Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016963/tk6075sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016963/tk6075Isup2.hkl |
The compound was prepared as a by-product of the reaction of H2WO4 with aniline in an ammonia (0.1 N) solution and recrystallized from water [N% calculated (H60N10O51W12): 4.35%; found 4.33%].
No H atoms were included in the refinement. One disordered water O atom (O9WA) was refined over two sites with final occupancies 0.52 (3)/0.48 (3) and a common U value of 0.045 (6) Å2. The largest residual electron-density peak was located 0.99 Å from W6 and the deepest hole 1.07 Å from W7.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996) and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 in WinGX (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(NH4)10[H2W12O42]·9H2O | Z = 2 |
Mr = 3222.78 | F(000) = 2852 |
Triclinic, P1 | Dx = 4.211 Mg m−3 |
a = 11.945 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.225 (5) Å | Cell parameters from 8000 reflections |
c = 16.780 (6) Å | θ = 2.3–26.3° |
α = 76.159 (5)° | µ = 26.20 mm−1 |
β = 80.985 (5)° | T = 168 K |
γ = 88.763 (5)° | Plate, colourless |
V = 2541.6 (15) Å3 | 0.44 × 0.14 × 0.06 mm |
Siemens CCD area-detector diffractometer | 10192 independent reflections |
Radiation source: fine-focus sealed tube | 7208 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.5°, θmin = 2.3° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (Blessing, 1995) | k = −16→16 |
Tmin = 0.355, Tmax = 0.592 | l = −20→20 |
32370 measured reflections |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0765P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
10192 reflections | Δρmax = 6.04 e Å−3 |
357 parameters | Δρmin = −5.45 e Å−3 |
0 restraints |
(NH4)10[H2W12O42]·9H2O | γ = 88.763 (5)° |
Mr = 3222.78 | V = 2541.6 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.945 (4) Å | Mo Kα radiation |
b = 13.225 (5) Å | µ = 26.20 mm−1 |
c = 16.780 (6) Å | T = 168 K |
α = 76.159 (5)° | 0.44 × 0.14 × 0.06 mm |
β = 80.985 (5)° |
Siemens CCD area-detector diffractometer | 10192 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 7208 reflections with I > 2σ(I) |
Tmin = 0.355, Tmax = 0.592 | Rint = 0.047 |
32370 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 357 parameters |
wR(F2) = 0.128 | 0 restraints |
S = 0.99 | Δρmax = 6.04 e Å−3 |
10192 reflections | Δρmin = −5.45 e Å−3 |
Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used. |
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. No hydrogen atoms were located and refined. The final fourier difference map peaks and troughs are all within 1.2 Å of W or anion oxygen atoms. 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) | |
W1 | 0.74798 (6) | 0.95682 (6) | 0.37941 (4) | 0.01354 (17) | |
W2 | 0.73015 (6) | 0.54717 (5) | −0.00374 (4) | 0.01202 (16) | |
W3 | 0.79439 (6) | 0.26622 (6) | 0.03953 (4) | 0.01433 (17) | |
W4 | 0.24171 (5) | 0.83230 (6) | 0.50908 (4) | 0.01244 (16) | |
W5 | 0.63869 (6) | 0.33572 (6) | 0.19582 (4) | 0.01309 (17) | |
W6 | 0.77893 (6) | 0.71536 (6) | 0.49179 (4) | 0.01443 (17) | |
W7 | 0.57800 (6) | 0.61552 (6) | 0.15959 (4) | 0.01321 (17) | |
W8 | 0.48069 (6) | 0.27743 (5) | 0.03180 (4) | 0.01227 (16) | |
W9 | 0.72927 (6) | 0.36805 (6) | 0.85211 (4) | 0.01396 (17) | |
W10 | 0.97795 (6) | 0.69413 (6) | 0.61159 (4) | 0.01386 (17) | |
