Tetra-μ-oxido-tetra-kis{dioxido[3-(2-pyrid-yl)-1H-pyrazole]molybdenum(VI)}.

In the title compound, [Mo(4)O(12)(C(8)H(7)N(3))(4)], the Mo(VI) ion has a distorted octa-hedral coordination completed by two terminal O atoms, two μ-oxide atoms and two N atoms from one 3-(2-pyrid-yl)-1H-pyrazole ligand. It is noteworthy that in the tetranuclear unit ( symmetry), any three Mo(VI) atoms define a plane, and the fourth lies 1.8 (1) Å out of that plane. The degree of linearity of the oxide bridges between two Mo atoms is 175.38 (13)°. Moreover, the N-H group forms an intra-molecular hydrogen bond (four per mol-ecule).

Related literature

For the properties and potential medical applications of polyoxometalate clusters, see: Pope & Müller (1991 ▶); Khenkin & Neumann (2008 ▶); Zhang et al. (2006 ▶, 2007 ▶, 2009 ▶). For Mo—O and Mo—N distances, see: Rana et al. (2003 ▶). For general background, see: Mezei et al. (2007 ▶).

Experimental

Crystal data

[Mo4O12(C8n class="Species">H7N3)4]

M = 1156.42

Tetragonal,

a = 14.4412 (16) Å

c = 9.094 (2) Å

V = 1896.6 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.37 mm−1

T = 298 K

0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.853, T max = 0.898

7579 measured reflections

1675 independent reflections

1316 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.064

S = 1.00

1675 reflections

139 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031717/zq2001sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031717/zq2001Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mo4O12(C8H7N3)4]	Dx = 2.025 Mg m−3
Mr = 1156.42	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/n	Cell parameters from 1675 reflections
Hall symbol: -P 4bc	θ = 2.0–25.0°
a = 14.4412 (16) Å	µ = 1.37 mm−1
c = 9.094 (2) Å	T = 298 K
V = 1896.6 (5) Å3	Block, colourless
Z = 2	0.12 × 0.10 × 0.08 mm
F(000) = 1136

Bruker APEXII CCD area-detector diffractometer	1675 independent reflections
Radiation source: fine-focus sealed tube	1316 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −17→16
Tmin = 0.853, Tmax = 0.898	k = −12→17
7579 measured reflections	l = −9→10

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0295P)2 + 2.0306P] where P = (Fo2 + 2Fc2)/3
1675 reflections	(Δ/σ)max = 0.001
139 parameters	Δρmax = 0.35 e Å−3
1 restraint	Δρmin = −0.35 e Å−3

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	0.642839 (18)	0.904662 (19)	0.19761 (3)	0.02233 (12)
N1	0.61994 (19)	0.90081 (18)	0.4404 (3)	0.0257 (6)
N2	0.6811 (2)	0.8938 (2)	0.5516 (3)	0.0311 (7)
N3	0.4862 (2)	0.8976 (2)	0.2532 (3)	0.0314 (7)
O1	0.76035 (15)	0.88536 (16)	0.2362 (2)	0.0302 (5)
O2	0.61894 (17)	0.86807 (17)	0.0193 (3)	0.0359 (6)
O3	0.63381 (18)	1.02324 (17)	0.1907 (3)	0.0370 (6)
C1	0.6375 (3)	0.8821 (3)	0.6815 (4)	0.0345 (9)
H1	0.6656	0.8765	0.7731	0.041*
C2	0.5439 (3)	0.8800 (2)	0.6536 (4)	0.0354 (9)
H2A	0.4963	0.8726	0.7215	0.042*
C3	0.5355 (2)	0.8917 (2)	0.4995 (4)	0.0283 (8)
C4	0.4595 (2)	0.8907 (2)	0.3953 (4)	0.0321 (8)
C5	0.3667 (3)	0.8828 (2)	0.4346 (5)	0.0413 (10)
H5	0.3492	0.8796	0.5329	0.050*
C6	0.3014 (3)	0.8798 (3)	0.3248 (5)	0.0519 (11)
H6	0.2391	0.8724	0.3477	0.062*
C7	0.3291 (3)	0.8878 (3)	0.1802 (5)	0.0504 (11)
H7	0.2853	0.8870	0.1054	0.060*
C8	0.4208 (3)	0.8969 (3)	0.1471 (5)	0.0423 (10)
H8	0.4386	0.9027	0.0492	0.051*
H1A	0.746 (3)	0.894 (3)	0.540 (5)	0.080*

