Bis{tris­[3-(2-pyrid­yl)-1H-pyrazole]cadmium(II)} dodeca­molybdo(V,VI)phosphate hexa­hydrate

Hao, L.; Wang, Y.; Zhang, X.; Chen, J.; Zhang, X.

doi:10.1107/S1600536810004307

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m268-m269

doi:10.1107/S1600536810004307

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Bis{tris[3-(2-pyridyl)-1H-pyrazole]cadmium(II)} dodecamolybdo(V,VI)phosphate hexahydrate

Lujiang Hao,^a Yan Wang,^a Xiaofei Zhang,^a Jiangkui Chen ^a and Xiutang Zhang ^b,^c ^*

^aCollege of Food and Biological Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China, ^bAdvanced Material Institute of Research, Department of Chemistry and Chemical Engineering, ShanDong Institute of Education, Jinan 250013, People's Republic of China, and ^cCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: xiutangzhang@yahoo.com.cn

(Received 26 January 2010; accepted 3 February 2010; online 6 February 2010)

The hydrothermally prepared title compound, [Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O, is isotypic with its Mn^II analogue [Hao et al. (2010 ). Acta Cryst. E66, m231–m232]. The Cd^II cation is in a distorted octahedral environment, coordinated by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands. In the reduced heteropolyanion, two O atoms of the central PO₄ group ( $[\overline{1}]$ symmetry) are equally disordered about an inversion centre. N—H⋯O and O—H⋯O hydrogen bonds contribute to the crystal packing. Compared with the Mn^II analogue, the Cd—N bond lengths are longer at 2.316 (7)–2.334 (6) Å, versus 2.224 (6)–2.283 (5) Å for Mn—N, whereas all other bond lengths and angles and the hydrogen-bonding motifs are very similar in the two structures.

Related literature

For the isotypic Mn^II compound, see Hao et al. (2010). For general background to polyoxometallates, see: Pope & Müller (1991 ). For polyoxometallates modified with amines, see: Zhang, Dou et al. (2009 ); Zhang, Wei et al. (2009 ). For the structures of other reduced heteropolyanions [PMo₁₂O₄₀]⁴⁻, see: Artero & Proust (2000 ); Kurmoo et al. (1998 ); Niu et al. (1999 ). For the role of amines in hydrothermal synthesis, see: Yang et al. (2003 ).

Experimental

Crystal data

[Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r = 3026.14
Monoclinic, C 2/c
a = 19.0326 (14) Å
b = 16.4779 (12) Å
c = 27.267 (2) Å
β = 105.187 (1)°
V = 8252.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 2.39 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.763, T_max = 0.832
21276 measured reflections
7254 independent reflections
6211 reflections with I > 2σ(I)
R_int = 0.105

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.125
S = 1.00
7254 reflections
592 parameters
H-atom parameters constrained
Δρ_max = 1.55 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N5	2.316 (7)
Cd1—N8	2.325 (7)
Cd1—N1	2.342 (6)
Cd1—N2	2.347 (6)
Cd1—N4	2.334 (7)
Cd1—N7	2.334 (6)
P1—O21Aⁱ	1.516 (8)
P1—O21Bⁱ	1.493 (8)
P1—O19Bⁱ	1.520 (7)
P1—O19Aⁱ	1.551 (7)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O17ⁱⁱ	0.86	1.95	2.803 (8)	171
N6—H6⋯O2W	0.86	2.25	3.102 (17)	173
N9—H9A⋯O1W	0.86	1.96	2.790 (11)	163
Symmetry code: (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004307/wm2302sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004307/wm2302Isup2.hkl

checkCIF report

Comment top

The design and synthesis of polyoxometalates has attracted continuous research interest not only because of their appealing structural and topological novelties, but also due to their interesting optical, electronic, magnetic, and catalytic properties, as well as their potential medical applications (Pope & 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 Fig. 1, the asymmetric unit of the title compound consists of three subunits, viz. of a complex [Cd(C₈H₇N₃)₃]²⁺ cation, half of a a [PMo₁₂O₄₀]^4- heteropolyanion and of three uncoordinated water molecules. The cadmium(II) ion is distorted octahedrally coordinated by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands.

The heteropolyanion [PMo₁₂O₄₀]^4- anion is an one-electron reduced derivative of [PMo₁₂O₄₀]^3-, similar to anions with different counter cations as reported by Artero & Proust (2000); Kurmoo et al. (1998); Niu et al. (1999). The employed organic ligand appears to adjust the pH value, and additionally supplies reducing electrons, which is a commonly observed feature of hydrothermal syntheses when organic amines are used to prepare various hybrid materials, zeolites or metal phosphates (Yang et al., 2003).

In the Keggin-type heteropolyanion, each Mo atom is surrounded by six O atoms and the P 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 PO₄ 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 P—O bond distances are in the normal range of 1.516 (8)–1.551 (7) Å. The Mo—O bond distances vary widely from 1.637 (4) to 2.509 (7) Å. The shortest Mo—O bonds are in the range of 1.637 (4)–1.661 (4) Å for the terminal oxygen atoms. The longest Mo—O lengths are in the range of 2.420 (7)–2.509 (7) Å for those oxygen atoms connected with both Mo and P 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).

The crystal structure of [(Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ is isotypic with the Mn²⁺ analogue, [(Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ (Hao et al., 2010). In comparison with the Mn(II) analogue, the Cd—N bond lengths are longer, 2.316 (7)–2.334 (6) Å versus 2.224 (6)–2.283 (5) Å for Mn—N, whereas all other bond lengths, angles and the hydrogen bonding motifs are very similar in the two structures.

Related literature top

For the isotypic Mn^II compound, see Hao et al. (2010). For general background to polyoxometallates, see: Pope & Müller (1991). For polyoxometallates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei et al. (2009). For the structure of another reduced heteropolyanion [PMo₁₂O₄₀]^4-, see: Artero & Proust (2000); Kurmoo et al. (1998); Niu et al. (1999). For the role of amines in hydrothermal synthesis, see: Yang et al. (2003).

