Bis[1,1′-(1,3-phenyl­enedimethyl­ene)di(1H-imidazol-3-ium)] β-octa­molybdate

Wang, X.-D.; Hou, G.-F.; Yu, Y.-H.; Gao, J.-S.

doi:10.1107/S1600536811053050

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page m50

doi:10.1107/S1600536811053050

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Bis[1,1′-(1,3-phenylenedimethylene)di(1H-imidazol-3-ium)] β-octamolybdate

Xiao-Dan Wang,^a Guang-Feng Hou,^a Ying-Hui Yu ^a and Jin-Sheng Gao ^a ^*

^aEngineering Research Center of Pesticides of Heilongjiang University, Heilongjiang University, Harbin 150050, People's Republic of China, and College of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 24 November 2011; accepted 9 December 2011; online 14 December 2011)

In the title compound, (C₁₄H₁₆N₄)₂[Mo₈O₂₆], the β-octamolybdate anion is centrosymmetric. N—H⋯O hydrogen bonds link the diimidazolium cations and the polyoxidoanions into a chain structure along [100]. π–π interactions between the imidazole rings and between the imidazole and benzene rings [centroid–centroid distances = 3.611 (2) and 3.689 (3) Å, respectively] connect the chains.

Related literature

For general background to polyoxidometalate-based organic-inorganic hybrid compounds, see: Xie et al. (2011 ); Xu et al. (1999 ). For the synthesis of the ligand, see: Yang et al. (2006 ).

Experimental

Crystal data

(C₁₄H₁₆N₄)₂[Mo₈O₂₆]
M_r = 1664.14
Monoclinic, P 2₁ /c
a = 12.163 (2) Å
b = 12.785 (3) Å
c = 14.937 (3) Å
β = 96.82 (3)°
V = 2306.3 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.780, T_max = 0.809
21595 measured reflections
5261 independent reflections
4579 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.057
S = 1.01
5261 reflections
324 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.12 e Å⁻³
Δρ_min = −1.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O12ⁱ	0.90 (1)	1.96 (2)	2.844 (4)	168 (4)
N4—H41⋯O5ⁱⁱ	0.90 (1)	2.51 (5)	3.003 (5)	115 (4)
N4—H41⋯O8ⁱⁱ	0.90 (1)	2.23 (4)	2.909 (5)	132 (5)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x+1, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053050/hy2492sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053050/hy2492Isup2.hkl

checkCIF report

Comment top

The synthesis and characterization of coordination networks based on the idea of self-assembly of specifically designed building blocks have been an area of rapid growth in recent years. In the last decades, more and more attention has been paid to the rational design and assembly of new polyoxometalate(POM)-based organic-inorganic hybrid compounds due to their structural diversities and abundant potential applications in catalysis, ion exchange, sorption and magnetism (Xie et al., 2011). Octamolybdate family with a variety of structural isomers is a kind of important POMs building blocks (Xu et al., 1999). The title compound was synthesized at a low pH value condition, as an unexpected product during the process of preparing POM-based Cu(II)–ligand complex. We report its structure here.

The asymmertric unit of the title compound contains one half of β-[Mo₈O₂₆]^4- polyoxoanion and one (1,3-phenylenedimethylene)-di-1H-imidazolium cation (Fig. 1). The polyoxoanion is centrosymmetric. N—H···O hydrogen bonds link the cations and polyoxoanions into a chain structure along [1 0 0] (Fig. 2, Table 1). π–π interactions between the imidazole rings and between the imidazole and benzene rings [centroid–centroid distances = 3.611 (2) and 3.689 (3) Å] connect the chains.

Related literature top

For general background to polyoxidometalate-based organic-inorganic hybrid compounds, see: Xie et al. (2011); Xu et al. (1999). For the synthesis of the ligand, see: Yang et al. (2006).

