Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019700/bt6186sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019700/bt6186Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (La-O) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.039
- wR factor = 0.124
- Data-to-parameter ratio = 12.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
ABSMU_01 Alert A The ratio of given/expected absorption coefficient lies outside the range 0.90 <> 1.10 Calculated value of mu = 7.885 Value of mu given = 3.942 DENSD_01 Alert A The ratio of the submitted crystal density and that calculated from the formula is outside the range 0.90 <> 1.10 Crystal density given = 2.501 Calculated crystal density = 5.002
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 60.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: H104 La4 O108 V20 Atom count from _chemical_formula_moiety:H52 La2 O54 V10 FORMU_01 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:H104 La4 O108 V20 Atom count from the _atom_site data: H52 La2 O54 V10 CELLZ_01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum H104 La4 O108 V20 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff H 208.00 104.00 104.00 La 8.00 4.00 4.00 O 216.00 108.00 108.00 V 40.00 20.00 20.00 Difference between formula and atom_site contents detected. ALERT: Large difference may be due to a symmetry error - see SYMMG tests CHEMW_03 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_weight 3407.27 TEST: Calculate formula weight from _atom_site_* atom mass num sum H 1.01 52.00 52.42 O 16.00 54.00 863.95 V 50.94 10.00 509.42 La 138.91 2.00 277.81 Calculated formula weight 1703.59 ALERT: The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.90 <> 1.10
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared as follows. NaV10O28.12H2O (1 mmol), La(NO3)3 (2 mmol) and distilled water (100 ml) were mixed to form an aqueous solution with stirring and the pH was adjusted to 4.0. The mixture was stirred for 4 h and placed in an ice-box at 277 K for a few weeks. Red crystals suitable for diffraction studies were obtained.
The positions of all H atoms were fixed geometrically; O—H = 0.82–0.96 Å. The site-occupation factors of the five water O atoms were refined, constraining them to 4.
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 SDP/VAX (Enraf-Nonius, 1989); data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.
[La(H2O)9]2[V10O28]·8H2O | F(000) = 1656 |
Mr = 1703.64 | Dx = 2.501 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 9.818 (2) Å | θ = 15.1–15.9° |
b = 11.935 (2) Å | µ = 3.94 mm−1 |
c = 19.514 (4) Å | T = 293 K |
β = 98.42 (3)° | Block, red |
V = 2262.0 (8) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 2 |
Enraf-nonius CAD-4 diffractometer | 3460 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω/2θ scans | h = −11→11 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→14 |
Tmin = 0.403, Tmax = 0.456 | l = 0→23 |
4226 measured reflections | 5 standard reflections every 300 reflections |
3979 independent reflections | intensity decay: 0.001% |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.067P)2 + 0.7084P] where P = (Fo2 + 2Fc2)/3 |
3979 reflections | (Δ/σ)max < 0.001 |
322 parameters | Δρmax = 0.79 e Å−3 |