Experimental top

A mixture of 3-(2-pyridyl)-1H-pyrazole (0.5 mmoL 0.07 g), sodium molybdate (0.4 mmoL, 0.10 g), cadmium sulfate (0.25 mmol, 0.04 g), and dipotassium hydrogenphosphate (0.22 mmol, 0.05 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. C₄₈H₅₄Cd₂Mo₁₂N₁₈O₄₆P: C, 19.05; H, 1.80; N, 8.33. Found: C, 18.95; H, 1.62; N, 7.03 %. IR(cm^-1): 3312, 3136, 1604, 1457, 1503, 1429, 1097, 1060, 950, 811, 765, 590, 498, 405.

TGA curve shows a separation of lattice water molecules and the organic ligands above 350 and 588 K, respectively. The overall thermal decomposition process can be described by the followed equation: 4C₄₈H₅₄Cd₂Mo₁₂N₁₈O₄₆P + 325O₂ = 108H₂O + 192CO₂ + 36N₂O₅ + 8CdO + 2P₂O₅ + 48MoO₃

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The 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]cadmium(II)} dodecamolybdo(V,VI)phosphate hexahydrate top

Crystal data top

[Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	F(000) = 5804
M_r = 3026.14	D_x = 2.436 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5617 reflections
a = 19.0326 (14) Å	θ = 2.5–28.4°
b = 16.4779 (12) Å	µ = 2.39 mm⁻¹
c = 27.267 (2) Å	T = 293 K
β = 105.187 (1)°	Block, colourless
V = 8252.8 (10) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7254 independent reflections
Radiation source: fine-focus sealed tube	6211 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.105
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→22
T_min = 0.763, T_max = 0.832	k = −19→13
21276 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.057P)² + 46.070P] where P = (F_o² + 2F_c²)/3
7254 reflections	(Δ/σ)_max = 0.001
592 parameters	Δρ_max = 1.55 e Å⁻³
0 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

[Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	V = 8252.8 (10) Å³
M_r = 3026.14	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.0326 (14) Å	µ = 2.39 mm⁻¹
b = 16.4779 (12) Å	T = 293 K
c = 27.267 (2) Å	0.12 × 0.10 × 0.08 mm
β = 105.187 (1)°

