Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017835/cv6211sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017835/cv6211Isup2.hkl |
CCDC reference: 222811
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.007 Å
- H-atom completeness 15%
- R factor = 0.036
- wR factor = 0.069
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ..... 0.98
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .. ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .. ? PLAT043_ALERT_1_C Check Reported Molecular Weight .............. 1544.87 PLAT044_ALERT_1_C Calculated and Reported Dx Differ ............ ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing). ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ..... ? PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) . 3.45 Ratio PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .. Na4 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .. O21 PLAT764_ALERT_4_C Overcomplete CIF Bond list Detected (Rep/Expd) 1.37 Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF .... 38.60 Deg. O2 -P1 -NA1 1.555 1.555 3.555
Alert level G FORMU01_ALERT_1_G 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: C4 H42 Co1 Mo4 Na8 O44 P4 Atom count from _chemical_formula_moiety:H36 Co1 Mo4 O30 FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C4 H42 Co1 Mo4 Na8 O44 P4 Atom count from the _atom_site data: C4 H6 Co1 Mo4 Na8 O44 P4 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C4 H42 Co Mo4 Na8 O44 P4 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 8.00 8.00 0.00 H 84.00 12.00 72.00 Co 2.00 2.00 0.00 Mo 8.00 8.00 0.00 Na 16.00 16.00 0.00 O 88.00 88.00 0.00 P 8.00 8.00 0.00 CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_weight 1544.87 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 4.00 48.04 H 1.01 6.00 6.05 Co 58.93 1.00 58.93 Mo 95.94 4.00 383.76 P 30.97 4.00 123.90 O 16.00 44.00 703.96 Na 22.99 8.00 183.92 Calculated formula weight 1508.56
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion
The synthesis of the title anion was accomplished by reacting Na2MoO4, hedp and CoCl2 according to the ratio of 12:1:1 at pH 5.5. The mixed solution was kept at 333 K for 2 h and was then filtrated. The clear filtrate was kept at room temperature. Within a few days, red block-shaped crystals formed in a very good yield. The elemental analysis results are completely in agreement with the structural composition of the title compound.
The H atoms on C atoms were treated as riding, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq of the parent atom. The positions of the water H atoms were not found.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The anion of the title compound, with the atom-numbering scheme and 50%-probability displacement ellipsoids. | |
Fig. 2. Packing diagram of the title compound. |
Na8[CoMo4O12(C2H3O7P2)2]·18H2O | Dx = 2.301 Mg m−3 |
