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Crystals of the title compound, [(C4H9)4N][MoOCl4(H2O)], were synthesized by the reaction of a hydro­chloric acid solution of H2MoO4 and [(C4H9)4N]Cl with the reducing agent N2H4·2HCl. The structure consists of an [MoOCl4(H2O)] anion and a tetra­butyl­ammonium cation. The MoV atom is coordinated by four chlorides, one terminal oxo and one aqua ligand in a distorted octahedral geometry. The Mo—Cl bond lengths are in the range 2.352 (2)–2.402 (1) Å, Mo—O(oxo) 1.647 (4) Å and Mo—OH2 2.340 (4) Å. Intermolecular O—H...Cl hydrogen bond lengths are in the range 3.232–3.336 Å for O...Cl.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016919/cf6112sup1.cif
Contains datablocks I, new

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016919/cf6112Isup2.hkl
Contains datablock I

CCDC reference: 175974

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.050
  • wR factor = 0.124
  • Data-to-parameter ratio = 19.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_360 Alert C Short C(sp3)-C(sp3) Bond C6 - C7 = 1.41 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Molybdenum in its higher oxidation states readily forms polynuclear anionic metal–oxygen clusters and many polymolybdates with a wide variety of geometrical and electronic structures have been reported (Pope & Müller, 1991; Müller et al., 1995, 1998; Müller & Serain, 2000). However, the synthesis of polymolybdates with bridging chlorine atoms is far less well developed. In the course of our work on the synthesis of chlorine-bridged polymolybdates, the title compound, (I), was unexpectedly obtained as single crystals.

The X-ray structure analysis of (I) reveals that the geometry of the [MoOCl4(H2O)]- anion is similar to those of its analogues (Bino & Cotton, 1979; Boorman et al., 1975; Cindric et al., 1996; Garner et al., 1977; Junk & Atwood, 1998; Kepert et al., 1997). As shown in Fig. 1, the coordination environment of the Mo atom is a distorted octahedron with the cis angles at Mo ranging from 80.4 (1) to 99.8 (2)°. The MoO bond length of 1.647 (4) Å and the Mo—Owater bond length of 2.340 (4) Å are of typical values for terminal oxygen and aqua bond lengths to Mo. The Mo—Cl bond lengths are in the range 2.352 (2)–2.402 (1) Å, the cis-Cl—Mo—Cl angles are 88.3 (1)–89.1 (1)°, and the O Mo—OH2 angle is 177.7 (2)°, so the [MoOCl4(H2O)]- anion deviates only slightly from C4v symmetry.

Anions are linked in pairs through O—H···Cl hydrogen bonds involving the aqua ligands (Table 2). As shown in the packing of the cations and anions in the crystal structure, there are no other significant interactions (Fig. 2).

Experimental top

A solution of H2MoO4 (4.86 g, 30 mmol) in 20 ml concentrated HCl and 20 ml water was stirred with N2H4·2HCl (0.75 g, 7.14 mmol) for about 1 h, resulting in a green mixture. [(C4H9)4N]Cl (2.77 g, 10 mmol) was added and the solution was filtered. Green crystals of the title compound formed after a few days.

