Bis{tris­[3-(2-pyrid­yl)-1H-pyrazole]zinc(II)} dodeca­molybdosilicate hexa­hydrate

Zhang, X.; Wei, P.; Zhu, W.; Li, B.; Hu, B.

doi:10.1107/S160053681000019X

Bis{tris[3-(2-pyridyl)-1H-pyrazole]zinc(II)} dodecamolybdosilicate hexahydrate

X. Zhang, P. Wei, W. Zhu, B. Li and B. Hu

The asymmetric unit of the title compound, [Zn(C₈H₇N₃)₃]₂[SiMo₁₂O₄₀]·6H₂O, consists of a complex [Zn(C₈H₇N₃)₃]²⁺ cation, half of a Keggin-type [SiMo₁₂O₄₀]⁴⁻ heteropolyanion and three uncoordinated water molecules. The Zn²⁺ cation is surrounded in a distorted octahedral coordination by six N atoms from three chelating 3-(2-pyridyl)pyrazole ligands. In the heteropolyanion, two O atoms of the central SiO₄ group ( $\overline{1}$ symmetry) are equally disordered about an inversion centre. N—H

O hydrogen bonding between the cations, anions and the uncoordinated water molecules leads to a consolidation of the structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681000019X/wm2292sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053681000019X/wm2292Isup2.hkl Contains datablock I

CCDC reference: 737033

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.015 Å
H-atom completeness 78%
Disorder in main residue
R factor = 0.049
wR factor = 0.112
Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O1W

Author Response: reliable H positions of the water molecules O1W-O3W could not be determined from Fourier maps, most probably due to disorder. Hence the structure was refined without H atoms of the uncoordinated water molecules

PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O2W

PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O3W


Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       4.35 Ratio
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O3
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O9
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        O11
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        O14
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        O19
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        Mo5
PLAT430_ALERT_2_B Short Inter D...A Contact  O1W    ..  O1W     ..       2.82 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O1W    ..  O2W     ..       2.82 Ang.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O7
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O10
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo6
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         15
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595        205
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT234_ALERT_4_C Large Hirshfeld Difference C2     --  C3      ..       0.17 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C7     --  C8      ..       0.25 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C48 H54 Mo12 N18 O46 Si1 Zn2
            Atom count from the _atom_site data:  C48 H42 Mo12 N18 O46 Si1 Zn2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C48 H54 Mo12 N18 O46 Si Zn2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        192.00    192.00    0.00
           H        216.00    168.00   48.00
           Mo        48.00     48.00    0.00
           N         72.00     72.00    0.00
           O        184.00    184.00    0.00
           Si         4.00      4.00    0.00
           Zn         8.00      8.00    0.00
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.      90.49
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................       6.00 Perc.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   3 ALERT level A = In general: serious problem
   9 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  22 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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 & Müller, 1991). In our research group, organic amines, such as 3-(2-pyridyl)pyrazole and pyrazine, are used to effectively modify polyoxomolybdates under hydrothermal condictions (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 title compound consists of three subunits, viz. of a complex [Zn(C₈H₇N₃)₃]²⁺ cation, a heteropolyanion [SiMo₁₂O₄₀]^4- anion and of uncoordinated water molecules. The zinc(II) ion is in a distorted octahedral coordination by six N atoms from three chelating 3-(2-pyridyl)pyrazole ligands. The Zn—N bond lengths are in the range of 2.134 (7)—2.196 (7) Å. In the Keggin-type heteropolyanion, each Mo atom is surrounded by six O atoms and the Si atom is located at the center of the anion. There are four kinds of O atoms present in the anion according to their coordination environments: O_a (O atoms in the disordered SiO₄ tetrahedron), O_b (bridging O atoms between two triplet groups of MoO₆ octahedra), O_c (bridging O atoms within one triplet group of MoO₆ octahedra) and O_d (terminal O atoms). The Si—O bond distances are in the normal range of 1.581 (8)—1.674 (8) compared to reported distances in other dodecamolybdosilicates (Wu et al., 2003). The Mo—O bond distances vary widely from 1.647 (5) to 2.447 (8) Å. The shortest Mo—O bonds are in the range of 1.647 (5)—1.675 (5) Å for the terminal oxygen atoms. The longest Mo—O lengths are in the range of 2.345 (8)—2.447 (8) Å for those oxygen atoms connected with both Mo and Si atoms.

N—H···O and O—H···O hydrogen bonding between the cationic and anionic moieties and the uncoordinated water molecules leads to a consolidation of the structure (Fig. 2; Table 2).

Related literature top

For general background to polyoxometalates, see: Pope & Müller (1991). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei et al. (2009). For the structure of another dodecamolybdosilicate, see: Wu et al. (2003).

Experimental top

A mixture of 3-(2-pyridyl)pyrazole (1 mmoL 0.14 g), sodium molybdate (2 mmoL, 0.48 g), sodium silicate nonahydrate (0.2 mmoL, 0.05 g) and zinc acetate (1 mmoL, 0.18 g) in 10 ml distilled water was sealed in a 25 ml Teflon-lined stainless steel autoclave and was kept at 433 K for three days. Colorless crystals suitable for the X-ray experiment were obtained. Anal. Calc. for C₄₈H₅₄Mo₁₂N₁₈O₄₆SiZn₂: C 19.67, H 1.84, N 8.60 %; Found: C 19.52, H 1.74, N 8.48 %.

Structure description top

N—H···O and O—H···O hydrogen bonding between the cationic and anionic moieties and the uncoordinated water molecules leads to a consolidation of the structure (Fig. 2; Table 2).

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The building blocks 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 crystal packing of the title compound, displayed with N—H···O and O—H···O hydrogen bonds as dashed lines.