Mr = 1544.87 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.660 (3) Å | Cell parameters from 2446 reflections |
b = 22.381 (8) Å | θ = 2.3–25.8° |
c = 10.441 (4) Å | µ = 1.80 mm−1 |
β = 99.049 (5)° | T = 298 K |
V = 2229.3 (14) Å3 | Block, red |
Z = 2 | 0.28 × 0.13 × 0.08 mm |
F(000) = 1522 |
Bruker SMART CCD area-detector diffractometer | 4434 independent reflections |
Radiation source: fine-focus sealed tube | 2784 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −12→11 |
Tmin = 0.632, Tmax = 0.869 | k = −27→12 |
12461 measured reflections | l = −13→13 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0182P)2] where P = (Fo2 + 2Fc2)/3 |
4434 reflections | (Δ/σ)max = 0.005 |
295 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.67 e Å−3 |
Na8[CoMo4O12(C2H3O7P2)2]·18H2O | V = 2229.3 (14) Å3 |
Mr = 1544.87 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.660 (3) Å | µ = 1.80 mm−1 |
b = 22.381 (8) Å | T = 298 K |
c = 10.441 (4) Å | 0.28 × 0.13 × 0.08 mm |
β = 99.049 (5)° |
Bruker SMART CCD area-detector diffractometer | 4434 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2784 reflections with I > 2σ(I) |
Tmin = 0.632, Tmax = 0.869 | Rint = 0.058 |
12461 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.61 e Å−3 |
4434 reflections | Δρmin = −0.67 e Å−3 |
295 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 | ||
Mo1 | −0.12374 (5) | 0.12553 (2) | 0.17579 (4) | 0.01872 (12) | |
Mo2 | 0.16637 (5) | 0.18133 (2) | 0.32637 (4) | 0.01953 (12) | |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.0184 (2) | |
Na1 | 0.0824 (2) | 0.06291 (11) | −0.2582 (2) | 0.0378 (6) | |
Na2 | 0.5771 (2) | 0.16266 (10) | 0.3648 (2) | 0.0329 (6) | |
Na3 | 0.0831 (2) | 0.33871 (12) | 0.1922 (2) | 0.0485 (7) | |
Na4 | 0.4156 (3) | 0.30286 (12) | 0.1834 (3) | 0.0570 (8) | |
P1 | 0.18111 (14) | 0.03598 (6) | 0.28463 (13) | 0.0191 (3) | |
P2 | 0.19697 (13) | 0.11605 (6) | 0.05250 (12) | 0.0176 (3) | |
O1 | 0.0746 (3) | 0.08418 (15) | 0.3183 (3) | 0.0199 (8) | |
O2 | 0.1104 (3) | −0.01204 (15) | 0.1948 (3) | 0.0223 (8) | |
O3 | 0.2689 (4) | 0.01161 (17) | 0.4065 (3) | 0.0302 (9) | |
O4 | 0.0874 (3) | 0.15448 (15) | 0.1112 (3) | 0.0174 (8) | |
O5 | 0.1314 (3) | 0.06809 (15) | −0.0387 (3) | 0.0198 (8) | |
O6 | 0.2951 (3) | 0.15678 (16) | −0.0061 (3) | 0.0256 (9) | |
O7 | 0.3258 (3) | 0.13260 (15) | 0.2865 (3) | 0.0202 (8) | |
O8 | −0.0256 (3) | 0.18937 (15) | 0.3018 (3) | 0.0237 (8) | |
O9 | −0.1147 (3) | 0.06137 (16) | 0.0824 (3) | 0.0247 (9) | |
O10 | −0.2394 (3) | 0.10619 (16) | 0.2796 (3) | 0.0262 (9) | |
O11 | −0.2148 (3) | 0.17514 (16) | 0.0667 (3) | 0.0259 (9) | |
O12 | 0.2117 (4) | 0.18257 (17) | 0.4921 (3) | 0.0314 (9) | |
O13 | 0.2220 (4) | 0.24900 (16) | 0.2755 (3) | 0.0294 (9) | |
O14 | 0.2670 (4) | 0.01666 (19) | −0.3326 (4) | 0.0393 (11) | |
