K₆H₂[TiW₁₁CoO₄₀]·13H₂O, with a mono­titanoundeca­tungstocobaltate(II) anion

Hexapotassium dihydrogen monotitanoundeca­tungsto­cobalt­ate(II) trideca­hydrate, K₆H₂[TiW₁₁CoO₄₀]·13H₂O, crystallizes from aqueous solution in the cubic space group P3m. The structure was refined as an inversion twin. The [TiW₁₁CoO₄₀]^8- anion has a Keggin structure with one W-atom site occupied by titanium and a central tetra­hedral CoO₄ group.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](o-O) = 0.010 Å
• H-atom completeness 1%
• Disorder in main residue
• R factor = 0.039
• wR factor = 0.097
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......         O5

Author Response: see _publ_section_exptl_refinement

PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......         O6

Author Response: see _publ_section_exptl_refinement

Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O4     ..  O5      ..       2.70 Ang.

Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.430
           From the CIF: _refine_ls_abs_structure_Flack_su    0.060
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.43
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT301_ALERT_3_C Main Residue  Disorder .........................      21.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      12.00 Perc.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              TI1  -O1   -W1     11.566   1.555  11.566
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              TI1  -O2   -W1      9.555   1.555   9.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              W1   -O2   -TI1     5.555   1.555   5.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              TI1  -O4   -W1      9.555   1.555   9.555

Alert level G
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:H28 Co1 K6 O53 Ti1 W11
            Atom count from the _atom_site data:  Co1 K6 O53 Ti1.004959 W11.0049
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    1
           From the CIF: _chemical_formula_sum  Co H28 K6 O53 Ti W11
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           Co         1.00      1.00    0.00
           H         28.00      0.00   28.00
           K          6.00      6.00    0.00
           O         53.00     53.00    0.00
           Ti         1.00      1.00    0.00
           W         11.00     11.00    0.00
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.44
           From the CIF: _reflns_number_total                730
           Count of symmetry unique reflns          429
           Completeness (_total/calc)            170.16%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       301
           Fraction of Friedel pairs measured     0.702
           Are heavy atom types Z>Si present        yes

   2 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Hexapotassium dihydrogen monotitanoundecatungstocobaltate(II) tridecahydrate

Crystal data

K6H2[TiW11CoO40]·13H2O	Dx = 4.410 Mg m^−3
Mr = 3240.00	Mo Kα radiation, λ = 0.71073 Å
Cubic, P43m	Cell parameters from 942 reflections
Hall symbol: P -4 2 3	θ = 2.7–28.1°
a = 10.6850 (16) Å	µ = 26.93 mm^−1
V = 1219.9 (3) Å^3	T = 273 K
Z = 1	Block, blue
F(000) = 1429	0.09 × 0.05 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer	730 independent reflections
Radiation source: fine-focus sealed tube	516 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.091
ω scans	θmax = 30.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.217, Tmax = 0.390	k = −10→14
8248 measured reflections	l = −14→11

Refinement

Refinement on F^2	H-atom parameters not defined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 8.0204P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.039	(Δ/σ)max < 0.001
wR(F^2) = 0.097	Δρmax = 1.64 e Å^−3
S = 0.98	Δρmin = −1.66 e Å^−3
730 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
45 parameters	Extinction coefficient: 0.0093 (8)
0 restraints	Absolute structure: Flack (1983), 315 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.43 (6)
Secondary atom site location: difference Fourier map