Bis{tris[3-(2-pyridyl)-1H-pyrazole]zinc(II)} dodecamolybdosilicate hexahydrate top

Crystal data top

[Zn(C₈H₇N₃)₃]₂[SiMo₁₂O₄₀]·6H₂O	F(000) = 5656
M_r = 2929.20	D_x = 2.354 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7081 reflections
a = 18.824 (4) Å	θ = 2.1–25.0°
b = 16.365 (3) Å	µ = 2.44 mm⁻¹
c = 27.749 (6) Å	T = 293 K
β = 104.74 (3)°	Block, colorless
V = 8267 (3) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7081 independent reflections
Radiation source: fine-focus sealed tube	5632 reflections with I > 2σ(I)'
Graphite monochromator	R_int = 0.050
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→22
T_min = 0.758, T_max = 0.829	k = −19→19
27894 measured reflections	l = −32→32

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.040P)² + 90.4942P] where P = (F_o² + 2F_c²)/3
7081 reflections	(Δ/σ)_max = 0.001
601 parameters	Δρ_max = 1.22 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Zn(C₈H₇N₃)₃]₂[SiMo₁₂O₄₀]·6H₂O	V = 8267 (3) Å³
M_r = 2929.20	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.824 (4) Å	µ = 2.44 mm⁻¹
b = 16.365 (3) Å	T = 293 K
c = 27.749 (6) Å	0.12 × 0.10 × 0.08 mm
β = 104.74 (3)°