W11 | 0.03978 (6) | 0.86744 (6) | 0.38909 (4) | 0.01235 (16) | |
W12 | 0.79219 (6) | 0.93179 (5) | 0.60835 (4) | 0.01192 (16) | |
O1 | 0.7572 (10) | 0.8874 (9) | 0.5149 (7) | 0.019 (3)* | |
O2 | 0.6321 (10) | 0.6984 (10) | 0.5222 (8) | 0.023 (3)* | |
O3 | 0.8168 (10) | 0.6752 (9) | 0.6027 (7) | 0.018 (3)* | |
O4 | 0.9111 (10) | 0.8465 (9) | 0.6200 (7) | 0.018 (3)* | |
O5 | 0.6818 (10) | 0.6890 (9) | 0.9529 (7) | 0.016 (3)* | |
O6 | 0.8752 (10) | 0.5646 (9) | −0.0285 (7) | 0.017 (3)* | |
O7 | 0.4692 (10) | 0.1441 (9) | 0.0742 (7) | 0.018 (3)* | |
O8 | 0.6864 (10) | 0.8690 (9) | 0.6871 (7) | 0.015 (3)* | |
O9 | 0.9183 (10) | 0.2845 (10) | 0.0789 (8) | 0.023 (3)* | |
O10 | 0.2561 (9) | 0.9151 (9) | 0.5909 (7) | 0.013 (3)* | |
O11 | 0.5484 (10) | 0.2561 (10) | 0.2756 (7) | 0.019 (3)* | |
O12 | 0.5721 (10) | 0.4637 (10) | 0.2057 (8) | 0.021 (3)* | |
O13 | 0.3526 (10) | 0.7403 (9) | 0.5225 (7) | 0.016 (3)* | |
O14 | 0.7209 (9) | 0.4136 (9) | 0.0713 (7) | 0.012 (2)* | |
O15 | 0.7613 (11) | 0.3456 (10) | 0.2401 (8) | 0.024 (3)* | |
O16 | 1.0314 (10) | 0.5834 (10) | 0.5767 (7) | 0.020 (3)* | |
O17 | 0.1193 (9) | 0.7646 (9) | 0.5937 (7) | 0.012 (2)* | |
O18 | 0.6916 (9) | 0.2266 (9) | 0.1419 (7) | 0.014 (3)* | |
O19 | 0.8407 (10) | 0.3489 (9) | −0.0705 (7) | 0.016 (3)* | |
O20 | 0.4125 (9) | 0.5979 (9) | 0.1860 (7) | 0.012 (3)* | |
O21 | 0.3147 (9) | 0.9435 (9) | 0.4289 (7) | 0.014 (3)* | |
O22 | 0.6330 (9) | 0.2925 (9) | −0.0215 (7) | 0.013 (3)* | |
O23 | 0.7434 (10) | 0.2434 (10) | 0.8315 (8) | 0.021 (3)* | |
O24 | 0.1003 (9) | 0.9479 (8) | 0.4842 (7) | 0.008 (2)* | |
O25 | 0.1766 (10) | 0.7846 (9) | 0.4322 (7) | 0.015 (3)* | |
O26 | 0.1567 (9) | 0.9705 (9) | 0.3326 (7) | 0.014 (3)* | |
O27 | 0.8166 (10) | 0.4451 (9) | 0.7695 (7) | 0.018 (3)* | |
O28 | 0.0291 (10) | 0.8051 (9) | 0.3120 (7) | 0.017 (3)* | |
O29 | 0.8118 (10) | 0.1420 (9) | 0.0179 (7) | 0.016 (3)* | |
O30 | 0.6922 (10) | 0.4991 (9) | −0.0899 (7) | 0.017 (3)* | |
O31 | 0.5434 (9) | 0.5611 (9) | 0.0472 (7) | 0.012 (2)* | |
O32 | 0.9556 (9) | 0.7730 (9) | 0.4819 (7) | 0.014 (3)* | |
O33 | 0.6062 (10) | 0.6618 (10) | 0.2421 (8) | 0.022 (3)* | |
O34 | 0.5994 (10) | 0.9378 (10) | 0.3947 (7) | 0.020 (3)* | |
O35 | 0.7828 (9) | 0.8110 (9) | 0.3847 (7) | 0.014 (3)* | |
O36 | 0.5550 (9) | 0.7400 (9) | 0.0831 (7) | 0.013 (3)* | |
O37 | 0.9281 (9) | 0.9651 (8) | 0.3834 (6) | 0.008 (2)* | |
O38 | 0.7754 (10) | 0.9995 (9) | 0.2702 (7) | 0.019 (3)* | |
O39 | 0.7213 (9) | 0.5994 (9) | 0.1060 (7) | 0.013 (3)* | |
O40 | 0.8211 (11) | 0.6054 (10) | 0.4563 (8) | 0.028 (3)* | |
O41 | 0.5052 (10) | 0.3325 (10) | 0.1132 (7) | 0.019 (3)* | |
O42 | 0.9603 (10) | 0.6513 (10) | 0.7193 (8) | 0.020 (3)* | |
O1W | −0.1030 (13) | 0.7632 (12) | 1.0322 (10) | 0.043 (4)* | |
O2W | 0.3456 (12) | 0.8820 (11) | 0.2535 (9) | 0.033 (3)* | |
O3W | 0.5940 (11) | 0.9221 (11) | 0.1167 (8) | 0.029 (3)* | |
O4W | 0.4676 (12) | 0.9492 (11) | 0.7699 (9) | 0.036 (4)* | |
O5W | 0.0691 (12) | 0.8292 (11) | 0.7559 (9) | 0.037 (4)* | |
O6W | 0.8432 (12) | 0.6733 (12) | 0.2592 (9) | 0.038 (4)* | |
O7W | 0.8190 (11) | 0.9533 (11) | 0.1215 (8) | 0.030 (3)* | |
O8W | 0.1458 (15) | 1.0431 (14) | 0.0771 (11) | 0.058 (5)* | |
O9WA | 0.483 (3) | 0.533 (2) | 0.548 (2) | 0.045 (6)* | 0.52 (3) |
O9WB | 0.485 (3) | 0.541 (3) | 0.606 (2) | 0.045 (6)* | 0.48 (3) |