Data collection top

Bruker APEXII CCD diffractometer	7254 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	6211 reflections with I > 2σ(I)
T_min = 0.763, T_max = 0.832	R_int = 0.105
21276 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.057P)² + 46.070P] where P = (F_o² + 2F_c²)/3
7254 reflections	Δρ_max = 1.55 e Å⁻³
592 parameters	Δρ_min = −0.82 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 > 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	Occ. (<1)
C1	0.2003 (5)	0.9040 (4)	0.0936 (3)	0.0523 (18)
H1	0.2436	0.9008	0.0841	0.063*
C2	0.1407 (5)	0.9372 (5)	0.0604 (3)	0.055 (2)
H2	0.1437	0.9559	0.0289	0.065*
C3	0.0772 (4)	0.9426 (5)	0.0738 (3)	0.0529 (19)
H3	0.0363	0.9655	0.0517	0.063*
C4	0.0741 (4)	0.9138 (5)	0.1202 (2)	0.0501 (18)
H4	0.0308	0.9162	0.1301	0.060*
C5	0.1369 (4)	0.8809 (4)	0.1527 (2)	0.0371 (14)
C6	0.1383 (4)	0.8536 (4)	0.2040 (2)	0.0416 (15)
C7	0.0812 (5)	0.8491 (7)	0.2271 (3)	0.070 (3)
H7	0.0327	0.8633	0.2136	0.084*
C8	0.1136 (6)	0.8186 (7)	0.2744 (3)	0.078 (3)
H8	0.0903	0.8076	0.2997	0.094*
C9	0.3372 (5)	0.9934 (5)	0.2687 (3)	0.061 (2)
H9	0.3085	0.9745	0.2891	0.073*
C10	0.3625 (6)	1.0678 (6)	0.2741 (3)	0.072 (3)
H10	0.3494	1.1012	0.2977	0.087*
C11	0.4017 (9)	1.0952 (10)	0.2501 (6)	0.125 (5)
H11	0.4196	1.1477	0.2570	0.150*
C12	0.4183 (7)	1.0575 (7)	0.2181 (5)	0.093 (4)
H12	0.4480	1.0809	0.1999	0.112*
C13	0.3945 (4)	0.9806 (5)	0.2078 (3)	0.055 (2)
C14	0.4148 (4)	0.9338 (6)	0.1693 (3)	0.058 (2)
C15	0.4670 (6)	0.9529 (8)	0.1422 (4)	0.094 (3)
H15	0.4966	0.9985	0.1451	0.113*
C16	0.4624 (6)	0.8789 (11)	0.1064 (4)	0.132 (6)
H16	0.4884	0.8698	0.0824	0.158*
C17	0.4153 (5)	0.7420 (6)	0.2994 (3)	0.066 (2)
H17	0.4208	0.7957	0.3102	0.079*
C18	0.4552 (6)	0.6849 (7)	0.3306 (4)	0.084 (3)
H18	0.4860	0.6987	0.3620	0.100*
C19	0.4482 (7)	0.6075 (7)	0.3142 (4)	0.097 (3)
H19	0.4756	0.5670	0.3341	0.116*
C20	0.4011 (7)	0.5879 (6)	0.2683 (4)	0.088 (3)
H20	0.3962	0.5345	0.2569	0.106*
C21	0.3613 (4)	0.6494 (5)	0.2394 (3)	0.0510 (18)
C22	0.3078 (5)	0.6333 (5)	0.1910 (3)	0.0537 (19)
C23	0.2869 (6)	0.5616 (6)	0.1655 (3)	0.070 (2)
H23	0.3043	0.5099	0.1757	0.084*
C24	0.2367 (7)	0.5815 (6)	0.1233 (4)	0.082 (3)
H24	0.2127	0.5459	0.0979	0.099*
Cd1	0.29910 (3)	0.82317 (3)	0.19989 (2)	0.04993 (16)
Mo1	0.24356 (3)	0.14473 (4)	0.112775 (19)	0.03963 (16)
Mo2	0.18969 (3)	0.45389 (3)	−0.01844 (2)	0.03810 (16)
Mo3	0.42042 (3)	0.31320 (4)	−0.01864 (2)	0.03638 (15)
Mo4	0.35147 (3)	0.40777 (3)	0.07580 (2)	0.03486 (15)
Mo5	0.41452 (3)	0.20314 (4)	0.09234 (2)	0.03702 (16)
Mo6	0.17953 (3)	0.34705 (4)	0.09257 (2)	0.03701 (16)
N1	0.1987 (3)	0.8760 (3)	0.1393 (2)	0.0404 (13)
N2	0.1995 (3)	0.8305 (4)	0.2354 (2)	0.0449 (14)
N3	0.1831 (4)	0.8077 (4)	0.2780 (2)	0.0535 (17)
H3A	0.2139	0.7885	0.3044	0.064*
N4	0.3528 (4)	0.9451 (4)	0.2340 (3)	0.0599 (17)
N5	0.3811 (4)	0.8630 (5)	0.1550 (3)	0.0623 (18)
N6	0.4094 (5)	0.8280 (6)	0.1188 (3)	0.088 (3)
H6	0.3967	0.7813	0.1054	0.106*
N7	0.3687 (4)	0.7268 (4)	0.2543 (3)	0.0540 (16)
N8	0.2707 (4)	0.6949 (4)	0.1647 (2)	0.0558 (16)
N9	0.2269 (4)	0.6618 (4)	0.1238 (3)	0.0661 (19)
H9A	0.1962	0.6884	0.1006	0.079*
O1	0.4052 (4)	0.3934 (3)	0.02395 (19)	0.0642 (16)
O2	0.1518 (3)	0.3937 (4)	0.13815 (18)	0.0588 (14)
O3	0.2429 (3)	0.0954 (3)	0.16477 (17)	0.0559 (14)
O4	0.3462 (3)	0.1774 (4)	0.1271 (2)	0.0707 (17)
O5	0.4032 (4)	0.3144 (3)	0.1061 (2)	0.0695 (17)
O6	0.2803 (3)	0.3886 (4)	0.1088 (2)	0.0637 (15)
O7	0.4496 (4)	0.2421 (3)	0.0358 (2)	0.0658 (16)
O8	0.4017 (3)	0.4809 (3)	0.11005 (19)	0.0580 (14)
O9	0.3983 (4)	0.2149 (3)	−0.0612 (2)	0.084 (2)
O10	0.4989 (3)	0.3398 (3)	−0.0294 (2)	0.0556 (13)
O11	0.2845 (3)	0.4671 (4)	0.0255 (2)	0.0693 (16)
O12	0.1054 (3)	0.3955 (4)	−0.0555 (2)	0.076 (2)
O13	0.1468 (4)	0.1374 (3)	0.0742 (3)	0.084 (2)
O14	0.1593 (3)	0.4231 (4)	0.0411 (2)	0.0680 (16)
O15	0.1625 (3)	0.5493 (3)	−0.0258 (2)	0.0643 (15)
O16	0.2700 (4)	0.0629 (4)	0.0726 (2)	0.085 (2)
O17	0.2257 (3)	0.2543 (3)	0.1295 (2)	0.0758 (18)
O18	0.4915 (3)	0.1816 (4)	0.13433 (18)	0.0575 (14)
O19A	0.2060 (4)	0.2389 (5)	0.0400 (3)	0.0249 (16)	0.50
O21A	0.3254 (4)	0.2809 (5)	0.0264 (3)	0.0286 (17)	0.50
O19B	0.2893 (4)	0.1874 (4)	0.0384 (3)	0.0269 (16)	0.50
O21B	0.2466 (4)	0.3295 (5)	0.0256 (3)	0.0283 (17)	0.50
O1W	0.1149 (5)	0.7162 (5)	0.0426 (3)	0.107 (3)
O2W	0.3647 (8)	0.6659 (10)	0.0613 (6)	0.207 (7)
O3W	0.5313 (8)	0.0724 (8)	0.0267 (7)	0.220 (8)