Experimental top

The 1,3-bis(imidazol-l-yl-methyl)benzene (bimb) ligand was synthesized following the literature method (Yang et al., 2006). The title compound was synthesized by mixing bimb (0.101 g, 0.5 mmol), Cu(NO₃)₂.4H₂O (0.102 g, 0.05 mmol), sodium molybdate (0.505 g, 2.5 mmol), H₂O (8 ml) and ethanol (2 ml) and stirring at room temperature for 10 min. The pH value of the mixture was adjusted to 2.0 with 1M HCl, and then the mixture was sealed in a Teflon-lined autoclave and heated at 125°C for 4 days. After slow cooling to room temperature, black block crystals were obtained in 22% yield based on Mo atoms.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level. Dashed lines denote hydrogen bonds. [Symmetry codes: (i) 1-x, 2-y, 2-z; (ii) x, 1+y, z; (iii) -1+x, 1+y, z.]
	Fig. 2. A view of the hydrogen-bonded chain structure along [1 0 0]. Dashed lines denote hydrogen bonds.

Bis[1,1'-(1,3-phenylenedimethylene)di(1H-imidazol-3-ium)] β-octamolybdate top

Crystal data top

(C₁₄H₁₆N₄)₂[Mo₈O₂₆]	F(000) = 1600
M_r = 1664.14	D_x = 2.396 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17887 reflections
a = 12.163 (2) Å	θ = 3.1–27.5°
b = 12.785 (3) Å	µ = 2.20 mm⁻¹
c = 14.937 (3) Å	T = 293 K
β = 96.82 (3)°	Block, colorless
V = 2306.3 (8) Å³	0.12 × 0.10 × 0.10 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	5261 independent reflections
Radiation source: fine-focus sealed tube	4579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scan	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.780, T_max = 0.809	k = −16→15
21595 measured reflections	l = −19→19

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0219P)² + 3.6973P] where P = (F_o² + 2F_c²)/3
5261 reflections	(Δ/σ)_max = 0.003
324 parameters	Δρ_max = 1.12 e Å⁻³
2 restraints	Δρ_min = −1.30 e Å⁻³

Crystal data top

(C₁₄H₁₆N₄)₂[Mo₈O₂₆]	V = 2306.3 (8) Å³
M_r = 1664.14	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.163 (2) Å	µ = 2.20 mm⁻¹
b = 12.785 (3) Å	T = 293 K
c = 14.937 (3) Å	0.12 × 0.10 × 0.10 mm
β = 96.82 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5261 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4579 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.809	R_int = 0.032
21595 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	2 restraints
wR(F²) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 1.12 e Å⁻³
5261 reflections	Δρ_min = −1.30 e Å⁻³
324 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.6205 (3)	0.5883 (3)	1.0719 (2)	0.0442 (9)
H1	0.6032	0.6216	1.1237	0.053*
C2	0.6426 (3)	0.6343 (3)	0.9957 (2)	0.0411 (8)
H2	0.6443	0.7059	0.9850	0.049*
C3	0.6529 (3)	0.4656 (3)	0.9766 (3)	0.0414 (8)
H3	0.6623	0.4003	0.9512	0.050*
C4	0.6943 (3)	0.5749 (3)	0.8462 (2)	0.0375 (8)
H4A	0.6747	0.6456	0.8269	0.045*
H4B	0.6542	0.5268	0.8039	0.045*
C5	0.8175 (3)	0.5588 (3)	0.8459 (2)	0.0334 (7)
C6	0.8932 (4)	0.6252 (3)	0.8933 (3)	0.0574 (11)
H6	0.8687	0.6820	0.9245	0.069*
C7	1.0057 (4)	0.6069 (4)	0.8944 (4)	0.0722 (15)
H7	1.0564	0.6506	0.9275	0.087*
C8	1.0431 (3)	0.5248 (4)	0.8469 (4)	0.0638 (13)
H8	1.1188	0.5140	0.8473	0.077*
C9	0.9687 (3)	0.4581 (3)	0.7984 (3)	0.0416 (9)
C10	0.8560 (3)	0.4767 (3)	0.7982 (2)	0.0332 (7)
H10	0.8054	0.4328	0.7652	0.040*
C11	1.0073 (3)	0.3659 (3)	0.7484 (3)	0.0517 (11)
H11A	0.9529	0.3499	0.6974	0.062*
H11B	1.0764	0.3833	0.7254	0.062*
C12	0.9427 (4)	0.2172 (4)	0.8436 (4)	0.0673 (14)
H12	0.8670	0.2300	0.8342	0.081*
C13	0.9922 (5)	0.1420 (4)	0.8937 (4)	0.0722 (15)
H13	0.9581	0.0920	0.9264	0.087*
C14	1.1198 (3)	0.2305 (3)	0.8354 (3)	0.0503 (10)
H14	1.1882	0.2521	0.8202	0.060*
Mo1	0.547848 (19)	0.90288 (2)	1.084672 (17)	0.02207 (6)
Mo2	0.30667 (2)	1.04699 (2)	1.134611 (18)	0.02643 (7)
Mo3	0.27124 (2)	0.86907 (2)	0.973110 (19)	0.02576 (7)
Mo4	0.45286 (2)	0.80953 (3)	0.81444 (2)	0.03626 (8)
N1	0.6622 (2)	0.5573 (2)	0.93667 (18)	0.0312 (6)
N2	0.6281 (3)	0.4835 (3)	1.0589 (2)	0.0463 (8)
N3	1.0240 (2)	0.2736 (3)	0.8073 (2)	0.0425 (7)
N4	1.1028 (4)	0.1517 (3)	0.8884 (3)	0.0622 (10)
O1	0.6277 (2)	0.9749 (2)	1.01029 (18)	0.0472 (7)
O2	0.6373 (2)	0.8237 (2)	1.14858 (18)	0.0477 (7)
O3	0.48333 (18)	0.9874 (2)	1.15775 (16)	0.0372 (6)
O4	0.2810 (2)	1.0400 (2)	1.24323 (16)	0.0439 (6)
O5	0.1925 (2)	1.1056 (2)	1.08042 (19)	0.0500 (7)
O6	0.27884 (17)	0.90605 (17)	1.09648 (15)	0.0298 (5)
O7	0.45232 (19)	0.82404 (19)	1.01803 (19)	0.0429 (6)
O8	0.1530 (2)	0.9344 (2)	0.93423 (17)	0.0417 (6)
O9	0.2328 (2)	0.7420 (2)	0.97568 (19)	0.0439 (6)
O10	0.33456 (19)	0.8728 (2)	0.85883 (16)	0.0361 (5)
O11	0.6000 (2)	0.82712 (18)	0.86168 (17)	0.0371 (5)
O12	0.4326 (2)	0.6786 (2)	0.8263 (2)	0.0548 (7)
O13	0.4385 (3)	0.8367 (2)	0.70317 (19)	0.0555 (7)
H21	0.619 (4)	0.433 (3)	1.099 (2)	0.066 (14)*
H41	1.155 (3)	0.107 (4)	0.911 (4)	0.10 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.052 (2)	0.054 (2)	0.0275 (18)	0.0126 (18)	0.0089 (15)	0.0002 (17)
C2	0.058 (2)	0.0311 (18)	0.035 (2)	0.0116 (16)	0.0088 (16)	−0.0002 (15)
C3	0.051 (2)	0.0339 (19)	0.039 (2)	0.0056 (16)	0.0056 (16)	0.0060 (15)
C4	0.0397 (19)	0.046 (2)	0.0268 (17)	0.0124 (15)	0.0046 (14)	0.0046 (15)
C5	0.0370 (18)	0.0339 (18)	0.0295 (17)	0.0007 (14)	0.0049 (13)	0.0056 (14)
C6	0.062 (3)	0.047 (2)	0.064 (3)	−0.013 (2)	0.012 (2)	−0.013 (2)
C7	0.048 (3)	0.074 (3)	0.093 (4)	−0.028 (2)	0.001 (2)	−0.012 (3)
C8	0.031 (2)	0.082 (4)	0.079 (3)	−0.004 (2)	0.010 (2)	0.010 (3)
C9	0.0353 (19)	0.052 (2)	0.039 (2)	0.0081 (16)	0.0115 (15)	0.0141 (17)
C10	0.0288 (16)	0.043 (2)	0.0277 (17)	0.0024 (14)	0.0033 (12)	0.0024 (14)
C11	0.049 (2)	0.063 (3)	0.047 (2)	0.022 (2)	0.0226 (18)	0.016 (2)
C12	0.044 (2)	0.076 (3)	0.087 (4)	0.012 (2)	0.025 (2)	0.026 (3)
C13	0.085 (4)	0.059 (3)	0.081 (4)	0.021 (3)	0.044 (3)	0.024 (3)
C14	0.038 (2)	0.056 (3)	0.057 (3)	0.0151 (18)	0.0060 (18)	0.006 (2)
Mo1	0.02070 (12)	0.02499 (13)	0.02034 (12)	0.00065 (9)	0.00169 (9)	0.00309 (10)
Mo2	0.02634 (13)	0.03154 (14)	0.02250 (13)	0.00129 (10)	0.00740 (10)	−0.00118 (11)
Mo3	0.02085 (12)	0.02662 (13)	0.03005 (15)	−0.00019 (10)	0.00399 (10)	−0.00093 (11)
Mo4	0.03172 (15)	0.04101 (17)	0.03793 (17)	0.01049 (12)	0.01196 (12)	0.01119 (13)
N1	0.0332 (14)	0.0329 (15)	0.0278 (14)	0.0086 (11)	0.0043 (11)	0.0027 (11)
N2	0.0480 (19)	0.052 (2)	0.0386 (18)	−0.0027 (15)	0.0048 (14)	0.0181 (15)
N3	0.0321 (15)	0.0544 (19)	0.0423 (18)	0.0143 (14)	0.0101 (13)	0.0102 (15)
N4	0.072 (3)	0.057 (2)	0.057 (2)	0.030 (2)	0.005 (2)	0.0138 (19)
O1	0.0685 (18)	0.0394 (14)	0.0395 (15)	−0.0240 (13)	0.0304 (13)	−0.0137 (11)
O2	0.0417 (14)	0.0540 (17)	0.0440 (16)	0.0217 (12)	−0.0092 (11)	0.0005 (13)
O3	0.0266 (12)	0.0462 (14)	0.0375 (14)	0.0049 (10)	−0.0015 (9)	−0.0123 (11)
O4	0.0429 (14)	0.0641 (18)	0.0268 (13)	−0.0067 (12)	0.0124 (10)	−0.0035 (12)
O5	0.0521 (16)	0.0485 (16)	0.0464 (16)	0.0204 (13)	−0.0062 (12)	−0.0066 (13)
O6	0.0279 (11)	0.0316 (12)	0.0299 (12)	−0.0047 (9)	0.0038 (9)	0.0041 (9)
O7	0.0268 (12)	0.0363 (14)	0.0635 (18)	0.0056 (10)	−0.0038 (11)	−0.0175 (12)
O8	0.0347 (13)	0.0524 (16)	0.0370 (14)	0.0147 (11)	−0.0001 (10)	−0.0028 (12)
O9	0.0382 (13)	0.0332 (13)	0.0588 (17)	−0.0100 (10)	−0.0004 (12)	−0.0036 (12)
O10	0.0316 (12)	0.0479 (15)	0.0290 (12)	0.0017 (10)	0.0045 (9)	−0.0064 (11)
O11	0.0449 (14)	0.0251 (11)	0.0435 (15)	0.0036 (10)	0.0149 (11)	−0.0008 (10)
O12	0.0512 (16)	0.0449 (16)	0.070 (2)	−0.0018 (13)	0.0158 (14)	0.0089 (14)
O13	0.073 (2)	0.0581 (18)	0.0390 (16)	0.0120 (15)	0.0235 (14)	0.0048 (14)

Geometric parameters (Å, º) top

C1—C2	1.336 (5)	C13—H13	0.9300
C1—N2	1.359 (5)	C14—N3	1.312 (5)
C1—H1	0.9300	C14—N4	1.313 (6)
C2—N1	1.362 (4)	C14—H14	0.9300
C2—H2	0.9300	Mo1—O2	1.695 (2)
C3—N2	1.319 (5)	Mo1—O7	1.756 (2)
C3—N1	1.326 (4)	Mo1—O3	1.783 (2)
C3—H3	0.9300	Mo1—O1	1.811 (2)
C4—N1	1.468 (4)	Mo2—O4	1.690 (2)
C4—C5	1.513 (5)	Mo2—O5	1.697 (3)
C4—H4A	0.9700	Mo2—O6	1.908 (2)
C4—H4B	0.9700	Mo2—O11ⁱ	1.966 (2)
C5—C10	1.381 (5)	Mo2—O3	2.267 (2)
C5—C6	1.384 (5)	Mo2—O1ⁱ	2.410 (3)
C6—C7	1.387 (7)	Mo3—O9	1.692 (2)
C6—H6	0.9300	Mo3—O8	1.704 (2)
C7—C8	1.374 (7)	Mo3—O6	1.894 (2)
C7—H7	0.9300	Mo3—O10	1.955 (2)
C8—C9	1.383 (6)	Mo3—O7	2.298 (2)
C8—H8	0.9300	Mo3—O1ⁱ	2.341 (2)
C9—C10	1.391 (5)	Mo4—O13	1.687 (3)
C9—C11	1.501 (6)	Mo4—O12	1.704 (3)
C10—H10	0.9300	Mo4—O10	1.842 (2)
C11—N3	1.472 (5)	Mo4—O11	1.858 (3)
C11—H11A	0.9700	N2—H21	0.901 (10)
C11—H11B	0.9700	N4—H41	0.896 (10)
C12—C13	1.320 (7)	O1—Mo3ⁱ	2.341 (2)
C12—N3	1.385 (5)	O1—Mo2ⁱ	2.410 (2)
C12—H12	0.9300	O11—Mo2ⁱ	1.966 (2)
C13—N4	1.364 (7)

C2—C1—N2	106.7 (3)	O4—Mo2—O6	100.96 (12)
C2—C1—H1	126.6	O5—Mo2—O6	99.70 (12)
N2—C1—H1	126.6	O4—Mo2—O11ⁱ	100.83 (12)
C1—C2—N1	107.6 (3)	O5—Mo2—O11ⁱ	95.11 (13)
C1—C2—H2	126.2	O6—Mo2—O11ⁱ	149.63 (10)
N1—C2—H2	126.2	O4—Mo2—O3	96.62 (11)
N2—C3—N1	107.9 (3)	O5—Mo2—O3	158.19 (12)
N2—C3—H3	126.1	O6—Mo2—O3	81.93 (9)
N1—C3—H3	126.1	O11ⁱ—Mo2—O3	74.76 (10)
N1—C4—C5	110.7 (3)	O4—Mo2—O1ⁱ	166.93 (12)
N1—C4—H4A	109.5	O5—Mo2—O1ⁱ	87.85 (12)
C5—C4—H4A	109.5	O6—Mo2—O1ⁱ	71.84 (9)
N1—C4—H4B	109.5	O11ⁱ—Mo2—O1ⁱ	82.45 (9)
C5—C4—H4B	109.5	O3—Mo2—O1ⁱ	71.88 (10)
H4A—C4—H4B	108.1	O9—Mo3—O8	104.73 (13)
C10—C5—C6	119.0 (4)	O9—Mo3—O6	101.50 (12)
C10—C5—C4	120.1 (3)	O8—Mo3—O6	98.69 (11)
C6—C5—C4	121.0 (3)	O9—Mo3—O10	100.47 (12)
C5—C6—C7	119.9 (4)	O8—Mo3—O10	95.41 (11)
C5—C6—H6	120.1	O6—Mo3—O10	149.84 (10)
C7—C6—H6	120.1	O9—Mo3—O7	90.60 (11)
C8—C7—C6	120.6 (4)	O8—Mo3—O7	164.34 (12)
C8—C7—H7	119.7	O6—Mo3—O7	81.03 (10)
C6—C7—H7	119.7	O10—Mo3—O7	78.34 (10)
C7—C8—C9	120.3 (4)	O9—Mo3—O1ⁱ	163.48 (12)
C7—C8—H8	119.8	O8—Mo3—O1ⁱ	91.69 (12)
C9—C8—H8	119.8	O6—Mo3—O1ⁱ	73.73 (9)
C8—C9—C10	118.6 (4)	O10—Mo3—O1ⁱ	79.36 (10)
C8—C9—C11	121.4 (4)	O7—Mo3—O1ⁱ	73.12 (10)
C10—C9—C11	120.0 (4)	O13—Mo4—O12	107.75 (16)
C5—C10—C9	121.5 (3)	O13—Mo4—O10	105.68 (13)
C5—C10—H10	119.2	O12—Mo4—O10	105.41 (13)
C9—C10—H10	119.2	O13—Mo4—O11	109.38 (14)
N3—C11—C9	111.1 (3)	O12—Mo4—O11	102.95 (12)
N3—C11—H11A	109.4	O10—Mo4—O11	124.66 (10)
C9—C11—H11A	109.4	C3—N1—C2	108.4 (3)
N3—C11—H11B	109.4	C3—N1—C4	126.6 (3)
C9—C11—H11B	109.4	C2—N1—C4	124.9 (3)
H11A—C11—H11B	108.0	C3—N2—C1	109.3 (3)
C13—C12—N3	107.7 (4)	C3—N2—H21	124 (3)
C13—C12—H12	126.2	C1—N2—H21	127 (3)
N3—C12—H12	126.2	C14—N3—C12	107.7 (4)
C12—C13—N4	106.7 (4)	C14—N3—C11	125.6 (3)
C12—C13—H13	126.7	C12—N3—C11	126.7 (3)
N4—C13—H13	126.7	C14—N4—C13	109.4 (4)
N3—C14—N4	108.6 (4)	C14—N4—H41	125 (4)
N3—C14—H14	125.7	C13—N4—H41	125 (4)
N4—C14—H14	125.7	Mo1—O1—Mo3ⁱ	132.92 (13)
O2—Mo1—O7	108.29 (13)	Mo1—O1—Mo2ⁱ	138.66 (13)
O2—Mo1—O3	108.47 (12)	Mo3ⁱ—O1—Mo2ⁱ	88.18 (8)
O7—Mo1—O3	112.67 (11)	Mo1—O3—Mo2	126.04 (12)
O2—Mo1—O1	107.09 (14)	Mo3—O6—Mo2	120.84 (11)
O7—Mo1—O1	108.11 (13)	Mo1—O7—Mo3	124.65 (12)
O3—Mo1—O1	111.99 (12)	Mo4—O10—Mo3	135.18 (14)
O4—Mo2—O5	104.33 (14)	Mo4—O11—Mo2ⁱ	129.54 (13)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O12ⁱⁱ	0.90 (1)	1.96 (2)	2.844 (4)	168 (4)
N4—H41···O5ⁱⁱⁱ	0.90 (1)	2.51 (5)	3.003 (5)	115 (4)
N4—H41···O8ⁱⁱⁱ	0.90 (1)	2.23 (4)	2.909 (5)	132 (5)

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

Experimental details

Crystal data
Chemical formula	(C₁₄H₁₆N₄)₂[Mo₈O₂₆]
M_r	1664.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.163 (2), 12.785 (3), 14.937 (3)
β (°)	96.82 (3)
V (Å³)	2306.3 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.12 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.780, 0.809
No. of measured, independent and observed [I > 2σ(I)] reflections	21595, 5261, 4579
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.057, 1.01
No. of reflections	5261
No. of parameters	324
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.12, −1.30

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O12ⁱ	0.90 (1)	1.96 (2)	2.844 (4)	168 (4)
N4—H41···O5ⁱⁱ	0.90 (1)	2.51 (5)	3.003 (5)	115 (4)
N4—H41···O8ⁱⁱ	0.90 (1)	2.23 (4)	2.909 (5)	132 (5)

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

Acknowledgements

The authors thank the Project of Innovation Service Platform of Heilongjiang Province (PG09J001) and Heilongjiang University for supporting this work.

References

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