Refinement top

H atoms on C atoms were generated geometrically. Aqua H atoms were clearly visible in different maps and were positioned geometrically and included in the structure-factor calculations as riding atoms with fixed isotropic displacement parameters.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXLTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The cation and anion of (I) shown with 30% probability ellipsoids.
[Figure 2] Fig. 2. Packing diagram of (I), viewed down the a axis.
Tetrabutylammonium(1+) tetrachloroaquaoxomolybdate(1-) top
Crystal data top
(C16H36N)[MoOCl4(H2O)]F(000) = 1068
Mr = 514.21Dx = 1.374 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.401 (1) ÅCell parameters from 3968 reflections
b = 15.770 (1) Åθ = 1.8–25.1°
c = 16.845 (1) ŵ = 0.97 mm1
β = 95.581 (1)°T = 293 K
V = 2485.6 (2) Å3Prism, green
Z = 40.45 × 0.20 × 0.10 mm
Data collection top
SMART CCD
diffractometer
4368 independent reflections
Radiation source: fine-focus sealed tube3157 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 25.1°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1111
Tmin = 0.644, Tmax = 0.908k = 1318
8905 measured reflectionsl = 2013
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.124 w = 1/[σ2(Fo2) + (0.0375P)2 + 3.4179P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
4368 reflectionsΔρmax = 0.54 e Å3
225 parametersΔρmin = 0.45 e Å3
3 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0010 (3)
Crystal data top
(C16H36N)[MoOCl4(H2O)]V = 2485.6 (2) Å3
Mr = 514.21Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.401 (1) ŵ = 0.97 mm1
b = 15.770 (1) ÅT = 293 K
c = 16.845 (1) Å0.45 × 0.20 × 0.10 mm
β = 95.581 (1)°
Data collection top
SMART CCD
diffractometer
4368 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
3157 reflections with I > 2σ(I)
Tmin = 0.644, Tmax = 0.908Rint = 0.033
8905 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0503 restraints
wR(F2) = 0.124H-atom parameters constrained
S = 1.15Δρmax = 0.54 e Å3
4368 reflectionsΔρmin = 0.45 e Å3
225 parameters
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
Mo0.90088 (5)0.37397 (3)0.87363 (3)0.05693 (18)
Cl10.80082 (17)0.38097 (10)0.99793 (9)0.0809 (4)
Cl20.99286 (18)0.23966 (9)0.91145 (10)0.0829 (5)
Cl30.86824 (16)0.52455 (8)0.86015 (8)0.0702 (4)
Cl41.06195 (17)0.38032 (9)0.77485 (8)0.0771 (4)
O0.7560 (4)0.3452 (3)0.8173 (2)0.0838 (12)
OW1.1030 (4)0.4205 (2)0.9538 (2)0.0684 (10)
HW11.13100.46970.94340.103*
HW21.10340.41551.00380.103*
C10.4262 (6)0.2423 (3)0.8743 (3)0.0658 (14)
H1A0.52230.26530.87920.079*
H1B0.36130.28840.85850.079*
C20.4693 (6)0.2167 (3)0.7339 (3)0.0668 (14)
H2A0.56510.23790.74840.080*
H2B0.47590.17310.69380.080*
C30.3621 (10)0.2617 (5)1.0945 (4)0.126 (3)
H3A0.37410.30991.12940.189*
H3B0.42040.21581.11630.189*
H3C0.26360.24461.08920.189*
C40.3593 (12)0.3941 (6)0.5871 (5)0.159 (4)
H4A0.40960.41710.54500.239*
H4B0.34000.43850.62350.239*
H4C0.27080.36970.56470.239*
C50.4479 (9)0.3279 (5)0.6301 (4)0.113 (3)
H5A0.53820.35290.65100.135*
H5B0.46860.28410.59250.135*
C60.6940 (9)0.0227 (5)0.9255 (5)0.122 (3)
H6A0.75370.07220.93100.183*
H6B0.59830.03910.90660.183*
H6C0.69360.00470.97640.183*
C70.7476 (8)0.0338 (4)0.8704 (4)0.100 (2)
H7A0.75030.00460.81990.120*
H7B0.84500.04860.88960.120*
C80.4057 (8)0.2849 (4)1.0146 (3)0.0867 (19)
H8A0.50390.30471.02090.104*
H8B0.34630.33140.99310.104*
C90.0455 (7)0.0004 (5)0.6413 (4)0.100 (2)
H9A0.05110.01920.64110.150*
H9B0.10920.04730.64340.150*
H9C0.05520.03240.59360.150*
C100.3798 (7)0.2883 (4)0.6968 (3)0.0833 (18)
H10A0.28620.26680.67710.100*
H10B0.36670.33080.73710.100*
C110.6622 (6)0.1152 (4)0.8558 (4)0.0796 (17)
H11A0.67070.14880.90430.096*
H11B0.70260.14790.81470.096*
C120.0822 (7)0.0560 (4)0.7130 (4)0.0887 (19)
H12A0.01490.10280.71120.106*
H12B0.07020.02340.76070.106*
C130.5070 (6)0.0993 (3)0.8308 (3)0.0670 (14)
H13A0.46620.07090.87440.080*
H13B0.50050.06040.78600.080*
C140.3937 (7)0.2116 (3)0.9551 (3)0.0725 (15)
H14A0.46040.16710.97320.087*
H14B0.29790.18820.95160.087*
C150.2296 (6)0.0912 (4)0.7196 (3)0.0731 (15)
H15A0.24260.12340.67180.088*
H15B0.29740.04470.72270.088*
C160.2616 (5)0.1479 (3)0.7915 (3)0.0635 (14)
H16A0.20160.19790.78460.076*
H16B0.23520.11800.83820.076*
N0.4152 (5)0.1761 (2)0.8072 (2)0.0591 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo0.0563 (3)0.0515 (3)0.0646 (3)0.0045 (2)0.0144 (2)0.0043 (2)
