—K2 | 95.9 (2) |
OB4—Mo3—Mo1 | 30.93 (13) | K1—OT8—K2 | 91.50 (15) |
OB6—Mo3—Mo1 | 126.78 (14) | Mo2—OT10—K1iv | 159.3 (3) |
OC3i—Mo3—Mo1 | 83.55 (11) | Mo3—OT12—K2vi | 134.1 (3) |
OC1—Mo3—Mo1 | 44.00 (10) | Mo3—OT12—K2ii | 142.8 (3) |
OT11—Mo3—Co | 128.7 (2) | K2vi—OT12—K2ii | 75.10 (15) |
OT12—Mo3—Co | 123.97 (19) | Mo3—OT12—K1ii | 98.1 (2) |
OB4—Mo3—Co | 74.68 (13) | K2vi—OT12—K1ii | 102.14 (16) |
OB6—Mo3—Co | 74.41 (13) | K2ii—OT12—K1ii | 95.97 (16) |
OC3i—Mo3—Co | 34.07 (11) | K1—OW14—K1vi | 106.4 (6) |
OC1—Mo3—Co | 34.11 (10) | N—ON16—K1v | 114.2 (5) |
Mo1—Mo3—Co | 60.064 (14) | N—ON16—K2 | 123.2 (5) |
OT11—Mo3—K1ii | 111.53 (19) | K1v—ON16—K2 | 118.4 (3) |
OT12—Mo3—K1ii | 55.54 (18) | N—ON16—K2v | 98.8 (7) |
OB4—Mo3—K1ii | 146.01 (15) | K1v—ON16—K2v | 111.3 (3) |
OB6—Mo3—K1ii | 40.95 (14) | K2—ON16—K2v | 81.2 (2) |
OC3i—Mo3—K1ii | 109.35 (11) | N—ON17—K2iii | 97.2 (2) |
OC1—Mo3—K1ii | 82.43 (11) | N—ON17—K2v | 97.2 (2) |
Mo1—Mo3—K1ii | 116.46 (4) | K2iii—ON17—K2v | 165.6 (5) |
Co—Mo3—K1ii | 96.71 (4) | ON16ix—N—ON16 | 122.1 (13) |
OT11—Mo3—Mo2 | 137.11 (19) | ON16ix—N—ON17 | 119.0 (7) |
OT12—Mo3—Mo2 | 107.4 (2) | ON16—N—ON17 | 119.0 (7) |
OB4—Mo3—Mo2 | 49.91 (13) | ON16ix—N—K2iii | 59.4 (5) |
OB6—Mo3—Mo2 | 100.73 (14) | ON16—N—K2iii | 168.9 (3) |
OC3i—Mo3—Mo2 | 57.17 (11) | ON17—N—K2iii | 60.80 (19) |
OC1—Mo3—Mo2 | 26.32 (10) | ON16ix—N—K2v | 168.9 (3) |
Mo1—Mo3—Mo2 | 30.146 (12) | ON16—N—K2v | 59.4 (5) |
Co—Mo3—Mo2 | 29.922 (9) | ON17—N—K2v | 60.80 (19) |
K1ii—Mo3—Mo2 | 108.60 (4) | K2iii—N—K2v | 121.6 (4) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y, z−1/2; (iii) x, −y, z+1/2; (iv) −x+1/2, −y−1/2, −z+1; (v) −x+1, −y, −z+2; (vi) −x+1, y, −z+3/2; (vii) −x+1/2, y−1/2, −z+3/2; (viii) −x+1/2, y+1/2, −z+3/2; (ix) −x+1, y, −z+5/2. |
Experimental details
Crystal data | |
Chemical formula | K3[H6CoMo6O24]·KNO3·4H2O |
Mr | 1315.09 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 24.191 (3), 10.9675 (16), 11.6115 (15) |
β (°) | 106.644 (9) |
V (Å3) | 2951.6 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.69 |
Crystal size (mm) | 0.20 × 0.15 × 0.07 |
Data collection | |
Diffractometer | Stoe Stadi-4 diffractometer |
Absorption correction | Numerical (Stoe & Cie, 1996) |
Tmin, Tmax | 0.463, 0.650 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3148, 3148, 2574 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.119, 1.09 |
No. of reflections | 3148 |
No. of parameters | 206 |
H-atom treatment | H-atom parameters not refined |
Calculated w = 1/[σ2(Fo2) + (0.053P)2 + 53.7384P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.88, −1.60 |
Computer programs: STADI4 (Stoe & Cie, 1996), STADI4, X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Co—OC1 | 1.907 (4) | Mo3—OB4 | 1.929 (5) |
Co—OC3 | 1.910 (4) | Mo3—OB6 | 1.947 (4) |
Co—OC2 | 1.919 (4) | Mo3—OC3i | 2.290 (4) |
Co—Mo1 | 3.3091 (7) | Mo3—OC1 | 2.312 (4) |