1 restraint | Δρmin = −0.79 e Å−3 |
[La(H2O)9]2[V10O28]·8H2O | V = 2262.0 (8) Å3 |
Mr = 1703.64 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.818 (2) Å | µ = 3.94 mm−1 |
b = 11.935 (2) Å | T = 293 K |
c = 19.514 (4) Å | 0.30 × 0.20 × 0.20 mm |
β = 98.42 (3)° |
Enraf-nonius CAD-4 diffractometer | 3460 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.403, Tmax = 0.456 | 5 standard reflections every 300 reflections |
4226 measured reflections | intensity decay: 0.001% |
3979 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 1 restraint |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.79 e Å−3 |
3979 reflections | Δρmin = −0.79 e Å−3 |
322 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) | |
O1W | 0.5178 (5) | 0.5362 (4) | 0.6431 (3) | 0.0390 (12) | |
H1WB | 0.6043 | 0.5462 | 0.6526 | 0.08 (3)* | |
H1WA | 0.4973 | 0.5160 | 0.6011 | 0.08 (4)* | |
O2W | 0.4188 (15) | 0.2303 (14) | 0.6324 (7) | 0.081 (4) | 0.54 |
H2WA | 0.3544 | 0.2208 | 0.5987 | 0.08 (7)* | 0.54 |
H2WB | 0.4422 | 0.2989 | 0.6349 | 0.08 (8)* | 0.54 |
O3W | 0.3216 (8) | 0.0736 (7) | 0.5484 (4) | 0.0390 (18) | 0.67 |
H3WA | 0.3339 | 0.0862 | 0.5068 | 0.08 (6)* | 0.67 |
H3WB | 0.2426 | 0.0971 | 0.5546 | 0.08 (6)* | 0.67 |
O4W | 0.2164 (7) | 0.9638 (6) | 0.6884 (4) | 0.0500 (16) | 0.85 |
H4WA | 0.2056 | 0.8948 | 0.6783 | 0.075* | 0.85 |
H4WB | 0.1690 | 0.9805 | 0.7201 | 0.060* | 0.85 |
O5W | 0.6931 (7) | 0.2731 (5) | 0.7205 (3) | 0.0576 (17) | 0.94 |
H5WA | 0.7803 | 0.2674 | 0.7262 | 0.08 (4)* | 0.94 |
H5WB | 0.6638 | 0.2866 | 0.6781 | 0.08 (4)* | 0.94 |
La1 | 0.66859 (3) | 0.89783 (3) | 0.665970 (16) | 0.01592 (14) | |
O1 | 0.4940 (5) | 1.0022 (5) | 0.7138 (3) | 0.0445 (13) | |
H1B | 0.5193 | 1.0133 | 0.7551 | 0.067* | |
H1A | 0.4099 | 0.9600 | 0.7080 | 0.067* | |
O2 | 0.8725 (5) | 0.7939 (5) | 0.7194 (3) | 0.0452 (13) | |
H2A | 0.9538 | 0.8362 | 0.7148 | 0.068* | |
H2B | 0.8761 | 0.7228 | 0.6967 | 0.068* | |
O3 | 0.8081 (5) | 1.0632 (4) | 0.7076 (3) | 0.0389 (12) | |
H3B | 0.9000 | 1.0544 | 0.6972 | 0.058* | |
H3A | 0.8106 | 1.0691 | 0.7568 | 0.058* | |
O4 | 0.6115 (5) | 1.0593 (4) | 0.5853 (3) | 0.0373 (11) | |
H4A | 0.6191 | 1.1251 | 0.6020 | 0.045* | |
H4B | 0.5482 | 1.0506 | 0.5510 | 0.045* | |
O5 | 0.4448 (5) | 0.8726 (4) | 0.5884 (3) | 0.0420 (13) | |
H5A | 0.4010 | 0.9441 | 0.5796 | 0.063* | |
H5B | 0.4616 | 0.8400 | 0.5455 | 0.063* | |
O6 | 0.8550 (5) | 0.9273 (4) | 0.5902 (3) | 0.0388 (12) | |
H6B | 0.8802 | 0.9905 | 0.5764 | 0.058* | |
H6A | 0.8881 | 0.8642 | 0.5808 | 0.058* | |
O7 | 0.6835 (5) | 0.7407 (4) | 0.5879 (3) | 0.0360 (11) | |
H7B | 0.6175 | 0.7159 | 0.5588 | 0.054* | |
H7A | 0.7649 | 0.7147 | 0.5944 | 0.054* | |
O8 | 0.5430 (6) | 0.7422 (4) | 0.7079 (3) | 0.0478 (14) | |
H8B | 0.4671 | 0.7221 | 0.6733 | 0.072* | |
H8A | 0.5088 | 0.7644 | 0.7495 | 0.072* | |
O9 | 0.6969 (6) | 0.8929 (4) | 0.7969 (3) | 0.0417 (13) | |
H9A | 0.7480 | 0.9439 | 0.8127 | 0.062* | |
H9B | 0.7366 | 0.8226 | 0.8133 | 0.062* | |
V1 | 0.29404 (10) | 0.85710 (9) | 0.97797 (5) | 0.0233 (3) | |
V2 | 0.14616 (10) | 1.06478 (8) | 1.02313 (5) | 0.0196 (2) | |
V3 | 0.09330 (11) | 0.82825 (9) | 1.08500 (5) | 0.0219 (3) | |
V4 | 0.02089 (11) | 0.73544 (9) | 0.93521 (6) | 0.0251 (3) | |