Data collection top

Bruker APEXII CCD diffractometer	7081 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	5632 reflections with I > 2σ(I)'
T_min = 0.758, T_max = 0.829	R_int = 0.050
27894 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.040P)² + 90.4942P] where P = (F_o² + 2F_c²)/3
7081 reflections	Δρ_max = 1.22 e Å⁻³
601 parameters	Δρ_min = −0.63 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Si1	0.2500	0.7500	0.5000	0.0259 (5)
Zn1	0.20485 (5)	0.18036 (6)	0.30659 (4)	0.0495 (2)
Mo1	0.32661 (4)	0.65322 (4)	0.41132 (2)	0.04445 (19)
Mo2	0.14843 (3)	0.59791 (4)	0.42128 (2)	0.04067 (18)
Mo3	0.25254 (4)	0.85217 (4)	0.38792 (2)	0.0493 (2)
Mo4	0.08217 (3)	0.80182 (4)	0.41417 (3)	0.04398 (19)
Mo5	0.30421 (4)	0.54390 (4)	0.51646 (3)	0.04711 (19)
Mo6	0.08169 (3)	0.67952 (4)	0.51953 (3)	0.04175 (18)
C1	0.1721 (5)	0.0214 (6)	0.2386 (4)	0.062 (2)
H1	0.2038	0.0432	0.2211	0.074*
C2	0.1437 (6)	−0.0550 (6)	0.2264 (4)	0.071 (3)
H2	0.1555	−0.0844	0.2008	0.085*
C3	0.0987 (7)	−0.0867 (8)	0.2518 (5)	0.092 (4)
H3	0.0796	−0.1389	0.2440	0.111*
C4	0.0811 (6)	−0.0452 (8)	0.2878 (5)	0.081 (3)
H4	0.0498	−0.0673	0.3055	0.097*
C5	0.1100 (4)	0.0311 (6)	0.2985 (3)	0.057 (2)
C6	0.0921 (5)	0.0815 (7)	0.3375 (4)	0.065 (3)
C7	0.0418 (5)	0.0710 (10)	0.3689 (5)	0.100 (5)
H7	0.0105	0.0273	0.3694	0.120*
C8	0.0516 (6)	0.1423 (9)	0.3984 (5)	0.084 (4)
H8	0.0269	0.1557	0.4224	0.101*
C9	0.0912 (5)	0.2438 (6)	0.2080 (4)	0.068 (3)
H9	0.0867	0.1889	0.1989	0.082*
C10	0.0527 (6)	0.2998 (8)	0.1755 (5)	0.089 (4)
H10	0.0228	0.2832	0.1450	0.107*
C11	0.0582 (6)	0.3805 (8)	0.1880 (4)	0.092 (4)
H11	0.0320	0.4197	0.1665	0.110*
C12	0.1037 (6)	0.4026 (7)	0.2336 (4)	0.086 (3)
H12	0.1083	0.4571	0.2434	0.103*
C13	0.1420 (5)	0.3430 (5)	0.2640 (3)	0.055 (2)
C14	0.1945 (5)	0.3607 (6)	0.3124 (3)	0.057 (2)
C15	0.2158 (6)	0.4342 (6)	0.3378 (4)	0.073 (3)
H15	0.1974	0.4861	0.3280	0.088*
C16	0.2680 (6)	0.4148 (7)	0.3790 (4)	0.074 (3)
H16	0.2928	0.4508	0.4035	0.089*
C17	0.2987 (4)	0.1008 (5)	0.4058 (3)	0.0471 (19)
H17	0.2562	0.1054	0.4169	0.057*
C18	0.3603 (5)	0.0661 (5)	0.4374 (3)	0.056 (2)
H18	0.3585	0.0477	0.4687	0.067*
C19	0.4222 (5)	0.0591 (5)	0.4225 (3)	0.053 (2)
H19	0.4639	0.0357	0.4433	0.063*
C20	0.4231 (4)	0.0872 (6)	0.3760 (3)	0.054 (2)
H20	0.4659	0.0835	0.3652	0.065*
C21	0.3604 (4)	0.1210 (4)	0.3454 (3)	0.0397 (17)
C22	0.3555 (4)	0.1495 (5)	0.2946 (3)	0.0416 (18)
C23	0.4101 (5)	0.1560 (7)	0.2682 (3)	0.067 (3)
H23	0.4597	0.1429	0.2794	0.080*
C24	0.3738 (6)	0.1861 (7)	0.2224 (4)	0.076 (3)
H24	0.3941	0.1963	0.1957	0.091*
N1	0.1557 (4)	0.0657 (4)	0.2749 (3)	0.0557 (18)
N2	0.1281 (4)	0.1523 (5)	0.3493 (3)	0.062 (2)
N3	0.1028 (5)	0.1869 (6)	0.3854 (3)	0.076 (2)
H3A	0.1181	0.2331	0.3988	0.091*
N4	0.1355 (4)	0.2636 (5)	0.2524 (3)	0.0543 (18)
N5	0.2323 (4)	0.2991 (4)	0.3376 (3)	0.0559 (18)
N6	0.2775 (4)	0.3336 (5)	0.3781 (3)	0.066 (2)
H6	0.3087	0.3068	0.4006	0.079*
N7	0.2976 (3)	0.1278 (4)	0.3605 (2)	0.0394 (14)
N8	0.2916 (4)	0.1760 (4)	0.2672 (2)	0.0467 (16)
N9	0.3042 (4)	0.1979 (5)	0.2231 (2)	0.061 (2)
H9A	0.2710	0.2171	0.1984	0.073*
O1	0.2556 (3)	0.9034 (4)	0.3374 (2)	0.0581 (15)
O2	0.3551 (3)	0.6067 (4)	0.3660 (2)	0.0603 (16)
O3	0.2143 (3)	0.5308 (5)	0.4729 (3)	0.092 (2)
O4	0.0056 (3)	0.8237 (4)	0.3718 (2)	0.0709 (19)
O5A	0.1705 (4)	0.7185 (5)	0.4728 (3)	0.0272 (19)	0.50
O5B	0.2051 (5)	0.8171 (5)	0.4590 (3)	0.029 (2)	0.50
O6	0.3318 (3)	0.4476 (3)	0.5234 (3)	0.0649 (17)
O7	0.0948 (4)	0.6044 (4)	0.4756 (2)	0.0711 (19)
O8	0.0983 (4)	0.5235 (4)	0.3883 (2)	0.0671 (18)
O9	0.0955 (4)	0.6878 (4)	0.3938 (2)	0.0730 (19)
O10	0.0468 (4)	0.7568 (4)	0.4653 (2)	0.0698 (19)
O11	0.2221 (3)	0.6113 (5)	0.3913 (2)	0.085 (2)
O12	0.0004 (3)	0.6534 (4)	0.5292 (3)	0.0649 (17)
O13	0.4022 (5)	0.7155 (4)	0.4407 (3)	0.113 (4)
O14	0.3436 (3)	0.5746 (5)	0.4594 (3)	0.092 (3)
O15	0.2669 (4)	0.5588 (5)	0.5708 (3)	0.113 (3)
O16A	0.2666 (7)	0.7439 (8)	0.3817 (5)	0.042 (3)	0.50
O16B	0.2893 (7)	0.7499 (7)	0.3635 (4)	0.034 (3)	0.50
O17	0.1467 (5)	0.6329 (4)	0.5734 (3)	0.112 (3)
O18	0.1061 (4)	0.9000 (5)	0.4463 (3)	0.100 (3)
O19	0.1530 (4)	0.8255 (4)	0.3747 (3)	0.089 (2)
O20A	0.3000 (4)	0.7634 (5)	0.4586 (3)	0.0257 (19)	0.50
O20B	0.2524 (5)	0.6636 (5)	0.4715 (3)	0.030 (2)	0.50
O1W	0.4635 (8)	0.4314 (11)	0.4744 (9)	0.278 (10)
O2W	0.3838 (4)	0.2836 (6)	0.4615 (3)	0.109 (3)
O3W	0.1316 (7)	0.3429 (7)	0.4336 (5)	0.159 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0238 (12)	0.0280 (13)	0.0247 (13)	0.0012 (10)	0.0038 (10)	−0.0011 (10)