O15 | 0.1455 (4) | 0.16576 (19) | −0.2635 (4) | 0.0398 (11) | |
O16 | −0.0628 (5) | 0.0895 (2) | −0.4498 (4) | 0.0553 (13) | |
O17 | 0.5490 (4) | 0.08430 (18) | 0.5262 (4) | 0.0380 (10) | |
O18 | 0.5278 (4) | 0.20830 (18) | 0.1525 (4) | 0.0358 (10) | |
O19 | 0.4917 (4) | 0.2284 (2) | 0.5209 (4) | 0.0423 (11) | |
O20 | 0.7857 (4) | 0.21692 (19) | 0.4718 (4) | 0.0412 (11) | |
O21 | 0.3029 (4) | 0.37110 (17) | 0.3058 (4) | 0.0350 (10) | |
O22 | −0.0500 (5) | 0.3941 (2) | 0.3119 (4) | 0.0599 (14) | |
C1 | 0.2929 (5) | 0.0824 (2) | 0.1999 (5) | 0.0199 (12) | |
C2 | 0.4256 (5) | 0.0499 (3) | 0.1756 (5) | 0.0267 (13) | |
H2A | 0.4004 | 0.0168 | 0.1181 | 0.040* | |
H2B | 0.4757 | 0.0355 | 0.2564 | 0.040* | |
H2C | 0.4841 | 0.0771 | 0.1369 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0196 (2) | 0.0152 (2) | 0.0218 (2) | 0.0000 (2) | 0.00487 (19) | −0.0020 (2) |
Mo2 | 0.0226 (2) | 0.0153 (2) | 0.0210 (2) | −0.0019 (2) | 0.00442 (19) | −0.0033 (2) |
Co1 | 0.0236 (6) | 0.0141 (5) | 0.0183 (5) | 0.0008 (4) | 0.0055 (4) | 0.0003 (4) |
Na1 | 0.0429 (14) | 0.0431 (15) | 0.0274 (12) | −0.0069 (12) | 0.0061 (10) | −0.0004 (12) |
Na2 | 0.0346 (12) | 0.0316 (14) | 0.0332 (13) | 0.0015 (11) | 0.0070 (10) | −0.0042 (11) |
Na3 | 0.0491 (15) | 0.0412 (16) | 0.0541 (17) | −0.0002 (13) | 0.0047 (13) | 0.0028 (13) |
Na4 | 0.0444 (15) | 0.0525 (18) | 0.0726 (19) | 0.0029 (14) | 0.0050 (14) | −0.0225 (15) |
P1 | 0.0239 (8) | 0.0151 (7) | 0.0181 (7) | 0.0011 (6) | 0.0028 (6) | 0.0016 (6) |
P2 | 0.0201 (7) | 0.0148 (7) | 0.0184 (7) | −0.0018 (6) | 0.0049 (6) | 0.0000 (6) |
O1 | 0.0212 (18) | 0.018 (2) | 0.0210 (18) | −0.0019 (16) | 0.0061 (15) | −0.0009 (16) |
O2 | 0.028 (2) | 0.015 (2) | 0.024 (2) | −0.0003 (16) | 0.0034 (16) | 0.0008 (16) |
O3 | 0.038 (2) | 0.029 (2) | 0.023 (2) | 0.0077 (19) | 0.0016 (17) | 0.0027 (18) |
O4 | 0.0206 (18) | 0.0146 (19) | 0.0183 (18) | 0.0015 (15) | 0.0069 (14) | −0.0013 (15) |
O5 | 0.027 (2) | 0.0133 (19) | 0.0201 (18) | −0.0036 (16) | 0.0074 (15) | −0.0029 (16) |
O6 | 0.027 (2) | 0.025 (2) | 0.026 (2) | −0.0049 (17) | 0.0072 (16) | 0.0004 (17) |
O7 | 0.0203 (18) | 0.0164 (19) | 0.0238 (19) | 0.0009 (16) | 0.0029 (15) | −0.0039 (16) |
O8 | 0.027 (2) | 0.017 (2) | 0.027 (2) | 0.0007 (17) | 0.0057 (16) | −0.0064 (17) |
O9 | 0.0233 (19) | 0.021 (2) | 0.030 (2) | 0.0000 (17) | 0.0059 (16) | −0.0066 (18) |
O10 | 0.0253 (19) | 0.020 (2) | 0.035 (2) | −0.0019 (17) | 0.0108 (17) | −0.0029 (18) |
O11 | 0.0255 (19) | 0.022 (2) | 0.030 (2) | 0.0051 (17) | 0.0037 (16) | 0.0030 (18) |
O12 | 0.040 (2) | 0.028 (2) | 0.026 (2) | −0.003 (2) | 0.0061 (17) | −0.0038 (19) |
O13 | 0.035 (2) | 0.016 (2) | 0.038 (2) | −0.0046 (17) | 0.0079 (18) | −0.0035 (18) |
O14 | 0.043 (2) | 0.040 (3) | 0.035 (2) | 0.003 (2) | 0.0058 (19) | 0.004 (2) |
O15 | 0.040 (2) | 0.042 (3) | 0.037 (2) | −0.005 (2) | 0.0049 (19) | 0.006 (2) |