N1 | 0.0376 (14) | 0.5051 (13) | 0.8531 (10) | 0.028 (4)* | |
N2 | 0.4886 (14) | 0.7698 (13) | 0.3589 (10) | 0.030 (4)* | |
N3 | 0.5117 (12) | 0.8746 (12) | 0.5726 (9) | 0.019 (3)* | |
N4 | 0.1081 (14) | 0.5867 (13) | 0.4019 (10) | 0.031 (4)* | |
N5 | 0.6703 (14) | 0.6391 (13) | 0.7488 (10) | 0.030 (4)* | |
N6 | 0.3588 (14) | 0.9477 (13) | 0.0542 (10) | 0.029 (4)* | |
N7 | 0.0286 (14) | 0.8380 (13) | 0.1376 (10) | 0.027 (4)* | |
N8 | 0.8216 (14) | 0.8202 (14) | 0.8280 (11) | 0.033 (4)* | |
N9 | 0.359 (2) | 0.574 (2) | 0.3631 (17) | 0.087 (9)* | |
N10 | 0.2488 (15) | 0.5320 (14) | 0.6392 (11) | 0.036 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.0086 (3) | 0.0164 (4) | 0.0148 (4) | 0.0019 (3) | −0.0054 (3) | 0.0000 (3) |
W2 | 0.0076 (3) | 0.0139 (4) | 0.0131 (4) | 0.0011 (3) | −0.0025 (3) | 0.0003 (3) |
W3 | 0.0097 (3) | 0.0176 (4) | 0.0141 (4) | 0.0033 (3) | −0.0034 (3) | 0.0000 (3) |
W4 | 0.0063 (3) | 0.0140 (4) | 0.0157 (4) | 0.0025 (3) | −0.0036 (3) | 0.0000 (3) |
W5 | 0.0101 (3) | 0.0148 (4) | 0.0125 (4) | 0.0015 (3) | −0.0033 (3) | 0.0013 (3) |
W6 | 0.0094 (3) | 0.0145 (4) | 0.0186 (4) | 0.0009 (3) | −0.0043 (3) | −0.0010 (3) |
W7 | 0.0102 (3) | 0.0156 (4) | 0.0133 (4) | 0.0019 (3) | −0.0041 (3) | −0.0011 (3) |
W8 | 0.0085 (3) | 0.0133 (4) | 0.0136 (4) | 0.0011 (3) | −0.0037 (3) | 0.0007 (3) |
W9 | 0.0099 (3) | 0.0174 (4) | 0.0133 (4) | 0.0029 (3) | −0.0027 (3) | −0.0007 (3) |
W10 | 0.0092 (3) | 0.0148 (4) | 0.0152 (4) | 0.0008 (3) | −0.0033 (3) | 0.0018 (3) |
W11 | 0.0072 (3) | 0.0157 (4) | 0.0130 (4) | 0.0011 (3) | −0.0026 (3) | −0.0005 (3) |
W12 | 0.0068 (3) | 0.0139 (4) | 0.0133 (4) | 0.0010 (3) | −0.0025 (3) | 0.0009 (3) |
W1—O38 | 1.764 (12) | W8—O22 | 1.889 (11) |
W1—O34 | 1.768 (12) | W8—O5iii | 1.972 (11) |
W1—O10i | 1.874 (12) | W8—O36iv | 2.104 (11) |
W1—O35 | 1.947 (12) | W8—O31iv | 2.267 (11) |
W1—O37 | 2.168 (10) | W9—O27 | 1.722 (12) |
W1—O1 | 2.258 (12) | W9—O23 | 1.763 (13) |
W2—O6 | 1.725 (12) | W9—O20iii | 1.910 (11) |
W2—O30 | 1.832 (12) | W9—O19v | 1.972 (11) |
W2—O14 | 1.902 (11) | W9—O30v | 2.188 (12) |
W2—O5ii | 1.952 (12) | W9—O22v | 2.257 (11) |
W2—O39 | 2.103 (11) | W10—O42 | 1.740 (12) |
W2—O31 | 2.281 (11) | W10—O16 | 1.774 (12) |
W3—O9 | 1.757 (12) | W10—O17vi | 1.893 (11) |
W3—O29 | 1.766 (12) | W10—O3 | 1.979 (12) |
W3—O19 | 1.911 (11) | W10—O4 | 2.179 (12) |
W3—O18 | 1.916 (11) | W10—O32 | 2.232 (11) |
W3—O14 | 2.265 (11) | W11—O28 | 1.714 (12) |
W3—O22 | 2.304 (11) | W11—O37vii | 1.835 (10) |
W4—O13 | 1.783 (12) | W11—O32vii | 1.905 (11) |
W4—O25 | 1.842 (11) | W11—O26 | 1.938 (11) |
W4—O21 | 1.864 (11) | W11—O25 | 2.075 (11) |
W4—O17 | 1.938 (11) | W11—O24 | 2.326 (11) |
W4—O10 | 1.979 (11) | W12—O8 | 1.740 (12) |
W4—O24 | 2.273 (10) | W12—O4 | 1.800 (12) |
W5—O11 | 1.728 (12) | W12—O1 | 1.906 (12) |
W5—O15 | 1.763 (12) | W12—O26i | 1.964 (12) |
W5—O12 | 1.886 (12) | W12—O21i | 2.099 (11) |
W5—O18 | 1.925 (12) | W12—O24i | 2.208 (11) |
W5—O14 | 2.183 (11) | O5—W2v | 1.952 (12) |
W5—O41 | 2.278 (12) | O5—W8iii | 1.972 (11) |
W6—O40 | 1.735 (14) | O10—W1i | 1.874 (12) |
W6—O2 | 1.752 (12) | O17—W10vii | 1.893 (11) |
W6—O35 | 1.929 (11) | O19—W9ii | 1.972 (11) |
W6—O3 | 1.931 (12) | O20—W9iii | 1.910 (11) |
W6—O32 | 2.228 (11) | O21—W12i | 2.099 (11) |
W6—O1 | 2.400 (12) | O22—W9ii | 2.257 (11) |
W7—O33 | 1.721 (13) | O24—W12i | 2.208 (11) |