Zn1	0.0419 (5)	0.0506 (6)	0.0561 (6)	0.0072 (4)	0.0128 (4)	0.0112 (5)
Mo1	0.0470 (4)	0.0519 (4)	0.0337 (4)	0.0140 (3)	0.0089 (3)	−0.0095 (3)
Mo2	0.0329 (3)	0.0450 (4)	0.0421 (4)	−0.0093 (3)	0.0058 (3)	−0.0105 (3)
Mo3	0.0725 (5)	0.0434 (4)	0.0306 (3)	−0.0072 (4)	0.0108 (3)	0.0056 (3)
Mo4	0.0293 (3)	0.0542 (4)	0.0425 (4)	0.0003 (3)	−0.0017 (3)	0.0035 (3)
Mo5	0.0524 (4)	0.0308 (4)	0.0637 (5)	0.0091 (3)	0.0250 (4)	0.0063 (3)
Mo6	0.0275 (3)	0.0455 (4)	0.0520 (4)	−0.0075 (3)	0.0095 (3)	−0.0032 (3)
C1	0.057 (6)	0.067 (6)	0.063 (6)	−0.005 (5)	0.017 (5)	0.016 (5)
C2	0.068 (6)	0.060 (6)	0.076 (7)	−0.002 (5)	0.003 (5)	−0.004 (5)
C3	0.074 (8)	0.079 (8)	0.105 (10)	−0.009 (6)	−0.016 (7)	0.012 (8)
C4	0.054 (6)	0.092 (9)	0.083 (8)	−0.020 (6)	−0.008 (6)	0.015 (7)
C5	0.033 (4)	0.063 (6)	0.066 (6)	−0.005 (4)	−0.005 (4)	0.020 (5)
C6	0.034 (4)	0.092 (8)	0.067 (6)	0.011 (5)	0.010 (4)	0.035 (6)
C7	0.042 (6)	0.140 (12)	0.115 (10)	0.002 (7)	0.014 (6)	0.076 (10)
C8	0.062 (7)	0.120 (10)	0.079 (8)	0.032 (7)	0.034 (6)	0.040 (8)
C9	0.068 (6)	0.066 (6)	0.061 (6)	−0.009 (5)	0.000 (5)	0.008 (5)
C10	0.081 (8)	0.088 (9)	0.084 (8)	0.004 (7)	−0.007 (6)	0.022 (7)
C11	0.084 (8)	0.083 (9)	0.086 (8)	0.019 (6)	−0.018 (7)	0.027 (7)
C12	0.087 (8)	0.059 (6)	0.097 (9)	0.017 (6)	−0.005 (7)	0.016 (6)
C13	0.051 (5)	0.052 (5)	0.063 (6)	0.008 (4)	0.013 (4)	0.006 (4)
C14	0.058 (5)	0.059 (6)	0.057 (5)	0.013 (4)	0.019 (4)	0.001 (5)
C15	0.099 (8)	0.061 (6)	0.063 (6)	0.021 (6)	0.025 (6)	−0.002 (5)
C16	0.100 (8)	0.072 (7)	0.053 (6)	0.008 (6)	0.025 (6)	−0.013 (5)
C17	0.043 (4)	0.050 (5)	0.051 (5)	−0.004 (4)	0.018 (4)	0.010 (4)
C18	0.073 (6)	0.059 (5)	0.029 (4)	−0.015 (5)	0.002 (4)	0.013 (4)
C19	0.045 (5)	0.058 (5)	0.047 (5)	−0.007 (4)	−0.001 (4)	0.009 (4)
C20	0.027 (4)	0.077 (6)	0.054 (5)	−0.001 (4)	0.002 (4)	0.012 (4)
C21	0.036 (4)	0.037 (4)	0.047 (4)	0.003 (3)	0.012 (3)	−0.001 (3)
C22	0.039 (4)	0.046 (5)	0.039 (4)	−0.004 (3)	0.011 (3)	0.010 (3)
C23	0.041 (5)	0.109 (8)	0.056 (6)	0.009 (5)	0.022 (4)	0.011 (5)
C24	0.068 (7)	0.114 (9)	0.055 (6)	−0.007 (6)	0.030 (5)	0.000 (6)
N1	0.044 (4)	0.053 (4)	0.068 (5)	0.001 (3)	0.009 (4)	0.015 (4)
N2	0.046 (4)	0.079 (6)	0.063 (5)	0.015 (4)	0.017 (4)	0.023 (4)
N3	0.066 (5)	0.083 (6)	0.080 (6)	0.023 (5)	0.019 (5)	0.021 (5)
N4	0.044 (4)	0.062 (5)	0.057 (5)	0.007 (3)	0.014 (3)	0.006 (4)
N5	0.049 (4)	0.053 (4)	0.062 (5)	0.007 (3)	0.008 (4)	0.002 (4)
N6	0.065 (5)	0.077 (6)	0.053 (5)	0.019 (4)	0.012 (4)	0.005 (4)
N7	0.036 (3)	0.045 (4)	0.039 (3)	0.007 (3)	0.011 (3)	0.009 (3)
N8	0.046 (4)	0.055 (4)	0.037 (4)	0.004 (3)	0.007 (3)	0.005 (3)
N9	0.075 (5)	0.071 (5)	0.033 (4)	0.002 (4)	0.007 (3)	0.016 (3)
O1	0.061 (4)	0.072 (4)	0.039 (3)	−0.012 (3)	0.007 (3)	0.013 (3)
O2	0.052 (3)	0.085 (4)	0.046 (3)	0.001 (3)	0.016 (3)	−0.028 (3)
O3	0.047 (3)	0.152 (6)	0.083 (4)	0.019 (4)	0.029 (3)	0.065 (4)
O4	0.052 (4)	0.102 (5)	0.049 (4)	0.031 (4)	−0.006 (3)	0.004 (3)
O5A	0.024 (4)	0.027 (5)	0.031 (5)	−0.001 (4)	0.009 (4)	−0.003 (4)
O5B	0.029 (5)	0.030 (5)	0.029 (5)	−0.004 (4)	0.005 (4)	−0.001 (4)
O6	0.062 (4)	0.030 (3)	0.103 (5)	0.013 (3)	0.020 (3)	0.011 (3)
O7	0.112 (5)	0.052 (4)	0.061 (4)	0.038 (4)	0.044 (4)	0.015 (3)
O8	0.083 (5)	0.054 (4)	0.060 (4)	−0.025 (3)	0.011 (3)	−0.021 (3)
O9	0.114 (6)	0.053 (4)	0.068 (4)	0.029 (4)	0.053 (4)	0.010 (3)
O10	0.119 (6)	0.051 (4)	0.054 (4)	0.032 (4)	0.048 (4)	0.012 (3)
O11	0.039 (3)	0.144 (7)	0.073 (4)	0.009 (4)	0.016 (3)	0.060 (5)
O12	0.050 (3)	0.063 (4)	0.094 (5)	−0.004 (3)	0.043 (3)	0.003 (3)
O13	0.131 (7)	0.035 (4)	0.113 (6)	0.021 (4)	−0.080 (5)	−0.017 (4)
O14	0.026 (3)	0.175 (8)	0.074 (4)	0.008 (4)	0.010 (3)	0.070 (5)
O15	0.102 (6)	0.123 (6)	0.147 (7)	−0.079 (5)	0.095 (6)	−0.093 (6)
O16A	0.038 (8)	0.056 (8)	0.030 (7)	−0.004 (6)	0.008 (5)	0.002 (6)
O16B	0.037 (7)	0.038 (6)	0.024 (7)	−0.002 (5)	0.001 (5)	−0.001 (5)
O17	0.124 (6)	0.040 (4)	0.116 (6)	0.026 (4)	−0.073 (5)	−0.025 (4)
O18	0.105 (6)	0.116 (6)	0.108 (6)	−0.068 (5)	0.080 (5)	−0.069 (5)
O19	0.093 (5)	0.088 (5)	0.108 (5)	−0.042 (4)	0.069 (4)	−0.046 (4)
O20A	0.023 (4)	0.030 (5)	0.024 (4)	−0.006 (4)	0.006 (4)	−0.006 (4)
O20B	0.034 (5)	0.031 (5)	0.027 (5)	0.000 (4)	0.012 (4)	−0.003 (4)
O1W	0.178 (14)	0.240 (17)	0.47 (3)	0.016 (12)	0.190 (18)	−0.077 (19)
O2W	0.080 (5)	0.143 (8)	0.090 (6)	0.026 (5)	−0.003 (4)	0.006 (5)
O3W	0.186 (11)	0.135 (9)	0.200 (12)	−0.027 (8)	0.128 (10)	−0.028 (8)