O16 | 0.061 (3) | 0.065 (3) | 0.037 (3) | −0.014 (3) | −0.002 (2) | 0.005 (2) |
O17 | 0.045 (2) | 0.028 (2) | 0.043 (3) | 0.002 (2) | 0.011 (2) | 0.002 (2) |
O18 | 0.036 (2) | 0.031 (2) | 0.042 (2) | 0.0024 (19) | 0.0095 (19) | 0.002 (2) |
O19 | 0.034 (2) | 0.041 (3) | 0.054 (3) | 0.002 (2) | 0.012 (2) | −0.019 (2) |
O20 | 0.037 (2) | 0.042 (3) | 0.045 (3) | 0.000 (2) | 0.008 (2) | −0.015 (2) |
O21 | 0.044 (2) | 0.024 (2) | 0.037 (2) | −0.002 (2) | 0.0038 (19) | −0.004 (2) |
O22 | 0.057 (3) | 0.067 (4) | 0.062 (3) | 0.006 (3) | 0.028 (2) | 0.014 (3) |
C1 | 0.020 (3) | 0.021 (3) | 0.019 (3) | 0.005 (2) | 0.002 (2) | 0.003 (2) |
C2 | 0.023 (3) | 0.026 (3) | 0.032 (3) | 0.003 (3) | 0.004 (2) | 0.000 (3) |
Mo1—O11 | 1.729 (3) | Na3—O22 | 2.293 (5) |
Mo1—O10 | 1.730 (3) | Na3—O21 | 2.377 (4) |
Mo1—O9 | 1.746 (4) | Na3—O19ii | 2.396 (5) |
Mo1—O8 | 2.068 (3) | Na3—O17ii | 2.429 (5) |
Mo1—O4 | 2.339 (3) | Na3—O13 | 2.494 (5) |
Mo1—O1 | 2.418 (3) | Na3—Na4 | 3.326 (4) |
Mo2—O12 | 1.717 (4) | Na3—Na2ii | 3.410 (4) |
Mo2—O13 | 1.719 (4) | Na4—O15iv | 2.312 (5) |
Mo2—O8 | 1.841 (3) | Na4—O21 | 2.364 (4) |
Mo2—O7 | 1.984 (3) | Na4—O20ii | 2.404 (5) |
Mo2—O4 | 2.335 (3) | Na4—O18 | 2.422 (5) |
Mo2—O1 | 2.345 (3) | Na4—O13 | 2.538 (4) |
Co1—O9 | 2.038 (3) | Na4—O16iv | 2.806 (6) |
Co1—O9i | 2.038 (3) | Na4—Na1iv | 3.418 (4) |
Co1—O5 | 2.064 (3) | P1—O3 | 1.515 (4) |
Co1—O5i | 2.064 (3) | P1—O2 | 1.516 (4) |
Co1—O2 | 2.160 (3) | P1—O1 | 1.568 (4) |
Co1—O2i | 2.160 (3) | P1—C1 | 1.824 (5) |
Co1—Na1 | 3.249 (2) | P1—Na1i | 3.351 (3) |
Co1—Na1i | 3.249 (2) | P2—O5 | 1.507 (3) |
Na1—O5 | 2.269 (4) | P2—O6 | 1.512 (4) |
Na1—O14 | 2.300 (5) | P2—O4 | 1.562 (3) |
Na1—O16 | 2.332 (5) | P2—C1 | 1.830 (5) |
Na1—O2i | 2.364 (4) | O2—Na1i | 2.364 (4) |
Na1—O15 | 2.384 (5) | O7—C1 | 1.446 (6) |
Na1—P1i | 3.351 (3) | O10—Na2v | 2.455 (4) |
Na1—Na4ii | 3.418 (4) | O15—Na4ii | 2.312 (5) |
Na2—O18 | 2.419 (5) | O16—Na4ii | 2.806 (6) |
Na2—O19 | 2.434 (4) | O17—Na3iv | 2.429 (5) |
Na2—O10iii | 2.455 (4) | O19—Na3iv | 2.396 (5) |
Na2—O20 | 2.465 (4) | O20—Na4iv | 2.404 (5) |
Na2—O17 | 2.476 (4) | C1—C2 | 1.529 (7) |
Na2—O7 | 2.527 (4) | C2—H2A | 0.9600 |
Na2—Na3iv | 3.410 (4) | C2—H2B | 0.9600 |
Na2—Na4 | 3.865 (4) | C2—H2C | 0.9600 |
O11—Mo1—O10 | 105.17 (16) | O22—Na3—O21 | 95.52 (18) |
O11—Mo1—O9 | 103.01 (17) | O22—Na3—O19ii | 125.03 (18) |
O10—Mo1—O9 | 103.78 (17) | O21—Na3—O19ii | 139.39 (17) |
O11—Mo1—O8 | 96.33 (15) | O22—Na3—O17ii | 88.93 (17) |
O10—Mo1—O8 | 92.92 (15) | O21—Na3—O17ii | 98.62 (16) |
O9—Mo1—O8 | 149.92 (14) | O19ii—Na3—O17ii | 85.39 (15) |
O11—Mo1—O4 | 90.49 (14) | O22—Na3—O13 | 124.16 (18) |
O10—Mo1—O4 | 158.27 (14) | O21—Na3—O13 | 71.46 (14) |
O9—Mo1—O4 | 86.80 (13) | O19ii—Na3—O13 | 82.55 (15) |
O8—Mo1—O4 | 70.05 (12) | O17ii—Na3—O13 | 145.58 (17) |
O11—Mo1—O1 | 157.41 (14) | O22—Na3—Na4 | 140.53 (16) |
O10—Mo1—O1 | 92.64 (14) | O21—Na3—Na4 | 45.29 (11) |
