Diaqua-1κO,2κO-(2,2′-bi-1H-imidazole-1κ2N3,N3′)(oxalato-2κ2O1,O2)di-μ-oxido-κ4O:O-dioxido-1κO,2κO-dimolyb­denum(V) trihydrate

Zhang, X.; Wei, P.; Shi, C.; Li, B.; Hu, B.

doi:10.1107/S1600536809052003

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages m26-m27

doi:10.1107/S1600536809052003

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Diaqua-1κO,2κO-(2,2′-bi-1H-imidazole-1κ²N³,N^3′)(oxalato-2κ²O¹,O²)di-μ-oxido-κ⁴O:O-dioxido-1κO,2κO-dimolybdenum(V) trihydrate

Xiutang Zhang,^a,^b ^* Peihai Wei,^a Congwen Shi,^a Bin Li ^a and Bo Hu ^a

^aAdvanced Material Institute of Research, Department of Chemistry and Chemical Engineering, ShanDong Institute of Education, Jinan, 250013, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, 252059, People's Republic of China
^*Correspondence e-mail: xiutangzhang@yahoo.com.cn

(Received 23 November 2009; accepted 3 December 2009; online 9 December 2009)

In the title compound, [Mo₂(C₂O₄)O₄(C₆H₆N₄)(H₂O)₂]·3H₂O, 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 H₂O molecule. The two distorted octahedrally coordinated Mo(V) atoms are linked together via O—O edge-sharing and Mo—Mo interactions with a Mo—Mo bond length of 2.564 (5) Å. Uncoordinated water molecules are situated in the voids of the crystal structure. N—H⋯O and O—H⋯O hydrogen bonding between the neutral molecules and the water molecules 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)(H₂O)₂]·3H₂O
M_r = 568.13
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.021
wR(F²) = 0.059
S = 1.00
3099 reflections
275 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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⋯O7^iv	0.8 (4)	1.8 (5)	2.65 (5)	172
O3W—H5W⋯O2^v	0.8 (4)	2.8 (7)	2.94 (7)	92
O5W—H9W⋯O3W^vi	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) -x+1, -y+1, -z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, y, z-1; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) -x, -y+1, -z; (vi) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052003/wm2286sup1.cif

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

checkCIF report

Comment top

The design and synthesis of polyoxometalates has attracted continuous research interest not only because of their appealing structural and topological novelties, but also due to their interesting optical, electronic, magnetic, and catalytic properties, as well as their potential medical applications (Pope et al., 1991). In our group, organic amines, such as 3-(2-pyridyl)pyrazole and pyrazine, are used to effectively modify polyoxomolybdates (Zhang, Dou et al., 2009); Zhang, Wei et al., 2009). Here, we describe the synthesis and structural characterization of the title compound.

As shown in Figure 1, the asymmetric unit contains two Mo(V) ions, one of which is chelated by one diimidazole ligand, and the other chelated by one oxalate anion. Both Mo(V) ions are coordinated by one associated water molecule and one terminal oxygen atom. The two Mo(V) ions are linked together by two µ-oxygen atoms and by Mo—Mo bonding (2.564 (5) Å). Moreover, three uncoordinated water molecules are found in the voids of the crystal packing. Hydrogen bonding interactions between the Mo-containing molecule and water molecules further consolidates the structure (Fig. 2; Table 2).

Related literature top

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 top

A mixture of diimidazole (1 mmoL), molybdenum trioxide (1 mmoL), and oxalic acid (1 mmoL) in 10 ml distilled water were sealed in a 25 ml Teflon-lined stainless steel autoclave which was kept at 433 K for three days. Colorless crystals suitable for the X-ray diffraction study were obtained. Anal. Calc. for C₈H₁₄Mo₂N₄O₁₃: C 16.96, H 2.47, N 9.89%; Found: C 16.85, H 2.40, N 9.78%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.
	Fig. 2. The packing diagram of the title compound with hydrogen bonds (dashed lines).

Diaqua-1κO,2κO-(2,2'-bi-1H-imidazole- 1κ²N³,N^3')(oxalato-2κ²O¹,O²)di- µ-oxido-κ⁴O:O-dioxido-1κO,2κO-dimolybdenum(V) trihydrate top

Crystal data top

[Mo₂(C₂O₄)O₄(C₆H₆N₄)(H₂O)₂]·3H₂O	F(000) = 1120
M_r = 568.13	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.036P)² + 1.2494P] where P = (F_o² + 2F_c²)/3
3099 reflections	(Δ/σ)_max = 0.001
275 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Mo₂(C₂O₄)O₄(C₆H₆N₄)(H₂O)₂]·3H₂O	V = 1772.4 (5) Å³
M_r = 568.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.7509 (16) Å	µ = 1.49 mm⁻¹
b = 14.517 (2) Å	T = 273 K
c = 11.3661 (17) Å	0.12 × 0.10 × 0.08 mm
β = 92.306 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3099 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2820 reflections with I > 2σ(I)
T_min = 0.841, T_max = 0.890	R_int = 0.020
11601 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.48 e Å⁻³
3099 reflections	Δρ_min = −0.36 e Å⁻³
275 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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O7^iv	0.8 (4)	1.8 (5)	2.65 (5)	172
O3W—H5W···O2^v	0.8 (4)	2.8 (7)	2.94 (7)	92
O5W—H9W···O3W^vi	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) −x+1, −y+1, −z; (ii) x, −y+1/2, z−1/2; (iii) x, y, z−1; (iv) x, −y+1/2, z+1/2; (v) −x, −y+1, −z; (vi) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Mo₂(C₂O₄)O₄(C₆H₆N₄)(H₂O)₂]·3H₂O
M_r	568.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	10.7509 (16), 14.517 (2), 11.3661 (17)
β (°)	92.306 (2)
V (Å³)	1772.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.49
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.841, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections	11601, 3099, 2820
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.059, 1.00
No. of reflections	3099
No. of parameters	275
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.36

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.86	2.02	2.84 (5)	160.2
N4—H4A···O3ⁱ	0.86	1.90	2.76 (5)	172.2
O1W—H1W···O6ⁱⁱ	0.8 (5)	1.9 (4)	2.66 (5)	168.00
O1W—H2W···O4Wⁱⁱⁱ	0.8 (4)	1.8 (5)	2.56 (6)	170.00
O2W—H4W···O7^iv	0.8 (4)	1.8 (5)	2.65 (5)	172.00
O3W—H5W···O2^v	0.8 (4)	2.8 (7)	2.94 (7)	92.00
O5W—H9W···O3W^vi	0.9 (5)	2.1 (6)	2.93 (7)	158.00
O2W—H3W···O3W	0.8 (2)	1.9 (3)	2.69 (7)	160.00

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

Acknowledgements

Financial support from the 973 Key Program of the MOST (2006CB932904 and 2007CB815304), the National Natural Science Foundation of China (20873150, 20821061 and 50772113) , the Chinese Academy of Sciences (KJCX2-YW-M05), Shandong Provincial Education Department and Shandong Institute of Education are gratefully acknowledged.

References

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