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
W1	0.26855 (4)	0.26855 (4)	0.49996 (19)	0.0358 (3)	0.91666
Ti1	0.26855 (4)	0.26855 (4)	0.49996 (19)	0.0358 (3)	0.08333
Co1	0.5000	0.5000	0.5000	0.0252 (11)
K1	0.0000	0.5000	0.5000	0.0423 (13)
K2	0.0000	0.0000	0.3680 (12)	0.069 (3)	0.50
O1	0.2273 (13)	0.3999 (10)	0.6001 (10)	0.045 (3)
O2	0.3970 (9)	0.3970 (9)	0.3970 (9)	0.027 (4)
O3	0.1555 (7)	0.1555 (7)	0.492 (3)	0.059 (4)
O4	0.1779 (13)	0.3594 (9)	0.3594 (9)	0.049 (4)
O5	0.0187 (19)	0.2204 (12)	0.2204 (12)	0.078 (6)
O6	0.0000	0.0000	0.0000	0.108 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.0244 (3)	0.0244 (3)	0.0586 (4)	−0.0045 (2)	0.0038 (7)	0.0038 (7)
Ti1	0.0244 (3)	0.0244 (3)	0.0586 (4)	−0.0045 (2)	0.0038 (7)	0.0038 (7)
Co1	0.0252 (11)	0.0252 (11)	0.0252 (11)	0.000	0.000	0.000
K1	0.021 (3)	0.053 (2)	0.053 (2)	0.000	0.000	0.000
K2	0.051 (5)	0.051 (5)	0.106 (9)	−0.035 (11)	0.000	0.000
O1	0.029 (7)	0.053 (6)	0.053 (6)	−0.002 (4)	0.002 (4)	0.005 (6)
O2	0.027 (4)	0.027 (4)	0.027 (4)	−0.003 (4)	−0.003 (4)	−0.003 (4)
O3	0.041 (3)	0.041 (3)	0.096 (11)	−0.006 (4)	0.009 (12)	0.009 (12)
O4	0.045 (9)	0.051 (5)	0.051 (5)	0.031 (5)	0.031 (5)	0.024 (7)
O5	0.029 (13)	0.102 (8)	0.102 (8)	0.000 (6)	0.000 (6)	−0.012 (9)
O6	0.108 (19)	0.108 (19)	0.108 (19)	0.000	0.000	0.000

Geometric parameters (Å, º)

