Poly[[2-(3-pyridinio)-1H,3H+-benzimidazolium] [μ4-oxido-di-μ3-oxido-tetra-μ2-oxido-hexa­oxidotetra­molybdenum(VI)]]

Chen, L.-J.; Lin, S.; Wu, X.-Y.; Chen, X.-H.

doi:10.1107/S160053680901294X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m505-m506

doi:10.1107/S160053680901294X

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Poly[[2-(3-pyridinio)-1H,3H⁺-benzimidazolium] [μ₄-oxido-di-μ₃-oxido-tetra-μ₂-oxido-hexaoxidotetramolybdenum(VI)]]

Li-Juan Chen,^a,^b ^* Shen Lin,^a Xiao-Yuan Wu ^b and Xiao-Hua Chen ^a

^aCollege of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian 350007, People's Republic of China, and ^bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Science, Fuzhou, Fujian 350002, People's Republic of China
^*Correspondence e-mail: ljchen@ms.fjirsm.ac.cn

(Received 30 March 2009; accepted 6 April 2009; online 10 April 2009)

The reaction of MoO₃ with 2-(3-pyridyl)benzoimidazole and water in the presence of MnSO₄·5H₂O at 453 K under hydrothermal conditions afforded the title compound, {(C₁₂H₁₁N₂)[Mo₄O₁₃]}_n, in which infinite molybdenum oxide anionic chains are charge-balanced by diprotonated 2-(3-pyridyl)benzoimidazole (H₂3-PBIM²⁺) cations. Eight [MoO₆] octahedra are edge-shared, forming compact octamolybdate subunits which are connected through pairs of Mo—O—Mo bridges into extended one-dimensional arrays propagating along the a-axis direction. The asymmetric unit of the metal oxide chain contains one half of the octamolybdate unit, denoted [Mo₄O₁₃], the other half being generated by an inversion center. These molybdenum oxide chains are further connected through the 2-(3-pyridinio)benzoimidazolium cations into a three-dimensional network via N—H⋯O hydrogen bonds. In addition, neighbouring diprotonated cations are arranged in a head-to-tail fashion with a plane-to-plane separation of 3.63 (10) Å, indicating the existence of weak aromatic π–π stacking interactions.

Related literature

For the properties, applications and reactivity of inorganic-organic hybrid materials, see: Pope (1983 ); Pope & Müller (1991 ); Kong et al. (2004 ). For chain, sheet and framework structural types, see: Hagrman et al. (1999 ); Lu et al. (2002 ). For related structures, see: Chakrabarti & Natarajan (2002 ); Janiak (2000 ); Modec et al. (2004 ); Xiao et al. (2005 ).

Experimental

Crystal data

(C₁₂H₁₁N₂)[Mo₄O₁₃]
M_r = 789.00
Triclinic, $[P \overline 1]$
a = 7.947 (3) Å
b = 11.503 (5) Å
c = 11.630 (5) Å
α = 70.038 (14)°
β = 76.856 (17)°
γ = 75.947 (17)°
V = 957.2 (7) Å³
Z = 2
Mo Kα radiation
μ = 2.64 mm⁻¹
T = 293 K
0.10 × 0.05 × 0.02 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ) T_min = 0.763, T_max = 0.949
6127 measured reflections
3358 independent reflections
2594 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.100
S = 1.01
3358 reflections
289 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—O2	1.690 (5)
Mo1—O11	1.776 (5)
Mo1—O9	1.875 (5)
Mo1—O10ⁱ	1.956 (5)
Mo1—O6	2.189 (5)
Mo1—O10	2.416 (5)
Mo2—O5	1.693 (5)
Mo2—O4	1.709 (5)
Mo2—O8	1.927 (5)
Mo2—O3	2.004 (5)
Mo2—O10	2.200 (5)
Mo2—O9	2.345 (5)
Mo3—O7	1.699 (5)
Mo3—O13	1.790 (5)
Mo3—O6ⁱ	1.880 (5)
Mo3—O3	1.922 (5)
Mo3—O11	2.229 (6)
Mo3—O10	2.242 (5)
Mo4—O1	1.682 (5)
Mo4—O12	1.719 (5)
Mo4—O8	1.965 (5)
Mo4—O13ⁱⁱ	2.012 (5)
Mo4—O6	2.160 (5)
Mo4—O9	2.266 (5)
Symmetry codes: (i) -x, -y+2, -z+1; (ii) x-1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱⁱⁱ	0.86	1.78	2.639 (8)	176
N3—H3A⋯O8	0.86	1.78	2.614 (8)	164
Symmetry code: (iii) x, y-1, z.