Geometric parameters (Å, º) top

Si1—O5A	1.581 (8)	C2—H2	0.9300
Si1—O5Aⁱ	1.581 (8)	C3—C4	1.320 (16)
Si1—O20Bⁱ	1.628 (8)	C3—H3	0.9300
Si1—O20B	1.628 (8)	C4—C5	1.364 (14)
Si1—O5B	1.650 (9)	C4—H4	0.9300
Si1—O5Bⁱ	1.650 (9)	C5—N1	1.333 (11)
Si1—O20Aⁱ	1.674 (8)	C5—C6	1.466 (14)
Si1—O20A	1.674 (8)	C6—N2	1.340 (12)
Zn1—N5	2.134 (7)	C6—C7	1.450 (14)
Zn1—N2	2.138 (8)	C7—C8	1.411 (18)
Zn1—N7	2.167 (6)	C7—H7	0.9300
Zn1—N1	2.176 (8)	C8—N3	1.329 (14)
Zn1—N8	2.186 (7)	C8—H8	0.9300
Zn1—N4	2.196 (7)	C9—N4	1.341 (11)
Mo1—O2	1.670 (5)	C9—C10	1.357 (14)
Mo1—O13	1.771 (7)	C9—H9	0.9300
Mo1—O14	1.823 (6)	C10—C11	1.363 (16)
Mo1—O16A	1.918 (13)	C10—H10	0.9300
Mo1—O11	2.023 (6)	C11—C12	1.382 (15)
Mo1—O16B	2.070 (12)	C11—H11	0.9300
Mo1—O20A	2.358 (8)	C12—C13	1.368 (13)
Mo1—O20B	2.439 (8)	C12—H12	0.9300
Mo2—O8	1.666 (5)	C13—N4	1.336 (11)
Mo2—O11	1.803 (6)	C13—C14	1.480 (12)
Mo2—O9	1.830 (6)	C14—N5	1.326 (11)
Mo2—O3	1.972 (6)	C14—C15	1.399 (13)
Mo2—O7	2.019 (6)	C15—C16	1.343 (14)
Mo2—O20B	2.353 (9)	C15—H15	0.9300
Mo2—O5A	2.411 (8)	C16—N6	1.342 (12)
Mo3—O1	1.647 (5)	C16—H16	0.9300
Mo3—O16A	1.806 (14)	C17—N7	1.328 (9)
Mo3—O19	1.867 (7)	C17—C18	1.383 (11)
Mo3—O17ⁱ	1.943 (7)	C17—H17	0.9300
Mo3—O15ⁱ	1.945 (7)	C18—C19	1.337 (12)
Mo3—O16B	1.994 (12)	C18—H18	0.9300
Mo3—O20A	2.423 (8)	C19—C20	1.375 (11)
Mo3—O5B	2.433 (9)	C19—H19	0.9300
Mo4—O4	1.651 (5)	C20—C21	1.382 (10)
Mo4—O18	1.837 (7)	C20—H20	0.9300
Mo4—O10	1.867 (6)	C21—N7	1.357 (9)
Mo4—O19	1.967 (6)	C21—C22	1.467 (10)
Mo4—O9	1.984 (6)	C22—N8	1.322 (9)
Mo4—O5B	2.345 (8)	C22—C23	1.410 (11)
Mo4—O5A	2.427 (8)	C23—C24	1.373 (13)
Mo5—O6	1.655 (5)	C23—H23	0.9300
Mo5—O3	1.825 (7)	C24—N9	1.331 (12)
Mo5—O15	1.834 (7)	C24—H24	0.9300
Mo5—O18ⁱ	1.968 (7)	N2—N3	1.339 (11)
Mo5—O14	1.975 (6)	N3—H3A	0.8600
Mo5—O20B	2.393 (9)	N5—N6	1.350 (10)
Mo5—O5Bⁱ	2.394 (9)	N6—H6	0.8600
Mo6—O12	1.675 (5)	N8—N9	1.351 (9)
Mo6—O7	1.792 (6)	N9—H9A	0.8600
Mo6—O17	1.839 (6)	O5A—O20B	1.794 (12)
Mo6—O10	1.947 (6)	O5A—O5B	1.816 (12)
Mo6—O13ⁱ	2.022 (6)	O5B—Mo5ⁱ	2.394 (9)
Mo6—O20Aⁱ	2.348 (8)	O13—Mo6ⁱ	2.022 (6)
Mo6—O5A	2.447 (8)	O15—Mo3ⁱ	1.945 (7)
C1—N1	1.340 (12)	O16A—O16B	0.747 (11)
C1—C2	1.368 (13)	O17—Mo3ⁱ	1.943 (7)
C1—H1	0.9300	O18—Mo5ⁱ	1.968 (7)
C2—C3	1.337 (16)	O20A—Mo6ⁱ	2.348 (8)