W1—O3	1.711 (11)	K1—W1^viii	3.7881 (6)
W1—O1^i	1.819 (4)	K1—Ti1^iii	3.7881 (6)
W1—O1	1.819 (4)	K2—O3	2.70 (2)
W1—O4^ii	2.034 (8)	K2—O3^ix	2.70 (2)
W1—O4	2.034 (8)	K2—O3^x	2.78 (2)
W1—O2	2.231 (7)	K2—O3^vi	2.78 (2)
W1—K1	3.7881 (6)	K2—K2^vi	2.82 (3)
W1—K1^ii	3.7881 (6)	K2—O5^xi	2.841 (8)
Co1—O2	1.906 (17)	K2—O5^ix	2.841 (8)
Co1—O2^iii	1.906 (17)	K2—O5	2.841 (8)
Co1—O2^iv	1.906 (17)	K2—O5^ii	2.841 (8)
Co1—O2^v	1.906 (17)	O1—Ti1^viii	1.819 (4)
K1—O4^iii	2.851 (12)	O1—W1^viii	1.819 (4)
K1—O4	2.851 (12)	O2—Ti1^xii	2.231 (7)
K1—O4^vi	2.851 (12)	O2—W1^ii	2.231 (7)
K1—O4^vii	2.851 (12)	O2—W1^xii	2.231 (7)
K1—O1^vi	2.861 (15)	O2—Ti1^ii	2.231 (7)
K1—O1	2.861 (15)	O3—K2^vi	2.78 (2)
K1—O1^iii	2.861 (16)	O4—Ti1^xii	2.034 (8)
K1—O1^vii	2.861 (15)	O4—W1^xii	2.034 (8)
K1—W1^iii	3.7881 (6)	O5—K2^xii	2.841 (8)
K1—Ti1^viii	3.7881 (6)
O3—W1—O1^i	113.8 (8)	O1—K1—W1^viii	27.50 (3)
O3—W1—O1	113.8 (8)	O1^iii—K1—W1^viii	66.5 (2)
O1^i—W1—O1	91.6 (9)	O1^vii—K1—W1^viii	113.5 (2)
O3—W1—O4^ii	87.9 (10)	W1^iii—K1—W1^viii	54.97 (5)
O1^i—W1—O4^ii	87.2 (5)	Ti1^viii—K1—W1^viii	0.000 (9)
O1—W1—O4^ii	156.5 (6)	O4^iii—K1—Ti1^iii	31.88 (16)
O3—W1—O4	87.9 (10)	O4—K1—Ti1^iii	80.7 (3)
O1^i—W1—O4	156.5 (6)	O4^vi—K1—Ti1^iii	148.11 (15)
O1—W1—O4	87.2 (5)	O4^vii—K1—Ti1^iii	99.3 (3)
O4^ii—W1—O4	84.8 (7)	O1^vi—K1—Ti1^iii	152.51 (3)
O3—W1—O2	147.6 (13)	O1—K1—Ti1^iii	66.5 (2)
O1^i—W1—O2	88.0 (5)	O1^iii—K1—Ti1^iii	27.50 (3)
O1—W1—O2	88.0 (5)	O1^vii—K1—Ti1^iii	113.5 (2)
O4^ii—W1—O2	68.6 (4)	W1^iii—K1—Ti1^iii	0.00 (6)
O4—W1—O2	68.6 (4)	Ti1^viii—K1—Ti1^iii	54.97 (5)
O3—W1—K1	85.762 (10)	W1^viii—K1—Ti1^iii	54.97 (5)
O1^i—W1—K1	137.9 (5)	O3—K2—O3^ix	121.2 (14)
O1—W1—K1	46.6 (5)	O3—K2—O3^x	74.7 (2)
O4^ii—W1—K1	132.3 (4)	O3^ix—K2—O3^x	74.7 (2)
O4—W1—K1	47.8 (3)	O3—K2—O3^vi	74.7 (2)
O2—W1—K1	93.69 (2)	O3^ix—K2—O3^vi	74.7 (2)
O3—W1—K1^ii	85.762 (9)	O3^x—K2—O3^vi	115.0 (14)
O1^i—W1—K1^ii	46.6 (5)	O3—K2—K2^vi	60.6 (7)
O1—W1—K1^ii	137.9 (5)	O3^ix—K2—K2^vi	60.6 (7)
O4^ii—W1—K1^ii	47.8 (3)	O3^x—K2—K2^vi	57.5 (7)
O4—W1—K1^ii	132.3 (4)	O3^vi—K2—K2^vi	57.5 (7)
O2—W1—K1^ii	93.69 (2)	O3—K2—O5^xi	145.7 (5)
K1—W1—K1^ii	171.512 (16)	O3^ix—K2—O5^xi	73.7 (6)
O2—Co1—O2^iii	109.471 (1)	O3^x—K2—O5^xi	138.6 (5)
O2—Co1—O2^iv	109.471 (1)	O3^vi—K2—O5^xi	81.1 (6)
O2^iii—Co1—O2^iv	109.471 (3)	K2^vi—K2—O5^xi	123.7 (4)
O2—Co1—O2^v	109.471 (1)	O3—K2—O5^ix	145.7 (5)
O2^iii—Co1—O2^v	109.471 (1)	O3^ix—K2—O5^ix	73.7 (6)
O2^iv—Co1—O2^v	109.471 (3)	O3^x—K2—O5^ix	81.1 (6)
O4^iii—K1—O4	96.3 (6)	O3^vi—K2—O5^ix	138.6 (5)
O4^iii—K1—O4^vi	116.4 (4)	K2^vi—K2—O5^ix	123.7 (4)
