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Acta Cryst. (2012). E68, m1467    [ doi:10.1107/S1600536812045850 ]

Bis(trimethylphenylammonium) [mu]-oxalato-bis[oxidodiperoxidomolybdate(VI)]

A. Oba and M. Hashimoto

Abstract top

A trimethylphenylammonium salt of a dinuclear [mu]-oxalate complex of diperoxidomonomolybdate units, (C9H14N)2[Mo2(C2O4)(O2)4O2], was obtained from an acidic aqueous solution; the dianion is located about a centre of inversion. Each Mo atom bears two peroxide groups together with one O atom from the oxalate group in its equatorial positions and one terminal O atom as well as another O atom from the oxalate in axial positions. The oxalate group acts as a tetradentate bridging ligand and bridges between the diperoxidomolybdate units.

Comment top

A novel dinuclear peroxidomolybdate complex with a bridging oxalate ligand was crystallized as a trimethylphenylammonium salt in the course of investigating complex formation of oxalate and peroxomolybdate in aiming at preparing an inorganic-organic hybrid material.

The compound consists of two trimethylphenylammonium cations and one dinuclear oxalato complex of diperoxidomolybdate (Figure 1). In the complex anion two diperoxidomolybdates are bridged by a tetradentate µ2 chelating oxalato ligand. Each molybdenum atom has two peroxo groups in its equatorial positions. The fifth equatorial position and one of the axial positions are occupied by O atoms of the oxalate ligand. The second axial position is occupied by the terminal oxo ligand. Each molybdenum atom thus exhibits a distorted pentagonal bipyramidal geometry, which is common in peroxidomolybdate compounds. C1, C1i, O6, O6i, O7, O7i, Mo1, Mo1i, O1 and O1i (symmetry operation, i(1 - x, 1 - y, -z)) are coplanar with a maximum deviation of 0.0240 (11) Å (O6) from the corresponding least square plane. Oxygen atoms of both peroxo ligands at each Mo atom are also coplanar. The deviation of the Mo atom from the least square plane toward the terminal oxygen atom is -0.401 (1) Å. These planes are almost perpendicular to the initially mentioned least square plane with dihedral angles 89.86 (5)°. There is no abnormal bond length and bond angles in the anion. Among Mo—O bonds in the equatorial plane Mo1—O6 (2.092 (1) Å) shows a slightly longer distance than others. C1—O7 (1.232 (2) Å) is slightly shorter than C1—O6 (1.275 (2) Å) probably because of weaker interaction of Mo1—O7 than Mo1—O6. Bond lengths in the trimethylphenylammonium cations are also normal. No special intermolecular interaction is observed in the packing.

The tungstate analogue of the present anion, [W2(C2O4)(O2)4O2], was reported as a tetrabutylanmonium salt by one of the authors (Hashimoto et al., 1987). The geometry of the complex anion of the tungsten compound is essentially identical to the molybdate one. The potassium salt of a mononuclear oxalato complex of a peroxidomolybdate was reported by Stomberg (Stomberg et al., 1985). The oxalate group of the mononuclear complex chelates to a molybdenum atom to form a Mo—O—C—C—O five-membered ring as found in the title compound. C—O distances of the non-coordinated O atoms of the oxalate group in the mononuclear complex (1.21 (1) and 1.22 (1) Å) are considerably shorter than C—O distances towards coordinationg oxygen atoms (1.30 (1) and 1.28 (1) Å), reflecting the coordination to the metal center. On the contrary, the 2:2 complex reported by Bayot et al., shows a different structural feature. The complex anion can be regarded as a dimer of Stomberg's mononuclear complex. However, one of the peroxo groups is replaced by two hydroxo groups to form a dimer of oxalatomonoperoxidomolybdate moieties doubly bridged by two µ2-OH groups (Bayot et al., 2004). The hydroxo groups thus occupy equatorial positions of the molybdenum atom. Distances and angles in the 2:2 complex show similar tendencies as Stomberg's 1:1 and the present 2:1 (Mo:oxalate) complexes, such as longer Mo—O(oxalate) distance than other Mo—O on the equatorial plane, and shorter C—O(equatorial) distances compared to C—O(axial) bonds.