O5A—Si1—O5Aⁱ	180.000 (1)	O17—Mo6—O13ⁱ	86.1 (3)
O5A—Si1—O20Bⁱ	112.0 (4)	O10—Mo6—O13ⁱ	81.0 (3)
O5Aⁱ—Si1—O20Bⁱ	68.0 (4)	O12—Mo6—O20Aⁱ	154.9 (3)
O5A—Si1—O20B	68.0 (4)	O7—Mo6—O20Aⁱ	99.4 (3)
O5Aⁱ—Si1—O20B	112.0 (4)	O17—Mo6—O20Aⁱ	64.2 (4)
O20Bⁱ—Si1—O20B	180.000 (2)	O10—Mo6—O20Aⁱ	93.0 (3)
O5A—Si1—O5B	68.3 (4)	O13ⁱ—Mo6—O20Aⁱ	61.3 (3)
O5Aⁱ—Si1—O5B	111.7 (4)	O12—Mo6—O5A	157.9 (3)
O20Bⁱ—Si1—O5B	71.6 (4)	O7—Mo6—O5A	65.6 (3)
O20B—Si1—O5B	108.4 (4)	O17—Mo6—O5A	97.8 (4)
O5A—Si1—O5Bⁱ	111.7 (4)	O10—Mo6—O5A	64.1 (3)
O5Aⁱ—Si1—O5Bⁱ	68.3 (4)	O13ⁱ—Mo6—O5A	92.3 (4)
O20Bⁱ—Si1—O5Bⁱ	108.4 (4)	O20Aⁱ—Mo6—O5A	45.7 (3)
O20B—Si1—O5Bⁱ	71.6 (4)	N1—C1—C2	122.0 (9)
O5B—Si1—O5Bⁱ	180.0 (5)	N1—C1—H1	119.0
O5A—Si1—O20Aⁱ	69.8 (4)	C2—C1—H1	119.0
O5Aⁱ—Si1—O20Aⁱ	110.2 (4)	C3—C2—C1	119.0 (11)
O20Bⁱ—Si1—O20Aⁱ	71.9 (4)	C3—C2—H2	120.5
O20B—Si1—O20Aⁱ	108.1 (4)	C1—C2—H2	120.5
O5B—Si1—O20Aⁱ	106.3 (4)	C2—C3—C4	121.0 (12)
O5Bⁱ—Si1—O20Aⁱ	73.7 (4)	C2—C3—H3	119.5
O5A—Si1—O20A	110.2 (4)	C4—C3—H3	119.5
O5Aⁱ—Si1—O20A	69.8 (4)	C3—C4—C5	118.2 (12)
O20Bⁱ—Si1—O20A	108.1 (4)	C3—C4—H4	120.9
O20B—Si1—O20A	71.9 (4)	C5—C4—H4	120.9
O5B—Si1—O20A	73.7 (4)	N1—C5—C4	123.6 (11)
O5Bⁱ—Si1—O20A	106.3 (4)	N1—C5—C6	115.0 (8)
O20Aⁱ—Si1—O20A	180.000 (2)	C4—C5—C6	121.4 (10)
N5—Zn1—N2	95.8 (3)	N2—C6—C7	108.9 (11)
N5—Zn1—N7	90.8 (3)	N2—C6—C5	118.0 (8)
N2—Zn1—N7	94.1 (2)	C7—C6—C5	133.1 (12)
N5—Zn1—N1	169.1 (3)	C8—C7—C6	103.9 (11)
N2—Zn1—N1	76.2 (3)	C8—C7—H7	128.0
N7—Zn1—N1	97.0 (2)	C6—C7—H7	128.0
N5—Zn1—N8	95.5 (3)	N3—C8—C7	107.0 (10)
N2—Zn1—N8	165.1 (3)	N3—C8—H8	126.5
N7—Zn1—N8	76.1 (2)	C7—C8—H8	126.5
N1—Zn1—N8	93.7 (3)	N4—C9—C10	123.2 (10)
N5—Zn1—N4	75.6 (3)	N4—C9—H9	118.4
N2—Zn1—N4	98.3 (3)	C10—C9—H9	118.4
N7—Zn1—N4	162.4 (3)	C9—C10—C11	119.5 (11)
N1—Zn1—N4	98.1 (3)	C9—C10—H10	120.2
N8—Zn1—N4	93.8 (2)	C11—C10—H10	120.3
O2—Mo1—O13	103.6 (4)	C10—C11—C12	118.4 (10)
O2—Mo1—O14	101.5 (4)	C10—C11—H11	120.8
O13—Mo1—O14	95.7 (3)	C12—C11—H11	120.8
O2—Mo1—O16A	107.3 (4)	C13—C12—C11	118.9 (11)
O13—Mo1—O16A	93.9 (4)	C13—C12—H12	120.5
O14—Mo1—O16A	146.5 (4)	C11—C12—H12	120.5
O2—Mo1—O11	96.6 (3)	N4—C13—C12	122.9 (9)
O13—Mo1—O11	158.8 (4)	N4—C13—C14	114.1 (8)
O14—Mo1—O11	86.5 (3)	C12—C13—C14	123.0 (9)
O16A—Mo1—O11	73.7 (4)	N5—C14—C15	110.0 (8)
O2—Mo1—O16B	89.3 (4)	N5—C14—C13	118.3 (8)
O13—Mo1—O16B	87.5 (4)	C15—C14—C13	131.6 (9)
O14—Mo1—O16B	167.7 (4)	C16—C15—C14	106.2 (9)
O16A—Mo1—O16B	21.2 (3)	C16—C15—H15	126.9
O11—Mo1—O16B	86.3 (4)	C14—C15—H15	126.9
O2—Mo1—O20A	157.2 (3)	C15—C16—N6	107.0 (9)
O13—Mo1—O20A	64.1 (4)	C15—C16—H16	126.5
O14—Mo1—O20A	98.9 (3)	N6—C16—H16	126.5
O16A—Mo1—O20A	57.4 (4)	N7—C17—C18	122.9 (7)
O11—Mo1—O20A	94.8 (3)	N7—C17—H17	118.5
O16B—Mo1—O20A	71.8 (4)	C18—C17—H17	118.5
O2—Mo1—O20B	153.6 (3)	C19—C18—C17	119.8 (8)
O13—Mo1—O20B	100.2 (4)	C19—C18—H18	120.1
O14—Mo1—O20B	64.7 (3)	C17—C18—H18	120.1
