Diaqua-1κO,2κO-(2,2'-bi-1H-imidazole-1κN,N)(oxalato-2κO,O)di-μ-oxido-κO:O-dioxido-1κO,2κO-dimolyb-denum(V) trihydrate.

In the title compound, [Mo(2)(C(2)O(4))O(4)(C(6)H(6)N(4))(H(2)O)(2)]·3H(2)O, the coordination polyhedra for both Mo(V) atoms consist of two bridging O atoms, two atoms of the chelating ligand (oxalate or diimidazole), a terminal O atom and one H(2)O mol-ecule. The two distorted octa-hedrally coordinated Mo(V) atoms are linked together via O-O edge-sharing and Mo-Mo inter-actions with a Mo-Mo bond length of 2.564 (5) Å. Uncoordinated water mol-ecules are situated in the voids of the crystal structure. N-H⋯O and O-H⋯O hydrogen bonding between the neutral mol-ecules and the water mol-ecules lead to a consolidation of the structure.

Related literature

For background to polyoxometalates, see: Pope & Müller (1991 ▶). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009 ▶); Zhang, Wei et al. (2009 ▶).

Experimental

Crystal data

[Mo2(C2O4)O4(C6H6N4)(n class="Chemical">H2O)2]·3H2O

M = 568.13

Monoclinic,

a = 10.7509 (16) Å

b = 14.517 (2) Å

c = 11.3661 (17) Å

β = 92.306 (2)°

V = 1772.4 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.49 mm−1

T = 273 K

0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.841, T max = 0.890

11601 measured reflections

3099 independent reflections

2820 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.059

S = 1.00

3099 reflections

275 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.36 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/S1600536809052003/wm2286sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052003/wm2286Isup2.hkl

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

[Mo2(C2O4)O4(C6H6N4)(H2O)2]·3H2O	F(000) = 1120
Mr = 568.13	Dx = 2.129 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3099 reflections
a = 10.7509 (16) Å	θ = 1.9–25.0°
b = 14.517 (2) Å	µ = 1.49 mm−1
c = 11.3661 (17) Å	T = 273 K
β = 92.306 (2)°	Block, colorless
V = 1772.4 (5) Å3	0.12 × 0.10 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	3099 independent reflections
Radiation source: fine-focus sealed tube	2820 reflections with I > 2σ(I)
graphite	Rint = 0.020
phi and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.841, Tmax = 0.890	k = −17→17
11601 measured reflections	l = −13→13