O9—Mo1—O1 | 85.68 (14) | O19ii—Na3—Na4 | 94.13 (13) |
O8—Mo1—O1 | 68.49 (12) | O17ii—Na3—Na4 | 100.05 (13) |
O4—Mo1—O1 | 68.96 (11) | O13—Na3—Na4 | 49.20 (10) |
O12—Mo2—O13 | 104.74 (18) | O22—Na3—Na2ii | 128.99 (15) |
O12—Mo2—O8 | 103.33 (16) | O21—Na3—Na2ii | 112.10 (13) |
O13—Mo2—O8 | 103.17 (16) | O19ii—Na3—Na2ii | 45.55 (11) |
O12—Mo2—O7 | 97.90 (16) | O17ii—Na3—Na2ii | 46.54 (11) |
O13—Mo2—O7 | 97.40 (15) | O13—Na3—Na2ii | 105.43 (12) |
O8—Mo2—O7 | 145.36 (14) | Na4—Na3—Na2ii | 80.47 (8) |
O12—Mo2—O4 | 165.20 (15) | O15iv—Na4—O21 | 100.41 (17) |
O13—Mo2—O4 | 90.01 (15) | O15iv—Na4—O20ii | 128.27 (18) |
O8—Mo2—O4 | 73.83 (13) | O21—Na4—O20ii | 113.42 (17) |
O7—Mo2—O4 | 78.65 (12) | O15iv—Na4—O18 | 82.21 (15) |
O12—Mo2—O1 | 94.95 (15) | O21—Na4—O18 | 152.90 (18) |
O13—Mo2—O1 | 160.21 (14) | O20ii—Na4—O18 | 84.06 (16) |
O8—Mo2—O1 | 73.65 (13) | O15iv—Na4—O13 | 142.23 (19) |
O7—Mo2—O1 | 77.55 (13) | O21—Na4—O13 | 70.88 (14) |
O4—Mo2—O1 | 70.27 (11) | O20ii—Na4—O13 | 87.23 (15) |
O9—Co1—O9i | 180.0 (2) | O18—Na4—O13 | 90.43 (15) |
O9—Co1—O5 | 88.69 (13) | O15iv—Na4—O16iv | 73.42 (16) |
O9i—Co1—O5 | 91.31 (13) | O21—Na4—O16iv | 77.85 (15) |
O9—Co1—O5i | 91.31 (13) | O20ii—Na4—O16iv | 76.78 (15) |
O9i—Co1—O5i | 88.69 (13) | O18—Na4—O16iv | 127.91 (16) |
O5—Co1—O5i | 180.0 (2) | O13—Na4—O16iv | 135.42 (16) |
O9—Co1—O2 | 84.68 (13) | O15iv—Na4—Na3 | 144.63 (15) |
O9i—Co1—O2 | 95.32 (13) | O21—Na4—Na3 | 45.60 (11) |
O5—Co1—O2 | 92.80 (12) | O20ii—Na4—Na3 | 72.72 (12) |
O5i—Co1—O2 | 87.20 (12) | O18—Na4—Na3 | 131.97 (14) |
O9—Co1—O2i | 95.32 (13) | O13—Na4—Na3 | 48.07 (10) |
O9i—Co1—O2i | 84.68 (13) | O16iv—Na4—Na3 | 87.35 (12) |
O5—Co1—O2i | 87.20 (12) | O15iv—Na4—Na1iv | 44.12 (12) |
O5i—Co1—O2i | 92.80 (12) | O21—Na4—Na1iv | 65.17 (12) |
O2—Co1—O2i | 180.0 (2) | O20ii—Na4—Na1iv | 119.27 (15) |
O9—Co1—Na1 | 106.17 (11) | O18—Na4—Na1iv | 125.69 (13) |
O9i—Co1—Na1 | 73.83 (11) | O13—Na4—Na1iv | 134.79 (13) |
O5—Co1—Na1 | 43.87 (10) | O16iv—Na4—Na1iv | 42.61 (10) |
O5i—Co1—Na1 | 136.13 (10) | Na3—Na4—Na1iv | 102.31 (9) |
O2—Co1—Na1 | 133.35 (10) | O15iv—Na4—Na2 | 80.25 (13) |
O2i—Co1—Na1 | 46.65 (10) | O21—Na4—Na2 | 116.38 (14) |
O9—Co1—Na1i | 73.83 (11) | O20ii—Na4—Na2 | 114.39 (14) |
O9i—Co1—Na1i | 106.17 (11) | O18—Na4—Na2 | 37.00 (11) |
O5—Co1—Na1i | 136.13 (10) | O13—Na4—Na2 | 72.14 (11) |
O5i—Co1—Na1i | 43.87 (10) | O16iv—Na4—Na2 | 152.16 (13) |
O2—Co1—Na1i | 46.65 (10) | Na3—Na4—Na2 | 119.97 (10) |
O2i—Co1—Na1i | 133.35 (10) | Na1iv—Na4—Na2 | 118.92 (9) |
Na1—Co1—Na1i | 180.00 (10) | O3—P1—O2 | 113.7 (2) |
O5—Na1—O14 | 108.32 (16) | O3—P1—O1 | 111.1 (2) |
O5—Na1—O16 | 148.76 (19) | O2—P1—O1 | 112.22 (19) |
O14—Na1—O16 | 102.64 (18) | O3—P1—C1 | 108.4 (2) |
O5—Na1—O2i | 77.91 (13) | O2—P1—C1 | 110.3 (2) |
O14—Na1—O2i | 124.36 (17) | O1—P1—C1 | 100.2 (2) |
O16—Na1—O2i | 88.22 (15) | O3—P1—Na1i | 98.56 (16) |