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999 )'; software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901294X/sj2606sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901294X/sj2606Isup2.hkl

checkCIF report

Comment top

The exploration of metal oxide-based inorganic-organic hybrid materials is of contemporary interest in the fields of solid state chemistry, not only because of their fascinating properties and potential applications in many fields, such as catalysis, sorption, electrical conductivity, magnetism and optical materials (Pope & Müller, 1991, Pope, 1983). Owing to their versatile stoichiometry, different structure, and high reactivity (Kong, 2004), molybdenum polyoxoanions are good candidates to function as building blocks for inorganic-organic hybrid materials. Through exploiting the strategy of synergistic interaction between organic and inorganic components, many examples of molybdenum oxide-based solid materials with one-dimensional chain, two-dimensional sheet and three-dimensional framework structures have been successfully synthesized (Hagrman et al., 1999, Lu et al., 2002). The organic components often function as charge compensating cations or as a linking bridges, to extend the molybdenum oxide building units into multi-dimensional networks. We report here the synthesis and crystal structure of the title compound, in which the organic component acts as a charge compensating cation.

The structure of title compound consists of an infinite molybdenum oxide chain which is charge balanced by diprotonated H₂3-PBIM²⁺ cations. As shown Fig. 1, every Mo atom is coordinated octahedrally by six O atoms. These can be divided into four groups according to their coordination environments: (i) Mo—O(t), 1.682 (5)–1.718 (5) Å; (ii) Mo—O(µ₂-O), 1.776 (5)–2.229 (6) Å; (iii) Mo—O(µ₃-O), 1.875 (5)- 2.345 (5) Å; (iv) Mo—O(µ₄-O), 1.956 (5)–2.416 (5) Å (Table 1).

The asymmetric unit of the metal oxide chain contains one half of the octamolybdate unit, denoted as [Mo₄O₁₃], the other half is generated by the inversion center. Four asymmetric [MoO₆] octahedra are edge- shared to form [Mo₄O₁₃]^2- unit. Two [Mo₄O₁₃]^2- units are stacked together by edge-sharing to give rise to γ-[Mo₈O₂₆]^4- octamolybdate clusters, which are linked together to form infinite one- dimensional chains propagating along the a-direction through sharing pairs of common vertices. Therefore, the molybdenum oxide chain may be regarded to be constructed from octamolybdate units joined at two oxo groups or from two groups of cis-edge-sharing tetranuclear units fused at two common corners. The octamolybdate chain in the title compound is structurally analogous to those found in [Me—NC₅H₅]₄[Mo₈O₂₆] (Modec et al., 2003), [H₂enMe]₂[Mo₈O₂₆] (Xiao et al., 2005), and [NH₃(CH₂)₂NH₃]₂[Mo₈O₂₆] (Chakrabarti & Natarajan, 2002).

In the solid state of the title compound, the one-dimensional molybdenum oxide chains are held together and extended to three-dimensional framework via strong N—H···O hydrogen bonding and weak aromatic π-π stacking interactions. As illustrated in Fig. 3, one of the imino groups and the pyridyl group in the H₂3-PBIM²⁺ ligands participate in the intermolecular hydrogen bonding with two µ₂-O atoms of the molybdenum oxide chains. The N···O separations are 2.639 (8) and 2.614 (8) Å with both H···O distances are 1.78 Å, falling into the normal range of the strong hydrogen bond interactions. The bond angles are 176.3 and 163.6 °, respectively. In addition, the neighbouring diprotonated H₂3-PBIM²⁺ ligands along the a-direction are arranged in a head-to-tail fashion with a plane-to-plane separation of 3.63 (10) Å, indicating the existence of weak aromatic π-π stacking interactions (Janiak, 2000).