V5 | 0.06799 (11) | 0.96833 (9) | 0.87162 (5) | 0.0227 (3) | |
O10 | 0.2080 (4) | 0.7287 (4) | 0.9422 (2) | 0.0260 (9) | |
O11 | 0.2494 (4) | 0.9315 (4) | 0.8926 (2) | 0.0260 (9) | |
O12 | 0.3050 (4) | 1.0141 (3) | 1.0193 (2) | 0.0242 (9) | |
O13 | 0.2683 (4) | 0.8157 (3) | 1.0685 (2) | 0.0241 (9) | |
O14 | 0.0254 (4) | 0.7104 (4) | 1.0300 (2) | 0.0259 (9) | |
O15 | 0.0083 (4) | 0.8269 (4) | 0.8548 (2) | 0.0261 (10) | |
O16 | 0.1006 (4) | 1.1095 (3) | 0.9276 (2) | 0.0208 (9) | |
O17 | 0.1206 (4) | 0.9900 (3) | 1.1083 (2) | 0.0199 (8) | |
O18 | 0.0967 (5) | 0.7778 (4) | 1.1623 (2) | 0.0325 (11) | |
O19 | −0.0293 (5) | 0.6153 (4) | 0.9032 (3) | 0.0388 (12) | |
O20 | 0.0570 (5) | 1.0199 (4) | 0.7947 (2) | 0.0321 (11) | |
O21 | 0.1663 (4) | 1.1937 (4) | 1.0572 (2) | 0.0254 (9) | |
O22 | 0.4543 (5) | 0.8292 (4) | 0.9797 (2) | 0.0328 (11) | |
O23 | −0.0694 (4) | 1.0880 (3) | 1.0195 (2) | 0.0219 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.038 (3) | 0.045 (3) | 0.034 (3) | −0.002 (2) | 0.004 (2) | −0.005 (2) |
O2W | 0.086 (10) | 0.050 (13) | 0.066 (9) | 0.041 (9) | 0.010 (8) | 0.014 (8) |
O3W | 0.038 (4) | 0.045 (4) | 0.034 (4) | −0.002 (4) | 0.004 (3) | −0.005 (3) |
O4W | 0.050 (4) | 0.050 (4) | 0.050 (4) | 0.000 (3) | 0.007 (3) | 0.000 (3) |
O5W | 0.070 (5) | 0.049 (4) | 0.052 (4) | 0.001 (3) | 0.006 (3) | 0.016 (3) |
La1 | 0.0187 (2) | 0.0127 (2) | 0.0159 (2) | 0.00020 (11) | 0.00115 (14) | −0.00258 (12) |
O1 | 0.041 (3) | 0.055 (3) | 0.038 (3) | 0.008 (3) | 0.006 (2) | −0.013 (2) |
O2 | 0.042 (3) | 0.055 (3) | 0.036 (3) | 0.015 (3) | −0.002 (2) | −0.008 (3) |
O3 | 0.040 (3) | 0.034 (3) | 0.040 (3) | 0.001 (2) | −0.003 (2) | −0.008 (2) |
O4 | 0.039 (3) | 0.032 (3) | 0.040 (3) | −0.001 (2) | 0.004 (2) | 0.010 (2) |
O5 | 0.040 (3) | 0.031 (3) | 0.051 (3) | 0.000 (2) | −0.010 (2) | −0.009 (2) |
O6 | 0.040 (3) | 0.022 (2) | 0.058 (3) | −0.004 (2) | 0.018 (3) | −0.001 (2) |
O7 | 0.029 (2) | 0.037 (3) | 0.040 (3) | 0.002 (2) | 0.000 (2) | −0.016 (2) |
O8 | 0.063 (4) | 0.041 (3) | 0.042 (3) | −0.018 (3) | 0.017 (3) | −0.007 (2) |
O9 | 0.048 (3) | 0.047 (3) | 0.028 (3) | 0.001 (2) | −0.001 (2) | −0.009 (2) |
V1 | 0.0229 (5) | 0.0218 (6) | 0.0244 (6) | 0.0021 (4) | 0.0014 (4) | 0.0013 (4) |
V2 | 0.0213 (5) | 0.0178 (5) | 0.0186 (5) | −0.0016 (4) | −0.0001 (4) | 0.0018 (4) |
V3 | 0.0264 (5) | 0.0186 (5) | 0.0201 (5) | 0.0017 (4) | 0.0019 (4) | 0.0045 (4) |
V4 | 0.0276 (6) | 0.0183 (5) | 0.0285 (6) | −0.0004 (4) | 0.0010 (4) | −0.0031 (4) |
V5 | 0.0259 (6) | 0.0234 (6) | 0.0183 (5) | 0.0020 (4) | 0.0015 (4) | 0.0013 (4) |
O10 | 0.028 (2) | 0.023 (2) | 0.025 (2) | 0.0028 (18) | 0.0004 (18) | −0.0023 (18) |
O11 | 0.027 (2) | 0.025 (2) | 0.026 (2) | 0.0022 (19) | 0.0045 (18) | 0.0029 (19) |
O12 | 0.023 (2) | 0.023 (2) | 0.025 (2) | −0.0026 (18) | −0.0016 (17) | 0.0025 (18) |
O13 | 0.025 (2) | 0.021 (2) | 0.025 (2) | 0.0027 (18) | 0.0011 (18) | 0.0032 (18) |
O14 | 0.030 (2) | 0.020 (2) | 0.028 (2) | −0.0009 (18) | 0.0030 (18) | 0.0033 (18) |
O15 | 0.028 (2) | 0.028 (2) | 0.021 (2) | −0.0004 (19) | 0.0000 (18) | −0.0037 (18) |
O16 | 0.025 (2) | 0.018 (2) | 0.018 (2) | −0.0015 (16) | 0.0005 (17) | 0.0008 (16) |
O17 | 0.022 (2) | 0.020 (2) | 0.0168 (19) | 0.0007 (17) | 0.0009 (16) | 0.0018 (16) |