	U11	U22	U33	U12	U13	U23
Mo1	0.02453 (18)	0.02550 (18)	0.01698 (17)	0.00112 (12)	0.00115 (11)	0.00047 (12)
N1	0.0347 (15)	0.0237 (14)	0.0187 (14)	0.0010 (12)	−0.0011 (12)	−0.0010 (11)
N2	0.0367 (17)	0.0338 (16)	0.0227 (16)	0.0002 (14)	0.0014 (13)	−0.0026 (13)
N3	0.0298 (16)	0.0315 (16)	0.0328 (16)	0.0037 (13)	−0.0038 (13)	−0.0050 (13)
O1	0.0245 (12)	0.0387 (14)	0.0273 (13)	0.0000 (11)	0.0026 (10)	0.0028 (11)
O2	0.0466 (15)	0.0403 (14)	0.0209 (13)	−0.0016 (12)	−0.0022 (11)	0.0006 (11)
O3	0.0448 (15)	0.0294 (13)	0.0368 (15)	0.0040 (11)	0.0047 (12)	0.0037 (11)
C1	0.044 (2)	0.039 (2)	0.0201 (19)	0.0018 (17)	0.0019 (16)	0.0017 (16)
C2	0.041 (2)	0.034 (2)	0.031 (2)	0.0022 (17)	0.0135 (17)	0.0045 (16)
C3	0.0357 (19)	0.0203 (17)	0.0289 (19)	0.0051 (14)	0.0086 (16)	−0.0006 (14)
C4	0.036 (2)	0.0216 (17)	0.039 (2)	0.0017 (15)	0.0111 (17)	0.0006 (16)
C5	0.034 (2)	0.035 (2)	0.055 (3)	0.0049 (17)	0.0090 (19)	0.0055 (19)
C6	0.033 (2)	0.055 (3)	0.067 (3)	0.0006 (19)	0.002 (2)	0.003 (2)
C7	0.033 (2)	0.067 (3)	0.051 (3)	0.005 (2)	−0.010 (2)	−0.007 (2)
C8	0.036 (2)	0.046 (2)	0.044 (2)	0.0043 (18)	−0.0021 (18)	−0.0070 (19)

Mo1—O3	1.719 (2)	C1—C2	1.375 (5)
Mo1—O2	1.740 (2)	C1—H1	0.9300
Mo1—O1	1.755 (2)	C2—C3	1.416 (5)
Mo1—O1i	2.207 (2)	C2—H2A	0.9300
Mo1—N1	2.233 (3)	C3—C4	1.449 (5)
Mo1—N3	2.320 (3)	C4—C5	1.392 (5)
N1—C3	1.340 (4)	C5—C6	1.374 (6)
N1—N2	1.346 (4)	C5—H5	0.9300
N2—C1	1.349 (4)	C6—C7	1.379 (6)
N2—H1A	0.94 (5)	C6—H6	0.9300
N3—C8	1.350 (5)	C7—C8	1.364 (6)
N3—C4	1.353 (5)	C7—H7	0.9300
O1—Mo1ii	2.207 (2)	C8—H8	0.9300
O3—Mo1—O2	104.69 (12)	N2—C1—C2	107.4 (3)
O3—Mo1—O1	103.82 (11)	N2—C1—H1	126.3
O2—Mo1—O1	109.26 (11)	C2—C1—H1	126.3
O3—Mo1—O1i	159.53 (10)	C1—C2—C3	105.4 (3)
O2—Mo1—O1i	86.03 (10)	C1—C2—H2A	127.3
O1—Mo1—O1i	88.51 (13)	C3—C2—H2A	127.3
O3—Mo1—N1	92.85 (10)	N1—C3—C2	109.3 (3)
O2—Mo1—N1	152.17 (11)	N1—C3—C4	115.3 (3)
O1—Mo1—N1	86.65 (10)	C2—C3—C4	135.3 (3)
O1i—Mo1—N1	71.30 (9)	N3—C4—C5	121.7 (4)
O3—Mo1—N3	88.74 (11)	N3—C4—C3	114.1 (3)
O2—Mo1—N3	89.78 (11)	C5—C4—C3	124.2 (3)
O1—Mo1—N3	153.15 (10)	C6—C5—C4	118.4 (4)
O1i—Mo1—N3	73.68 (9)	C6—C5—H5	120.8
N1—Mo1—N3	68.85 (10)	C4—C5—H5	120.8
C3—N1—N2	106.7 (3)	C5—C6—C7	119.5 (4)
C3—N1—Mo1	122.3 (2)	C5—C6—H6	120.3
N2—N1—Mo1	130.4 (2)	C7—C6—H6	120.3
N1—N2—C1	111.2 (3)	C8—C7—C6	120.0 (4)
N1—N2—H1A	124 (3)	C8—C7—H7	120.0
C1—N2—H1A	124 (3)	C6—C7—H7	120.0
C8—N3—C4	118.9 (3)	N3—C8—C7	121.4 (4)
C8—N3—Mo1	121.8 (3)	N3—C8—H8	119.3
C4—N3—Mo1	119.3 (2)	C7—C8—H8	119.3
Mo1—O1—Mo1ii	175.38 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1A···O2ii	0.94 (5)	1.86 (5)	2.783 (4)	168 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1A⋯O2i	0.94 (5)	1.86 (5)	2.783 (4)	168 (4)

Symmetry code: (i) .