Related literature top

For the properties, applications and reactivity of inorganic-organic hybrid materials, see: Pope (1983); Pope & Müller (1991); Kong et al. (2004). For chain, sheet and framework structural types, see: Hagrman et al. (1999); Lu et al. (2002). For related structures, see: Chakrabarti & Natarajan (2002); Janiak (2000); Modec et al. (2004); Xiao et al. (2005).

Experimental top

A mixture of MoO₃, MnSO₄.5H₂O, 2-(3-pyridyl)benzoimidazole and H₂O in the molar ratio 1.0:1.2:1.0:1835 was sealed in a 18 ml Teflon-lined Parr acid digestion bomb and heated for 3 days at 453 K and autogeneous pressure. After allowing the reaction mixture to cool down to room temperature, colorless needle-like crystals of title compound were collected, washed with water and air dried.

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999)'; software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A molecular drawing of (I), showing 30% probability displacement ellipsoids.
	Fig. 2. A polyhedral representation of the infinite chain in title compound and the γ-[Mo₈O₂₆]^4-. All C, N and H atoms were omitted for clarity.
	Fig. 3. Packing diagram of title compound along a axis. Broken lines indicate hydrogen bonds. All H atoms, which do not participate in the bydrogen bonds, have been omitted for clarity.

Poly[[2-(3-pyridinio)-1H,3H⁺-benzimidazolium] [µ₄-oxido-di-µ₃-oxido-tetra-µ₂-oxido-hexaoxidotetramolybdenum(VI)]] top

Crystal data top

(C₁₂H₁₁N₂)[Mo₄O₁₃]	Z = 2
M_r = 789.00	F(000) = 752
Triclinic, P1	D_x = 2.738 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.947 (3) Å	Cell parameters from 2049 reflections
b = 11.503 (5) Å	θ = 3.0–25.0°
c = 11.630 (5) Å	µ = 2.64 mm⁻¹
α = 70.038 (14)°	T = 293 K
β = 76.856 (17)°	Prism, colorless
γ = 75.947 (17)°	0.10 × 0.05 × 0.02 mm
V = 957.2 (7) Å³

Data collection top

Rigaku Mercury CCD diffractometer	3358 independent reflections
Radiation source: fine-focus sealed tube	2594 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	k = −13→12
T_min = 0.763, T_max = 0.949	l = −13→13
6127 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0416P)²] where P = (F_o² + 2F_c²)/3
3358 reflections	(Δ/σ)_max = 0.001
289 parameters	Δρ_max = 0.98 e Å⁻³
6 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

(C₁₂H₁₁N₂)[Mo₄O₁₃]	γ = 75.947 (17)°
M_r = 789.00	V = 957.2 (7) Å³
Triclinic, P1	Z = 2
a = 7.947 (3) Å	Mo Kα radiation
b = 11.503 (5) Å	µ = 2.64 mm⁻¹
c = 11.630 (5) Å	T = 293 K
α = 70.038 (14)°	0.10 × 0.05 × 0.02 mm
β = 76.856 (17)°