O4—K1—O4^vi	116.4 (4)	O5^xi—K2—O5^ix	64.9 (8)
O4^iii—K1—O4^vii	116.4 (4)	O3—K2—O5	73.7 (6)
O4—K1—O4^vii	116.4 (4)	O3^ix—K2—O5	145.7 (5)
O4^vi—K1—O4^vii	96.3 (6)	O3^x—K2—O5	138.6 (5)
O4^iii—K1—O1^vi	163.7 (3)	O3^vi—K2—O5	81.1 (6)
O4—K1—O1^vi	99.9 (5)	K2^vi—K2—O5	123.7 (4)
O4^vi—K1—O1^vi	55.5 (3)	O5^xi—K2—O5	78.9 (8)
O4^vii—K1—O1^vi	55.5 (3)	O5^ix—K2—O5	112.5 (8)
O4^iii—K1—O1	55.5 (3)	O3—K2—O5^ii	73.7 (6)
O4—K1—O1	55.5 (3)	O3^ix—K2—O5^ii	145.7 (5)
O4^vi—K1—O1	99.9 (5)	O3^x—K2—O5^ii	81.1 (6)
O4^vii—K1—O1	163.7 (3)	O3^vi—K2—O5^ii	138.6 (5)
O1^vi—K1—O1	136.1 (3)	K2^vi—K2—O5^ii	123.7 (4)
O4^iii—K1—O1^iii	55.5 (3)	O5^xi—K2—O5^ii	112.5 (8)
O4—K1—O1^iii	55.5 (3)	O5^ix—K2—O5^ii	78.9 (8)
O4^vi—K1—O1^iii	163.7 (3)	O5—K2—O5^ii	64.9 (8)
O4^vii—K1—O1^iii	99.9 (5)	Ti1^viii—O1—W1^viii	0.000 (15)
O1^vi—K1—O1^iii	136.1 (3)	Ti1^viii—O1—W1	148.1 (9)
O1—K1—O1^iii	63.8 (5)	W1^viii—O1—W1	148.1 (9)
O4^iii—K1—O1^vii	99.9 (5)	Ti1^viii—O1—K1	105.9 (5)
O4—K1—O1^vii	163.7 (3)	W1^viii—O1—K1	105.9 (5)
O4^vi—K1—O1^vii	55.5 (3)	W1—O1—K1	105.9 (5)
O4^vii—K1—O1^vii	55.5 (3)	Co1—O2—W1	115.2 (4)
O1^vi—K1—O1^vii	63.8 (5)	Co1—O2—Ti1^xii	115.2 (4)
O1—K1—O1^vii	136.1 (3)	W1—O2—Ti1^xii	103.2 (5)
O1^iii—K1—O1^vii	136.1 (3)	Co1—O2—W1^ii	115.2 (4)
O4^iii—K1—W1^iii	31.88 (16)	W1—O2—W1^ii	103.2 (5)
O4—K1—W1^iii	80.7 (3)	Ti1^xii—O2—W1^ii	103.2 (5)
O4^vi—K1—W1^iii	148.11 (15)	Co1—O2—W1^xii	115.2 (4)
O4^vii—K1—W1^iii	99.3 (3)	W1—O2—W1^xii	103.2 (5)
O1^vi—K1—W1^iii	152.51 (3)	Ti1^xii—O2—W1^xii	0.000 (15)
O1—K1—W1^iii	66.5 (2)	W1^ii—O2—W1^xii	103.2 (5)
O1^iii—K1—W1^iii	27.50 (3)	Co1—O2—Ti1^ii	115.2 (4)
O1^vii—K1—W1^iii	113.5 (2)	W1—O2—Ti1^ii	103.2 (5)
O4^iii—K1—Ti1^viii	31.88 (16)	Ti1^xii—O2—Ti1^ii	103.2 (5)
O4—K1—Ti1^viii	80.7 (3)	W1^ii—O2—Ti1^ii	0.00 (3)
O4^vi—K1—Ti1^viii	99.3 (3)	W1^xii—O2—Ti1^ii	103.2 (5)
O4^vii—K1—Ti1^viii	148.11 (15)	W1—O3—K2	153.5 (18)
O1^vi—K1—Ti1^viii	152.51 (3)	W1—O3—K2^vi	144.6 (19)
O1—K1—Ti1^viii	27.50 (3)	K2—O3—K2^vi	61.9 (5)
O1^iii—K1—Ti1^viii	66.5 (2)	Ti1^xii—O4—W1^xii	0.00 (8)
O1^vii—K1—Ti1^viii	113.5 (2)	Ti1^xii—O4—W1	118.6 (7)
W1^iii—K1—Ti1^viii	54.97 (5)	W1^xii—O4—W1	118.6 (7)
O4^iii—K1—W1^viii	31.88 (16)	Ti1^xii—O4—K1	100.4 (4)
O4—K1—W1^viii	80.7 (3)	W1^xii—O4—K1	100.4 (4)
O4^vi—K1—W1^viii	99.3 (3)	W1—O4—K1	100.4 (4)
O4^vii—K1—W1^viii	148.11 (15)	K2^xii—O5—K2	156.3 (8)
O1^vi—K1—W1^viii	152.51 (3)

Symmetry codes: (i) −z+1, x, −y+1; (ii) z, x, y; (iii) x, −y+1, −z+1; (iv) −x+1, −y+1, z; (v) −x+1, y, −z+1; (vi) −x, y, −z+1; (vii) −x, −y+1, z; (viii) y, −z+1, −x+1; (ix) −x, −y, z; (x) x, −y, −z+1; (xi) −z, −x, y; (xii) y, z, x.