O18 | 0.039 (3) | 0.031 (2) | 0.027 (2) | 0.001 (2) | 0.004 (2) | 0.010 (2) |
O19 | 0.039 (3) | 0.026 (3) | 0.049 (3) | −0.001 (2) | −0.001 (2) | −0.003 (2) |
O20 | 0.035 (3) | 0.037 (3) | 0.025 (2) | 0.001 (2) | 0.0037 (19) | 0.003 (2) |
O21 | 0.026 (2) | 0.023 (2) | 0.025 (2) | 0.0007 (18) | −0.0006 (18) | −0.0036 (18) |
O22 | 0.028 (2) | 0.037 (3) | 0.033 (3) | 0.002 (2) | 0.0004 (19) | 0.003 (2) |
O23 | 0.023 (2) | 0.024 (2) | 0.019 (2) | −0.0014 (17) | 0.0008 (17) | 0.0001 (17) |
O1W—H1WB | 0.8502 | V1—V4 | 3.0563 (16) |
O1W—H1WA | 0.8499 | V1—V2 | 3.0664 (15) |
O2W—H2WA | 0.8500 | V1—V3 | 3.0936 (17) |
O2W—H2WB | 0.8501 | V1—V5 | 3.1058 (17) |
O3W—H3WA | 0.8501 | V2—O21 | 1.677 (4) |
O3W—H3WB | 0.8502 | V2—O12 | 1.685 (4) |
O4W—H4WA | 0.8500 | V2—O16 | 1.927 (4) |
O4W—H4WB | 0.8501 | V2—O17 | 1.935 (4) |
O5W—H5WA | 0.8500 | V2—O23i | 2.098 (4) |
O5W—H5WB | 0.8500 | V2—O23 | 2.126 (4) |
La1—O1 | 2.414 (5) | V2—V4i | 3.0703 (15) |
La1—O7 | 2.433 (4) | V3—O18 | 1.620 (4) |
La1—O8 | 2.437 (5) | V3—O13 | 1.799 (4) |
La1—O2 | 2.454 (5) | V3—O14 | 1.835 (4) |
La1—O3 | 2.470 (5) | V3—O17 | 1.992 (4) |
La1—O5 | 2.497 (5) | V3—O16i | 2.025 (4) |
La1—O4 | 2.500 (5) | V3—O23i | 2.253 (4) |
La1—O9 | 2.529 (5) | V3—V5i | 3.0840 (15) |
La1—O6 | 2.540 (5) | V3—V4 | 3.1093 (16) |
O1—H1B | 0.8200 | V4—O19 | 1.612 (5) |
O1—H1A | 0.9596 | V4—O10 | 1.824 (4) |
O2—H2A | 0.9600 | V4—O14 | 1.867 (4) |
O2—H2B | 0.9604 | V4—O15 | 1.900 (4) |
O3—H3B | 0.9600 | V4—O21i | 2.048 (4) |
O3—H3A | 0.9598 | V4—O23i | 2.307 (4) |
O4—H4A | 0.8500 | V4—V2i | 3.0703 (15) |
O4—H4B | 0.8500 | V4—V5 | 3.1061 (16) |
O5—H5A | 0.9601 | V5—O20 | 1.610 (4) |
O5—H5B | 0.9600 | V5—O15 | 1.801 (5) |
O6—H6B | 0.8501 | V5—O11 | 1.823 (4) |
O6—H6A | 0.8501 | V5—O16 | 2.008 (4) |
O7—H7B | 0.8501 | V5—O17i | 2.010 (4) |
O7—H7A | 0.8499 | V5—O23i | 2.226 (4) |
O8—H8B | 0.9602 | V5—V3i | 3.0840 (15) |
O8—H8A | 0.9598 | O16—V3i | 2.025 (4) |
O9—H9A | 0.8200 | O17—V5i | 2.010 (4) |
O9—H9B | 0.9600 | O21—V4i | 2.048 (4) |
V1—O22 | 1.604 (5) | O23—V2i | 2.098 (4) |
V1—O10 | 1.837 (4) | O23—V5i | 2.226 (4) |
V1—O11 | 1.882 (4) | O23—V3i | 2.253 (4) |
V1—O13 | 1.888 (4) | O23—V4i | 2.307 (4) |
V1—O12 | 2.037 (4) | O23—V1i | 2.308 (4) |
V1—O23i | 2.308 (4) | ||
H1WB—O1W—H1WA | 109.8 | O13—V3—O14 | 96.10 (19) |
H2WA—O2W—H2WB | 109.7 | O18—V3—O17 | 99.4 (2) |
H3WA—O3W—H3WB | 109.7 | O13—V3—O17 | 91.21 (18) |
H4WA—O4W—H4WB | 109.5 | O14—V3—O17 | 154.38 (18) |
H5WA—O5W—H5WB | 109.5 | O18—V3—O16i | 98.1 (2) |
O1—La1—O7 | 138.63 (17) | O13—V3—O16i | 156.05 (18) |
O1—La1—O8 | 80.83 (18) | O14—V3—O16i | 87.47 (18) |
O7—La1—O8 | 72.70 (17) | O17—V3—O16i | 76.39 (16) |
O1—La1—O2 | 132.66 (17) | O18—V3—O23i | 173.3 (2) |
O7—La1—O2 | 75.92 (17) | O13—V3—O23i | 81.41 (17) |
O8—La1—O2 | 83.9 (2) | O14—V3—O23i | 80.19 (17) |
O1—La1—O3 | 81.46 (18) | O17—V3—O23i | 76.67 (15) |
O7—La1—O3 | 137.73 (17) | O16i—V3—O23i | 75.86 (16) |
O8—La1—O3 | 141.44 (18) | O18—V3—V5i | 88.74 (17) |
O2—La1—O3 | 83.42 (18) | O13—V3—V5i | 131.02 (14) |
O1—La1—O5 | 71.63 (18) | O14—V3—V5i | 127.39 (14) |
O7—La1—O5 | 69.87 (17) | O17—V3—V5i | 39.81 (12) |
O8—La1—O5 | 70.61 (19) | O16i—V3—V5i | 39.92 (11) |
O2—La1—O5 | 141.94 (18) | O23i—V3—V5i | 84.83 (11) |