W7—O39 | 1.838 (11) | O26—W12i | 1.964 (12) |
W7—O36 | 1.875 (11) | O30—W9ii | 2.188 (12) |
W7—O20 | 1.964 (11) | O31—W8iv | 2.267 (11) |
W7—O12 | 1.970 (12) | O32—W11vi | 1.905 (11) |
W7—O31 | 2.270 (11) | O36—W8iv | 2.104 (11) |
W8—O7 | 1.736 (12) | O37—W11vi | 1.835 (10) |
W8—O41 | 1.759 (12) | O9WA—O9WB | 1.01 (4) |
O38—W1—O34 | 100.1 (5) | O7—W8—O5iii | 98.7 (5) |
O38—W1—O10i | 100.4 (5) | O41—W8—O5iii | 92.2 (5) |
O34—W1—O10i | 95.9 (5) | O22—W8—O5iii | 155.8 (5) |
O38—W1—O35 | 96.4 (5) | O7—W8—O36iv | 91.9 (5) |
O34—W1—O35 | 94.8 (5) | O41—W8—O36iv | 162.3 (5) |
O10i—W1—O35 | 158.1 (5) | O22—W8—O36iv | 84.8 (5) |
O38—W1—O37 | 89.7 (5) | O5iii—W8—O36iv | 81.9 (5) |
O34—W1—O37 | 169.9 (5) | O7—W8—O31iv | 162.1 (5) |
O10i—W1—O37 | 84.4 (4) | O41—W8—O31iv | 89.8 (5) |
O35—W1—O37 | 81.8 (4) | O22—W8—O31iv | 85.8 (4) |
O38—W1—O1 | 165.8 (5) | O5iii—W8—O31iv | 71.0 (4) |
O34—W1—O1 | 92.4 (5) | O36iv—W8—O31iv | 72.5 (4) |
O10i—W1—O1 | 84.8 (5) | O27—W9—O23 | 103.1 (6) |
O35—W1—O1 | 75.7 (5) | O27—W9—O20iii | 98.6 (5) |
O37—W1—O1 | 77.6 (4) | O23—W9—O20iii | 97.8 (5) |
O6—W2—O30 | 103.5 (5) | O27—W9—O19v | 95.4 (5) |
O6—W2—O14 | 100.4 (5) | O23—W9—O19v | 96.4 (5) |
O30—W2—O14 | 94.5 (5) | O20iii—W9—O19v | 157.3 (5) |
O6—W2—O5ii | 100.0 (5) | O27—W9—O30v | 91.5 (5) |
O30—W2—O5ii | 93.9 (5) | O23—W9—O30v | 164.9 (5) |
O14—W2—O5ii | 155.4 (5) | O20iii—W9—O30v | 83.6 (5) |
O6—W2—O39 | 93.5 (5) | O19v—W9—O30v | 78.2 (5) |
O30—W2—O39 | 163.0 (5) | O27—W9—O22v | 165.5 (5) |
O14—W2—O39 | 83.0 (5) | O23—W9—O22v | 88.3 (5) |
O5ii—W2—O39 | 82.2 (5) | O20iii—W9—O22v | 88.7 (4) |
O6—W2—O31 | 163.8 (5) | O19v—W9—O22v | 74.1 (4) |
O30—W2—O31 | 90.9 (5) | O30v—W9—O22v | 76.8 (4) |
O14—W2—O31 | 85.7 (4) | O42—W10—O16 | 103.5 (6) |
O5ii—W2—O31 | 71.0 (4) | O42—W10—O17vi | 99.1 (5) |
O39—W2—O31 | 72.2 (4) | O16—W10—O17vi | 96.2 (5) |
O9—W3—O29 | 103.5 (6) | O42—W10—O3 | 95.4 (5) |
O9—W3—O19 | 96.9 (5) | O16—W10—O3 | 97.7 (5) |
O29—W3—O19 | 98.3 (5) | O17vi—W10—O3 | 157.0 (5) |
O9—W3—O18 | 99.3 (5) | O42—W10—O4 | 91.4 (5) |
O29—W3—O18 | 98.2 (5) | O16—W10—O4 | 165.0 (5) |
O19—W3—O18 | 153.5 (5) | O17vi—W10—O4 | 82.9 (5) |
O9—W3—O14 | 90.7 (5) | O3—W10—O4 | 78.9 (5) |
O29—W3—O14 | 164.2 (5) | O42—W10—O32 | 163.7 (5) |
O19—W3—O14 | 86.8 (4) | O16—W10—O32 | 89.7 (5) |
O18—W3—O14 | 72.2 (4) | O17vi—W10—O32 | 88.9 (4) |
O9—W3—O22 | 163.9 (5) | O3—W10—O32 | 73.0 (4) |
O29—W3—O22 | 91.2 (5) | O4—W10—O32 | 75.3 (4) |
O19—W3—O22 | 74.0 (4) | O28—W11—O37vii | 105.9 (5) |
O18—W3—O22 | 85.0 (4) | O28—W11—O32vii | 100.3 (5) |
O14—W3—O22 | 75.8 (4) | O37vii—W11—O32vii | 93.5 (5) |
O13—W4—O25 | 98.9 (5) | O28—W11—O26 | 100.5 (5) |
O13—W4—O21 | 102.1 (5) | O37vii—W11—O26 | 92.6 (5) |
O25—W4—O21 | 92.8 (5) | O32vii—W11—O26 | 155.8 (5) |
O13—W4—O17 | 102.2 (5) | O28—W11—O25 | 96.7 (5) |
O25—W4—O17 | 88.6 (5) | O37vii—W11—O25 | 157.4 (5) |
O21—W4—O17 | 155.1 (5) | O32vii—W11—O25 | 82.9 (5) |
O13—W4—O10 | 103.4 (5) | O26—W11—O25 | 82.6 (5) |
O25—W4—O10 | 157.4 (5) | O28—W11—O24 | 166.3 (5) |
O21—W4—O10 | 86.5 (5) | O37vii—W11—O24 | 85.0 (4) |
O17—W4—O10 | 82.8 (5) | O32vii—W11—O24 | 87.0 (4) |
O13—W4—O24 | 176.5 (5) | O26—W11—O24 | 70.2 (4) |
O25—W4—O24 | 78.0 (4) | O25—W11—O24 | 72.6 (4) |
O21—W4—O24 | 76.7 (4) | O8—W12—O4 | 103.5 (5) |
O17—W4—O24 | 79.2 (4) | O8—W12—O1 | 101.9 (5) |
O10—W4—O24 | 79.8 (4) | O4—W12—O1 | 93.6 (5) |