O5—Na1—O15 | 87.73 (15) | O2—P1—Na1i | 38.60 (14) |
O14—Na1—O15 | 102.25 (16) | O1—P1—Na1i | 87.48 (14) |
O16—Na1—O15 | 81.69 (17) | C1—P1—Na1i | 146.71 (17) |
O2i—Na1—O15 | 133.39 (16) | O5—P2—O6 | 113.68 (19) |
O5—Na1—Co1 | 39.07 (9) | O5—P2—O4 | 113.39 (18) |
O14—Na1—Co1 | 112.91 (13) | O6—P2—O4 | 109.5 (2) |
O16—Na1—Co1 | 129.00 (14) | O5—P2—C1 | 110.2 (2) |
O2i—Na1—Co1 | 41.64 (9) | O6—P2—C1 | 108.8 (2) |
O15—Na1—Co1 | 122.30 (13) | O4—P2—C1 | 100.5 (2) |
O5—Na1—P1i | 98.75 (11) | P1—O1—Mo2 | 112.84 (17) |
O14—Na1—P1i | 107.11 (14) | P1—O1—Mo1 | 127.57 (18) |
O16—Na1—P1i | 75.60 (13) | Mo2—O1—Mo1 | 85.74 (11) |
O2i—Na1—P1i | 23.59 (9) | P1—O2—Co1 | 127.0 (2) |
O15—Na1—P1i | 146.03 (13) | P1—O2—Na1i | 117.8 (2) |
Co1—Na1—P1i | 60.02 (5) | Co1—O2—Na1i | 91.71 (13) |
O5—Na1—Na4ii | 98.80 (13) | P2—O4—Mo2 | 112.35 (17) |
O14—Na1—Na4ii | 134.74 (14) | P2—O4—Mo1 | 129.50 (19) |
O16—Na1—Na4ii | 54.53 (14) | Mo2—O4—Mo1 | 87.78 (11) |
O2i—Na1—Na4ii | 95.93 (12) | P2—O5—Co1 | 127.77 (19) |
O15—Na1—Na4ii | 42.46 (11) | P2—O5—Na1 | 132.5 (2) |
Co1—Na1—Na4ii | 111.02 (8) | Co1—O5—Na1 | 97.06 (14) |
P1i—Na1—Na4ii | 103.60 (8) | C1—O7—Mo2 | 117.2 (3) |
O18—Na2—O19 | 108.64 (16) | C1—O7—Na2 | 121.0 (3) |
O18—Na2—O10iii | 86.26 (14) | Mo2—O7—Na2 | 121.56 (16) |
O19—Na2—O10iii | 153.34 (15) | Mo2—O8—Mo1 | 111.85 (16) |
O18—Na2—O20 | 103.66 (16) | Mo1—O9—Co1 | 150.26 (19) |
O19—Na2—O20 | 74.78 (14) | Mo1—O10—Na2v | 132.27 (19) |
O10iii—Na2—O20 | 80.34 (14) | Mo2—O13—Na3 | 129.78 (19) |
O18—Na2—O17 | 153.62 (16) | Mo2—O13—Na4 | 145.1 (2) |
O19—Na2—O17 | 83.55 (16) | Na3—O13—Na4 | 82.74 (14) |
O10iii—Na2—O17 | 92.55 (14) | Na4ii—O15—Na1 | 93.41 (16) |
O20—Na2—O17 | 102.10 (15) | Na1—O16—Na4ii | 82.85 (15) |
O18—Na2—O7 | 77.02 (13) | Na3iv—O17—Na2 | 88.07 (16) |
O19—Na2—O7 | 88.20 (13) | Na2—O18—Na4 | 105.93 (17) |
O10iii—Na2—O7 | 117.21 (14) | Na3iv—O19—Na2 | 89.82 (16) |
O20—Na2—O7 | 162.33 (16) | Na4iv—O20—Na2 | 126.7 (2) |
O17—Na2—O7 | 80.18 (14) | Na4—O21—Na3 | 89.10 (15) |
O18—Na2—Na3iv | 153.16 (13) | O7—C1—C2 | 111.4 (4) |
O19—Na2—Na3iv | 44.63 (12) | O7—C1—P1 | 103.2 (3) |
O10iii—Na2—Na3iv | 117.32 (12) | C2—C1—P1 | 112.7 (4) |
O20—Na2—Na3iv | 70.51 (12) | O7—C1—P2 | 103.8 (3) |
O17—Na2—Na3iv | 45.40 (11) | C2—C1—P2 | 112.5 (3) |
O7—Na2—Na3iv | 100.72 (11) | P1—C1—P2 | 112.5 (3) |
O18—Na2—Na4 | 37.07 (10) | C1—C2—H2A | 109.5 |
O19—Na2—Na4 | 71.58 (13) | C1—C2—H2B | 109.5 |
O10iii—Na2—Na4 | 119.95 (12) | H2A—C2—H2B | 109.5 |
O20—Na2—Na4 | 93.45 (13) | C1—C2—H2C | 109.5 |
O17—Na2—Na4 | 146.05 (12) | H2A—C2—H2C | 109.5 |
O7—Na2—Na4 | 76.38 (10) | H2B—C2—H2C | 109.5 |
Na3iv—Na2—Na4 | 116.13 (8) |
Symmetry codes: (i) −x, −y, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1, y, z; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | Na8[CoMo4O12(C2H3O7P2)2]·18H2O |