P1	0.2500	0.2500	0.0000	0.0216 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.059 (5)	0.049 (4)	0.052 (4)	−0.001 (4)	0.022 (4)	0.016 (3)
C2	0.065 (6)	0.054 (4)	0.042 (4)	−0.013 (4)	0.010 (4)	0.013 (4)
C3	0.041 (4)	0.059 (5)	0.047 (4)	−0.006 (4)	−0.008 (3)	0.011 (4)
C4	0.035 (4)	0.075 (5)	0.039 (4)	−0.001 (4)	0.006 (3)	0.006 (4)
C5	0.032 (4)	0.038 (3)	0.040 (3)	−0.003 (3)	0.008 (3)	0.000 (3)
C6	0.034 (4)	0.054 (4)	0.036 (3)	0.002 (3)	0.008 (3)	0.004 (3)
C7	0.047 (5)	0.117 (8)	0.050 (5)	0.014 (5)	0.021 (4)	0.019 (5)
C8	0.069 (7)	0.124 (9)	0.050 (5)	0.015 (6)	0.030 (4)	0.025 (5)
C9	0.077 (6)	0.051 (5)	0.066 (5)	0.010 (4)	0.040 (4)	0.018 (4)
C10	0.083 (7)	0.071 (6)	0.053 (5)	−0.002 (5)	0.001 (4)	−0.001 (5)
C11	0.118 (9)	0.118 (9)	0.122 (8)	0.001 (7)	0.002 (7)	0.010 (7)
C12	0.087 (8)	0.080 (7)	0.086 (7)	−0.020 (6)	−0.026 (6)	0.035 (6)
C13	0.033 (4)	0.055 (5)	0.067 (5)	0.000 (4)	−0.005 (3)	0.020 (4)
C14	0.033 (4)	0.071 (5)	0.065 (5)	−0.001 (4)	0.003 (3)	0.028 (4)
C15	0.054 (6)	0.122 (7)	0.099 (6)	−0.014 (5)	0.006 (5)	0.051 (6)
C16	0.062 (6)	0.288 (18)	0.060 (6)	0.104 (9)	0.043 (5)	0.069 (9)
C17	0.065 (6)	0.066 (5)	0.058 (5)	0.002 (5)	0.001 (4)	0.002 (4)
C18	0.075 (7)	0.091 (8)	0.073 (6)	0.001 (6)	−0.001 (5)	0.015 (6)
C19	0.090 (7)	0.086 (6)	0.098 (6)	0.007 (5)	−0.003 (5)	0.037 (6)
C20	0.109 (9)	0.052 (5)	0.091 (7)	0.019 (5)	0.004 (6)	0.017 (5)
C21	0.052 (5)	0.047 (4)	0.059 (5)	0.015 (4)	0.024 (4)	0.012 (4)
C22	0.063 (5)	0.044 (4)	0.060 (5)	0.015 (4)	0.026 (4)	0.004 (4)
C23	0.089 (7)	0.056 (5)	0.063 (5)	0.013 (5)	0.018 (5)	−0.001 (4)
C24	0.115 (9)	0.061 (6)	0.073 (6)	0.001 (6)	0.029 (6)	−0.023 (5)
Cd1	0.0367 (3)	0.0416 (3)	0.0716 (4)	0.0045 (2)	0.0144 (3)	0.0096 (3)
Mo1	0.0479 (4)	0.0429 (3)	0.0267 (3)	−0.0076 (3)	0.0072 (2)	0.0037 (2)
Mo2	0.0380 (3)	0.0301 (3)	0.0478 (3)	0.0041 (2)	0.0139 (2)	−0.0001 (2)
Mo3	0.0245 (3)	0.0445 (3)	0.0420 (3)	−0.0052 (2)	0.0119 (2)	−0.0008 (2)
Mo4	0.0295 (3)	0.0380 (3)	0.0363 (3)	−0.0073 (2)	0.0071 (2)	−0.0097 (2)
Mo5	0.0251 (3)	0.0505 (3)	0.0324 (3)	0.0016 (2)	0.0020 (2)	0.0006 (2)
Mo6	0.0360 (3)	0.0450 (3)	0.0312 (3)	0.0049 (2)	0.0107 (2)	−0.0108 (2)
N1	0.037 (3)	0.042 (3)	0.044 (3)	−0.001 (3)	0.014 (2)	0.006 (3)
N2	0.040 (3)	0.055 (4)	0.038 (3)	0.002 (3)	0.007 (2)	0.008 (3)
N3	0.055 (4)	0.067 (4)	0.035 (3)	0.001 (3)	0.006 (3)	0.013 (3)
N4	0.046 (4)	0.049 (4)	0.087 (5)	−0.002 (3)	0.022 (4)	0.006 (4)
N5	0.042 (4)	0.070 (5)	0.080 (5)	0.011 (3)	0.026 (3)	0.013 (4)
N6	0.076 (6)	0.094 (6)	0.089 (6)	0.027 (5)	0.012 (5)	−0.009 (5)
N7	0.048 (4)	0.052 (4)	0.062 (4)	0.005 (3)	0.015 (3)	0.008 (3)
N8	0.053 (4)	0.054 (4)	0.057 (4)	0.004 (3)	0.008 (3)	−0.004 (3)
N9	0.068 (5)	0.066 (4)	0.061 (4)	0.006 (4)	0.010 (4)	−0.004 (4)
O1	0.098 (4)	0.057 (3)	0.051 (3)	0.032 (3)	0.043 (3)	0.019 (2)
O2	0.046 (3)	0.091 (4)	0.046 (3)	0.002 (3)	0.023 (2)	−0.026 (3)
O3	0.058 (3)	0.073 (4)	0.034 (2)	−0.016 (3)	0.006 (2)	0.013 (2)
O4	0.068 (4)	0.080 (4)	0.081 (4)	−0.038 (3)	0.047 (3)	−0.041 (3)
O5	0.106 (5)	0.058 (3)	0.064 (3)	0.032 (3)	0.057 (3)	0.017 (3)
O6	0.037 (3)	0.096 (4)	0.058 (3)	0.000 (3)	0.014 (2)	0.030 (3)
O7	0.103 (4)	0.055 (3)	0.056 (3)	0.032 (3)	0.050 (3)	0.012 (3)
O8	0.061 (4)	0.055 (3)	0.051 (3)	−0.024 (3)	0.004 (2)	−0.009 (3)
O9	0.081 (5)	0.042 (3)	0.090 (4)	0.010 (3)	−0.047 (4)	−0.019 (3)
O10	0.040 (3)	0.058 (3)	0.079 (3)	−0.007 (2)	0.033 (3)	−0.010 (3)
O11	0.038 (3)	0.111 (4)	0.060 (3)	0.006 (3)	0.015 (2)	0.037 (3)
O12	0.069 (4)	0.094 (5)	0.083 (4)	−0.043 (4)	0.051 (3)	−0.052 (4)
O13	0.080 (5)	0.040 (3)	0.095 (4)	0.006 (3)	−0.044 (4)	−0.017 (3)
O14	0.032 (3)	0.112 (4)	0.058 (3)	−0.001 (3)	0.008 (2)	0.029 (3)
O15	0.052 (4)	0.039 (3)	0.099 (4)	0.010 (2)	0.015 (3)	0.008 (3)
O16	0.074 (4)	0.106 (5)	0.094 (4)	−0.059 (4)	0.056 (4)	−0.062 (4)
O17	0.067 (4)	0.045 (3)	0.083 (4)	0.002 (3)	−0.038 (3)	−0.014 (3)
O18	0.042 (3)	0.078 (4)	0.044 (3)	0.017 (3)	−0.003 (2)	0.002 (3)
O19A	0.024 (4)	0.029 (4)	0.021 (4)	−0.003 (3)	0.005 (3)	−0.011 (3)
O21A	0.023 (4)	0.034 (4)	0.029 (4)	−0.006 (3)	0.008 (3)	−0.004 (3)
O19B	0.027 (4)	0.024 (4)	0.030 (4)	−0.003 (3)	0.007 (3)	0.001 (3)
O21B	0.022 (4)	0.035 (4)	0.029 (4)	−0.002 (3)	0.009 (3)	−0.001 (3)
O1W	0.086 (6)	0.108 (6)	0.110 (6)	0.018 (5)	−0.005 (4)	0.008 (5)
O2W	0.170 (14)	0.254 (16)	0.239 (14)	−0.062 (11)	0.126 (12)	−0.079 (12)
O3W	0.199 (14)	0.149 (10)	0.39 (2)	−0.012 (9)	0.210 (15)	−0.082 (12)
P1	0.0184 (10)	0.0271 (10)	0.0191 (9)	−0.0006 (8)	0.0046 (7)	−0.0017 (8)