Co—Mo2 | 3.3106 (7) | K1—OW14 | 2.627 (16) |
Co—Mo3 | 3.3123 (7) | K1—OB6ii | 2.690 (5) |
Mo1—OT7 | 1.715 (5) | K1—OT10iii | 2.760 (6) |
Mo1—OT8 | 1.721 (5) | K1—ON16iv | 2.786 (8) |
Mo1—OB4 | 1.921 (5) | K1—OT7 | 2.915 (6) |
Mo1—OB5 | 1.951 (5) | K1—OW14v | 3.100 (19) |
Mo1—OC2 | 2.274 (4) | K1—OT12ii | 3.197 (6) |
Mo1—OC1 | 2.293 (4) | K1—OT8 | 3.205 (6) |
Mo1—Mo3 | 3.2994 (9) | K1—OW13vi | 3.207 (8) |
Mo1—Mo2 | 3.3282 (9) | K2—OW15 | 2.645 (18) |
Mo2—OT10 | 1.712 (5) | K2—OT7ii | 2.781 (6) |
Mo2—OT9 | 1.718 (5) | K2—OB4 | 2.819 (5) |
Mo2—OB6i | 1.902 (5) | K2—ON16 | 2.826 (7) |
Mo2—OB5 | 1.947 (5) | K2—ON16iv | 2.859 (10) |
Mo2—OC2 | 2.274 (4) | K2—ON17iv | 2.888 (2) |
Mo2—OC3 | 2.298 (4) | K2—OT12v | 2.996 (6) |
Mo2—Mo3i | 3.3045 (9) | K2—OT12ii | 3.075 (7) |
Mo3—OT11 | 1.709 (5) | N—ON17 | 1.239 (15) |
Mo3—OT12 | 1.719 (5) | N—ON16vii | 1.232 (9) |
Mo1—Co—Mo2 | 60.368 (16) | Co—Mo1—Mo2 | 59.839 (15) |
Mo1—Co—Mo3 | 59.775 (15) | ON16vii—N—ON16 | 122.1 (13) |
Mo2—Co—Mo3 | 120.140 (15) | ON16vii—N—ON17 | 119.0 (7) |
Mo3—Mo1—Mo2 | 120.00 (2) | ON16—N—ON17 | 119.0 (7) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y, z+1/2; (iii) −x+1/2, −y−1/2, −z+1; (iv) −x+1, −y, −z+2; (v) −x+1, y, −z+3/2; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x+1, y, −z+5/2. |
Obtaining suitable crystals for the structure determination of some kinds of B-type Anderson-structure heteropolyanions, such as [H6Xn+Mo6O24](6-n)- (X: Co2+, Co3+, Ni2+, Fe3+) (Anderson, 1937), is difficult. The salts of these polyanions have a cleavage property like mica because of the repulsion of interanions by six undissociated H atoms bound to O atoms in XO6. The bulky counter-cation acts as a separator between the interanions in the crystal packing. Single crystals of some compounds, such as (18-crown-6.K+)2K[H6CoMo6O24].12H2O (Nagano et al., 1990) and [Ga(H2O)6]3[H6CoMo6O24].10H2O (Panneerselvam et al., 1996), have been were obtained. The role of potassium nitrate in the crystallization of these crystals is important.
The present polyanion is close to having D3 d(−3 m) symmetry. The definition of O atoms in the polyanion is the same as in the previous report (Panneerselvam et al., 1996); On is the a nitrate O atom. The Mo—O distances show a similar tendency to those found in (18-crown-6.K+)2K[H6CoMo6O24].12H2O (Nagano et al., 1990), Na3[H6CoMo6O24]·8H2O (Nolan et al., 1998) and [Ga(H2O)6]3[H6CoMo6O24].10H2O (Panneerselvam et al., 1996). KNO3 not only contributes to the charge balance but also packs the cavity made by the polyanion with K+ and Ow. N and On17 atoms are located on the twofold axis. Reasonable displacement parameters of Ow14 and Ow15 were obtained by reducing the occupancy to 0.5. The K1 and K2 ions are coordinated to O atoms as [K1(Ot)4(Ob)(Ow)(On)]+ and [K2(Ot)3(Ob)(Ow)(On)3]+. The distances between K and O atoms are in the range 2.63 (2)–3.21 (8) Å.