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.036P)2 + 1.2494P] where P = (Fo2 + 2Fc2)/3
3099 reflections	(Δ/σ)max = 0.001
275 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.36 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	0.4186 (3)	0.2145 (3)	0.0209 (3)	0.0233 (14)
Mo2	0.2035 (4)	0.2602 (3)	0.0911 (3)	0.0250 (14)
C1	0.659 (4)	0.326 (3)	0.056 (4)	0.026 (10)
C2	0.591 (4)	0.381 (3)	−0.030 (4)	0.025 (10)
C3	0.436 (4)	0.411 (3)	−0.151 (4)	0.030 (10)
H3	0.3598	0.4076	−0.1927	0.036*
C4	0.523 (5)	0.478 (3)	−0.163 (4)	0.033 (11)
H4	0.5168	0.5278	−0.2146	0.040*
C5	0.788 (5)	0.267 (4)	0.188 (5)	0.038 (12)
H5	0.8565	0.2586	0.2395	0.045*
C6	0.691 (4)	0.208 (3)	0.170 (4)	0.033 (11)
H6	0.6819	0.1520	0.2078	0.040*
C7	0.108 (4)	0.427 (3)	−0.044 (4)	0.028 (10)
C8	0.007 (4)	0.352 (3)	−0.060 (4)	0.030 (10)
N1	0.479 (3)	0.351 (3)	−0.066 (3)	0.026 (8)
N2	0.620 (4)	0.458 (3)	−0.087 (3)	0.029 (9)
H2	0.6881	0.4889	−0.0777	0.035*
N3	0.609 (4)	0.246 (3)	0.086 (3)	0.028 (9)
N4	0.767 (3)	0.341 (3)	0.115 (3)	0.031 (9)
H4A	0.8137	0.3886	0.1091	0.038*
O1	0.028 (3)	0.279 (2)	0.004 (3)	0.032 (8)
O2	−0.084 (3)	0.364 (3)	−0.125 (3)	0.042 (9)
O3	0.100 (3)	0.497 (2)	−0.103 (3)	0.040 (8)
O4	0.195 (3)	0.407 (2)	0.032 (3)	0.029 (7)
O5	0.161 (3)	0.160 (2)	0.149 (3)	0.040 (8)
O6	0.370 (3)	0.288 (2)	0.154 (3)	0.028 (7)
O7	0.261 (3)	0.232 (2)	−0.065 (3)	0.028 (7)
O8	0.431 (3)	0.106 (2)	0.070 (3)	0.037 (8)
O1W	0.488 (3)	0.171 (3)	−0.143 (3)	0.038 (8)
O2W	0.135 (3)	0.328 (2)	0.245 (3)	0.037 (8)
O3W	0.078 (6)	0.499 (4)	0.315 (5)	0.081 (16)
O4W	0.678 (4)	0.065 (3)	0.860 (4)	0.050 (10)
O5W	0.905 (4)	0.104 (3)	0.965 (4)	0.065 (12)
H1W	0.46 (5)	0.18 (5)	−0.21 (3)	0.080*
H2W	0.55 (4)	0.14 (4)	−0.15 (5)	0.080*
H3W	0.12 (6)	0.384 (14)	0.25 (3)	0.080*
H4W	0.18 (6)	0.31 (4)	0.30 (4)	0.080*
H7W	0.65 (5)	0.02 (3)	0.89 (6)	0.080*
H8W	0.74 (4)	0.08 (4)	0.90 (5)	0.080*
H9W	0.93 (6)	0.08 (5)	1.03 (3)	0.080*
H10W	0.94 (6)	0.08 (5)	0.91 (3)	0.080*
H5W	0.15 (2)	0.50 (6)	0.29 (6)	0.080*
H6W	0.03 (5)	0.52 (6)	0.27 (5)	0.1 (4)*

	U11	U22	U33	U12	U13	U23
Mo1	0.028 (2)	0.022 (2)	0.020 (2)	−0.0018 (15)	−0.0015 (16)	0.0013 (15)
Mo2	0.026 (2)	0.027 (2)	0.022 (2)	−0.0032 (15)	−0.0012 (16)	0.0014 (15)
C1	0.03 (2)	0.03 (2)	0.02 (2)	0.000 (19)	0.001 (18)	−0.001 (19)
C2	0.03 (2)	0.02 (2)	0.02 (2)	−0.002 (18)	0.001 (18)	0.001 (18)
C3	0.03 (3)	0.03 (2)	0.03 (2)	0.00 (2)	−0.01 (2)	0.002 (19)
C4	0.04 (3)	0.03 (2)	0.03 (2)	0.00 (2)	0.00 (2)	0.01 (2)
C5	0.03 (3)	0.05 (3)	0.04 (3)	0.01 (2)	−0.01 (2)	0.01 (2)
C6	0.03 (3)	0.03 (3)	0.03 (3)	0.01 (2)	0.00 (2)	0.01 (2)
C7	0.03 (2)	0.03 (3)	0.02 (2)	0.00 (2)	0.002 (19)	−0.002 (19)
C8	0.03 (3)	0.03 (3)	0.03 (2)	0.00 (2)	0.00 (2)	0.00 (2)
N1	0.03 (2)	0.024 (19)	0.024 (19)	−0.001 (16)	−0.002 (16)	0.002 (15)
N2	0.03 (2)	0.03 (2)	0.03 (2)	−0.007 (17)	−0.001 (17)	0.003 (16)
N3	0.03 (2)	0.03 (2)	0.03 (2)	−0.001 (16)	−0.001 (17)	0.005 (16)
N4	0.03 (2)	0.03 (2)	0.03 (2)	−0.005 (17)	−0.003 (17)	0.005 (18)
O1	0.027 (17)	0.031 (18)	0.038 (19)	−0.006 (14)	−0.003 (15)	0.004 (15)
O2	0.038 (19)	0.04 (2)	0.05 (2)	−0.004 (16)	−0.019 (17)	0.000 (17)
O3	0.04 (2)	0.032 (19)	0.04 (2)	−0.007 (16)	−0.008 (16)	0.010 (16)
O4	0.027 (16)	0.027 (17)	0.031 (17)	−0.004 (13)	−0.005 (14)	0.000 (14)
O5	0.04 (2)	0.04 (2)	0.04 (2)	−0.007 (16)	0.004 (16)	0.009 (17)
O6	0.028 (17)	0.033 (18)	0.024 (16)	−0.002 (14)	−0.002 (13)	−0.002 (13)
O7	0.031 (17)	0.031 (17)	0.022 (16)	−0.003 (14)	−0.003 (13)	−0.001 (13)
O8	0.04 (2)	0.027 (18)	0.038 (19)	−0.001 (15)	−0.001 (16)	0.004 (15)
O1W	0.05 (2)	0.04 (2)	0.024 (17)	0.016 (17)	−0.002 (15)	−0.003 (16)
O2W	0.04 (2)	0.05 (2)	0.025 (17)	0.009 (17)	0.000 (15)	0.002 (15)
O3W	0.12 (4)	0.06 (3)	0.06 (3)	0.03 (3)	−0.02 (3)	0.00 (3)
O4W	0.04 (2)	0.04 (2)	0.07 (3)	−0.001 (18)	−0.01 (2)	0.01 (2)
O5W	0.06 (3)	0.06 (3)	0.07 (3)	−0.01 (2)	−0.01 (3)	0.00 (3)