Data collection top

Rigaku Mercury CCD diffractometer	3358 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	2594 reflections with I > 2σ(I)
T_min = 0.763, T_max = 0.949	R_int = 0.047
6127 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	6 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.01	Δρ_max = 0.98 e Å⁻³
3358 reflections	Δρ_min = −1.14 e Å⁻³
289 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	−0.16871 (9)	1.12585 (6)	0.46162 (6)	0.00650 (17)
Mo2	0.11157 (9)	1.09175 (6)	0.19220 (6)	0.00741 (17)
Mo3	0.26045 (9)	1.15843 (6)	0.40116 (6)	0.00665 (17)
Mo4	−0.28939 (9)	1.02948 (6)	0.25245 (6)	0.00758 (18)
O1	−0.3420 (7)	0.8971 (5)	0.2506 (5)	0.0133 (12)
O2	−0.3693 (7)	1.1971 (4)	0.5145 (5)	0.0105 (12)
O3	0.1859 (7)	1.2201 (4)	0.2416 (5)	0.0085 (11)
O4	0.0616 (7)	1.2015 (5)	0.0567 (5)	0.0128 (12)
O5	0.3085 (7)	1.0059 (5)	0.1528 (5)	0.0137 (12)
O6	−0.2454 (7)	0.9638 (4)	0.4425 (5)	0.0104 (12)
O7	0.2797 (7)	1.2922 (5)	0.4247 (5)	0.0115 (12)
O8	−0.0349 (7)	0.9717 (4)	0.2159 (5)	0.0083 (11)
O9	−0.1648 (7)	1.1673 (4)	0.2906 (5)	0.0096 (11)
O10	0.1167 (7)	1.0169 (4)	0.3927 (5)	0.0094 (11)
O11	−0.0233 (7)	1.2188 (4)	0.4667 (5)	0.0100 (11)
O12	−0.3228 (7)	1.1403 (5)	0.1127 (5)	0.0139 (12)
O13	0.4808 (7)	1.0993 (5)	0.3414 (5)	0.0112 (12)
N1	0.2675 (9)	0.4044 (6)	0.0410 (6)	0.0101 (14)
H1A	0.2439	0.3421	0.1048	0.012*
N2	0.2821 (9)	0.5971 (6)	−0.0789 (6)	0.0163 (16)
H2A	0.2683	0.6778	−0.1040	0.020*
N3	0.0301 (9)	0.7334 (6)	0.2313 (6)	0.0129 (15)
H3A	0.0292	0.8091	0.2287	0.016*
C1	0.3678 (11)	0.5190 (7)	−0.1506 (7)	0.0111 (17)
C2	0.4479 (11)	0.5449 (7)	−0.2742 (7)	0.0164 (19)
H2B	0.4529	0.6267	−0.3251	0.020*
C3	0.5193 (11)	0.4427 (8)	−0.3171 (8)	0.0184 (19)
H3B	0.5757	0.4556	−0.3986	0.022*
C4	0.5087 (10)	0.3195 (7)	−0.2404 (7)	0.0134 (17)
H4A	0.5561	0.2535	−0.2738	0.016*
C5	0.4315 (11)	0.2924 (7)	−0.1185 (7)	0.0161 (18)
H5A	0.4289	0.2101	−0.0682	0.019*
C6	0.3569 (10)	0.3953 (7)	−0.0735 (7)	0.0121 (17)
C7	0.2234 (10)	0.5267 (7)	0.0365 (7)	0.0107 (17)
C8	0.1258 (10)	0.5724 (6)	0.1383 (7)	0.0110 (17)
C9	0.1228 (10)	0.6933 (7)	0.1385 (7)	0.0075 (16)
H9A	0.1863	0.7462	0.0729	0.009*
C10	−0.0629 (12)	0.6621 (7)	0.3295 (7)	0.0176 (19)
H10A	−0.1266	0.6943	0.3931	0.021*
C11	−0.0631 (11)	0.5392 (7)	0.3352 (7)	0.0152 (18)
H11A	−0.1241	0.4876	0.4038	0.018*
C12	0.0270 (12)	0.4951 (7)	0.2394 (8)	0.0182 (19)
H12A	0.0234	0.4144	0.2406	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0066 (4)	0.0062 (3)	0.0058 (3)	−0.0016 (3)	−0.0010 (3)	−0.0003 (2)
Mo2	0.0072 (4)	0.0076 (3)	0.0064 (3)	−0.0024 (3)	−0.0002 (3)	−0.0007 (2)
Mo3	0.0067 (4)	0.0060 (3)	0.0063 (3)	−0.0027 (3)	−0.0014 (3)	0.0005 (2)
Mo4	0.0078 (4)	0.0079 (3)	0.0066 (4)	−0.0027 (3)	−0.0011 (3)	−0.0007 (2)
O1	0.018 (3)	0.012 (3)	0.010 (3)	−0.007 (2)	−0.004 (2)	−0.001 (2)
O2	0.007 (3)	0.011 (3)	0.012 (3)	0.001 (2)	−0.001 (2)	−0.002 (2)
O3	0.009 (3)	0.007 (3)	0.009 (3)	−0.001 (2)	−0.003 (2)	0.000 (2)
O4	0.013 (3)	0.013 (3)	0.012 (3)	−0.004 (2)	−0.004 (2)	−0.001 (2)
O5	0.013 (3)	0.011 (3)	0.015 (3)	0.003 (2)	−0.003 (3)	−0.006 (2)
O6	0.010 (3)	0.013 (3)	0.009 (3)	−0.003 (2)	−0.003 (2)	−0.001 (2)
O7	0.011 (3)	0.014 (3)	0.009 (3)	−0.001 (2)	−0.001 (2)	−0.005 (2)
O8	0.007 (3)	0.007 (2)	0.009 (3)	−0.004 (2)	0.002 (2)	0.000 (2)
O9	0.013 (3)	0.007 (3)	0.006 (3)	−0.002 (2)	−0.001 (2)	0.002 (2)
O10	0.012 (3)	0.007 (3)	0.009 (3)	0.000 (2)	−0.006 (2)	0.000 (2)
O11	0.011 (3)	0.007 (3)	0.012 (3)	0.000 (2)	−0.006 (2)	−0.002 (2)
O12	0.015 (3)	0.015 (3)	0.011 (3)	−0.004 (2)	−0.002 (2)	−0.002 (2)
O13	0.006 (3)	0.017 (3)	0.010 (3)	−0.004 (2)	−0.003 (2)	−0.001 (2)
N1	0.014 (4)	0.010 (3)	0.004 (3)	−0.005 (3)	0.004 (3)	−0.002 (2)
N2	0.023 (4)	0.003 (3)	0.019 (4)	0.005 (3)	−0.008 (3)	0.001 (3)
N3	0.012 (4)	0.006 (3)	0.020 (4)	0.003 (3)	−0.007 (3)	−0.004 (3)
C1	0.014 (4)	0.008 (4)	0.010 (4)	−0.004 (3)	−0.002 (3)	0.000 (3)
C2	0.021 (5)	0.015 (4)	0.008 (4)	−0.008 (4)	0.003 (4)	0.004 (3)
C3	0.012 (5)	0.023 (5)	0.023 (5)	−0.001 (4)	−0.008 (4)	−0.009 (4)
C4	0.006 (4)	0.016 (4)	0.018 (5)	−0.001 (3)	−0.001 (4)	−0.007 (3)
C5	0.024 (5)	0.015 (4)	0.013 (4)	−0.010 (4)	−0.003 (4)	−0.004 (3)
C6	0.009 (4)	0.016 (4)	0.016 (4)	−0.005 (3)	−0.006 (4)	−0.007 (3)
C7	0.011 (4)	0.007 (4)	0.013 (4)	−0.002 (3)	0.000 (3)	−0.003 (3)
C8	0.010 (4)	0.003 (3)	0.015 (4)	0.003 (3)	−0.002 (3)	0.002 (3)
C9	0.003 (4)	0.011 (4)	0.006 (4)	−0.001 (3)	−0.001 (3)	0.001 (3)
C10	0.024 (5)	0.018 (4)	0.009 (4)	−0.001 (4)	0.000 (4)	−0.007 (3)
C11	0.019 (5)	0.004 (4)	0.016 (4)	0.003 (3)	−0.002 (4)	0.002 (3)
C12	0.026 (5)	0.013 (4)	0.018 (5)	−0.008 (4)	−0.009 (4)	−0.001 (3)