Geometric parameters (Å, º) top

C1—N1	1.334 (8)	Mo1—O19B	2.509 (7)
C1—C2	1.366 (11)	Mo2—O15	1.650 (5)
C1—H1	0.9300	Mo2—O16ⁱ	1.854 (5)
C2—C3	1.352 (12)	Mo2—O11	1.900 (6)
C2—H2	0.9300	Mo2—O14	1.927 (5)
C3—C4	1.369 (10)	Mo2—O12	1.916 (6)
C3—H3	0.9300	Mo2—O21B	2.477 (8)
C4—C5	1.398 (10)	Mo2—O19Bⁱ	2.447 (7)
C4—H4	0.9300	Mo3—O10	1.655 (5)
C5—N1	1.324 (8)	Mo3—O1	1.831 (5)
C5—C6	1.462 (9)	Mo3—O7	1.858 (5)
C6—N2	1.310 (9)	Mo3—O13ⁱ	1.892 (6)
C6—C7	1.392 (11)	Mo3—O9	1.972 (5)
C7—C8	1.372 (12)	Mo3—O19Aⁱ	2.476 (7)
C7—H7	0.9300	Mo3—O21A	2.496 (7)
C8—N3	1.313 (11)	Mo4—O8	1.664 (5)
C8—H8	0.9300	Mo4—O6	1.840 (5)
C9—N4	1.328 (10)	Mo4—O11	1.882 (6)
C9—C10	1.312 (13)	Mo4—O5	1.896 (5)
C9—H9	0.9300	Mo4—O1	1.964 (5)
C10—C11	1.201 (18)	Mo4—O21B	2.468 (8)
C10—H10	0.9300	Mo4—O21A	2.466 (8)
C11—C12	1.179 (18)	Mo5—O18	1.645 (5)
C11—H11	0.9300	Mo5—O4	1.849 (5)
C12—C13	1.350 (13)	Mo5—O5	1.894 (5)
C12—H12	0.9300	Mo5—O12ⁱ	1.897 (5)
C13—N4	1.335 (10)	Mo5—O7	1.943 (5)
C13—C14	1.434 (12)	Mo5—O19B	2.464 (8)
C14—N5	1.340 (11)	Mo5—O21A	2.480 (8)
C14—C15	1.421 (13)	Mo6—O2	1.661 (4)
C15—C16	1.549 (19)	Mo6—O9ⁱ	1.818 (6)
C15—H15	0.9300	Mo6—O14	1.847 (5)
C16—N6	1.419 (17)	Mo6—O17	1.913 (6)
C16—H16	0.9300	Mo6—O6	1.975 (6)
C17—N7	1.338 (11)	Mo6—O19A	2.420 (7)
C17—C18	1.359 (13)	Mo6—O21B	2.505 (7)
C17—H17	0.9300	N2—N3	1.334 (8)
C18—C19	1.346 (15)	N3—H3A	0.8600
C18—H18	0.9300	N5—N6	1.368 (11)
C19—C20	1.373 (15)	N6—H6	0.8600
C19—H19	0.9300	N8—N9	1.323 (9)
C20—C21	1.381 (11)	N9—H9A	0.8600
C20—H20	0.9300	O9—Mo6ⁱ	1.818 (6)
C21—N7	1.335 (10)	O12—Mo5ⁱ	1.897 (5)
C21—C22	1.464 (12)	O13—Mo3ⁱ	1.892 (6)
C22—N8	1.333 (10)	O16—Mo2ⁱ	1.854 (5)
C22—C23	1.376 (12)	O19A—P1	1.551 (7)
C23—C24	1.330 (14)	O19A—O21Aⁱ	1.784 (10)
C23—H23	0.9300	O19A—Mo3ⁱ	2.476 (7)
C24—N9	1.336 (11)	O21A—P1	1.516 (8)
C24—H24	0.9300	O21A—O21B	1.695 (11)
Cd1—N5	2.316 (7)	O21A—O19Aⁱ	1.784 (10)
Cd1—N8	2.325 (7)	O21A—O19B	1.752 (10)
Cd1—N1	2.342 (6)	O19B—P1	1.520 (7)
Cd1—N2	2.347 (6)	O19B—O21Bⁱ	1.721 (10)
Cd1—N4	2.334 (7)	O19B—Mo2ⁱ	2.447 (7)
Cd1—N7	2.334 (6)	O21B—P1	1.493 (8)
Mo1—O3	1.637 (4)	O21B—O19Bⁱ	1.721 (10)
Mo1—O13	1.871 (6)	P1—O21Aⁱ	1.516 (8)
Mo1—O16	1.888 (6)	P1—O21Bⁱ	1.493 (8)
Mo1—O17	1.914 (6)	P1—O19Bⁱ	1.520 (7)
Mo1—O4	1.964 (6)	P1—O19Aⁱ	1.551 (7)
Mo1—O19A	2.472 (7)