Mo1—O8	1.68 (3)	C5—C6	1.35 (7)
Mo1—O7	1.94 (3)	C5—N4	1.37 (6)
Mo1—O6	1.94 (3)	C5—H5	0.9300
Mo1—O1W	2.13 (3)	C6—N3	1.39 (6)
Mo1—N3	2.20 (4)	C6—H6	0.9300
Mo1—N1	2.31 (4)	C7—O3	1.22 (6)
Mo1—Mo2	2.564 (5)	C7—O4	1.28 (5)
Mo2—O5	1.68 (3)	C7—C8	1.55 (6)
Mo2—O6	1.94 (3)	C8—O2	1.22 (6)
Mo2—O7	1.94 (3)	C8—O1	1.29 (6)
Mo2—O1	2.11 (3)	N2—H2	0.8600
Mo2—O2W	2.16 (3)	N4—H4A	0.8600
Mo2—O4	2.23 (3)	O1W—H1W	0.8 (5)
C1—N3	1.33 (6)	O1W—H2W	0.8 (4)
C1—N4	1.34 (6)	O2W—H3W	0.82 (16)
C1—C2	1.44 (6)	O2W—H4W	0.8 (6)
C2—N1	1.33 (5)	O3W—H5W	0.8 (4)
C2—N2	1.33 (6)	O3W—H6W	0.8 (7)
C3—C4	1.35 (7)	O4W—H7W	0.8 (5)
C3—N1	1.37 (6)	O4W—H8W	0.8 (6)
C3—H3	0.9300	O5W—H9W	0.9 (5)
C4—N2	1.37 (6)	O5W—H10W	0.8 (5)
C4—H4	0.9300
O8—Mo1—O7	110.2 (15)	N4—C1—C2	131 (4)
O8—Mo1—O6	106.3 (15)	N1—C2—N2	111 (4)
O7—Mo1—O6	93.4 (13)	N1—C2—C1	117 (4)
O8—Mo1—O1W	89.1 (16)	N2—C2—C1	132 (4)
O7—Mo1—O1W	85.9 (13)	C4—C3—N1	109 (4)
O6—Mo1—O1W	163.7 (14)	C4—C3—H3	125.7
O8—Mo1—N3	91.4 (15)	N1—C3—H3	125.7
O7—Mo1—N3	158.0 (14)	C3—C4—N2	107 (4)
O6—Mo1—N3	84.3 (14)	C3—C4—H4	126.3
O1W—Mo1—N3	90.2 (14)	N2—C4—H4	126.3
O8—Mo1—N1	157.9 (15)	C6—C5—N4	107 (4)
O7—Mo1—N1	85.8 (13)	C6—C5—H5	126.4
O6—Mo1—N1	87.1 (13)	N4—C5—H5	126.4
O1W—Mo1—N1	76.6 (14)	C5—C6—N3	109 (4)
N3—Mo1—N1	72.2 (13)	C5—C6—H6	125.7
O8—Mo1—Mo2	101.5 (12)	N3—C6—H6	125.7
O7—Mo1—Mo2	48.7 (10)	O3—C7—O4	127 (4)
O6—Mo1—Mo2	48.6 (9)	O3—C7—C8	119 (4)
O1W—Mo1—Mo2	134.5 (10)	O4—C7—C8	114 (4)
N3—Mo1—Mo2	132.9 (10)	O2—C8—O1	125 (4)
N1—Mo1—Mo2	100.5 (9)	O2—C8—C7	121 (4)
O5—Mo2—O6	107.5 (15)	O1—C8—C7	114 (4)
O5—Mo2—O7	106.2 (16)	C2—N1—C3	106 (4)
O6—Mo2—O7	93.4 (13)	C2—N1—Mo1	115 (3)
O5—Mo2—O1	92.7 (15)	C3—N1—Mo1	139 (3)
O6—Mo2—O1	159.4 (13)	C2—N2—C4	107 (4)