O16A—Mo1—O20B	82.1 (4)	C18—C19—C20	118.7 (8)
O11—Mo1—O20B	61.7 (3)	C18—C19—H19	120.7
O16B—Mo1—O20B	103.1 (4)	C20—C19—H19	120.7
O20A—Mo1—O20B	47.6 (3)	C19—C20—C21	119.9 (8)
O8—Mo2—O11	103.3 (4)	C19—C20—H20	120.0
O8—Mo2—O9	100.7 (3)	C21—C20—H20	120.1
O11—Mo2—O9	96.4 (3)	N7—C21—C20	121.2 (7)
O8—Mo2—O3	99.0 (4)	N7—C21—C22	115.1 (6)
O11—Mo2—O3	89.2 (3)	C20—C21—C22	123.6 (7)
O9—Mo2—O3	157.6 (4)	N8—C22—C23	110.8 (7)
O8—Mo2—O7	97.3 (3)	N8—C22—C21	118.9 (7)
O11—Mo2—O7	158.0 (3)	C23—C22—C21	130.3 (7)
O9—Mo2—O7	86.9 (2)	C24—C23—C22	104.5 (8)
O3—Mo2—O7	80.2 (3)	C24—C23—H23	127.8
O8—Mo2—O20B	158.3 (3)	C22—C23—H23	127.8
O11—Mo2—O20B	66.1 (3)	N9—C24—C23	107.4 (8)
O9—Mo2—O20B	99.3 (3)	N9—C24—H24	126.3
O3—Mo2—O20B	63.3 (3)	C23—C24—H24	126.3
O7—Mo2—O20B	91.9 (3)	C5—N1—C1	116.2 (8)
O8—Mo2—O5A	155.9 (3)	C5—N1—Zn1	115.4 (7)
O11—Mo2—O5A	97.9 (3)	C1—N1—Zn1	127.9 (6)
O9—Mo2—O5A	65.3 (3)	N3—N2—C6	107.0 (8)
O3—Mo2—O5A	92.5 (3)	N3—N2—Zn1	138.0 (7)
O7—Mo2—O5A	63.7 (3)	C6—N2—Zn1	115.0 (7)
O20B—Mo2—O5A	44.2 (3)	C8—N3—N2	113.1 (10)
O1—Mo3—O16A	112.4 (5)	C8—N3—H3A	123.5
O1—Mo3—O19	101.7 (3)	N2—N3—H3A	123.5
O16A—Mo3—O19	85.2 (5)	C9—N4—C13	117.0 (8)
O1—Mo3—O17ⁱ	99.5 (4)	C9—N4—Zn1	127.0 (7)
O16A—Mo3—O17ⁱ	91.7 (4)	C13—N4—Zn1	115.9 (6)
O19—Mo3—O17ⁱ	158.1 (4)	C14—N5—N6	105.1 (7)
O1—Mo3—O15ⁱ	100.0 (4)	C14—N5—Zn1	116.0 (6)
O16A—Mo3—O15ⁱ	147.7 (5)	N6—N5—Zn1	138.9 (6)
O19—Mo3—O15ⁱ	87.8 (3)	C16—N6—N5	111.7 (8)
O17ⁱ—Mo3—O15ⁱ	83.3 (3)	C16—N6—H6	124.1
O1—Mo3—O16B	92.7 (4)	N5—N6—H6	124.2
O16A—Mo3—O16B	22.0 (4)	C17—N7—C21	117.4 (6)
O19—Mo3—O16B	98.9 (4)	C17—N7—Zn1	127.0 (5)
O17ⁱ—Mo3—O16B	85.3 (4)	C21—N7—Zn1	115.6 (5)
O15ⁱ—Mo3—O16B	164.2 (5)	C22—N8—N9	105.3 (6)
O1—Mo3—O20A	155.4 (3)	C22—N8—Zn1	114.1 (5)
O16A—Mo3—O20A	57.0 (4)	N9—N8—Zn1	140.3 (5)
O19—Mo3—O20A	99.4 (3)	C24—N9—N8	112.1 (7)
O17ⁱ—Mo3—O20A	61.4 (3)	C24—N9—H9A	124.0
O15ⁱ—Mo3—O20A	93.3 (4)	N8—N9—H9A	124.0
O16B—Mo3—O20A	71.5 (4)	Mo5—O3—Mo2	136.1 (5)
O1—Mo3—O5B	155.5 (3)	Si1—O5A—O20B	57.2 (4)
O16A—Mo3—O5B	86.5 (5)	Si1—O5A—O5B	57.6 (4)
O19—Mo3—O5B	63.0 (3)	O20B—O5A—O5B	94.8 (5)
O17ⁱ—Mo3—O5B	95.2 (4)	Si1—O5A—Mo2	123.3 (4)
O15ⁱ—Mo3—O5B	62.4 (3)	O20B—O5A—Mo2	66.2 (4)
O16B—Mo3—O5B	108.0 (4)	O5B—O5A—Mo2	128.3 (5)
O20A—Mo3—O5B	48.5 (3)	Si1—O5A—Mo4	122.7 (4)
O4—Mo4—O18	102.6 (4)	O20B—O5A—Mo4	135.5 (5)
O4—Mo4—O10	102.2 (3)	O5B—O5A—Mo4	65.3 (4)
O18—Mo4—O10	93.9 (3)	Mo2—O5A—Mo4	94.4 (3)
O4—Mo4—O19	98.9 (4)	Si1—O5A—Mo6	121.6 (4)
O18—Mo4—O19	88.9 (3)	O20B—O5A—Mo6	126.0 (5)
O10—Mo4—O19	157.6 (3)	O5B—O5A—Mo6	132.3 (5)
O4—Mo4—O9	98.7 (3)	Mo2—O5A—Mo6	93.6 (3)
O18—Mo4—O9	158.1 (4)	Mo4—O5A—Mo6	93.3 (3)
O10—Mo4—O9	86.6 (2)	Si1—O5B—O5A	54.0 (4)
O19—Mo4—O9	82.8 (3)	Si1—O5B—Mo4	123.9 (4)
O4—Mo4—O5B	156.9 (3)	O5A—O5B—Mo4	70.1 (4)
O18—Mo4—O5B	64.1 (4)	Si1—O5B—Mo5ⁱ	119.9 (4)
O10—Mo4—O5B	97.6 (3)	O5A—O5B—Mo5ⁱ	136.7 (5)