N1—C1—C2	122.6 (7)	O18—Mo5—O4	102.2 (3)
N1—C1—H1	118.6	O18—Mo5—O5	101.4 (3)
C2—C1—H1	118.7	O4—Mo5—O5	89.3 (3)
C1—C2—C3	119.5 (7)	O18—Mo5—O12ⁱ	101.6 (3)
C1—C2—H2	120.5	O4—Mo5—O12ⁱ	90.3 (2)
C3—C2—H2	120.0	O5—Mo5—O12ⁱ	156.5 (3)
C4—C3—C2	119.0 (7)	O18—Mo5—O7	101.2 (3)
C4—C3—H3	120.4	O4—Mo5—O7	156.6 (3)
C2—C3—H3	120.6	O5—Mo5—O7	85.3 (2)
C3—C4—C5	118.9 (7)	O12ⁱ—Mo5—O7	85.7 (2)
C3—C4—H4	120.6	O18—Mo5—O19B	159.9 (3)
C5—C4—H4	120.5	O4—Mo5—O19B	65.3 (3)
N1—C5—C4	121.5 (6)	O5—Mo5—O19B	94.5 (3)
N1—C5—C6	116.9 (6)	O12ⁱ—Mo5—O19B	64.3 (3)
C4—C5—C6	121.5 (6)	O7—Mo5—O19B	92.3 (3)
N2—C6—C7	110.8 (6)	O18—Mo5—O21A	158.6 (3)
N2—C6—C5	120.3 (6)	O4—Mo5—O21A	92.9 (3)
C7—C6—C5	128.9 (7)	O5—Mo5—O21A	63.4 (3)
C8—C7—C6	103.5 (8)	O12ⁱ—Mo5—O21A	93.2 (3)
C8—C7—H7	128.3	O7—Mo5—O21A	64.3 (2)
C6—C7—H7	128.3	O19B—Mo5—O21A	41.5 (2)
N3—C8—C7	108.4 (7)	O2—Mo6—O9ⁱ	103.5 (3)
N3—C8—H8	125.8	O2—Mo6—O14	102.2 (3)
C7—C8—H8	125.7	O9ⁱ—Mo6—O14	92.4 (3)
N4—C9—C10	119.7 (8)	O2—Mo6—O17	99.7 (3)
N4—C9—H9	120.0	O9ⁱ—Mo6—O17	90.3 (2)
C10—C9—H9	120.3	O14—Mo6—O17	156.7 (3)
C11—C10—C9	123.6 (13)	O2—Mo6—O6	98.8 (3)
C11—C10—H10	118.7	O9ⁱ—Mo6—O6	157.5 (3)
C9—C10—H10	117.7	O14—Mo6—O6	86.1 (2)
C12—C11—C10	121.9 (18)	O17—Mo6—O6	82.7 (3)
C12—C11—H11	119.3	O2—Mo6—O19A	160.0 (3)
C10—C11—H11	118.8	O9ⁱ—Mo6—O19A	65.0 (3)
C11—C12—C13	120.6 (15)	O14—Mo6—O19A	94.8 (3)
C11—C12—H12	119.6	O17—Mo6—O19A	65.5 (3)
C13—C12—H12	119.8	O6—Mo6—O19A	92.7 (3)
N4—C13—C12	120.9 (10)	O2—Mo6—O21B	157.2 (3)
N4—C13—C14	117.9 (7)	O9ⁱ—Mo6—O21B	95.7 (3)
C12—C13—C14	121.2 (10)	O14—Mo6—O21B	64.4 (3)
N5—C14—C15	112.8 (9)	O17—Mo6—O21B	92.3 (3)
N5—C14—C13	118.7 (7)	O6—Mo6—O21B	63.5 (2)
C15—C14—C13	128.4 (9)	O19A—Mo6—O21B	42.1 (3)
C14—C15—C16	102.8 (9)	C1—N1—C5	118.5 (6)
C14—C15—H15	129.2	C1—N1—Cd1	125.0 (5)
C16—C15—H15	128.0	C5—N1—Cd1	116.5 (4)
N6—C16—C15	104.0 (7)	C6—N2—N3	106.2 (6)
N6—C16—H16	127.6	C6—N2—Cd1	115.0 (4)
C15—C16—H16	128.4	N3—N2—Cd1	138.1 (5)
N7—C17—C18	125.0 (9)	C8—N3—N2	111.0 (6)
N7—C17—H17	117.6	C8—N3—H3A	124.5
C18—C17—H17	117.5	N2—N3—H3A	124.5
C17—C18—C19	117.2 (10)	C13—N4—C9	113.2 (7)
C17—C18—H18	121.3	C13—N4—Cd1	115.1 (6)
C19—C18—H18	121.5	C9—N4—Cd1	130.1 (6)
C20—C19—C18	120.6 (10)	C14—N5—N6	109.1 (7)
C20—C19—H19	119.6	C14—N5—Cd1	115.5 (6)
C18—C19—H19	119.8	N6—N5—Cd1	135.1 (6)
C19—C20—C21	118.5 (10)	N5—N6—C16	111.2 (9)
C19—C20—H20	120.7	N5—N6—H6	124.1
C21—C20—H20	120.8	C16—N6—H6	124.7
N7—C21—C20	121.9 (8)	C17—N7—C21	116.7 (7)
N7—C21—C22	116.1 (7)	C17—N7—Cd1	125.9 (6)
C20—C21—C22	122.0 (8)	C21—N7—Cd1	117.4 (5)
N8—C22—C23	109.9 (7)	N9—N8—C22	105.5 (7)
N8—C22—C21	119.4 (7)	N9—N8—Cd1	138.5 (5)
C23—C22—C21	130.7 (7)	C22—N8—Cd1	116.0 (5)
C24—C23—C22	105.8 (8)	N8—N9—C24	111.0 (8)
C24—C23—H23	127.1	N8—N9—H9A	124.5
C22—C23—H23	127.0	C24—N9—H9A	124.4
N9—C24—C23	107.8 (9)	Mo3—O1—Mo4	137.9 (3)
N9—C24—H24	126.2	Mo5—O4—Mo1	139.2 (3)
C23—C24—H24	126.0	Mo5—O5—Mo4	140.5 (4)
N5—Cd1—N8	99.0 (3)	Mo4—O6—Mo6	138.2 (3)
N5—Cd1—N1	93.4 (2)	Mo3—O7—Mo5	138.5 (3)
N8—Cd1—N1	89.4 (2)	Mo6ⁱ—O9—Mo3	139.5 (4)
N5—Cd1—N2	158.8 (2)	Mo4—O11—Mo2	138.6 (4)
N8—Cd1—N2	95.2 (2)	Mo5ⁱ—O12—Mo2	137.1 (4)
N1—Cd1—N2	71.01 (19)	Mo1—O13—Mo3ⁱ	141.4 (4)
N5—Cd1—N4	71.4 (3)	Mo6—O14—Mo2	140.4 (4)
N8—Cd1—N4	167.7 (2)	Mo2ⁱ—O16—Mo1	142.9 (4)
N1—Cd1—N4	98.7 (2)	Mo1—O17—Mo6	135.6 (3)
N2—Cd1—N4	96.2 (2)	P1—O19A—O21Aⁱ	53.5 (3)
N5—Cd1—N7	100.3 (2)	P1—O19A—Mo6	124.4 (4)
N8—Cd1—N7	71.1 (2)	O21Aⁱ—O19A—Mo6	132.0 (5)
N1—Cd1—N7	157.5 (2)	P1—O19A—Mo3ⁱ	123.0 (4)
N2—Cd1—N7	99.1 (2)	O21Aⁱ—O19A—Mo3ⁱ	69.5 (3)
N4—Cd1—N7	102.5 (2)	Mo6—O19A—Mo3ⁱ	93.1 (3)
O3—Mo1—O13	103.0 (3)	P1—O19A—Mo1	122.9 (4)
O3—Mo1—O16	102.2 (3)	O21Aⁱ—O19A—Mo1	130.5 (5)
O13—Mo1—O16	90.0 (3)	Mo6—O19A—Mo1	92.8 (2)
O3—Mo1—O17	102.7 (3)	Mo3ⁱ—O19A—Mo1	91.7 (2)
O13—Mo1—O17	89.1 (2)	P1—O21A—O21B	55.1 (4)