Mr | 1544.87 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.660 (3), 22.381 (8), 10.441 (4) |
β (°) | 99.049 (5) |
V (Å3) | 2229.3 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.28 × 0.13 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.632, 0.869 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12461, 4434, 2784 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.069, 0.85 |
No. of reflections | 4434 |
No. of parameters | 295 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.67 |
Computer programs: SMART (Bruker, 1999), SMART, SHELXTL (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Mo1—O11 | 1.729 (3) | Co1—O5 | 2.064 (3) |
Mo1—O10 | 1.730 (3) | Co1—O5i | 2.064 (3) |
Mo1—O9 | 1.746 (4) | Co1—O2 | 2.160 (3) |
Mo1—O8 | 2.068 (3) | Co1—O2i | 2.160 (3) |
Mo1—O4 | 2.339 (3) | P1—O3 | 1.515 (4) |
Mo1—O1 | 2.418 (3) | P1—O2 | 1.516 (4) |
Mo2—O12 | 1.717 (4) | P1—O1 | 1.568 (4) |
Mo2—O13 | 1.719 (4) | P1—C1 | 1.824 (5) |
Mo2—O8 | 1.841 (3) | P2—O5 | 1.507 (3) |
Mo2—O7 | 1.984 (3) | P2—O6 | 1.512 (4) |
Mo2—O4 | 2.335 (3) | P2—O4 | 1.562 (3) |
Mo2—O1 | 2.345 (3) | P2—C1 | 1.830 (5) |
Co1—O9 | 2.038 (3) | O7—C1 | 1.446 (6) |
Co1—O9i | 2.038 (3) | ||
O11—Mo1—O10 | 105.17 (16) | O12—Mo2—O1 | 94.95 (15) |
O11—Mo1—O9 | 103.01 (17) | O13—Mo2—O1 | 160.21 (14) |
O10—Mo1—O9 | 103.78 (17) | O8—Mo2—O1 | 73.65 (13) |
O11—Mo1—O8 | 96.33 (15) | O7—Mo2—O1 | 77.55 (13) |
O10—Mo1—O8 | 92.92 (15) | O4—Mo2—O1 | 70.27 (11) |
O9—Mo1—O8 | 149.92 (14) | O9—Co1—O9i | 180.0 (2) |
O11—Mo1—O4 | 90.49 (14) | O9—Co1—O5 | 88.69 (13) |
O10—Mo1—O4 | 158.27 (14) | O9i—Co1—O5 | 91.31 (13) |
O9—Mo1—O4 | 86.80 (13) | O9—Co1—O5i | 91.31 (13) |
O8—Mo1—O4 | 70.05 (12) | O9i—Co1—O5i | 88.69 (13) |
O11—Mo1—O1 | 157.41 (14) | O5—Co1—O5i | 180.0 (2) |
O10—Mo1—O1 | 92.64 (14) | O9—Co1—O2 | 84.68 (13) |
O9—Mo1—O1 | 85.68 (14) | O9i—Co1—O2 | 95.32 (13) |
O8—Mo1—O1 | 68.49 (12) | O5—Co1—O2 | 92.80 (12) |
O4—Mo1—O1 | 68.96 (11) | O5i—Co1—O2 | 87.20 (12) |
O12—Mo2—O13 | 104.74 (18) | O9—Co1—O2i | 95.32 (13) |
O12—Mo2—O8 | 103.33 (16) | O9i—Co1—O2i | 84.68 (13) |
O13—Mo2—O8 | 103.17 (16) | O5—Co1—O2i | 87.20 (12) |
O12—Mo2—O7 | 97.90 (16) | O5i—Co1—O2i | 92.80 (12) |
O13—Mo2—O7 | 97.40 (15) | O2—Co1—O2i | 180.0 (2) |
O8—Mo2—O7 | 145.36 (14) | P1—O1—Mo2 | 112.84 (17) |
O12—Mo2—O4 | 165.20 (15) | P1—O1—Mo1 | 127.57 (18) |
O13—Mo2—O4 | 90.01 (15) | Mo2—O1—Mo1 | 85.74 (11) |
O8—Mo2—O4 | 73.83 (13) | P1—O2—Co1 | 127.0 (2) |
O7—Mo2—O4 | 78.65 (12) |
Symmetry code: (i) −x, −y, −z. |