O3—La1—O5 | 133.77 (17) | O18—V3—V1 | 137.90 (17) |
O1—La1—O4 | 74.87 (18) | O13—V3—V1 | 33.86 (13) |
O7—La1—O4 | 103.21 (18) | O14—V3—V1 | 84.43 (14) |
O8—La1—O4 | 136.18 (18) | O17—V3—V1 | 88.20 (12) |
O2—La1—O4 | 138.69 (18) | O16i—V3—V1 | 123.89 (12) |
O3—La1—O4 | 69.73 (17) | O23i—V3—V1 | 48.04 (11) |
O5—La1—O4 | 67.35 (17) | V5i—V3—V1 | 120.08 (4) |
O1—La1—O9 | 66.50 (17) | O18—V3—V4 | 135.54 (18) |
O7—La1—O9 | 127.31 (17) | O13—V3—V4 | 84.00 (14) |
O8—La1—O9 | 68.22 (18) | O14—V3—V4 | 33.21 (13) |
O2—La1—O9 | 66.21 (17) | O17—V3—V4 | 124.35 (12) |
O3—La1—O9 | 73.33 (17) | O16i—V3—V4 | 86.26 (12) |
O5—La1—O9 | 124.48 (18) | O23i—V3—V4 | 47.75 (11) |
O4—La1—O9 | 129.45 (17) | V5i—V3—V4 | 118.85 (4) |
O1—La1—O6 | 140.02 (17) | V1—V3—V4 | 59.04 (4) |
O7—La1—O6 | 68.16 (16) | O19—V4—O10 | 103.7 (2) |
O8—La1—O6 | 138.11 (17) | O19—V4—O14 | 101.7 (2) |
O2—La1—O6 | 72.84 (17) | O10—V4—O14 | 92.34 (19) |
O3—La1—O6 | 70.66 (17) | O19—V4—O15 | 102.2 (2) |
O5—La1—O6 | 107.99 (18) | O10—V4—O15 | 91.74 (19) |
O4—La1—O6 | 68.95 (16) | O14—V4—O15 | 154.02 (19) |
O9—La1—O6 | 127.52 (18) | O19—V4—O21i | 99.7 (2) |
La1—O1—H1B | 109.5 | O10—V4—O21i | 156.57 (19) |
La1—O1—H1A | 109.3 | O14—V4—O21i | 83.47 (18) |
H1B—O1—H1A | 109.4 | O15—V4—O21i | 82.64 (18) |
La1—O2—H2A | 109.4 | O19—V4—O23i | 174.2 (2) |
La1—O2—H2B | 109.5 | O10—V4—O23i | 82.08 (17) |
H2A—O2—H2B | 109.5 | O14—V4—O23i | 78.10 (17) |
La1—O3—H3B | 109.7 | O15—V4—O23i | 77.08 (17) |
La1—O3—H3A | 108.6 | O21i—V4—O23i | 74.50 (16) |
H3B—O3—H3A | 109.5 | O19—V4—V1 | 137.26 (19) |
La1—O4—H4A | 118.1 | O10—V4—V1 | 33.55 (14) |
La1—O4—H4B | 118.1 | O14—V4—V1 | 85.01 (14) |
H4A—O4—H4B | 115.4 | O15—V4—V1 | 84.32 (13) |
La1—O5—H5A | 109.5 | O21i—V4—V1 | 123.03 (13) |
La1—O5—H5B | 109.3 | O23i—V4—V1 | 48.53 (11) |
H5A—O5—H5B | 109.5 | O19—V4—V2i | 130.44 (19) |
La1—O6—H6B | 125.2 | O10—V4—V2i | 125.85 (14) |
La1—O6—H6A | 109.5 | O14—V4—V2i | 78.38 (14) |
H6B—O6—H6A | 125.4 | O15—V4—V2i | 78.46 (14) |
La1—O7—H7B | 125.3 | O21i—V4—V2i | 30.74 (12) |
La1—O7—H7A | 109.4 | O23i—V4—V2i | 43.77 (11) |
H7B—O7—H7A | 125.4 | V1—V4—V2i | 92.30 (4) |
La1—O8—H8B | 109.4 | O19—V4—V5 | 134.1 (2) |
La1—O8—H8A | 109.3 | O10—V4—V5 | 82.08 (14) |
H8B—O8—H8A | 109.5 | O14—V4—V5 | 123.76 (14) |
La1—O9—H9A | 109.5 | O15—V4—V5 | 31.98 (13) |
La1—O9—H9B | 109.8 | O21i—V4—V5 | 81.20 (13) |
H9A—O9—H9B | 109.0 | O23i—V4—V5 | 45.67 (11) |
O22—V1—O10 | 103.3 (2) | V1—V4—V5 | 60.52 (4) |
O22—V1—O11 | 102.5 (2) | V2i—V4—V5 | 61.79 (4) |
O10—V1—O11 | 91.3 (2) | O19—V4—V3 | 134.1 (2) |
O22—V1—O13 | 101.0 (2) | O10—V4—V3 | 81.72 (14) |
O10—V1—O13 | 91.16 (19) | O14—V4—V3 | 32.56 (13) |
O11—V1—O13 | 155.05 (19) | O15—V4—V3 | 123.36 (14) |
O22—V1—O12 | 100.8 (2) | O21i—V4—V3 | 82.48 (12) |
O10—V1—O12 | 155.85 (19) | O23i—V4—V3 | 46.28 (11) |
O11—V1—O12 | 84.79 (18) | V1—V4—V3 | 60.22 (4) |
O13—V1—O12 | 82.88 (18) | V2i—V4—V3 | 62.09 (4) |
O22—V1—O23i | 174.9 (2) | V5—V4—V3 | 91.71 (4) |
O10—V1—O23i | 81.79 (17) | O20—V5—O15 | 102.3 (2) |
O11—V1—O23i | 77.63 (17) | O20—V5—O11 | 103.3 (2) |
O13—V1—O23i | 78.17 (16) | O15—V5—O11 | 95.5 (2) |
O12—V1—O23i | 74.09 (15) | O20—V5—O16 | 99.8 (2) |
O22—V1—V4 | 136.58 (18) | O15—V5—O16 | 155.10 (19) |
O10—V1—V4 | 33.27 (14) | O11—V5—O16 | 90.46 (19) |