Cl10.0827 (10)0.0806 (10)0.0857 (10)0.0039 (8)0.0402 (8)0.0027 (8)
Cl20.0916 (11)0.0562 (8)0.1048 (11)0.0037 (7)0.0290 (9)0.0058 (7)
Cl30.0821 (10)0.0561 (7)0.0743 (9)0.0041 (7)0.0167 (7)0.0020 (6)
Cl40.0912 (10)0.0713 (9)0.0746 (9)0.0025 (8)0.0371 (8)0.0044 (7)
O0.078 (3)0.080 (3)0.091 (3)0.011 (2)0.004 (2)0.011 (2)
OW0.067 (2)0.068 (2)0.071 (2)0.003 (2)0.009 (2)0.0078 (19)
C10.080 (4)0.051 (3)0.069 (3)0.004 (3)0.017 (3)0.008 (3)
C20.074 (4)0.057 (3)0.072 (3)0.003 (3)0.023 (3)0.002 (3)
C30.187 (9)0.109 (6)0.084 (5)0.013 (6)0.028 (5)0.025 (4)
C40.258 (13)0.119 (7)0.097 (6)0.031 (8)0.008 (7)0.038 (5)
C50.157 (8)0.098 (5)0.086 (5)0.012 (5)0.030 (5)0.020 (4)
C60.126 (7)0.098 (6)0.141 (7)0.000 (5)0.004 (6)0.008 (5)
C70.111 (6)0.082 (5)0.103 (5)0.012 (4)0.004 (4)0.002 (4)
C80.109 (5)0.074 (4)0.078 (4)0.001 (4)0.012 (4)0.018 (3)
C90.084 (5)0.097 (5)0.116 (6)0.018 (4)0.006 (4)0.002 (4)
C100.111 (5)0.066 (4)0.075 (4)0.010 (4)0.018 (4)0.007 (3)
C110.072 (4)0.071 (4)0.097 (4)0.006 (3)0.010 (3)0.004 (3)
C120.068 (4)0.104 (5)0.095 (5)0.011 (4)0.012 (3)0.003 (4)
C130.078 (4)0.048 (3)0.075 (4)0.003 (3)0.007 (3)0.006 (2)
C140.090 (4)0.061 (3)0.067 (3)0.002 (3)0.015 (3)0.004 (3)
C150.066 (4)0.072 (4)0.082 (4)0.003 (3)0.015 (3)0.006 (3)
C160.061 (3)0.061 (3)0.071 (3)0.001 (3)0.020 (3)0.000 (3)
N0.067 (3)0.042 (2)0.071 (3)0.003 (2)0.016 (2)0.0017 (19)
Geometric parameters (Å, º) top
Mo—O1.647 (4)C6—H6C0.960
Mo—OW2.340 (4)C7—C111.521 (8)
Mo—Cl22.352 (2)C7—H7A0.970
Mo—Cl42.358 (1)C7—H7B0.970
Mo—Cl12.380 (1)C8—C141.528 (7)
Mo—Cl32.402 (1)C8—H8A0.970
OW—HW10.843C8—H8B0.970
OW—HW20.846C9—C121.506 (9)
C1—C141.504 (7)C9—H9A0.960
C1—N1.534 (6)C9—H9B0.960
C1—H1A0.970C9—H9C0.960
C1—H1B0.970C10—H10A0.970
C2—C101.506 (7)C10—H10B0.970
C2—N1.523 (6)C11—C131.500 (7)
C2—H2A0.970C11—H11A0.970
C2—H2B0.970C11—H11B0.970
C3—C81.490 (8)C12—C151.486 (8)
C3—H3A0.960C12—H12A0.970
C3—H3B0.960C12—H12B0.970
C3—H3C0.960C13—N1.517 (6)
C4—C51.481 (10)C13—H13A0.970
C4—H4A0.960C13—H13B0.970
C4—H4B0.960C14—H14A0.970
C4—H4C0.960C14—H14B0.970
C5—C101.485 (8)C15—C161.511 (7)
C5—H5A0.970C15—H15A0.970
C5—H5B0.970C15—H15B0.970
C6—C71.414 (10)C16—N1.510 (6)
C6—H6A0.960C16—H16A0.970
C6—H6B0.960C16—H16B0.970
O—Mo—OW177.7 (2)C3—C8—C14113.4 (5)
O—Mo—Cl299.8 (2)C3—C8—H8A108.9
OW—Mo—Cl282.48 (11)C14—C8—H8A108.9
O—Mo—Cl499.0 (2)C3—C8—H8B108.9
OW—Mo—Cl481.5 (1)C14—C8—H8B108.9
Cl2—Mo—Cl489.1 (1)H8A—C8—H8B107.7
O—Mo—Cl198.3 (2)C12—C9—H9A109.5
OW—Mo—Cl181.1 (1)C12—C9—H9B109.5
Cl2—Mo—Cl188.3 (1)H9A—C9—H9B109.5
Cl4—Mo—Cl1162.7 (1)C12—C9—H9C109.5
O—Mo—Cl397.3 (2)H9A—C9—H9C109.5
OW—Mo—Cl380.4 (1)H9B—C9—H9C109.5
Cl2—Mo—Cl3162.9 (1)C5—C10—C2111.3 (6)
Cl4—Mo—Cl388.6 (1)C5—C10—H10A109.4
Cl1—Mo—Cl388.8 (1)C2—C10—H10A109.4
Mo—OW—HW1115C5—C10—H10B109.4
Mo—OW—HW2118C2—C10—H10B109.4
HW1—OW—HW2109H10A—C10—H10B108.0
C14—C1—N116.3 (4)C13—C11—C7112.8 (5)
C14—C1—H1A108.2C13—C11—H11A109.0
N—C1—H1A108.2C7—C11—H11A109.0
C14—C1—H1B108.2C13—C11—H11B109.0
N—C1—H1B108.2C7—C11—H11B109.0
H1A—C1—H1B107.4H11A—C11—H11B107.8
C10—C2—N115.8 (4)C15—C12—C9114.6 (6)
C10—C2—H2A108.3C15—C12—H12A108.6
N—C2—H2A108.3C9—C12—H12A108.6
C10—C2—H2B108.3C15—C12—H12B108.6
N—C2—H2B108.3C9—C12—H12B108.6
H2A—C2—H2B107.4H12A—C12—H12B107.6
C8—C3—H3A109.5C11—C13—N116.9 (4)
C8—C3—H3B109.5C11—C13—H13A108.1
H3A—C3—H3B109.5N—C13—H13A108.1
C8—C3—H3C109.5C11—C13—H13B108.1
H3A—C3—H3C109.5N—C13—H13B108.1
H3B—C3—H3C109.5H13A—C13—H13B107.3
C5—C4—H4A109.5C1—C14—C8110.0 (5)
C5—C4—H4B109.5C1—C14—H14A109.7
H4A—C4—H4B109.5C8—C14—H14A109.7
C5—C4—H4C109.5C1—C14—H14B109.7
H4A—C4—H4C109.5C8—C14—H14B109.7
H4B—C4—H4C109.5H14A—C14—H14B108.2
C4—C5—C10113.8 (7)C12—C15—C16113.1 (5)
C4—C5—H5A108.8C12—C15—H15A109.0
C10—C5—H5A108.8C16—C15—H15A109.0
C4—C5—H5B108.8C12—C15—H15B109.0
C10—C5—H5B108.8C16—C15—H15B109.0
H5A—C5—H5B107.7H15A—C15—H15B107.8
C7—C6—H6A109.5N—C16—C15115.3 (4)
C7—C6—H6B109.5N—C16—H16A108.5
H6A—C6—H6B109.5C15—C16—H16A108.5
C7—C6—H6C109.5N—C16—H16B108.5
H6A—C6—H6C109.5C15—C16—H16B108.5
H6B—C6—H6C109.5H16A—C16—H16B107.5
C6—C7—C11115.0 (7)C16—N—C13108.7 (4)
C6—C7—H7A108.5C16—N—C2111.8 (4)
C11—C7—H7A108.5C13—N—C2108.8 (4)
C6—C7—H7B108.5C16—N—C1108.9 (4)
C11—C7—H7B108.5C13—N—C1110.8 (4)
H7A—C7—H7B107.5C2—N—C1107.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW—HW1···Cl1i0.842.613.338 (4)145
OW—HW2···Cl3i0.852.473.238 (4)151
Symmetry code: (i) x+2, y+1, z+2.

