Bis­(tetra­methyl­ammonium) nona­decaoxohexamolybdenum(VI) mono­hydrate

The six Mo atoms in the title compound, (C₄H₁₂N)₂[Mo₆O₁₉].H₂O, form a standard octahedral cage through bridging O atoms. The [Mo₆O₁₉]^2- anion as a whole has O_h symmetry with three crystallographic fourfold axes aligned along Mo-O-Mo. There exist weak O...O hydrogen bonds (O100...O3 2.951 Å) between the terminal O3 atoms of the anions and O100 atoms of the solvate hydrates in the unit cell.

S1. Comment

The title compound has the same anion as the following compounds: C₁₂H₃₇N₉P₃⁺ (Allcock et al., 1973), C₂₀H₄₀MoN₄S₈⁺ (Garner et al., 1978), C₁₂H₂₄O₆K⁺·H₂O (Nagano & Sasaki, 1979), Ph₄As⁺ (Clegg et al., 1982), C₁₆H₃₆N⁺ (Dahlstrom et al., 1982; Rheingold et al., 1993; Boyle et al., 1998), C₂₂H₂₂O₂P⁺ and C₂₂H₂₂P⁺ (Arzoumanian et al., 1985), C₁₂H₂₄O₆·H₃O⁺ (Shoemaker et al., 1986), C₃₉H₃₃Mo₂O₄P₂⁺ (Riera et al., 1988), C₁₄H₂₁ClN₂Rh⁺ (Zhang et al., 1989), C₁₀H₈S₈⁺ (Triki et al., 1991), C₆H₄S₄⁺ (Attanasio et al., 1991; Triki et al., 1992), C₂₀H₃₀N₁₀Re₂₄⁺ (Bernstein & Dunbar, 1992), C₁₅H₃₅C₁₁FeN₅O₅₂⁺ (Lu et al., 1992), C₂₀H₁₆S₄⁺ (Triki et al., 1994), C₈H₂₀N⁺ (Liu et al., 1995), C₁₄H₂₀FeN⁺ (Veya & Kochi, 1995), C₁₆H₁₉N₂⁺ (Xu et al., 1995), C₂₀H₂₁N₂⁺ (Xu et al., 1995), C₂₃H₁₇O⁺ (Xu et al., 1996), C₂₀H₂₈NaO₈⁺ (Lu et al., 1996), C₁₆H₁₆N₂S₂⁺ (Bellec et al., 1997), C₇₂H₆₀AgP₄⁺ (Long et al., 1997) and C₃₆H₃₀NP₂⁺ (Hoppe et al., 1997).

S2. Experimental

The title compound was obtained in an attempt to synthesize new polyoxomolybdates in both reaction systems of Na₂MoO₄·2H₂O (2.0 g, 8.3 mmol), (CHO)₂ (3 ml), 3.5% HCl (1 ml), NH₄VO₃ (1.0 g, 8.6 mmol), [(CH₃)₄N]Br (1.0 g, 6.5 mmol) and H₂O (60 ml), or of Na₂MoO₄·2H₂O (2.15 g, 8.9 mmol), NH₄VO₃ (0.5 g, 4.3 mmol), [(CH₃)₄N]Cl (2.0 g, 18.2 mmol), NH₂OH·HCl (3.14 g, 45.2 mmol), Al₂O₃ (234.51 mg, 2.3 mmol) and H₂O (110 ml).

S3. Refinement

The H atom on C1 was located and refined isotropically. The water H atoms were not located.

Computing details

Data collection: Enraf-Nonius CONTROL software; cell refinement: MolEN/VAX (Fair, 1990); data reduction: MolEN/VAX (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Bis(tetramethylammonium)Nonadecaoxohexamolybdenum(VI) Solvate Hydrate

Crystal data

(C4H12N)2[Mo6O19]·H2O	Dx = 2.635 Mg m^−3
Mr = 1043.93	Mo Kα radiation, λ = 0.71073 Å
Cubic, Fm3m	Cell parameters from 25 reflections
Hall symbol: -F 4 2 3	θ = 15.4–16.6°
a = 13.8148 (16) Å	µ = 2.85 mm^−1
V = 2636.5 (5) Å^3	T = 293 K
Z = 4	Octahedron, orange–red
F(000) = 2000	0.53 × 0.48 × 0.45 mm

Data collection

Enraf-Nonius CAD-4 II diffractometer	Rint = 0.047
Radiation source: fine-focus sealed tube	θmax = 25.9°, θmin = 2.6°
Graphite monochromator	h = −9→16
ω–2θ scans	k = −15→12
1396 measured reflections	l = −16→9
167 independent reflections	3 standard reflections every 300 reflections
149 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0431P)^2 + 29.6855P] where P = (Fo^2 + 2Fc^2)/3
S = 1.33	(Δ/σ)max < 0.001
167 reflections	Δρmax = 0.70 e Å^−3
21 parameters	Δρmin = −0.40 e Å^−3
4 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (2)