O19—Mo4—O5B	63.7 (3)	Mo4—O5B—Mo5ⁱ	96.8 (3)
O9—Mo4—O5B	94.1 (3)	Si1—O5B—Mo3	119.1 (4)
O4—Mo4—O5A	157.5 (3)	O5A—O5B—Mo3	127.3 (5)
O18—Mo4—O5A	97.2 (4)	Mo4—O5B—Mo3	96.4 (3)
O10—Mo4—O5A	65.5 (3)	Mo5ⁱ—O5B—Mo3	94.3 (3)
O19—Mo4—O5A	92.2 (3)	Mo6—O7—Mo2	136.5 (4)
O9—Mo4—O5A	63.1 (3)	Mo2—O9—Mo4	137.1 (4)
O5B—Mo4—O5A	44.7 (3)	Mo4—O10—Mo6	136.8 (4)
O6—Mo5—O3	100.1 (4)	Mo2—O11—Mo1	136.3 (4)
O6—Mo5—O15	101.9 (4)	Mo1—O13—Mo6ⁱ	137.0 (5)
O3—Mo5—O15	94.3 (3)	Mo1—O14—Mo5	137.3 (4)
O6—Mo5—O18ⁱ	100.4 (4)	Mo5—O15—Mo3ⁱ	138.8 (5)
O3—Mo5—O18ⁱ	158.4 (4)	O16B—O16A—Mo3	93.4 (18)
O15—Mo5—O18ⁱ	87.9 (3)	O16B—O16A—Mo1	90.9 (17)
O6—Mo5—O14	99.5 (3)	Mo3—O16A—Mo1	143.4 (7)
O3—Mo5—O14	88.4 (3)	O16A—O16B—Mo3	64.7 (16)
O15—Mo5—O14	157.6 (4)	O16A—O16B—Mo1	67.9 (16)
O18ⁱ—Mo5—O14	81.7 (3)	Mo3—O16B—Mo1	120.9 (6)
O6—Mo5—O20B	156.1 (3)	Mo6—O17—Mo3ⁱ	138.7 (5)
O3—Mo5—O20B	64.2 (3)	Mo4—O18—Mo5ⁱ	137.2 (5)
O15—Mo5—O20B	97.4 (4)	Mo3—O19—Mo4	136.5 (4)
O18ⁱ—Mo5—O20B	94.2 (4)	Si1—O20A—Mo6ⁱ	122.5 (4)
O14—Mo5—O20B	63.9 (3)	Si1—O20A—Mo1	121.2 (4)
O6—Mo5—O5Bⁱ	156.3 (3)	Mo6ⁱ—O20A—Mo1	97.2 (3)
O3—Mo5—O5Bⁱ	100.2 (3)	Si1—O20A—Mo3	118.6 (4)
O15—Mo5—O5Bⁱ	64.5 (3)	Mo6ⁱ—O20A—Mo3	95.8 (3)
O18ⁱ—Mo5—O5Bⁱ	61.5 (3)	Mo1—O20A—Mo3	95.4 (3)
O14—Mo5—O5Bⁱ	93.2 (3)	Si1—O20B—O5A	54.8 (4)
O20B—Mo5—O5Bⁱ	47.2 (3)	Si1—O20B—Mo2	124.2 (5)
O12—Mo6—O7	102.9 (3)	O5A—O20B—Mo2	69.6 (4)
O12—Mo6—O17	102.1 (4)	Si1—O20B—Mo5	121.0 (4)
O7—Mo6—O17	95.2 (3)	O5A—O20B—Mo5	129.6 (5)
O12—Mo6—O10	98.4 (3)	Mo2—O20B—Mo5	95.9 (3)
O7—Mo6—O10	89.9 (2)	Si1—O20B—Mo1	119.0 (4)
O17—Mo6—O10	157.1 (4)	O5A—O20B—Mo1	133.9 (5)
O12—Mo6—O13ⁱ	98.4 (4)	Mo2—O20B—Mo1	95.7 (3)
O7—Mo6—O13ⁱ	157.9 (4)	Mo5—O20B—Mo1	94.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9A···O16Aⁱⁱ	0.86	2.20	2.972 (14)	149
N9—H9A···O16Bⁱⁱ	0.86	1.88	2.728 (13)	168
N6—H6···O2W	0.86	1.95	2.770 (11)	160
N3—H3A···O3W	0.86	2.02	2.870 (15)	167

Symmetry code: (ii) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₇N₃)₃]₂[SiMo₁₂O₄₀]·6H₂O
M_r	2929.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.824 (4), 16.365 (3), 27.749 (6)
β (°)	104.74 (3)
V (Å³)	8267 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.44
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.758, 0.829
No. of measured, independent and observed [I > 2σ(I)'] reflections	27894, 7081, 5632
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.112, 1.00
No. of reflections	7081
No. of parameters	601
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.040P)² + 90.4942P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.22, −0.63

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

Selected bond lengths (Å) top

Si1—O5A	1.581 (8)	Zn1—N2	2.138 (8)
Si1—O20B	1.628 (8)	Zn1—N7	2.167 (6)
Si1—O5B	1.650 (9)	Zn1—N1	2.176 (8)
Si1—O20A	1.674 (8)	Zn1—N8	2.186 (7)
Zn1—N5	2.134 (7)	Zn1—N4	2.196 (7)