Related literature top

For the structure of the closely related tetrabutylammonium peroxidotungstate analogue, see Hashimoto et al. (1987). For the structures of related molybdate complexes, see Stomberg & Olson (1985); Bayot et al. (2004).

Experimental top

The single-crystal subjected to the X-ray analysis was obtained in the following way. Sodium molybdate dihydrate (14.52 g, 0.0600 mol) and oxalic acid dihydrate (3.78 g, 0.0300 mol) were dissolved in ca 60 ml water. To this solution 10 ml of 30% H2O2 (ca 0.10 mol) was added and the volume was adjusted to 100 ml. The pH of the resulted solution was adjusted to 2 with ca 13 mol L-1 nitric acid. To the solution was added 1.0 ml of 1.0 mol L-1 aqueous trimethylphenylammonium chloride solution and the mixture was kept at room temperature. Block shaped crystals appeared in one day (yield 25%).

Refinement top

Hydrogen atoms have been calculated in idealized positions with C–H bond lengths of 0.93 Å (aromatic) and 0.96 Å (methyl). They were refined using a riding model with Ueq(H) = 1.2 × Uiso(C) for aromatic and Ueq(H) = 1.5 × Uiso(C) for methyl groups.

Computing details top

Data collection: CrystalClear SM (Rigaku, 2008); cell refinement: CrystalClear SM (Rigaku, 2008); data reduction: CrystalClear SM (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with thermal ellipsoinds drawn at the 50% probability level for non-H atoms. Symmetry code: (i) 1 - x, 1 - y, -z.
Bis(trimethylphenylammonium) µ-oxalato-bis[oxidodiperoxidomolybdate(VI)] top
Crystal data top
(C9H14N)2[Mo2(C2O4)(O2)4O2]F(000) = 716
Mr = 712.32Dx = 1.761 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 5064 reflections
a = 9.860 (2) Åθ = 2.9–30.0°
b = 9.975 (2) ŵ = 1.00 mm1
c = 13.691 (3) ÅT = 93 K
β = 94.023 (3)°Block, pale yellow
V = 1343.2 (5) Å30.20 × 0.17 × 0.17 mm
Z = 2
Data collection top
Rigaku Saturn724+
diffractometer
3843 independent reflections
Radiation source: fine-focus rotating anode3621 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 28.5174 pixels mm-1θmax = 30.0°, θmin = 2.5°
CCD scansh = 1313
Absorption correction: numerical
(NUMABS; Higashi, 2000)
k = 1410
Tmin = 0.888, Tmax = 0.914l = 1916
11791 measured reflections
Refinement top
Refinement on F2Primary atom site location: Patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters not refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0409P)2 + 1.5201P]
where P = (Fo2 + 2Fc2)/3
3843 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 1.84 e Å3
0 restraintsΔρmin = 0.69 e Å3
Crystal data top
(C9H14N)2[Mo2(C2O4)(O2)4O2]V = 1343.2 (5) Å3