Geometric parameters (Å, º) top

Mo1—O2	1.690 (5)	N1—H1A	0.8600
Mo1—O11	1.776 (5)	N2—C7	1.353 (10)
Mo1—O9	1.875 (5)	N2—C1	1.386 (10)
Mo1—O10ⁱ	1.956 (5)	N2—H2A	0.8600
Mo1—O6	2.189 (5)	N3—C9	1.317 (10)
Mo1—O10	2.416 (5)	N3—C10	1.339 (11)
Mo2—O5	1.693 (5)	N3—H3A	0.8600
Mo2—O4	1.709 (5)	C1—C2	1.395 (11)
Mo2—O8	1.927 (5)	C1—C6	1.410 (10)
Mo2—O3	2.004 (5)	C2—C3	1.378 (11)
Mo2—O10	2.200 (5)	C2—H2B	0.9300
Mo2—O9	2.345 (5)	C3—C4	1.404 (11)
Mo3—O7	1.699 (5)	C3—H3B	0.9300
Mo3—O13	1.790 (5)	C4—C5	1.371 (11)
Mo3—O6ⁱ	1.880 (5)	C4—H4A	0.9300
Mo3—O3	1.922 (5)	C5—C6	1.402 (11)
Mo3—O11	2.229 (6)	C5—H5A	0.9300
Mo3—O10	2.242 (5)	C7—C8	1.445 (11)
Mo4—O1	1.682 (5)	C8—C9	1.385 (10)
Mo4—O12	1.719 (5)	C8—C12	1.413 (11)
Mo4—O8	1.965 (5)	C9—H9A	0.9300
Mo4—O13ⁱⁱ	2.012 (5)	C10—C11	1.393 (11)
Mo4—O6	2.160 (5)	C10—H10A	0.9300
Mo4—O9	2.266 (5)	C11—C12	1.363 (11)
N1—C7	1.350 (9)	C11—H11A	0.9300
N1—C6	1.384 (10)	C12—H12A	0.9300