O11—W5—O15 | 103.7 (6) | O8—W12—O26i | 97.4 (5) |
O11—W5—O12 | 97.4 (6) | O4—W12—O26i | 95.5 (5) |
O15—W5—O12 | 99.0 (6) | O1—W12—O26i | 156.1 (5) |
O11—W5—O18 | 95.2 (5) | O8—W12—O21i | 91.5 (5) |
O15—W5—O18 | 96.7 (5) | O4—W12—O21i | 164.8 (5) |
O12—W5—O18 | 156.9 (5) | O1—W12—O21i | 84.7 (5) |
O11—W5—O14 | 161.3 (5) | O26i—W12—O21i | 80.8 (4) |
O15—W5—O14 | 92.8 (5) | O8—W12—O24i | 163.2 (5) |
O12—W5—O14 | 88.4 (5) | O4—W12—O24i | 91.0 (5) |
O18—W5—O14 | 74.0 (4) | O1—W12—O24i | 85.4 (5) |
O11—W5—O41 | 87.4 (5) | O26i—W12—O24i | 72.5 (4) |
O15—W5—O41 | 168.1 (5) | O21i—W12—O24i | 73.8 (4) |
O12—W5—O41 | 83.6 (5) | W12—O1—W1 | 138.3 (6) |
O18—W5—O41 | 77.7 (5) | W12—O1—W6 | 126.5 (6) |
O14—W5—O41 | 75.5 (4) | W1—O1—W6 | 91.7 (4) |
O40—W6—O2 | 104.3 (6) | W6—O3—W10 | 115.8 (6) |
O40—W6—O35 | 97.5 (6) | W12—O4—W10 | 145.6 (7) |
O2—W6—O35 | 99.9 (5) | W2v—O5—W8iii | 119.9 (6) |
O40—W6—O3 | 100.2 (6) | W1i—O10—W4 | 150.5 (6) |
O2—W6—O3 | 95.9 (5) | W5—O12—W7 | 145.1 (7) |
O35—W6—O3 | 152.5 (5) | W2—O14—W5 | 139.9 (6) |
O40—W6—O32 | 93.9 (5) | W2—O14—W3 | 124.9 (5) |
O2—W6—O32 | 160.6 (5) | W5—O14—W3 | 94.9 (4) |
O35—W6—O32 | 84.0 (4) | W10vii—O17—W4 | 144.0 (6) |
O3—W6—O32 | 74.0 (5) | W3—O18—W5 | 117.1 (6) |
O40—W6—O1 | 166.0 (5) | W3—O19—W9ii | 117.3 (6) |
O2—W6—O1 | 87.4 (5) | W9iii—O20—W7 | 146.1 (6) |
O35—W6—O1 | 72.7 (4) | W4—O21—W12i | 113.8 (5) |
O3—W6—O1 | 85.8 (5) | W8—O22—W9ii | 137.7 (6) |
O32—W6—O1 | 75.5 (4) | W8—O22—W3 | 127.7 (5) |
O33—W7—O39 | 102.0 (5) | W9ii—O22—W3 | 93.3 (4) |
O33—W7—O36 | 101.1 (5) | W12i—O24—W4 | 95.7 (4) |
O39—W7—O36 | 93.3 (5) | W12i—O24—W11 | 96.2 (4) |
O33—W7—O20 | 100.9 (5) | W4—O24—W11 | 92.9 (4) |
O39—W7—O20 | 156.4 (5) | W4—O25—W11 | 116.5 (6) |
O36—W7—O20 | 87.7 (5) | W11—O26—W12i | 119.8 (6) |
O33—W7—O12 | 102.3 (5) | W2—O30—W9ii | 139.2 (6) |
O39—W7—O12 | 87.6 (5) | W8iv—O31—W7 | 95.6 (4) |
O36—W7—O12 | 155.8 (5) | W8iv—O31—W2 | 96.7 (4) |
O20—W7—O12 | 82.0 (5) | W7—O31—W2 | 94.6 (4) |
O33—W7—O31 | 177.6 (5) | W11vi—O32—W6 | 126.6 (5) |
O39—W7—O31 | 77.3 (4) | W11vi—O32—W10 | 137.3 (6) |
O36—W7—O31 | 76.7 (4) | W6—O32—W10 | 95.9 (4) |
O20—W7—O31 | 80.1 (4) | W6—O35—W1 | 119.2 (6) |
O12—W7—O31 | 80.0 (5) | W7—O36—W8iv | 115.2 (6) |
O7—W8—O41 | 105.5 (6) | W11vi—O37—W1 | 132.9 (6) |
O7—W8—O22 | 101.8 (5) | W7—O39—W2 | 116.0 (5) |
O41—W8—O22 | 94.4 (5) | W8—O41—W5 | 140.2 (7) |
O8—W12—O1—W1 | 137.3 (9) | O41—W8—O22—W3 | 39.8 (7) |
O4—W12—O1—W1 | −118.1 (9) | O5iii—W8—O22—W3 | 145.4 (9) |
O26i—W12—O1—W1 | −5.8 (18) | O36iv—W8—O22—W3 | −157.9 (7) |
O21i—W12—O1—W1 | 46.8 (9) | O31iv—W8—O22—W3 | 129.3 (7) |
O24i—W12—O1—W1 | −27.3 (9) | O9—W3—O22—W8 | −104.1 (18) |
O8—W12—O1—W6 | −70.4 (7) | O29—W3—O22—W8 | 100.3 (7) |
O4—W12—O1—W6 | 34.3 (7) | O19—W3—O22—W8 | −161.4 (8) |
O26i—W12—O1—W6 | 146.6 (9) | O18—W3—O22—W8 | 2.2 (7) |
O21i—W12—O1—W6 | −160.8 (7) | O14—W3—O22—W8 | −70.7 (7) |
O24i—W12—O1—W6 | 125.0 (7) | O9—W3—O22—W9ii | 64.9 (19) |
O38—W1—O1—W12 | 95 (2) | O29—W3—O22—W9ii | −90.7 (5) |
O34—W1—O1—W12 | −113.3 (9) | O19—W3—O22—W9ii | 7.5 (4) |
O10i—W1—O1—W12 | −17.6 (9) | O18—W3—O22—W9ii | 171.2 (5) |
O35—W1—O1—W12 | 152.3 (10) | O14—W3—O22—W9ii | 98.2 (4) |
O37—W1—O1—W12 | 67.8 (9) | O25—W4—O24—W12i | −96.6 (5) |
O38—W1—O1—W6 | −63 (2) | O21—W4—O24—W12i | −0.7 (4) |
O34—W1—O1—W6 | 88.6 (5) | O17—W4—O24—W12i | 172.6 (5) |