O11—V1—V4 | 84.33 (14) | O20—V5—O17i | 98.6 (2) |
O13—V1—V4 | 84.19 (13) | O15—V5—O17i | 89.02 (18) |
O12—V1—V4 | 122.60 (13) | O11—V5—O17i | 156.06 (19) |
O23i—V1—V4 | 48.52 (10) | O16—V5—O17i | 76.36 (17) |
O22—V1—V2 | 131.74 (18) | O20—V5—O23i | 174.0 (2) |
O10—V1—V2 | 124.94 (14) | O15—V5—O23i | 81.21 (17) |
O11—V1—V2 | 79.33 (14) | O11—V5—O23i | 81.00 (18) |
O13—V1—V2 | 78.94 (13) | O16—V5—O23i | 75.87 (16) |
O12—V1—V2 | 30.95 (12) | O17i—V5—O23i | 76.47 (16) |
O23i—V1—V2 | 43.15 (10) | O20—V5—V3i | 89.32 (17) |
V4—V1—V2 | 91.66 (4) | O15—V5—V3i | 128.41 (14) |
O22—V1—V3 | 133.04 (18) | O11—V5—V3i | 130.76 (15) |
O10—V1—V3 | 81.99 (14) | O16—V5—V3i | 40.31 (12) |
O11—V1—V3 | 124.17 (14) | O17i—V5—V3i | 39.39 (12) |
O13—V1—V3 | 32.07 (12) | O23i—V5—V3i | 84.70 (11) |
O12—V1—V3 | 80.61 (13) | O20—V5—V1 | 136.84 (17) |
O23i—V1—V3 | 46.54 (11) | O15—V5—V1 | 84.42 (14) |
V4—V1—V3 | 60.74 (4) | O11—V5—V1 | 33.65 (14) |
V2—V1—V3 | 61.36 (3) | O16—V5—V1 | 87.34 (12) |
O22—V1—V5 | 134.90 (18) | O17i—V5—V1 | 124.32 (12) |
O10—V1—V5 | 81.90 (14) | O23i—V5—V1 | 47.87 (11) |
O11—V1—V5 | 32.44 (13) | V3i—V5—V1 | 119.90 (4) |
O13—V1—V5 | 123.83 (13) | O20—V5—V4 | 136.08 (18) |
O12—V1—V5 | 82.12 (12) | O15—V5—V4 | 33.97 (14) |
O23i—V1—V5 | 45.67 (11) | O11—V5—V4 | 83.81 (14) |
V4—V1—V5 | 60.53 (4) | O16—V5—V4 | 123.67 (12) |
V2—V1—V5 | 61.60 (3) | O17i—V5—V4 | 87.03 (12) |
V3—V1—V5 | 92.01 (4) | O23i—V5—V4 | 47.85 (11) |
O21—V2—O12 | 106.9 (2) | V3i—V5—V4 | 118.84 (5) |
O21—V2—O16 | 97.28 (19) | V1—V5—V4 | 58.95 (3) |
O12—V2—O16 | 98.2 (2) | V4—O10—V1 | 113.2 (2) |
O21—V2—O17 | 96.04 (19) | V5—O11—V1 | 113.9 (2) |
O12—V2—O17 | 96.29 (19) | V2—O12—V1 | 110.6 (2) |
O16—V2—O17 | 156.54 (18) | V3—O13—V1 | 114.1 (2) |
O21—V2—O23i | 165.88 (19) | V3—O14—V4 | 114.2 (2) |
O12—V2—O23i | 87.21 (19) | V5—O15—V4 | 114.1 (2) |
O16—V2—O23i | 80.67 (16) | V2—O16—V5 | 106.85 (18) |
O17—V2—O23i | 81.70 (17) | V2—O16—V3i | 107.5 (2) |
O21—V2—O23 | 87.28 (18) | V5—O16—V3i | 99.77 (18) |
O12—V2—O23 | 165.75 (19) | V2—O17—V3 | 106.32 (19) |
O16—V2—O23 | 80.96 (18) | V2—O17—V5i | 107.01 (19) |
O17—V2—O23 | 80.48 (17) | V3—O17—V5i | 100.80 (18) |
O23i—V2—O23 | 78.60 (17) | V2—O21—V4i | 110.6 (2) |
O21—V2—V1 | 145.34 (15) | V2i—O23—V2 | 101.40 (17) |
O12—V2—V1 | 38.44 (14) | V2i—O23—V5i | 93.89 (16) |
O16—V2—V1 | 89.92 (13) | V2—O23—V5i | 93.55 (16) |
O17—V2—V1 | 90.03 (13) | V2i—O23—V3i | 92.44 (16) |
O23i—V2—V1 | 48.78 (12) | V2—O23—V3i | 93.37 (17) |
O23—V2—V1 | 127.38 (12) | V5i—O23—V3i | 169.5 (2) |
O21—V2—V4i | 38.63 (14) | V2i—O23—V4i | 171.0 (2) |
O12—V2—V4i | 145.53 (15) | V2—O23—V4i | 87.57 (15) |
O16—V2—V4i | 89.06 (13) | V5i—O23—V4i | 86.48 (15) |
O17—V2—V4i | 89.38 (13) | V3i—O23—V4i | 85.97 (14) |
O23i—V2—V4i | 127.26 (12) | V2i—O23—V1i | 88.08 (15) |
O23—V2—V4i | 48.66 (11) | V2—O23—V1i | 170.5 (2) |
V1—V2—V4i | 176.03 (5) | V5i—O23—V1i | 86.46 (15) |
O18—V3—O13 | 104.2 (2) | V3i—O23—V1i | 85.42 (14) |
O18—V3—O14 | 102.5 (2) | V4i—O23—V1i | 82.95 (14) |
Symmetry code: (i) −x, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O9 | 0.82 | 2.31 | 2.712 (7) | 111 |
O1—H1A···O4W | 0.96 | 1.88 | 2.737 (8) | 147 |
O2W—H2WA···O3W | 0.85 | 2.02 | 2.58 (2) | 123 |
O4W—H4WB···O20 | 0.85 | 2.01 | 2.855 (8) | 180 |