O2—Mo1—O11	104.1 (2)	Mo3ⁱ—O6—Mo4	149.5 (3)
O2—Mo1—O9	104.5 (2)	Mo3ⁱ—O6—Mo1	107.8 (2)
O11—Mo1—O9	101.6 (2)	Mo4—O6—Mo1	102.4 (2)
O2—Mo1—O10ⁱ	101.7 (2)	Mo2—O8—Mo4	116.1 (2)
O11—Mo1—O10ⁱ	98.2 (2)	Mo1—O9—Mo4	109.5 (2)
O9—Mo1—O10ⁱ	142.0 (2)	Mo1—O9—Mo2	111.1 (2)
O2—Mo1—O6	98.6 (2)	Mo4—O9—Mo2	91.48 (18)
O11—Mo1—O6	156.9 (2)	Mo1ⁱ—O10—Mo2	149.5 (3)
O9—Mo1—O6	76.6 (2)	Mo1ⁱ—O10—Mo3	103.1 (2)
O10ⁱ—Mo1—O6	72.61 (19)	Mo2—O10—Mo3	96.11 (19)
O2—Mo1—O10	177.8 (2)	Mo1ⁱ—O10—Mo1	103.8 (2)
O11—Mo1—O10	76.9 (2)	Mo2—O10—Mo1	98.11 (18)
O9—Mo1—O10	77.1 (2)	Mo3—O10—Mo1	93.98 (18)
O10ⁱ—Mo1—O10	76.2 (2)	Mo1—O11—Mo3	116.2 (2)
O6—Mo1—O10	80.29 (19)	Mo3—O13—Mo4ⁱⁱⁱ	170.5 (3)
O5—Mo2—O4	105.2 (3)	C7—N1—C6	109.3 (6)
O5—Mo2—O8	98.6 (2)	C7—N1—H1A	125.4
O4—Mo2—O8	102.0 (2)	C6—N1—H1A	125.4
O5—Mo2—O3	101.2 (2)	C7—N2—C1	109.5 (6)
O4—Mo2—O3	90.8 (2)	C7—N2—H2A	125.2
O8—Mo2—O3	152.7 (2)	C1—N2—H2A	125.2
O5—Mo2—O10	94.9 (2)	C9—N3—C10	123.3 (7)
O4—Mo2—O10	156.3 (2)	C9—N3—H3A	118.3
O8—Mo2—O10	87.0 (2)	C10—N3—H3A	118.3
O3—Mo2—O10	72.70 (19)	N2—C1—C2	131.8 (7)
O5—Mo2—O9	165.8 (2)	N2—C1—C6	106.1 (7)
O4—Mo2—O9	88.3 (2)	C2—C1—C6	122.1 (7)
O8—Mo2—O9	73.7 (2)	C3—C2—C1	116.4 (7)
O3—Mo2—O9	82.7 (2)	C3—C2—H2B	121.8
O10—Mo2—O9	73.09 (18)	C1—C2—H2B	121.8
O7—Mo3—O13	103.0 (2)	C2—C3—C4	121.5 (8)
O7—Mo3—O6ⁱ	106.4 (2)	C2—C3—H3B	119.3
O13—Mo3—O6ⁱ	97.5 (2)	C4—C3—H3B	119.3
O7—Mo3—O3	102.6 (2)	C5—C4—C3	122.8 (8)
O13—Mo3—O3	93.5 (2)	C5—C4—H4A	118.6
O6ⁱ—Mo3—O3	145.6 (2)	C3—C4—H4A	118.6
O7—Mo3—O11	82.9 (2)	C4—C5—C6	116.5 (7)
O13—Mo3—O11	173.7 (2)	C4—C5—H5A	121.7
O6ⁱ—Mo3—O11	82.6 (2)	C6—C5—H5A	121.7
O3—Mo3—O11	83.0 (2)	N1—C6—C5	132.6 (7)
O7—Mo3—O10	155.7 (2)	N1—C6—C1	106.7 (7)
O13—Mo3—O10	101.2 (2)	C5—C6—C1	120.6 (8)
O6ⁱ—Mo3—O10	72.7 (2)	N1—C7—N2	108.4 (7)
O3—Mo3—O10	73.22 (19)	N1—C7—C8	124.8 (7)
O11—Mo3—O10	72.83 (19)	N2—C7—C8	126.7 (7)
O1—Mo4—O12	106.8 (2)	C9—C8—C12	118.2 (7)
O1—Mo4—O8	94.3 (2)	C9—C8—C7	121.4 (7)
O12—Mo4—O8	99.6 (2)	C12—C8—C7	120.4 (7)
O1—Mo4—O13ⁱⁱ	98.9 (3)	N3—C9—C8	120.2 (7)
O12—Mo4—O13ⁱⁱ	92.9 (2)	N3—C9—H9A	119.9
O8—Mo4—O13ⁱⁱ	158.5 (2)	C8—C9—H9A	119.9
O1—Mo4—O6	97.2 (2)	N3—C10—C11	119.1 (8)
O12—Mo4—O6	155.4 (2)	N3—C10—H10A	120.4
O8—Mo4—O6	84.1 (2)	C11—C10—H10A	120.4
O13ⁱⁱ—Mo4—O6	77.4 (2)	C12—C11—C10	119.5 (8)
O1—Mo4—O9	163.5 (2)	C12—C11—H11A	120.2
O12—Mo4—O9	87.6 (2)	C10—C11—H11A	120.2
O8—Mo4—O9	74.95 (19)	C11—C12—C8	119.7 (7)
O13ⁱⁱ—Mo4—O9	88.2 (2)	C11—C12—H12A	120.2
O6—Mo4—O9	69.69 (18)	C8—C12—H12A	120.2
Mo3—O3—Mo2	114.6 (2)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z; (iii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3^iv	0.86	1.78	2.639 (8)	176
N3—H3A···O8	0.86	1.78	2.614 (8)	164