O10i—W1—O1—W6 | −175.7 (5) | O10—W4—O24—W12i | 88.1 (4) |
O35—W1—O1—W6 | −5.8 (4) | O25—W4—O24—W11 | 0.0 (4) |
O37—W1—O1—W6 | −90.3 (4) | O21—W4—O24—W11 | 95.8 (5) |
O40—W6—O1—W12 | −110 (2) | O17—W4—O24—W11 | −90.9 (4) |
O2—W6—O1—W12 | 102.7 (8) | O10—W4—O24—W11 | −175.4 (5) |
O35—W6—O1—W12 | −156.1 (8) | O28—W11—O24—W12i | 57 (2) |
O3—W6—O1—W12 | 6.6 (7) | O37vii—W11—O24—W12i | −86.7 (4) |
O32—W6—O1—W12 | −67.9 (7) | O32vii—W11—O24—W12i | 179.5 (5) |
O40—W6—O1—W1 | 52 (2) | O26—W11—O24—W12i | 7.9 (4) |
O2—W6—O1—W1 | −95.3 (5) | O25—W11—O24—W12i | 96.1 (5) |
O35—W6—O1—W1 | 5.9 (4) | O28—W11—O24—W4 | −39 (2) |
O3—W6—O1—W1 | 168.6 (5) | O37vii—W11—O24—W4 | 177.3 (4) |
O32—W6—O1—W1 | 94.1 (4) | O32vii—W11—O24—W4 | 83.5 (4) |
O40—W6—O3—W10 | 81.2 (7) | O26—W11—O24—W4 | −88.2 (5) |
O2—W6—O3—W10 | −173.1 (7) | O25—W11—O24—W4 | 0.0 (4) |
O35—W6—O3—W10 | −48.1 (14) | O13—W4—O25—W11 | −178.5 (6) |
O32—W6—O3—W10 | −10.0 (6) | O21—W4—O25—W11 | −75.7 (6) |
O1—W6—O3—W10 | −86.2 (6) | O17—W4—O25—W11 | 79.3 (6) |
O42—W10—O3—W6 | 178.4 (7) | O10—W4—O25—W11 | 12.0 (16) |
O16—W10—O3—W6 | −77.2 (7) | O24—W4—O25—W11 | 0.0 (5) |
O17vi—W10—O3—W6 | 49.3 (15) | O28—W11—O25—W4 | 171.3 (6) |
O4—W10—O3—W6 | 88.0 (6) | O37vii—W11—O25—W4 | −7.2 (16) |
O32—W10—O3—W6 | 10.1 (6) | O32vii—W11—O25—W4 | −89.1 (7) |
O8—W12—O4—W10 | 66.4 (12) | O26—W11—O25—W4 | 71.5 (6) |
O1—W12—O4—W10 | −36.7 (12) | O24—W11—O25—W4 | 0.0 (5) |
O26i—W12—O4—W10 | 165.4 (11) | O28—W11—O26—W12i | −179.7 (6) |
O21i—W12—O4—W10 | −119.5 (18) | O37vii—W11—O26—W12i | 73.6 (6) |
O24i—W12—O4—W10 | −122.1 (11) | O32vii—W11—O26—W12i | −30.8 (15) |
O42—W10—O4—W12 | −106.3 (12) | O25—W11—O26—W12i | −84.2 (6) |
O16—W10—O4—W12 | 67 (2) | O24—W11—O26—W12i | −10.1 (5) |
O17vi—W10—O4—W12 | 154.7 (12) | O6—W2—O30—W9ii | 59.9 (10) |
O3—W10—O4—W12 | −11.1 (11) | O14—W2—O30—W9ii | −41.9 (10) |
O32—W10—O4—W12 | 64.0 (11) | O5ii—W2—O30—W9ii | 161.3 (9) |
O13—W4—O10—W1i | 140.8 (13) | O39—W2—O30—W9ii | −122.6 (14) |
O25—W4—O10—W1i | −50 (2) | O31—W2—O30—W9ii | −127.7 (9) |
O21—W4—O10—W1i | 39.1 (13) | O39—W7—O31—W8iv | −96.7 (5) |
O17—W4—O10—W1i | −118.3 (13) | O36—W7—O31—W8iv | −0.1 (4) |
O24—W4—O10—W1i | −38.0 (12) | O20—W7—O31—W8iv | 89.9 (4) |
O11—W5—O12—W7 | −178.4 (12) | O12—W7—O31—W8iv | 173.5 (5) |
O15—W5—O12—W7 | 76.3 (12) | O39—W7—O31—W2 | 0.5 (4) |
O18—W5—O12—W7 | −56 (2) | O36—W7—O31—W2 | 97.1 (5) |
O14—W5—O12—W7 | −16.3 (12) | O20—W7—O31—W2 | −172.9 (5) |
O41—W5—O12—W7 | −91.9 (12) | O12—W7—O31—W2 | −89.4 (5) |
O33—W7—O12—W5 | −117.9 (12) | O6—W2—O31—W8iv | 66.6 (17) |
O39—W7—O12—W5 | −16.1 (12) | O30—W2—O31—W8iv | −85.8 (5) |
O36—W7—O12—W5 | 76.8 (17) | O14—W2—O31—W8iv | 179.7 (5) |
O20—W7—O12—W5 | 142.6 (12) | O5ii—W2—O31—W8iv | 8.1 (4) |
O31—W7—O12—W5 | 61.3 (11) | O39—W2—O31—W8iv | 95.8 (5) |
O6—W2—O14—W5 | 128.4 (9) | O6—W2—O31—W7 | −29.6 (18) |
O30—W2—O14—W5 | −127.0 (9) | O30—W2—O31—W7 | 178.0 (5) |
O5ii—W2—O14—W5 | −17.4 (17) | O14—W2—O31—W7 | 83.5 (4) |
O39—W2—O14—W5 | 36.0 (8) | O5ii—W2—O31—W7 | −88.2 (5) |
O31—W2—O14—W5 | −36.5 (9) | O39—W2—O31—W7 | −0.4 (4) |
O6—W2—O14—W3 | −59.6 (7) | O40—W6—O32—W11vi | 92.6 (8) |
O30—W2—O14—W3 | 45.0 (7) | O2—W6—O32—W11vi | −107.5 (15) |
O5ii—W2—O14—W3 | 154.6 (9) | O35—W6—O32—W11vi | −4.6 (7) |
O39—W2—O14—W3 | −152.0 (7) | O3—W6—O32—W11vi | −168.0 (8) |
O31—W2—O14—W3 | 135.5 (6) | O1—W6—O32—W11vi | −78.2 (7) |