O5W—H5WB···O2W | 0.85 | 2.53 | 3.019 (18) | 118 |
O1W—H1WB···O11ii | 0.85 | 2.26 | 2.781 (7) | 120 |
O5W—H5WB···O11ii | 0.85 | 2.44 | 3.020 (8) | 126 |
O2—H2B···O20ii | 0.96 | 2.51 | 3.363 (7) | 148 |
O7—H7A···O16ii | 0.85 | 1.92 | 2.689 (6) | 151 |
O1W—H1WA···O12iii | 0.85 | 2.31 | 3.013 (7) | 140 |
O2W—H2WA···O21iii | 0.85 | 2.16 | 2.838 (14) | 137 |
O3W—H3WB···O21iii | 0.85 | 2.61 | 3.185 (9) | 126 |
O4W—H4WA···O18iii | 0.85 | 2.32 | 3.128 (8) | 159 |
O5—H5B···O22iii | 0.96 | 2.39 | 3.220 (7) | 145 |
O7—H7B···O22iii | 0.85 | 2.12 | 2.971 (6) | 174 |
O8—H8B···O13iii | 0.96 | 2.65 | 3.606 (7) | 173 |
O3W—H3WA···O6iv | 0.85 | 2.45 | 2.991 (9) | 122 |
O3W—H3WA···O4iv | 0.85 | 2.61 | 3.202 (10) | 128 |
O3W—H3WB···O19v | 0.85 | 2.37 | 3.190 (10) | 162 |
O4W—H4WA···O5Wvi | 0.85 | 2.53 | 2.944 (9) | 111 |
O5W—H5WA···O18vii | 0.85 | 2.39 | 2.912 (8) | 120 |
O1—H1B···O1Wvi | 0.82 | 2.09 | 2.841 (7) | 153 |
O3—H3B···O19vi | 0.96 | 2.59 | 3.339 (8) | 135 |
O4—H4A···O10vi | 0.85 | 2.36 | 2.792 (6) | 112 |
O6—H6B···O19vi | 0.85 | 2.09 | 2.814 (7) | 143 |
O8—H8A···O5Wvi | 0.96 | 2.15 | 2.899 (9) | 134 |
O8—H8A···O2Wvi | 0.96 | 2.35 | 3.087 (15) | 134 |
O3—H3B···O20viii | 0.96 | 2.30 | 2.814 (7) | 112 |
O3—H3A···O18ix | 0.96 | 2.50 | 3.198 (7) | 130 |
O4—H4A···O2Wx | 0.85 | 2.48 | 3.016 (14) | 122 |
O4—H4B···O3Wx | 0.85 | 2.23 | 2.837 (9) | 128 |
O5—H5A···O3Wx | 0.96 | 1.80 | 2.748 (10) | 171 |
O6—H6A···O14xi | 0.85 | 2.00 | 2.731 (6) | 144 |
O9—H9A···O17ix | 0.82 | 2.02 | 2.761 (6) | 150 |
O9—H9B···O21ix | 0.96 | 2.57 | 3.140 (7) | 118 |
Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+1, −z+1; (v) −x, y−1/2, −z+3/2; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+1, −y+1, −z+2; (viii) x+1, y, z; (ix) −x+1, −y+2, −z+2; (x) x, y+1, z; (xi) x+1, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [La(H2O)9]2[V10O28]·8H2O |
Mr | 1703.64 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.818 (2), 11.935 (2), 19.514 (4) |
β (°) | 98.42 (3) |
V (Å3) | 2262.0 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.94 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Enraf-nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.403, 0.456 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4226, 3979, 3460 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.124, 1.07 |
No. of reflections | 3979 |
No. of parameters | 322 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −0.79 |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 SDP/VAX (Enraf-Nonius, 1989), TEXSAN (Molecular Structure Corporation, 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O9 | 0.82 | 2.31 | 2.712 (7) | 110.5 |
O1—H1A···O4W | 0.96 | 1.88 | 2.737 (8) | 146.8 |
O2W—H2WA···O3W | 0.85 | 2.02 | 2.58 (2) | 122.7 |
O4W—H4WB···O20 | 0.85 | 2.01 | 2.855 (8) | 180.0 |
O5W—H5WB···O2W | 0.85 | 2.53 | 3.019 (18) | 117.5 |
O1W—H1WB···O11i | 0.85 | 2.26 | 2.781 (7) | 120.1 |
O5W—H5WB···O11i | 0.85 | 2.44 | 3.020 (8) | 126.0 |
O2—H2B···O20i | 0.96 | 2.51 | 3.363 (7) | 148.1 |
O7—H7A···O16i | 0.85 | 1.92 | 2.689 (6) | 150.6 |
O1W—H1WA···O12ii | 0.85 | 2.31 | 3.013 (7) | 139.8 |
O2W—H2WA···O21ii | 0.85 | 2.16 | 2.838 (14) | 136.5 |
O3W—H3WB···O21ii | 0.85 | 2.61 | 3.185 (9) | 126.1 |
O4W—H4WA···O18ii | 0.85 | 2.32 | 3.128 (8) | 158.5 |