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In recent years, metal organophosphonate systems have received considerable attention because of their unusual structural chemistry and their applications as sorbents, catalysts and catalyst supports, and ion exchangers (Rodrigues et al., 1986; Rosenthal et al., 1992; Burwell et al., 1992; Cao et al., 1991). Furthermore, the organophosphonate group has also been shown to form molecular anion clusters with molybdenum (Kwak et al., 1975; Stalick et al., 1976). In this kind of compound, it is ordinary to form Mo5 (Yayasaki et al., 1987; Finn et al., 2001), Mo6 (Yayasaki et al., 1987; Kortz et al., 1995; Cao et al., 1993; Khan et al., 1993), Mo7 (Yayasaki et al., 1987; Dumas et al., 2002) polyoxomolybdate, the MoO6 octahedra being linked by sharing edge or angle.
The H+/MoO42−/hedp (hedp = 1-hydroxyethylidenediphosphonate) acid system has been investigated (Tolkacheva et al., 1992). The complexes are formed with Mo:L (L = hedp) ratios of 1:2, 2:2, 2:1, 3:1 and 6:1, mainly depending on pH. A few transition metal–hedp complexes have been structurally characterized, including M(hedpH2)2 (M = Ni, Fe), M2(hedpH2)2 (M = Cu, Fe) and M3(hedp)2 (M = Cu) (Zheng et al., 2002). A number of one-dimensional lanthanide–hedpHn (n = 1–3; Nash et al., 1998) compounds have also been structurally characterized. However, the transition metal/MoO42−/hedp system has not been reported. In this paper, we describe the synthesis and structure of Na8[CoMo4O12{MeC(O)(PO3)2}2].18H2O.
The geometric parameters of the title compound are listed in Table 1. The anion [CoMo4O12{MeC(O)(PO3)2}2]8− and crystal packing of the compound are illustrated in Figs. 1 and 2, respectively. The tetramolybdocobalt diphosphonate polyanion, [CoMo4O12{MeC(O)(PO3)2}2]8−, consists of a CoII atom connecting two [Mo2O6{MeC(O)(PO3)2}]5− fragments. Each of the fragments donates three oxo groups, two of them come from {CPO3} groups of the chelating hedp ligand and the third from the oxo group bridging to a molybdenum site. The anion possesses of C2 h symmetry, the six-bonded CoII atom lies on the center of symmetry. Each of Mo6+ cation in the title compound has a distorted octahedal configuration with two apical Mo···O bonds ranging from 1.717 to 1.731 Å and four other Mo···O bond at length ranging from 1.745 to 2.419 Å. Based on the valence-bond calculations, the bond values for the two molybdenum are 5.985 and 5.967, respectively, indicating that Mo atoms have oxidation state +6. Another structural feature in [CoMo4O12{MeC(O)(PO3)2}2]8− is the presence of a pair of face-sharing octahedral of MoO6. The edge- and angle-sharing octahedral are ordinary as the fundamental octahedral connecting fashions in the polyoxomolybdate anions, but the face-sharing octahedralof MoO6 is rare. The two Mo atoms within a pair in the title compound are nonbonded to each other according to the average Mo—Mo distance of 3.24 Å.
In contrast with the most of diphosphonates the short length of the MeC(O)– tether in hedp permits formation of stable six-membered rings with the metal ions. In Fig. 1, one can see that there exist three types of six-membered rings in the anion, namely, Co—O—Mo—O—P—O, Co—O—P—C—P—O and Mo—O—P—C—P—O.