O11—W5—O14—W2 | 107.8 (16) | O40—W6—O32—W10 | −91.5 (5) |
O15—W5—O14—W2 | −99.6 (9) | O2—W6—O32—W10 | 68.5 (16) |
O12—W5—O14—W2 | −0.7 (9) | O35—W6—O32—W10 | 171.4 (5) |
O18—W5—O14—W2 | 164.2 (10) | O3—W6—O32—W10 | 8.0 (4) |
O41—W5—O14—W2 | 83.1 (9) | O1—W6—O32—W10 | 97.8 (5) |
O11—W5—O14—W3 | −65.7 (16) | O42—W10—O32—W11vi | 121.3 (17) |
O15—W5—O14—W3 | 87.0 (5) | O16—W10—O32—W11vi | −94.5 (9) |
O12—W5—O14—W3 | −174.1 (5) | O17vi—W10—O32—W11vi | 1.7 (9) |
O18—W5—O14—W3 | −9.2 (4) | O3—W10—O32—W11vi | 167.4 (10) |
O41—W5—O14—W3 | −90.3 (4) | O4—W10—O32—W11vi | 84.7 (9) |
O9—W3—O14—W2 | 94.9 (7) | O42—W10—O32—W6 | −53.9 (19) |
O29—W3—O14—W2 | −111.3 (17) | O16—W10—O32—W6 | 90.2 (5) |
O19—W3—O14—W2 | −2.0 (7) | O17vi—W10—O32—W6 | −173.6 (5) |
O18—W3—O14—W2 | −165.5 (8) | O3—W10—O32—W6 | −7.9 (4) |
O22—W3—O14—W2 | −76.3 (6) | O4—W10—O32—W6 | −90.6 (5) |
O9—W3—O14—W5 | −90.2 (5) | O40—W6—O35—W1 | −177.7 (7) |
O29—W3—O14—W5 | 63.6 (18) | O2—W6—O35—W1 | 76.3 (7) |
O19—W3—O14—W5 | 172.9 (5) | O3—W6—O35—W1 | −47.9 (13) |
O18—W3—O14—W5 | 9.3 (4) | O32—W6—O35—W1 | −84.5 (6) |
O22—W3—O14—W5 | 98.5 (4) | O1—W6—O35—W1 | −7.9 (5) |
O13—W4—O17—W10vii | −107.1 (11) | O38—W1—O35—W6 | 176.2 (6) |
O25—W4—O17—W10vii | −8.4 (11) | O34—W1—O35—W6 | −83.0 (7) |
O21—W4—O17—W10vii | 85.2 (15) | O10i—W1—O35—W6 | 36.2 (16) |
O10—W4—O17—W10vii | 150.6 (11) | O37—W1—O35—W6 | 87.4 (6) |
O24—W4—O17—W10vii | 69.7 (10) | O1—W1—O35—W6 | 8.3 (6) |
O9—W3—O18—W5 | 75.9 (7) | O33—W7—O36—W8iv | 179.1 (6) |
O29—W3—O18—W5 | −179.0 (6) | O39—W7—O36—W8iv | 76.2 (6) |
O19—W3—O18—W5 | −51.1 (14) | O20—W7—O36—W8iv | −80.3 (6) |
O14—W3—O18—W5 | −11.9 (5) | O12—W7—O36—W8iv | −15.5 (15) |
O22—W3—O18—W5 | −88.5 (6) | O31—W7—O36—W8iv | 0.1 (5) |
O11—W5—O18—W3 | 176.6 (6) | O38—W1—O37—W11vi | −96.5 (8) |
O15—W5—O18—W3 | −78.8 (7) | O34—W1—O37—W11vi | 71 (3) |
O12—W5—O18—W3 | 53.8 (15) | O10i—W1—O37—W11vi | 162.9 (8) |
O14—W5—O18—W3 | 12.2 (5) | O35—W1—O37—W11vi | −0.1 (7) |
O41—W5—O18—W3 | 90.5 (6) | O1—W1—O37—W11vi | 77.0 (8) |
O9—W3—O19—W9ii | −176.1 (7) | O33—W7—O39—W2 | −178.2 (6) |
O29—W3—O19—W9ii | 79.1 (7) | O36—W7—O39—W2 | −76.1 (6) |
O18—W3—O19—W9ii | −48.7 (14) | O20—W7—O39—W2 | 15.8 (15) |
O14—W3—O19—W9ii | −85.8 (6) | O12—W7—O39—W2 | 79.7 (6) |
O22—W3—O19—W9ii | −9.7 (5) | O31—W7—O39—W2 | −0.6 (5) |
O33—W7—O20—W9iii | 124.8 (11) | O6—W2—O39—W7 | 172.7 (6) |
O39—W7—O20—W9iii | −69.2 (18) | O30—W2—O39—W7 | −4.8 (19) |
O36—W7—O20—W9iii | 23.9 (11) | O14—W2—O39—W7 | −87.2 (6) |
O12—W7—O20—W9iii | −134.1 (12) | O5ii—W2—O39—W7 | 73.1 (6) |
O31—W7—O20—W9iii | −53.0 (11) | O31—W2—O39—W7 | 0.6 (5) |
O13—W4—O21—W12i | 177.5 (6) | O7—W8—O41—W5 | 65.4 (11) |
O25—W4—O21—W12i | 77.8 (6) | O22—W8—O41—W5 | −38.2 (10) |
O17—W4—O21—W12i | −14.8 (14) | O5iii—W8—O41—W5 | 165.1 (10) |
O10—W4—O21—W12i | −79.5 (6) | O36iv—W8—O41—W5 | −124.9 (14) |
O24—W4—O21—W12i | 0.8 (5) | O31iv—W8—O41—W5 | −123.9 (10) |
O7—W8—O22—W9ii | 129.5 (9) | O11—W5—O41—W8 | −106.4 (11) |
O41—W8—O22—W9ii | −123.6 (9) | O15—W5—O41—W8 | 53 (3) |
O5iii—W8—O22—W9ii | −18.1 (17) | O12—W5—O41—W8 | 155.9 (11) |
O36iv—W8—O22—W9ii | 38.6 (8) | O18—W5—O41—W8 | −10.5 (10) |
O31iv—W8—O22—W9ii | −34.2 (8) | O14—W5—O41—W8 | 65.9 (10) |
O7—W8—O22—W3 | −67.0 (8) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x, y, z+1; (vi) x+1, y, z; (vii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (NH4)10[H2W12O42]·9H2O |