O5—H5B···O22ii | 0.96 | 2.39 | 3.220 (7) | 144.7 |
O7—H7B···O22ii | 0.85 | 2.12 | 2.971 (6) | 173.6 |
O8—H8B···O13ii | 0.96 | 2.65 | 3.606 (7) | 173.4 |
O3W—H3WA···O6iii | 0.85 | 2.45 | 2.991 (9) | 121.8 |
O3W—H3WA···O4iii | 0.85 | 2.61 | 3.202 (10) | 127.7 |
O3W—H3WB···O19iv | 0.85 | 2.37 | 3.190 (10) | 162.0 |
O4W—H4WA···O5Wv | 0.85 | 2.53 | 2.944 (9) | 110.7 |
O5W—H5WA···O18vi | 0.85 | 2.39 | 2.912 (8) | 120.2 |
O1—H1B···O1Wv | 0.82 | 2.09 | 2.841 (7) | 152.5 |
O3—H3B···O19v | 0.96 | 2.59 | 3.339 (8) | 135.2 |
O4—H4A···O10v | 0.85 | 2.36 | 2.792 (6) | 111.7 |
O6—H6B···O19v | 0.85 | 2.09 | 2.814 (7) | 143.3 |
O8—H8A···O5Wv | 0.96 | 2.15 | 2.899 (9) | 133.9 |
O8—H8A···O2Wv | 0.96 | 2.35 | 3.087 (15) | 133.6 |
O3—H3B···O20vii | 0.96 | 2.30 | 2.814 (7) | 112.4 |
O3—H3A···O18viii | 0.96 | 2.50 | 3.198 (7) | 129.8 |
O4—H4A···O2Wix | 0.85 | 2.48 | 3.016 (14) | 122.2 |
O4—H4B···O3Wix | 0.85 | 2.23 | 2.837 (9) | 127.9 |
O5—H5A···O3Wix | 0.96 | 1.80 | 2.748 (10) | 170.5 |
O6—H6A···O14x | 0.85 | 2.00 | 2.731 (6) | 144.0 |
O9—H9A···O17viii | 0.82 | 2.02 | 2.761 (6) | 149.8 |
O9—H9B···O21viii | 0.96 | 2.57 | 3.140 (7) | 118.0 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x, y−1/2, −z+3/2; (v) −x+1, y+1/2, −z+3/2; (vi) −x+1, −y+1, −z+2; (vii) x+1, y, z; (viii) −x+1, −y+2, −z+2; (ix) x, y+1, z; (x) x+1, −y+3/2, z−1/2. |
Since the idea of supramolecular chemistry was brought forward by Lehn (1988), polyacid supramolecular chemistry has fast developed due to the fact that polyacid supramolecular compounds possess the ability to store electrons. Polyacids belong to a kind of ligand which can form a supramolecule with organic or inorganic ions, and possess electricity, magnetic and non-linear optical properties. In order to investigate the relativity between the macroproperty and microproperty of polyacid supramolecular compounds, the novel title compound was synthesized.
The crystal data of the title compound shows that V cluster plays a main role with with a 6- charge and La(H2O)9 with a 3+ charge plays a guest role in the polyacid supramolecular compound. The oxidation number of La is three and the oxidation number of V is five. All the coordination polyhedrons of V are distorted octahedrons. The O atoms as bridging ligands coordinate to V with four types: (i) end coordinated (O18, O19, O20 and O22), with V—O distances in the range 1.604 (5)–1.620 (4) Å; (ii) bridged coordination (O10, O11, O12, O13, O14, O15 and O21), with V—O distances in the range 1.677 (4)–2.037 (4) Å; (iii) tribridged coordination (O16 and O17), with V—O distances in the range 1.927 (4)–1.935 (4) Å; and (iv) hexbridged coordination (O23), with V—O distances in the range 2.098 (4)–2.308 (4) Å. The V—V distances are in the range 3.0563 (16)–3.1093 (16) Å, the O—V—O bond angles are in the range 74.09 (15)–174.9 (2)°, and the V—O—V bond angles are in the range 82.95 (14)–171.0 (2)°. The La(H2O)9 cations are arranged as pillars (see Fig. 3) along the a axis, with La—O distances in the range 2.414 (5)–2.540 (5) Å. There are 35 hydrogen bonds formed (Table 2) in a molecule of the polyacid supramolecular compound, with O···O distance in the range 2.58 (2)–3.606 (7) Å, which form a three-dimensional network.