O16—Mo1—O17	154.6 (3)	P1—O21A—O19Aⁱ	55.4 (3)
O3—Mo1—O4	101.3 (3)	O21B—O21A—O19Aⁱ	90.7 (5)
O13—Mo1—O4	155.7 (3)	P1—O21A—O19B	54.9 (4)
O16—Mo1—O4	84.8 (2)	O21B—O21A—O19B	91.7 (5)
O17—Mo1—O4	85.6 (3)	O19Aⁱ—O21A—O19B	89.1 (5)
O3—Mo1—O19A	160.1 (3)	P1—O21A—Mo5	123.6 (4)
O13—Mo1—O19A	63.5 (3)	O21B—O21A—Mo5	133.5 (5)
O16—Mo1—O19A	92.7 (3)	O19Aⁱ—O21A—Mo5	128.7 (5)
O17—Mo1—O19A	64.3 (2)	O19B—O21A—Mo5	68.8 (4)
O4—Mo1—O19A	92.9 (3)	P1—O21A—Mo4	125.0 (4)
O3—Mo1—O19B	157.3 (3)	O21B—O21A—Mo4	70.0 (4)
O13—Mo1—O19B	93.6 (3)	O19Aⁱ—O21A—Mo4	132.5 (5)
O16—Mo1—O19B	61.9 (3)	O19B—O21A—Mo4	132.6 (4)
O17—Mo1—O19B	92.8 (3)	Mo5—O21A—Mo4	92.4 (2)
O4—Mo1—O19B	63.0 (3)	P1—O21A—Mo3	123.7 (4)
O19A—Mo1—O19B	42.6 (2)	O21B—O21A—Mo3	130.2 (5)
O15—Mo2—O16ⁱ	103.1 (3)	O19Aⁱ—O21A—Mo3	68.4 (3)
O15—Mo2—O11	100.5 (3)	O19B—O21A—Mo3	130.5 (5)
O16ⁱ—Mo2—O11	89.8 (3)	Mo5—O21A—Mo3	91.2 (3)
O15—Mo2—O14	101.5 (3)	Mo4—O21A—Mo3	91.1 (3)
O16ⁱ—Mo2—O14	155.4 (3)	P1—O19B—O21A	54.6 (3)
O11—Mo2—O14	86.8 (2)	P1—O19B—O21Bⁱ	54.4 (4)
O15—Mo2—O12	102.8 (3)	O21A—O19B—O21Bⁱ	91.4 (5)
O16ⁱ—Mo2—O12	88.3 (2)	P1—O19B—Mo5	124.4 (4)
O11—Mo2—O12	156.4 (3)	O21A—O19B—Mo5	69.7 (4)
O14—Mo2—O12	85.3 (2)	O21Bⁱ—O19B—Mo5	133.4 (5)
O15—Mo2—O21B	158.5 (3)	P1—O19B—Mo2ⁱ	124.9 (4)
O16ⁱ—Mo2—O21B	92.4 (3)	O21A—O19B—Mo2ⁱ	134.5 (5)
O11—Mo2—O21B	64.3 (3)	O21Bⁱ—O19B—Mo2ⁱ	70.5 (4)
O14—Mo2—O21B	64.1 (3)	Mo5—O19B—Mo2ⁱ	92.5 (3)
O12—Mo2—O21B	92.3 (3)	P1—O19B—Mo1	122.3 (4)
O15—Mo2—O19Bⁱ	160.6 (3)	O21A—O19B—Mo1	129.3 (4)
O16ⁱ—Mo2—O19Bⁱ	63.6 (3)	O21Bⁱ—O19B—Mo1	130.1 (5)
O11—Mo2—O19Bⁱ	93.8 (3)	Mo5—O19B—Mo1	91.9 (2)
O14—Mo2—O19Bⁱ	92.3 (3)	Mo2ⁱ—O19B—Mo1	91.4 (2)
O12—Mo2—O19Bⁱ	64.4 (3)	P1—O21B—O21A	56.3 (4)
O21B—Mo2—O19Bⁱ	40.9 (2)	P1—O21B—O19Bⁱ	55.9 (4)
O10—Mo3—O1	102.8 (3)	O21A—O21B—O19Bⁱ	93.1 (5)
O10—Mo3—O7	102.3 (3)	P1—O21B—Mo4	126.2 (4)
O1—Mo3—O7	90.7 (2)	O21A—O21B—Mo4	69.8 (4)
O10—Mo3—O13ⁱ	101.3 (3)	O19Bⁱ—O21B—Mo4	134.1 (5)
O1—Mo3—O13ⁱ	90.7 (3)	P1—O21B—Mo2	124.5 (4)
O7—Mo3—O13ⁱ	155.4 (3)	O21A—O21B—Mo2	132.1 (5)
O10—Mo3—O9	100.2 (3)	O19Bⁱ—O21B—Mo2	68.6 (4)
O1—Mo3—O9	157.0 (3)	Mo4—O21B—Mo2	91.4 (3)
O7—Mo3—O9	85.7 (3)	P1—O21B—Mo6	122.3 (4)
O13ⁱ—Mo3—O9	83.5 (2)	O21A—O21B—Mo6	131.5 (5)
O10—Mo3—O19Aⁱ	156.4 (3)	O19Bⁱ—O21B—Mo6	127.9 (5)
O1—Mo3—O19Aⁱ	95.4 (3)	Mo4—O21B—Mo6	91.6 (3)
O7—Mo3—O19Aⁱ	92.2 (3)	Mo2—O21B—Mo6	90.9 (3)
O13ⁱ—Mo3—O19Aⁱ	63.2 (3)	O21A—P1—O21Aⁱ	180.0 (7)
O9—Mo3—O19Aⁱ	62.1 (3)	O21A—P1—O21B	68.6 (4)
O10—Mo3—O21A	161.4 (3)	O21Aⁱ—P1—O21B	111.4 (4)
O1—Mo3—O21A	65.6 (3)	O21A—P1—O21Bⁱ	111.4 (4)
O7—Mo3—O21A	64.9 (3)	O21Aⁱ—P1—O21Bⁱ	68.6 (4)
O13ⁱ—Mo3—O21A	93.5 (3)	O21B—P1—O21Bⁱ	180.0 (6)
O9—Mo3—O21A	92.5 (3)	O21A—P1—O19B	70.5 (4)
O19Aⁱ—Mo3—O21A	42.1 (2)	O21Aⁱ—P1—O19B	109.5 (4)
O8—Mo4—O6	103.7 (3)	O21B—P1—O19B	110.3 (4)
O8—Mo4—O11	102.2 (3)	O21Bⁱ—P1—O19B	69.7 (4)
O6—Mo4—O11	90.1 (2)	O21A—P1—O19Bⁱ	109.5 (4)
O8—Mo4—O5	100.8 (3)	O21Aⁱ—P1—O19Bⁱ	70.5 (4)
O6—Mo4—O5	90.7 (2)	O21B—P1—O19Bⁱ	69.7 (4)
O11—Mo4—O5	156.1 (3)	O21Bⁱ—P1—O19Bⁱ	110.3 (4)
O8—Mo4—O1	99.2 (3)	O19B—P1—O19Bⁱ	180.0 (6)
O6—Mo4—O1	157.0 (3)	O21A—P1—O19A	108.9 (4)
O11—Mo4—O1	85.4 (2)	O21Aⁱ—P1—O19A	71.1 (4)
O5—Mo4—O1	84.7 (2)	O21B—P1—O19A	71.1 (4)
O8—Mo4—O21B	162.1 (3)	O21Bⁱ—P1—O19A	108.9 (4)
O6—Mo4—O21B	65.8 (3)	O19B—P1—O19A	72.2 (4)
O11—Mo4—O21B	64.7 (3)	O19Bⁱ—P1—O19A	107.8 (4)
O5—Mo4—O21B	94.0 (3)	O21A—P1—O19Aⁱ	71.1 (4)
O1—Mo4—O21B	92.0 (3)	O21Aⁱ—P1—O19Aⁱ	108.9 (4)
O8—Mo4—O21A	157.5 (3)	O21B—P1—O19Aⁱ	108.9 (4)
O6—Mo4—O21A	93.0 (3)	O21Bⁱ—P1—O19Aⁱ	71.1 (4)
O11—Mo4—O21A	92.4 (3)	O19B—P1—O19Aⁱ	107.8 (4)
O5—Mo4—O21A	63.7 (3)	O19Bⁱ—P1—O19Aⁱ	72.2 (4)
O1—Mo4—O21A	64.7 (2)	O19A—P1—O19Aⁱ	180.0 (7)
O21B—Mo4—O21A	40.2 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O17ⁱⁱ	0.86	1.95	2.803 (8)	171
N6—H6···O2W	0.86	2.25	3.102 (17)	173
N9—H9A···O1W	0.86	1.96	2.790 (11)	163