Mr = 712.32Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.860 (2) ŵ = 1.00 mm1
b = 9.975 (2) ÅT = 93 K
c = 13.691 (3) Å0.20 × 0.17 × 0.17 mm
β = 94.023 (3)°
Data collection top
Rigaku Saturn724+
diffractometer
3843 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 2000)
3621 reflections with I > 2σ(I)
Tmin = 0.888, Tmax = 0.914Rint = 0.021
11791 measured reflectionsθmax = 30.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters not refined
wR(F2) = 0.080Δρmax = 1.84 e Å3
S = 1.06Δρmin = 0.69 e Å3
3843 reflectionsAbsolute structure: ?
172 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
Mo10.354779 (14)0.254491 (13)0.035607 (10)0.01536 (7)
O10.38434 (13)0.09445 (13)0.00536 (9)0.0205 (2)
O20.45582 (16)0.27065 (15)0.16277 (11)0.0248 (3)
O30.30966 (17)0.24598 (13)0.17011 (11)0.0249 (3)
O40.16612 (15)0.28161 (16)0.00396 (12)0.0272 (3)
O50.25414 (14)0.31884 (15)0.08269 (10)0.0269 (3)
O60.52797 (13)0.32966 (12)0.02533 (9)0.0192 (2)
O70.35239 (13)0.48958 (13)0.06131 (11)0.0231 (3)
C10.55099 (17)0.45548 (17)0.02518 (12)0.0172 (3)
N10.00978 (16)0.42328 (15)0.22184 (11)0.0198 (3)
C20.0346 (2)0.5196 (2)0.14525 (14)0.0258 (4)
H2A0.05340.60550.17470.039*
H2B0.03660.52850.09410.039*
H2C0.11510.48590.11820.039*
C30.1020 (2)0.4182 (2)0.30216 (14)0.0248 (4)
H3A0.11810.50670.32810.037*
H3B0.18360.38480.27640.037*
H3C0.07580.35990.35330.037*
C40.1357 (2)0.4769 (2)0.26505 (14)0.0277 (4)
H4A0.11650.56350.29350.042*
H4B0.16290.41660.31470.042*
H4C0.20770.48490.21440.042*
C50.04052 (17)0.28802 (19)0.17753 (12)0.0187 (3)
C60.02069 (18)0.17351 (18)0.21818 (13)0.0213 (3)
H60.08210.17950.27280.026*
C70.0117 (2)0.0493 (2)0.17563 (16)0.0274 (4)
H70.02860.02810.20210.033*
C80.1029 (2)0.0402 (2)0.09455 (17)0.0321 (4)
H80.12280.04270.06590.039*
C90.1647 (2)0.1554 (3)0.05603 (16)0.0339 (5)
H90.22730.14920.00220.041*
C100.1338 (2)0.2797 (2)0.09723 (15)0.0275 (4)
H100.17540.35670.07120.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.01690 (9)0.01264 (9)0.01686 (9)0.00015 (4)0.00347 (6)0.00104 (4)
O10.0238 (6)0.0166 (6)0.0214 (6)0.0016 (5)0.0033 (5)0.0005 (4)
O20.0280 (7)0.0265 (6)0.0195 (6)0.0020 (5)0.0003 (5)0.0021 (5)
O30.0313 (8)0.0228 (7)0.0218 (7)0.0015 (5)0.0106 (6)0.0004 (4)
O40.0194 (6)0.0273 (7)0.0351 (8)0.0008 (5)0.0046 (5)0.0042 (6)
O50.0250 (6)0.0293 (7)0.0264 (7)0.0021 (5)0.0007 (5)0.0080 (6)
O60.0195 (6)0.0141 (5)0.0250 (6)0.0007 (4)0.0079 (5)0.0004 (4)
O70.0218 (6)0.0161 (6)0.0328 (7)0.0004 (5)0.0122 (5)0.0001 (5)
C10.0171 (7)0.0152 (7)0.0198 (7)0.0021 (5)0.0047 (6)0.0010 (6)
N10.0242 (7)0.0187 (7)0.0170 (6)0.0050 (5)0.0059 (5)0.0003 (5)
C20.0348 (10)0.0207 (8)0.0232 (8)0.0046 (7)0.0110 (7)0.0048 (7)