Mr | 3222.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 168 |
a, b, c (Å) | 11.945 (4), 13.225 (5), 16.780 (6) |
α, β, γ (°) | 76.159 (5), 80.985 (5), 88.763 (5) |
V (Å3) | 2541.6 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 26.20 |
Crystal size (mm) | 0.44 × 0.14 × 0.06 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.355, 0.592 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32370, 10192, 7208 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.128, 0.99 |
No. of reflections | 10192 |
No. of parameters | 357 |
Δρmax, Δρmin (e Å−3) | 6.04, −5.45 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996) and SADABS (Sheldrick, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 in WinGX (Farrugia, 1997), SHELXL97.
W1—O38 | 1.764 (12) | W1—O37 | 2.168 (10) |
W1—O34 | 1.768 (12) | W1—O1 | 2.258 (12) |
W1—O10i | 1.874 (12) | W6—O1 | 2.400 (12) |
W1—O35 | 1.947 (12) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
The title compound, (I), was prepared as a by-product while attempting to use aniline as an organic amine inter-layer spacer molecule for new inorganic oxide-layered compounds. The crystal structure comprises [H2W12O42]10− anions (Fig. 1) bound in an infinite three-dimensional network through hydrogen bonding with NH4+ cations and water molecules. There are at least 42 contacts between the anion O atoms, amine N atoms and water O atoms within normal hydrogen-bonding distances, e.g. O22···O2W 2.76 (2) Å.
The two independent anions per cell are centrosymmetric and are essentially identical (truly isomorphic) with those in (NH4)6[H6W12O42].10H2O (Averbuch-Pouchot et al., 1979, hereafter AVEPOU). The final cell composition is inferred from the consistency of the refined displacement parameters of the water O atoms and ammonium cation N atoms, the analytical data and the proximity of cations to each other, since the X-ray scattering of the H atoms cannot be determined unambiguously in the presence of the W atoms. The atom-numbering scheme for the anions follows that in AVEPOU, with the coordinates transformed into one asymmetric unit. The cell volume here is slightly larger [2542 (2) Å3 at 168 K compared with 2540 Å3 at 293 K for AVEPOU], as expected from the greater total number of cations and water molecules. Other structures found on the Cambridge Structural Database (Allen & Kennard, 1993; Conquest, 2002) containing the same [H2W12O42]10− anion are the closely related (NH4)10[H2W12O42].10H2O, which crystallizes in space group Pbca, as reported by Allman (1971) and a decasodium diglycine salt (Naruke et al., 2000). A summary of the expected geometry of the anions is given in the paper reporting Na10[H2W12O42].20H2O (Evans & Rollins, 1976). The internally self-consistent range of W—O distances are indicated in Table 1 by those found for W1.
A larger crystal from another preparation was also examined; it had a slightly smaller cell [2510 (1) Å3 at 168 K], but the diffraction data was not as good with an internal agreement Rint of 0.068 and the subsequent refinement was less stable. The isomorphicity of the anion coordinates reported here with those in the six-cation structure AVEPOU suggest that this larger crystal could be made up of plate-like twins, possibly with variable cation/water composition.