O7—Mo2—O1	84.9 (13)	C2—N2—H2	126.5
O5—Mo2—O2W	88.3 (16)	C4—N2—H2	126.5
O6—Mo2—O2W	86.8 (13)	C1—N3—C6	106 (4)
O7—Mo2—O2W	164.7 (13)	C1—N3—Mo1	118 (3)
O1—Mo2—O2W	89.6 (13)	C6—N3—Mo1	135 (3)
O5—Mo2—O4	160.2 (15)	C1—N4—C5	107 (4)
O6—Mo2—O4	86.4 (12)	C1—N4—H4A	126.3
O7—Mo2—O4	86.5 (12)	C5—N4—H4A	126.3
O1—Mo2—O4	73.0 (11)	C8—O1—Mo2	120 (3)
O2W—Mo2—O4	78.3 (12)	C7—O4—Mo2	116 (3)
O5—Mo2—Mo1	99.3 (12)	Mo2—O6—Mo1	82.7 (12)
O6—Mo2—Mo1	48.7 (9)	Mo1—O7—Mo2	82.7 (12)
O7—Mo2—Mo1	48.6 (9)	H1W—O1W—H2W	106.00
O1—Mo2—Mo1	133.5 (10)	H3W—O2W—H4W	112.00
O2W—Mo2—Mo1	135.2 (9)	H5W—O3W—H6W	112.00
O4—Mo2—Mo1	100.4 (8)	H7W—O4W—H8W	107.00
N3—C1—N4	111 (4)	H9W—O5W—H10W	111.00
N3—C1—C2	118 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4i	0.86	2.02	2.84 (5)	160
N4—H4A···O3i	0.86	1.90	2.76 (5)	172
O1W—H1W···O6ii	0.8 (5)	1.9 (4)	2.66 (5)	168
O1W—H2W···O4Wiii	0.8 (4)	1.8 (5)	2.56 (6)	170
O2W—H4W···O7iv	0.8 (4)	1.8 (5)	2.65 (5)	172
O3W—H5W···O2v	0.8 (4)	2.8 (7)	2.94 (7)	92
O5W—H9W···O3Wvi	0.9 (5)	2.1 (6)	2.93 (7)	158
O2W—H3W···O3W	0.8 (2)	1.9 (3)	2.69 (7)	160

Table 1

Selected bond lengths (Å)

Mo1—O8	1.68 (3)
Mo1—O7	1.94 (3)
Mo1—O6	1.94 (3)
Mo1—O1W	2.13 (3)
Mo1—N3	2.20 (4)
Mo1—N1	2.31 (4)
Mo2—O5	1.68 (3)
Mo2—O6	1.94 (3)
Mo2—O7	1.94 (3)
Mo2—O1	2.11 (3)
Mo2—O2W	2.16 (3)
Mo2—O4	2.23 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4i	0.86	2.02	2.84 (5)	160
N4—H4A⋯O3i	0.86	1.90	2.76 (5)	172
O1W—H1W⋯O6ii	0.8 (5)	1.9 (4)	2.66 (5)	168
O1W—H2W⋯O4Wiii	0.8 (4)	1.8 (5)	2.56 (6)	170
O2W—H4W⋯O7iv	0.8 (4)	1.8 (5)	2.65 (5)	172
O3W—H5W⋯O2v	0.8 (4)	2.8 (7)	2.94 (7)	92
O5W—H9W⋯O3Wvi	0.9 (5)	2.1 (6)	2.93 (7)	158
O2W—H3W⋯O3W	0.8 (2)	1.9 (3)	2.69 (7)	160

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .