Bis(4,4′-bipyridinium) dodeca­tungsto­silicate 4,4′-bipyridine hexa­hydrate

Ma, F.-X.; Zhao, Q.

doi:10.1107/S1600536808027566

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1224

doi:10.1107/S1600536808027566

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Bis(4,4′-bipyridinium) dodecatungstosilicate 4,4′-bipyridine hexahydrate

Feng-Xia Ma ^a ^* and Quan Zhao ^a,^b

^aJilin Agricultural Science and Technology College, Jilin 132101, People's Republic of China, and ^bNortheast Forestry University, People's Republic of China
^*Correspondence e-mail: fengxia_ma@126.com

(Received 13 June 2008; accepted 28 August 2008; online 6 September 2008)

The title compound, (C₁₀H₁₀N₂)₂[SiW₁₂O₄₀]·C₁₀H₈N₂·6H₂O or (4,4′-bipyH₂)₂[SiW₁₂O₄₀].(4,4′-bipy)·6H₂O (4,4′-bipy is 4,4′-bipyridine), was prepared under hydrothermal conditions. The asymmetric unit contains a discrete Keggin-type [SiW₁₂O₄₀]⁴⁻ anion (located on a twofold axis), one 4,4′-bipy (located on a twofold axis), two (4,4′-bipyH₂)²⁺ cations and six uncoordinated water molecules. The polyoxoanion is constructed from a central SiO₄ tetrahedron which shares its O atoms with four trinuclear W₃O₁₃ groups, each of which is made up of three edge-sharing WO₆ octahedra. The water molecules and [SiW₁₂O₄₀]⁴⁻ anions are linked through hydrogen bonds.

Related literature

For related literature, see: Hill (1998 ); Kurth et al. (2001 ); Misono (1987 ); Pope (1983 ). H₄SiW₁₂O₄₀.nH₂O was prepared according to literature procedures (Rocchiccioli-Deltcheff et al., 1983 ).

Experimental

Crystal data

(C₁₀H₁₀N₂)₂[SiW₁₂O₄₀]·C₁₀H₈N₂·6H₂O
M_r = 3454.85
Monoclinic, C 2/c
a = 15.491 (5) Å
b = 18.096 (5) Å
c = 20.921 (5) Å
β = 100.834 (5)°
V = 5760 (3) Å³
Z = 4
Mo Kα radiation
μ = 23.99 mm⁻¹
T = 293 (2) K
0.15 × 0.12 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.041, T_max = 0.095
15853 measured reflections
5652 independent reflections
5214 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.101
S = 1.10
5652 reflections
455 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 3.60 e Å⁻³
Δρ_min = −3.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O3W	0.89 (10)	2.15 (11)	2.699 (11)	119 (7)
O1W—H1B⋯O2W	0.81 (9)	2.31 (9)	2.749 (12)	115 (10)
O1W—H1B⋯O20	0.81 (9)	2.54 (11)	2.844 (10)	104 (8)
N1—H1N⋯O2W	0.78 (9)	1.97 (9)	2.754 (12)	172 (14)
O3W—H3A⋯O18	0.91 (9)	2.24 (10)	2.878 (10)	127 (9)

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027566/rk2097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027566/rk2097Isup2.hkl

checkCIF report

Comment top

Polyoxometalates (POMs) have been known for more than 200 years, but continue to receive attention due to their versatile structures and applications in medicine, materials science, catalysis (Misono, 1987; Pope, 1983; Hill, 1998).

The structure of the title compound is built from one independent 4,4'–bipyridines (4,4'-bipy) (placed on twofold axis by N3/C13/C14/N4) and two protonated 4,4'–bipyridines (4,4'-bipyH₂)²⁺, and Keggin–type anion [SiW₁₂O₄₀]^4- (placed on twofold axis) and six water molecules (Fig. 1). In the well known Keggin structure, there are 12 WO₆–octahedra and one SiO₄–tetrahedron. The 12 WO₆–octahedra can be categorized into four W₃O₁₃ trinuclear groups, each of which is made of three edge–sharing WO₆–octahedra and are joined to each other by sharing corners. The SiO₄–tetrahedron is located in the centre of the polyoxoanion by sharing its O atoms with the four W₃O₁₃–groups. In the Keggin anion, the Si—O and W—O distances as well as the corresponding angles are very similar to those of H₄SiW₁₂O₄₀ (Kurth et al., 2001). The water molecules and [SiW₁₂O₄₀]^4- anions are linked through hydrogen bonds. It can be seen that all of the H atoms come from water molecules. The O atoms, which come from the [SiW₁₂O₄₀]^4- anions, are also involved in hydrogen bonds and play the role of acceptors.

Related literature top

For related literature, see: Hill (1998); Kurth et al. (2001); Misono (1987); Pope (1983). H₄SiW₁₂O₄₀.nH₂O was prepared according to literature procedures (Rocchiccioli-Deltcheff et al., 1983).

Experimental top

The H₄SiW₁₂O₄₀^.nH₂O was prepared according to the method given by Rocchiccioli-Deltcheff et al., (1983). The starting mixture of H₄SiW₁₂O₄₀^.nH₂O (0.302 g), 4,4'-bipy (0.026 g), and H₂O (10 ml) was adjusted to pH = 5.6 by addition of 2 mol.L^-1 NaOH under stirring for 30 min. The final solution was transferred into a 25 ml teflon lined autoclave and was heated at 453 K for 96 h. Then, the autoclave was cooled with a rate of 10 K.h^-1 to room temperature. Black block–like crystals were filtered off, washed with distilled water and dried at ambient temperature (45% yield on W).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitraryv radius. Symmetry codes: i = -x+2, y, -z+3/2; ii = -x+1, y, -z+3/2.

Bis(4,4'-bipyridinium) dodecatungstosilicate 4,4'-bipyridine hexahydrate top

Crystal data top

(C₁₀H₁₀N₂)₂[SiW₁₂O₄₀]·C₁₀H₈N₂·6H₂O	F(000) = 6128
M_r = 3454.85	D_x = 3.984 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 5214 reflections
a = 15.491 (5) Å	θ = 1.8–26.0°
b = 18.096 (5) Å	µ = 23.99 mm⁻¹
c = 20.921 (5) Å	T = 293 K
β = 100.834 (5)°	Block, black
V = 5760 (3) Å³	0.15 × 0.12 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	5652 independent reflections
Radiation source: Rotor target	5214 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 10.0 pixels mm^-1	θ_max = 26.0°, θ_min = 1.8°
ω scans	h = −19→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
T_min = 0.041, T_max = 0.095	l = −23→25
15853 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.049P)² + 129.9363P] where P = (F_o² + 2F_c²)/3
5652 reflections	(Δ/σ)_max = 0.002
455 parameters	Δρ_max = 3.60 e Å⁻³
8 restraints	Δρ_min = −3.50 e Å⁻³

Crystal data top

(C₁₀H₁₀N₂)₂[SiW₁₂O₄₀]·C₁₀H₈N₂·6H₂O	V = 5760 (3) Å³
M_r = 3454.85	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.491 (5) Å	µ = 23.99 mm⁻¹
b = 18.096 (5) Å	T = 293 K
c = 20.921 (5) Å	0.15 × 0.12 × 0.10 mm
β = 100.834 (5)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5652 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5214 reflections with I > 2σ(I)
T_min = 0.041, T_max = 0.095	R_int = 0.042
15853 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	8 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.049P)² + 129.9363P] where P = (F_o² + 2F_c²)/3
5652 reflections	Δρ_max = 3.60 e Å⁻³
455 parameters	Δρ_min = −3.50 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 largeas 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
Si1	1.0000	0.14417 (15)	0.7500	0.0055 (5)
W1	0.98109 (2)	0.004870 (18)	0.865205 (16)	0.01358 (10)
W2	0.81326 (2)	0.150489 (19)	0.823667 (17)	0.01562 (10)
W3	0.83728 (2)	0.008359 (18)	0.701365 (16)	0.01280 (10)
W4	0.86857 (2)	0.136541 (19)	0.593364 (17)	0.01711 (10)
W5	0.83464 (2)	0.280029 (18)	0.712749 (16)	0.01327 (10)
W6	1.03445 (2)	0.282564 (18)	0.639007 (16)	0.01417 (10)
C1	0.7254 (7)	0.6611 (5)	0.4178 (5)	0.0264 (14)
H1	0.7714	0.6664	0.3953	0.032*
C2	0.6599 (7)	0.7125 (5)	0.4101 (5)	0.0254 (13)
H2	0.6598	0.7520	0.3816	0.031*
C3	0.5934 (6)	0.7045 (5)	0.4454 (5)	0.0210 (13)
C4	0.5952 (7)	0.6445 (5)	0.4877 (5)	0.0223 (13)
H4	0.5515	0.6386	0.5123	0.027*
C5	0.6624 (7)	0.5948 (5)	0.4922 (5)	0.0266 (13)
H5	0.6649	0.5544	0.5200	0.032*
C6	0.5183 (6)	0.7587 (5)	0.4376 (5)	0.0210 (13)
C7	0.4350 (6)	0.7337 (5)	0.4437 (5)	0.0219 (13)
H7	0.4262	0.6843	0.4530	0.026*
C8	0.3650 (7)	0.7838 (5)	0.4357 (5)	0.0228 (14)
H8	0.3090	0.7681	0.4396	0.027*
C9	0.4582 (6)	0.8799 (5)	0.4160 (5)	0.0240 (14)
H9	0.4648	0.9297	0.4069	0.029*
C10	0.5303 (7)	0.8325 (5)	0.4228 (5)	0.0227 (13)
H10	0.5850	0.8498	0.4175	0.027*
C11	0.5736 (6)	−0.0110 (5)	0.7442 (4)	0.0195 (13)
H11	0.6235	−0.0379	0.7401	0.023*
C12	0.5755 (6)	0.0660 (5)	0.7443 (4)	0.0174 (12)
H12	0.6269	0.0908	0.7406	0.021*
C13	0.5000	0.1061 (7)	0.7500	0.0159 (14)
C14	0.5000	0.1881 (6)	0.7500	0.0146 (14)
C15	0.5682 (6)	0.2278 (5)	0.7320 (4)	0.0174 (12)
H15	0.6147	0.2029	0.7193	0.021*
C16	0.5676 (6)	0.3045 (5)	0.7328 (4)	0.0206 (13)
H16	0.6141	0.3307	0.7214	0.025*
N1	0.7246 (6)	0.6045 (5)	0.4565 (4)	0.0265 (13)
H1N	0.770 (5)	0.584 (6)	0.461 (6)	0.040*
N2	0.3794 (6)	0.8539 (4)	0.4226 (4)	0.0252 (14)
H2N	0.334 (5)	0.875 (6)	0.419 (6)	0.038*
N3	0.5000	−0.0457 (6)	0.7500	0.0192 (16)
N4	0.5000	0.3407 (6)	0.7500	0.0192 (16)
O1	0.9447 (4)	−0.0617 (3)	0.9112 (3)	0.0163 (12)
O2	1.0599 (4)	0.0597 (3)	0.9308 (3)	0.0120 (10)
O3	1.0822 (4)	−0.0439 (3)	0.8440 (3)	0.0122 (10)
O5	0.8959 (4)	0.0815 (3)	0.8665 (3)	0.0116 (9)
O6	0.8667 (4)	0.2281 (3)	0.8797 (3)	0.0134 (9)
O7	0.7236 (4)	0.1323 (3)	0.8568 (3)	0.0165 (11)
O8	0.7635 (4)	0.2270 (3)	0.7623 (3)	0.0146 (8)
O9	0.7957 (4)	0.0824 (3)	0.7520 (3)	0.0141 (8)
O10	0.9299 (4)	0.1957 (3)	0.7773 (3)	0.0104 (8)
O11	0.9167 (4)	−0.0197 (3)	0.7808 (3)	0.0135 (9)
O12	0.7571 (4)	−0.0570 (3)	0.6969 (3)	0.0198 (12)
O13	0.9484 (4)	0.0926 (3)	0.6913 (3)	0.0096 (8)
O14	0.7932 (4)	0.0625 (3)	0.6220 (3)	0.0135 (9)
O15	0.8026 (4)	0.1562 (3)	0.5197 (3)	0.0184 (12)
O16	0.9609 (4)	0.2067 (3)	0.5959 (3)	0.0136 (9)
O17	0.8220 (4)	0.2048 (3)	0.6488 (3)	0.0146 (9)
O18	0.7599 (4)	0.3442 (3)	0.6770 (3)	0.0198 (12)
O19	1.1124 (4)	0.3313 (3)	0.7084 (3)	0.0136 (10)
O20	1.0266 (5)	0.3501 (3)	0.5807 (3)	0.0214 (13)
O21	0.9400 (4)	0.3087 (3)	0.6807 (3)	0.0159 (9)
O1W	0.9247 (5)	0.4797 (4)	0.5870 (4)	0.0332 (12)
H1A	0.890 (7)	0.469 (7)	0.615 (4)	0.050*
H1B	0.920 (8)	0.457 (6)	0.553 (4)	0.050*
O2W	0.8790 (5)	0.5277 (4)	0.4605 (4)	0.0319 (13)
H2A	0.932 (7)	0.547 (6)	0.463 (5)	0.048*
H2B	0.859 (7)	0.506 (6)	0.427 (4)	0.048*
O3W	0.7508 (5)	0.4587 (4)	0.5805 (4)	0.0380 (13)
H3A	0.780 (8)	0.416 (4)	0.594 (5)	0.057*
H3B	0.763 (9)	0.487 (5)	0.618 (4)	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0050 (12)	0.0012 (11)	0.0111 (12)	0.000	0.0033 (10)	0.000
W1	0.0161 (2)	0.00723 (17)	0.01860 (19)	0.00094 (13)	0.00648 (14)	0.00361 (12)
W2	0.0143 (2)	0.01192 (18)	0.02205 (19)	0.00164 (13)	0.00714 (14)	−0.00002 (13)
W3	0.0121 (2)	0.00709 (17)	0.01982 (18)	−0.00403 (12)	0.00457 (13)	−0.00200 (12)
W4	0.0176 (2)	0.01453 (19)	0.01848 (19)	0.00010 (14)	0.00146 (14)	0.00044 (13)
W5	0.0137 (2)	0.00674 (17)	0.01943 (18)	0.00445 (12)	0.00332 (13)	0.00175 (12)
W6	0.0179 (2)	0.00714 (17)	0.01819 (18)	−0.00104 (13)	0.00512 (14)	0.00300 (12)
C1	0.022 (3)	0.022 (3)	0.037 (3)	0.000 (2)	0.010 (2)	−0.002 (2)
C2	0.023 (3)	0.019 (2)	0.035 (3)	0.001 (2)	0.008 (2)	0.000 (2)
C3	0.018 (3)	0.017 (2)	0.029 (3)	0.000 (2)	0.007 (2)	−0.002 (2)
C4	0.019 (2)	0.018 (2)	0.031 (2)	0.001 (2)	0.007 (2)	−0.001 (2)
C5	0.023 (3)	0.022 (3)	0.034 (3)	0.001 (2)	0.005 (2)	0.001 (2)
C6	0.020 (3)	0.015 (2)	0.028 (3)	0.002 (2)	0.005 (2)	0.000 (2)
C7	0.020 (3)	0.017 (2)	0.030 (3)	0.003 (2)	0.006 (2)	0.000 (2)
C8	0.019 (3)	0.019 (3)	0.032 (3)	0.003 (3)	0.009 (3)	0.002 (3)
C9	0.023 (3)	0.016 (3)	0.033 (3)	0.002 (3)	0.006 (3)	−0.002 (3)
C10	0.021 (3)	0.016 (2)	0.031 (3)	0.000 (2)	0.007 (2)	0.000 (2)
C11	0.018 (2)	0.012 (2)	0.029 (2)	0.001 (2)	0.003 (2)	−0.002 (2)
C12	0.016 (2)	0.011 (2)	0.025 (2)	0.000 (2)	0.003 (2)	0.000 (2)
C13	0.015 (3)	0.010 (3)	0.022 (3)	0.000	0.002 (2)	0.000
C14	0.014 (3)	0.009 (3)	0.021 (3)	0.000	0.004 (2)	0.000
C15	0.016 (2)	0.011 (2)	0.025 (2)	0.000 (2)	0.004 (2)	0.000 (2)
C16	0.020 (3)	0.014 (2)	0.028 (3)	−0.002 (2)	0.004 (2)	0.002 (2)
N1	0.020 (3)	0.021 (2)	0.038 (3)	0.004 (2)	0.005 (2)	−0.004 (2)
N2	0.023 (3)	0.019 (3)	0.034 (3)	0.006 (2)	0.008 (2)	0.001 (2)
N3	0.018 (3)	0.011 (3)	0.029 (3)	0.000	0.004 (3)	0.000
N4	0.019 (3)	0.013 (3)	0.025 (3)	0.000	0.002 (3)	0.000
O1	0.018 (3)	0.010 (3)	0.023 (3)	0.001 (2)	0.007 (2)	0.007 (2)
O2	0.011 (2)	0.0089 (19)	0.016 (2)	0.0007 (18)	0.0036 (17)	0.0043 (17)
O3	0.013 (2)	0.005 (2)	0.019 (2)	0.0014 (18)	0.0047 (18)	0.0035 (18)
O5	0.0132 (18)	0.0082 (17)	0.0149 (17)	−0.0005 (16)	0.0060 (15)	0.0017 (15)
O6	0.0144 (19)	0.0075 (18)	0.0190 (18)	0.0021 (16)	0.0049 (17)	−0.0011 (16)
O7	0.015 (3)	0.014 (2)	0.021 (2)	0.003 (2)	0.006 (2)	0.000 (2)
O8	0.0131 (17)	0.0107 (16)	0.0201 (16)	0.0028 (15)	0.0037 (15)	0.0016 (15)
O9	0.0138 (16)	0.0097 (15)	0.0194 (15)	0.0000 (14)	0.0050 (14)	−0.0002 (14)
O10	0.0116 (17)	0.0047 (16)	0.0155 (16)	0.0012 (15)	0.0039 (15)	0.0004 (14)
O11	0.0158 (18)	0.0084 (17)	0.0171 (18)	−0.0005 (16)	0.0049 (16)	0.0026 (16)
O12	0.016 (3)	0.014 (3)	0.030 (3)	−0.004 (2)	0.007 (2)	−0.002 (2)
O13	0.0106 (16)	0.0052 (16)	0.0142 (16)	0.0010 (15)	0.0054 (14)	−0.0004 (14)
O14	0.0119 (18)	0.0090 (17)	0.0194 (17)	−0.0019 (16)	0.0025 (16)	−0.0018 (16)
O15	0.019 (3)	0.016 (3)	0.019 (3)	0.002 (2)	0.002 (2)	0.004 (2)
O16	0.0141 (19)	0.0090 (18)	0.0189 (18)	0.0006 (17)	0.0061 (16)	0.0016 (16)
O17	0.0140 (17)	0.0103 (16)	0.0193 (16)	0.0017 (15)	0.0023 (15)	0.0004 (15)
O18	0.022 (3)	0.016 (2)	0.023 (3)	0.009 (2)	0.007 (2)	0.007 (2)
O19	0.015 (2)	0.005 (2)	0.021 (2)	−0.0026 (18)	0.0053 (18)	0.0020 (18)
O20	0.025 (3)	0.015 (3)	0.026 (3)	0.000 (2)	0.008 (2)	0.012 (2)
O21	0.0165 (18)	0.0096 (17)	0.0224 (18)	0.0011 (16)	0.0053 (16)	0.0014 (16)
O1W	0.029 (2)	0.026 (2)	0.044 (2)	−0.001 (2)	0.006 (2)	0.005 (2)
O2W	0.025 (3)	0.026 (3)	0.045 (3)	0.001 (2)	0.008 (2)	−0.003 (2)
O3W	0.032 (3)	0.033 (2)	0.048 (3)	0.001 (2)	0.005 (2)	0.007 (2)

Geometric parameters (Å, º) top

Si1—O10	1.614 (6)	C3—C4	1.397 (13)
Si1—O10ⁱ	1.614 (6)	C3—C6	1.507 (13)
Si1—O13	1.627 (5)	C4—C5	1.366 (13)
Si1—O13ⁱ	1.627 (5)	C4—H4	0.9300
W1—O1	1.703 (6)	C5—N1	1.337 (14)
W1—O11	1.911 (5)	C5—H5	0.9300
W1—O5	1.918 (6)	C6—C10	1.391 (13)
W1—O3	1.921 (6)	C6—C7	1.395 (14)
W1—O2	1.931 (6)	C7—C8	1.400 (13)
W1—O13ⁱ	2.366 (5)	C7—H7	0.9300
W2—O7	1.697 (6)	C8—N2	1.325 (12)
W2—O5	1.889 (5)	C8—H8	0.9300
W2—O6	1.915 (6)	C9—N2	1.340 (13)
W2—O9	1.921 (6)	C9—C10	1.394 (14)
W2—O8	1.945 (6)	C9—H9	0.9300
W2—O10	2.353 (6)	C10—H10	0.9300
W3—O12	1.706 (6)	C11—N3	1.327 (11)
W3—O9	1.894 (6)	C11—C12	1.395 (12)
W3—O14	1.939 (6)	C11—H11	0.9300
W3—O11	1.940 (5)	C12—C13	1.400 (11)
W3—O3ⁱ	1.948 (6)	C12—H12	0.9300
W3—O13	2.338 (5)	C13—C12ⁱⁱ	1.400 (11)
W4—O15	1.719 (6)	C13—C14	1.483 (17)
W4—O2ⁱ	1.904 (6)	C14—C15ⁱⁱ	1.388 (11)
W4—O16	1.907 (6)	C14—C15	1.388 (11)
W4—O17	1.924 (6)	C15—C16	1.387 (12)
W4—O14	1.943 (6)	C15—H15	0.9300
W4—O13	2.325 (5)	C16—N4	1.341 (11)
W5—O18	1.709 (6)	C16—H16	0.9300
W5—O17	1.894 (6)	N1—H1N	0.79 (6)
W5—O8	1.909 (6)	N2—H2N	0.79 (6)
W5—O19ⁱ	1.935 (6)	N3—C11ⁱⁱ	1.327 (11)
W5—O21	1.948 (6)	N4—C16ⁱⁱ	1.341 (11)
W5—O10	2.363 (5)	O2—W4ⁱ	1.904 (6)
W6—O20	1.715 (6)	O3—W3ⁱ	1.948 (6)
W6—O21	1.898 (6)	O6—W6ⁱ	1.923 (6)
W6—O16	1.900 (6)	O10—W6ⁱ	2.341 (5)
W6—O19	1.919 (6)	O13—W1ⁱ	2.366 (5)
W6—O6ⁱ	1.923 (6)	O19—W5ⁱ	1.935 (6)
W6—O10ⁱ	2.341 (5)	O1W—H1A	0.89 (6)
C1—N1	1.306 (13)	O1W—H1B	0.81 (6)
C1—C2	1.364 (14)	O2W—H2A	0.88 (9)
C1—H1	0.9300	O2W—H2B	0.80 (6)
C2—C3	1.383 (14)	O3W—H3A	0.92 (6)
C2—H2	0.9300	O3W—H3B	0.93 (6)

O10—Si1—O10ⁱ	109.4 (4)	O19—W6—O6ⁱ	88.7 (2)
O10—Si1—O13	109.3 (3)	O20—W6—O10ⁱ	170.4 (3)
O10ⁱ—Si1—O13	109.4 (3)	O21—W6—O10ⁱ	85.3 (2)
O10—Si1—O13ⁱ	109.4 (3)	O16—W6—O10ⁱ	84.6 (2)
O10ⁱ—Si1—O13ⁱ	109.3 (3)	O19—W6—O10ⁱ	73.5 (2)
O13—Si1—O13ⁱ	110.0 (4)	O6ⁱ—W6—O10ⁱ	74.0 (2)
O1—W1—O11	100.7 (3)	N1—C1—C2	120.9 (10)
O1—W1—O5	101.7 (3)	N1—C1—H1	119.5
O11—W1—O5	86.6 (2)	C2—C1—H1	119.5
O1—W1—O3	100.2 (3)	C1—C2—C3	118.5 (10)
O11—W1—O3	89.2 (2)	C1—C2—H2	120.8
O5—W1—O3	158.2 (2)	C3—C2—H2	120.8
O1—W1—O2	101.2 (3)	C2—C3—C4	119.5 (9)
O11—W1—O2	158.0 (2)	C2—C3—C6	120.7 (9)
O5—W1—O2	87.9 (2)	C4—C3—C6	119.8 (9)
O3—W1—O2	88.0 (2)	C5—C4—C3	118.6 (10)
O1—W1—O13ⁱ	172.0 (2)	C5—C4—H4	120.7
O11—W1—O13ⁱ	84.5 (2)	C3—C4—H4	120.7
O5—W1—O13ⁱ	84.6 (2)	N1—C5—C4	119.7 (9)
O3—W1—O13ⁱ	73.7 (2)	N1—C5—H5	120.2
O2—W1—O13ⁱ	73.8 (2)	C4—C5—H5	120.2
O7—W2—O5	102.2 (3)	C10—C6—C7	119.7 (9)
O7—W2—O6	100.6 (3)	C10—C6—C3	121.1 (9)
O5—W2—O6	91.0 (2)	C7—C6—C3	119.2 (8)
O7—W2—O9	100.8 (3)	C6—C7—C8	119.3 (9)
O5—W2—O9	86.0 (2)	C6—C7—H7	120.4
O6—W2—O9	158.5 (3)	C8—C7—H7	120.4
O7—W2—O8	98.9 (3)	N2—C8—C7	119.2 (9)
O5—W2—O8	158.8 (3)	N2—C8—H8	120.4
O6—W2—O8	87.4 (2)	C7—C8—H8	120.4
O9—W2—O8	87.8 (2)	N2—C9—C10	120.0 (9)
O7—W2—O10	170.8 (2)	N2—C9—H9	120.0
O5—W2—O10	85.5 (2)	C10—C9—H9	120.0
O6—W2—O10	73.8 (2)	C6—C10—C9	118.4 (9)
O9—W2—O10	84.7 (2)	C6—C10—H10	120.8
O8—W2—O10	73.8 (2)	C9—C10—H10	120.8
O12—W3—O9	101.6 (3)	N3—C11—C12	119.3 (9)
O12—W3—O14	99.7 (3)	N3—C11—H11	120.3
O9—W3—O14	91.1 (2)	C12—C11—H11	120.3
O12—W3—O11	101.7 (3)	C11—C12—C13	120.1 (9)
O9—W3—O11	86.2 (2)	C11—C12—H12	119.9
O14—W3—O11	158.5 (2)	C13—C12—H12	119.9
O12—W3—O3ⁱ	99.4 (3)	C12ⁱⁱ—C13—C12	117.5 (11)
O9—W3—O3ⁱ	158.7 (2)	C12ⁱⁱ—C13—C14	121.2 (6)
O14—W3—O3ⁱ	89.0 (2)	C12—C13—C14	121.2 (6)
O11—W3—O3ⁱ	85.9 (2)	C15ⁱⁱ—C14—C15	117.5 (11)
O12—W3—O13	171.3 (2)	C15ⁱⁱ—C14—C13	121.2 (6)
O9—W3—O13	85.6 (2)	C15—C14—C13	121.2 (5)
O14—W3—O13	74.9 (2)	C16—C15—C14	120.5 (9)
O11—W3—O13	83.6 (2)	C16—C15—H15	119.7
O3ⁱ—W3—O13	73.9 (2)	C14—C15—H15	119.7
O15—W4—O2ⁱ	101.0 (3)	N4—C16—C15	120.0 (9)
O15—W4—O16	101.7 (3)	N4—C16—H16	120.0
O2ⁱ—W4—O16	91.3 (2)	C15—C16—H16	120.0
O15—W4—O17	100.4 (3)	C1—N1—C5	122.8 (9)
O2ⁱ—W4—O17	158.6 (2)	C1—N1—H1N	109 (9)
O16—W4—O17	85.4 (3)	C5—N1—H1N	127 (9)
O15—W4—O14	97.4 (3)	C8—N2—C9	123.4 (9)
O2ⁱ—W4—O14	89.5 (2)	C8—N2—H2N	108 (9)
O16—W4—O14	160.3 (2)	C9—N2—H2N	129 (9)
O17—W4—O14	86.7 (2)	C11ⁱⁱ—N3—C11	123.6 (11)
O15—W4—O13	171.5 (2)	C16ⁱⁱ—N4—C16	121.4 (11)
O2ⁱ—W4—O13	75.2 (2)	W4ⁱ—O2—W1	120.5 (3)
O16—W4—O13	86.1 (2)	W1—O3—W3ⁱ	121.0 (3)
O17—W4—O13	83.5 (2)	W2—O5—W1	151.4 (3)
O14—W4—O13	75.1 (2)	W2—O6—W6ⁱ	121.3 (3)
O18—W5—O17	102.0 (3)	W5—O8—W2	121.2 (3)
O18—W5—O8	99.6 (3)	W3—O9—W2	151.4 (3)
O17—W5—O8	91.6 (3)	Si1—O10—W6ⁱ	125.0 (3)
O18—W5—O19ⁱ	101.0 (3)	Si1—O10—W2	124.4 (3)
O17—W5—O19ⁱ	156.7 (2)	W6ⁱ—O10—W2	90.93 (19)
O8—W5—O19ⁱ	88.5 (3)	Si1—O10—W5	124.1 (3)
O18—W5—O21	102.2 (3)	W6ⁱ—O10—W5	91.59 (19)
O17—W5—O21	86.0 (3)	W2—O10—W5	90.8 (2)
O8—W5—O21	158.1 (2)	W1—O11—W3	150.2 (3)
O19ⁱ—W5—O21	85.3 (2)	Si1—O13—W4	125.0 (3)
O18—W5—O10	171.0 (3)	Si1—O13—W3	124.9 (3)
O17—W5—O10	84.8 (2)	W4—O13—W3	91.37 (19)
O8—W5—O10	74.2 (2)	Si1—O13—W1ⁱ	123.6 (3)
O19ⁱ—W5—O10	72.7 (2)	W4—O13—W1ⁱ	90.46 (18)
O21—W5—O10	84.0 (2)	W3—O13—W1ⁱ	91.39 (18)
O20—W6—O21	101.0 (3)	W3—O14—W4	118.5 (3)
O20—W6—O16	102.7 (3)	W6—O16—W4	150.9 (3)
O21—W6—O16	87.3 (3)	W5—O17—W4	152.4 (3)
O20—W6—O19	99.3 (3)	W6—O19—W5ⁱ	122.0 (3)
O21—W6—O19	88.2 (3)	W6—O21—W5	149.3 (3)
O16—W6—O19	158.0 (2)	H1A—O1W—H1B	119 (9)
O20—W6—O6ⁱ	99.9 (3)	H2A—O2W—H2B	117 (10)
O21—W6—O6ⁱ	159.0 (2)	H3A—O3W—H3B	102 (6)
O16—W6—O6ⁱ	87.8 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3W	0.89 (10)	2.15 (11)	2.699 (11)	119 (7)
O1W—H1B···O2W	0.81 (9)	2.31 (9)	2.749 (12)	115 (10)
O1W—H1B···O20	0.81 (9)	2.54 (11)	2.844 (10)	104 (8)
N1—H1N···O2W	0.78 (9)	1.97 (9)	2.754 (12)	172 (14)
O3W—H3A···O18	0.91 (9)	2.24 (10)	2.878 (10)	127 (9)

Experimental details

Crystal data
Chemical formula	(C₁₀H₁₀N₂)₂[SiW₁₂O₄₀]·C₁₀H₈N₂·6H₂O
M_r	3454.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.491 (5), 18.096 (5), 20.921 (5)
β (°)	100.834 (5)
V (Å³)	5760 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	23.99
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.041, 0.095
No. of measured, independent and observed [I > 2σ(I)] reflections	15853, 5652, 5214
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.101, 1.10
No. of reflections	5652
No. of parameters	455
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.049P)² + 129.9363P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	3.60, −3.50

Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3W	0.89 (10)	2.15 (11)	2.699 (11)	119 (7)
O1W—H1B···O2W	0.81 (9)	2.31 (9)	2.749 (12)	115 (10)
O1W—H1B···O20	0.81 (9)	2.54 (11)	2.844 (10)	104 (8)
N1—H1N···O2W	0.78 (9)	1.97 (9)	2.754 (12)	172 (14)
O3W—H3A···O18	0.91 (9)	2.24 (10)	2.878 (10)	127 (9)

Acknowledgements

The authors thank Jilin Agricultural Science and Technology College (China) for support.

References

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