Experimental details

Crystal data
Chemical formula(C16H36N)[MoOCl4(H2O)]
Mr514.21
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)9.401 (1), 15.770 (1), 16.845 (1)
β (°) 95.581 (1)
V3)2485.6 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.97
Crystal size (mm)0.45 × 0.20 × 0.10
Data collection
DiffractometerSMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.644, 0.908
No. of measured, independent and
observed [I > 2σ(I)] reflections
8905, 4368, 3157
Rint0.033
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.124, 1.15
No. of reflections4368
No. of parameters225
No. of restraints3
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.45

Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1994), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXLTL (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
Mo—O1.647 (4)Mo—Cl42.358 (1)
Mo—OW2.340 (4)Mo—Cl12.380 (1)
Mo—Cl22.352 (2)Mo—Cl32.402 (1)
O—Mo—OW177.7 (2)Cl2—Mo—Cl188.3 (1)
O—Mo—Cl299.8 (2)Cl4—Mo—Cl1162.7 (1)
OW—Mo—Cl282.48 (11)O—Mo—Cl397.3 (2)
O—Mo—Cl499.0 (2)OW—Mo—Cl380.4 (1)
OW—Mo—Cl481.5 (1)Cl2—Mo—Cl3162.9 (1)
Cl2—Mo—Cl489.1 (1)Cl4—Mo—Cl388.6 (1)
O—Mo—Cl198.3 (2)Cl1—Mo—Cl388.8 (1)
OW—Mo—Cl181.1 (1)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW—HW1···Cl1i0.842.613.338 (4)145
OW—HW2···Cl3i0.852.473.238 (4)151
Symmetry code: (i) x+2, y+1, z+2.
 

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