Symmetry code: (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₁N₂)[Mo₄O₁₃]
M_r	789.00
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.947 (3), 11.503 (5), 11.630 (5)
α, β, γ (°)	70.038 (14), 76.856 (17), 75.947 (17)
V (Å³)	957.2 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.64
Crystal size (mm)	0.10 × 0.05 × 0.02

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2002)
T_min, T_max	0.763, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	6127, 3358, 2594
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.100, 1.01
No. of reflections	3358
No. of parameters	289
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −1.14

Computer programs: CrystalClear (Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999)'.

Selected bond lengths (Å) top

Mo1—O2	1.690 (5)	Mo3—O7	1.699 (5)
Mo1—O11	1.776 (5)	Mo3—O13	1.790 (5)
Mo1—O9	1.875 (5)	Mo3—O6ⁱ	1.880 (5)
Mo1—O10ⁱ	1.956 (5)	Mo3—O3	1.922 (5)
Mo1—O6	2.189 (5)	Mo3—O11	2.229 (6)
Mo1—O10	2.416 (5)	Mo3—O10	2.242 (5)
Mo2—O5	1.693 (5)	Mo4—O1	1.682 (5)
Mo2—O4	1.709 (5)	Mo4—O12	1.719 (5)
Mo2—O8	1.927 (5)	Mo4—O8	1.965 (5)
Mo2—O3	2.004 (5)	Mo4—O13ⁱⁱ	2.012 (5)
Mo2—O10	2.200 (5)	Mo4—O6	2.160 (5)
Mo2—O9	2.345 (5)	Mo4—O9	2.266 (5)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱⁱⁱ	0.86	1.78	2.639 (8)	176.3
N3—H3A···O8	0.86	1.78	2.614 (8)	163.6

Symmetry code: (iii) x, y−1, z.

Acknowledgements

This work was supported by the Natural Science Foundation of Fujian Province (2006 F3141, 2008 J0142).

References

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