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
Mo1	0	0.66666 (8)	0.5000	0.0387 (7)
N1	0.2500	0.7500	0.2500	0.032 (4)
C1	0.1884 (7)	0.8116 (7)	0.3116 (7)	0.061 (4)
H1	0.1481 (7)	0.766 (2)	0.3519 (7)	0.06 (2)*
O1	0	0.5000	0.5000	0.025 (4)
O2	0	0.6351 (3)	0.6351 (3)	0.0366 (15)
O3	0	0.7864 (7)	0.5000	0.048 (3)
O100	0	1	0.5000	0.047 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0432 (7)	0.0295 (9)	0.0432 (7)	0.000	0.000	0.000
N1	0.032 (4)	0.032 (4)	0.032 (4)	0.000	0.000	0.000
C1	0.061 (4)	0.061 (4)	0.061 (4)	0.011 (4)	0.011 (4)	−0.011 (4)
O1	0.025 (4)	0.025 (4)	0.025 (4)	0.000	0.000	0.000
O2	0.047 (4)	0.031 (2)	0.031 (2)	0.000	0.000	−0.004 (3)
O3	0.058 (4)	0.028 (5)	0.058 (4)	0.000	0.000	0.000
O100	0.047 (6)	0.047 (6)	0.047 (6)	0.000	0.000	0.000

Geometric parameters (Å, º)

Mo1—O3	1.654 (10)	N1—C1^vi	1.474 (16)
Mo1—O2	1.916 (3)	N1—C1	1.474 (16)
Mo1—O2^i	1.916 (3)	O1—Mo1^vii	2.3023 (12)
Mo1—O2^ii	1.916 (3)	O1—Mo1^viii	2.3023 (12)
Mo1—O2^iii	1.916 (3)	O1—Mo1^ix	2.3023 (12)
Mo1—O1	2.3023 (12)	O1—Mo1^x	2.3023 (12)
N1—C1^iv	1.474 (16)	O1—Mo1^iii	2.3023 (12)
N1—C1^v	1.474 (16)	O2—Mo1^ix	1.916 (3)
O3—Mo1—O2	103.17 (17)	C1^v—N1—C1	109.471 (1)
O3—Mo1—O2^i	103.17 (17)	C1^vi—N1—C1	109.5
O2—Mo1—O2^i	153.7 (3)	Mo1—O1—Mo1^vii	90.0
O3—Mo1—O2^ii	103.17 (17)	Mo1—O1—Mo1^viii	180.0
O2—Mo1—O2^ii	87.02 (8)	Mo1^vii—O1—Mo1^viii	90.0
O2^i—Mo1—O2^ii	87.02 (8)	Mo1—O1—Mo1^ix	90.0
O3—Mo1—O2^iii	103.17 (17)	Mo1^vii—O1—Mo1^ix	90.0
O2—Mo1—O2^iii	87.02 (8)	Mo1^viii—O1—Mo1^ix	90.0
O2^i—Mo1—O2^iii	87.02 (8)	Mo1—O1—Mo1^x	90.0
O2^ii—Mo1—O2^iii	153.7 (3)	Mo1^vii—O1—Mo1^x	90.0
O3—Mo1—O1	180.000 (2)	Mo1^viii—O1—Mo1^x	90.0
O2—Mo1—O1	76.83 (17)	Mo1^ix—O1—Mo1^x	180.0
O2^i—Mo1—O1	76.83 (17)	Mo1—O1—Mo1^iii	90.0
O2^ii—Mo1—O1	76.83 (17)	Mo1^vii—O1—Mo1^iii	180.0
O2^iii—Mo1—O1	76.83 (17)	Mo1^viii—O1—Mo1^iii	90.0
C1^iv—N1—C1^v	109.471 (2)	Mo1^ix—O1—Mo1^iii	90.0
C1^iv—N1—C1^vi	109.471 (1)	Mo1^x—O1—Mo1^iii	90.0
C1^v—N1—C1^vi	109.471 (5)	Mo1—O2—Mo1^ix	116.3 (3)
C1^iv—N1—C1	109.471 (1)

Symmetry codes: (i) x, y, −z+1; (ii) −y+1/2, z, −x+1/2; (iii) y−1/2, z, x+1/2; (iv) x, −y+3/2, −z+1/2; (v) −x+1/2, y, −z+1/2; (vi) −x+1/2, −y+3/2, z; (vii) −y+1/2, −z+1, −x+1/2; (viii) −x, −y+1, −z+1; (ix) z−1/2, x+1/2, y; (x) −z+1/2, −x+1/2, −y+1.