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

Experimental details

Crystal data
Chemical formula	[Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r	3026.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	19.0326 (14), 16.4779 (12), 27.267 (2)
β (°)	105.187 (1)
V (Å³)	8252.8 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.39
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.763, 0.832
No. of measured, independent and observed [I > 2σ(I)] reflections	21276, 7254, 6211
R_int	0.105
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.125, 1.00
No. of reflections	7254
No. of parameters	592
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.057P)² + 46.070P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.55, −0.82

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

Selected bond lengths (Å) top

Cd1—N5	2.316 (7)	Cd1—N7	2.334 (6)
Cd1—N8	2.325 (7)	P1—O21Aⁱ	1.516 (8)
Cd1—N1	2.342 (6)	P1—O21Bⁱ	1.493 (8)
Cd1—N2	2.347 (6)	P1—O19Bⁱ	1.520 (7)
Cd1—N4	2.334 (7)	P1—O19Aⁱ	1.551 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O17ⁱⁱ	0.86	1.95	2.803 (8)	171.00
N6—H6···O2W	0.86	2.25	3.102 (17)	172.6
N9—H9A···O1W	0.86	1.96	2.790 (11)	162.9

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

Acknowledgements

Financial support from the International Cooperation Programme for Excellent Lecturers of 2008 from Shandong Provincial Education Department, the Research Award Fund for Outstanding Young and Middle-aged Scientists of Shandong Province (grant No. 2008BS04022), Shandong Provincial Education Department and Shandong Institute of Education is gratefully acknowledged.

References

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Hao, L., Ma, C., Chen, J., Zhang, X. & Zhang, X. (2010). Acta Cryst. E66, m231–m232. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 66| Part 3| March 2010| Pages m268-m269

doi:10.1107/S1600536810004307

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis{tris­­[3-(2-pyrid­yl)-1H-pyrazole]cadmium(II)} dodeca­molybdo(V,VI)phosphate hexa­hydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis{tris[3-(2-pyridyl)-1H-pyrazole]cadmium(II)} dodecamolybdo(V,VI)phosphate hexahydrate