C30.0314 (9)0.0223 (9)0.0202 (8)0.0007 (7)0.0008 (7)0.0044 (7)
C40.0319 (9)0.0300 (10)0.0227 (8)0.0127 (8)0.0127 (7)0.0034 (7)
C50.0175 (7)0.0223 (8)0.0168 (7)0.0007 (6)0.0043 (6)0.0017 (6)
C60.0206 (7)0.0206 (8)0.0227 (8)0.0007 (6)0.0024 (6)0.0010 (6)
C70.0248 (8)0.0215 (9)0.0368 (10)0.0017 (7)0.0081 (7)0.0035 (8)
C80.0258 (9)0.0358 (11)0.0359 (11)0.0122 (8)0.0092 (8)0.0141 (9)
C90.0259 (9)0.0486 (13)0.0267 (9)0.0091 (9)0.0020 (7)0.0075 (9)
C100.0215 (9)0.0393 (10)0.0214 (8)0.0023 (8)0.0007 (7)0.0020 (8)
Geometric parameters (Å, º) top
Mo1—O11.6799 (13)C2—H2C0.9600
Mo1—O41.9198 (15)C3—H3A0.9600
Mo1—O31.9264 (16)C3—H3B0.9600
Mo1—O51.9479 (14)C3—H3C0.9600
Mo1—O21.9510 (15)C4—H4A0.9600
Mo1—O62.0915 (12)C4—H4B0.9600
Mo1—O72.3716 (14)C4—H4C0.9600
O2—O31.472 (2)C5—C101.386 (3)
O4—O51.478 (2)C5—C61.390 (3)
O6—C11.275 (2)C6—C71.397 (3)
O7—C1i1.232 (2)C6—H60.9300
C1—O7i1.232 (2)C7—C81.382 (3)
C1—C1i1.540 (3)C7—H70.9300
N1—C51.501 (2)C8—C91.387 (4)
N1—C31.502 (2)C8—H80.9300
N1—C21.509 (2)C9—C101.387 (3)
N1—C41.511 (2)C9—H90.9300
C2—H2A0.9600C10—H100.9300
C2—H2B0.9600
O1—Mo1—O4104.23 (7)N1—C2—H2A109.5
O1—Mo1—O3104.45 (6)N1—C2—H2B109.5
O4—Mo1—O389.53 (7)H2A—C2—H2B109.5
O1—Mo1—O5101.26 (6)N1—C2—H2C109.5
O4—Mo1—O544.92 (6)H2A—C2—H2C109.5
O3—Mo1—O5132.14 (7)H2B—C2—H2C109.5
O1—Mo1—O2102.24 (6)N1—C3—H3A109.5
O4—Mo1—O2131.62 (7)N1—C3—H3B109.5
O3—Mo1—O244.63 (7)H3A—C3—H3B109.5
O5—Mo1—O2155.95 (6)N1—C3—H3C109.5
O1—Mo1—O694.69 (6)H3A—C3—H3C109.5
O4—Mo1—O6129.72 (6)H3B—C3—H3C109.5
O3—Mo1—O6130.31 (6)N1—C4—H4A109.5
O5—Mo1—O686.14 (6)N1—C4—H4B109.5
O2—Mo1—O686.92 (6)H4A—C4—H4B109.5
O1—Mo1—O7168.51 (5)N1—C4—H4C109.5
O4—Mo1—O783.28 (6)H4A—C4—H4C109.5
O3—Mo1—O784.05 (5)H4B—C4—H4C109.5
O5—Mo1—O777.75 (6)C10—C5—C6120.92 (19)
O2—Mo1—O778.21 (6)C10—C5—N1118.58 (17)
O6—Mo1—O773.84 (4)C6—C5—N1120.47 (15)
O3—O2—Mo166.80 (9)C5—C6—C7118.82 (18)
O2—O3—Mo168.57 (8)C5—C6—H6120.6
O5—O4—Mo168.55 (8)C7—C6—H6120.6
O4—O5—Mo166.53 (8)C8—C7—C6120.7 (2)
C1—O6—Mo1120.15 (10)C8—C7—H7119.7
C1i—O7—Mo1111.35 (11)C6—C7—H7119.7
O7i—C1—O6125.41 (15)C7—C8—C9119.67 (19)
O7i—C1—C1i118.07 (19)C7—C8—H8120.2
O6—C1—C1i116.52 (18)C9—C8—H8120.2
C5—N1—C3112.48 (14)C8—C9—C10120.51 (19)
C5—N1—C2110.57 (14)C8—C9—H9119.7
C3—N1—C2107.24 (15)C10—C9—H9119.7
C5—N1—C4109.18 (15)C5—C10—C9119.4 (2)
C3—N1—C4107.85 (14)C5—C10—H10120.3
C2—N1—C4109.44 (14)C9—C10—H10120.3
Symmetry code: (i) x+1, y+1, z.
Acknowledgements top

Part of the work was supported financially by Grant in Aid No. 19550065 distributed by the Japan Society for the Promotion of Science (JSPS).

references
References top

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