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

Hao, L.; Liu, T.; Chen, J.; Zhang, X.

doi:10.1107/S1600536810005945

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m319-m320

doi:10.1107/S1600536810005945

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

Lujiang Hao,^a ^* Tongjun Liu,^a Jiangkui Chen ^a and Xiaofei Zhang ^a

^aCollege of Food and Biological Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China
^*Correspondence e-mail: lujianghao001@yahoo.com.cn

(Received 8 February 2010; accepted 13 February 2010; online 20 February 2010)

The hydrothermally prepared title compound, [Ni(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O, is a member of the isotypic series [(M(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O where M is Mn, Cd, and Fe. The Ni²⁺ cation is in a distorted octahedral environment, coordinated by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands. In the one-electron 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 isotypic structures, the main difference is related with the M—N bond lengths, whereas all other bond lengths, angles and the hydrogen-bonding motifs are very similar.

Related literature

For the isotypic analogues, see: Hao, Ma et al. (2010 ) for M = Mn; Hao, Wang et al. (2010 ) for M = Cd; Hao, Liu, et al. (2010 ) for M = Fe. 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 structures of other reduced heteropolyanions with composition [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

[Ni(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r = 2918.76
Monoclinic, C 2/c
a = 18.741 (4) Å
b = 16.285 (3) Å
c = 27.678 (6) Å
β = 103.83 (3)°
V = 8202 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.34 mm⁻¹
T = 293 K
0.42 × 0.27 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.440, T_max = 0.652
22802 measured reflections
7216 independent reflections
5310 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.155
S = 1.00
7216 reflections
592 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 1.58 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N5	2.077 (19)
Ni1—N8	2.06 (2)
Ni1—N2	2.084 (19)
Ni1—N4	2.13 (2)
Ni1—N1	2.118 (17)
Ni1—N7	2.14 (2)
P1—O21Aⁱ	1.49 (2)
P1—O21Bⁱ	1.50 (3)
P1—O19Bⁱ	1.55 (3)
P1—O19Aⁱ	1.57 (3)
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	2.05	2.83 (3)	149
N6—H6⋯O2W	0.86	1.99	2.84 (5)	166
N9—H9A⋯O1W	0.86	1.92	2.74 (3)	160
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/S1600536810005945/wm2306sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005945/wm2306Isup2.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 Figure 1, the asymmetric unit of the title compound consists of three subunits, viz. of a complex [Ni(C₈H₇N₃)₃]²⁺ cation, half of a heteropolyanion [PMo₁₂O₄₀]^4- and of three uncoordinated water molecules. The nickel(II) ion is in a distorted octahedral coordination by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands.

The heteropolyanion [PMo₁₂O₄₀]^4- anion is a 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 1.49 (2)—1.57 (3) Å. The Mo—O bond distances vary widely from 1.653 (15) to 2.55 (2) Å. The shortest Mo—O bonds are in the range of 1.653 (15)—1.665 (16) Å for the terminal oxygen atoms. The longest Mo—O lengths are in the range of 2.44 (2)—2.55 (2) 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 [(Ni(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ is isotypic with the Mn²⁺, Cd²⁺, and Fe²⁺ analogues, [(Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ (Hao, Ma et al. (2010).), [(Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ (Hao, Wang et al. (2010).), [(Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ (Hao, Liu et al., 2010). In comparison with the Mn²⁺, Cd²⁺, and Fe²⁺ analogues, the Ni—N bond lengths are somewhat shorter at 2.077 (19)—2.14 (2) Å, versus 2.224 (6)—2.283 (5) Å for Mn—N, 2.085 (19)—2.15 (2) Å for Fe—N, and 2.316 (7)—2.334 (6) Å for Cd—N, whereas all other bond lengths and angles and the hydrogen-bonding motifs are very similar in the four structures.

Related literature top

For the isotypic analogues, see: Hao, Ma et al. (2010) for M = Mn; Hao, Wang et al. (2010) for M = Cd; Hao, Liu, et al. (2010) for M = Fe. 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 structures of other reduced heteropolyanions with composition [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), nickel(II) chloride hexahydrate (0.25 mmol, 0.05 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. Green crystals suitable for the X-ray experiment were obtained. IR(cm^-1): 3376, 3136, 2961, 1614, 1568, 1522, 1457, 1439, 1364, 1300, 1097, 950, 913, 812, 636, 507.

TGA curve shows a separation of lattice water molecules and the organic ligands above 343 and 682 K, respectively. The overall thermal decomposition process can be described by the followed equation: 4C₄₈H₅₄Ni₂Mo₁₂N₁₈O₄₆P + 325O₂ = 108H₂O + 192CO₂ + 36N₂O₅ + 8NiO + 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]nickel(II)} dodecamolybdo(V,VI)phosphate hexahydrate top

Crystal data top

[Ni(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	F(000) = 5644
M_r = 2918.76	D_x = 2.364 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7216 reflections
a = 18.741 (4) Å	θ = 1.7–25.0°
b = 16.285 (3) Å	µ = 2.34 mm⁻¹
c = 27.678 (6) Å	T = 293 K
β = 103.83 (3)°	Block, green
V = 8202 (3) Å³	0.42 × 0.27 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7216 independent reflections
Radiation source: fine-focus sealed tube	5310 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→22
T_min = 0.440, T_max = 0.652	k = −17→19
22802 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.088P)² + 10.3967P] where P = (F_o² + 2F_c²)/3
7216 reflections	(Δ/σ)_max = 0.001
592 parameters	Δρ_max = 1.58 e Å⁻³
18 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Ni(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	V = 8202 (3) Å³
M_r = 2918.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.741 (4) Å	µ = 2.34 mm⁻¹
b = 16.285 (3) Å	T = 293 K
c = 27.678 (6) Å	0.42 × 0.27 × 0.20 mm
β = 103.83 (3)°

Data collection top

Bruker APEXII CCD diffractometer	7216 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	5310 reflections with I > 2σ(I)
T_min = 0.440, T_max = 0.652	R_int = 0.062
22802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	18 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.088P)² + 10.3967P] where P = (F_o² + 2F_c²)/3
7216 reflections	Δρ_max = 1.58 e Å⁻³
592 parameters	Δρ_min = −0.67 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	0.2023 (14)	0.8990 (15)	0.0923 (9)	0.049 (6)
H1	0.2445	0.8942	0.0803	0.059*
C2	0.1420 (14)	0.9332 (15)	0.0634 (8)	0.051 (6)
H2	0.1428	0.9526	0.0320	0.062*
C3	0.0798 (15)	0.9396 (17)	0.0799 (9)	0.058 (7)
H3	0.0379	0.9631	0.0598	0.070*
C4	0.0790 (14)	0.9114 (18)	0.1261 (10)	0.061 (7)
H4	0.0365	0.9150	0.1378	0.073*
C5	0.1416 (12)	0.8778 (14)	0.1549 (8)	0.040 (5)
C6	0.1465 (13)	0.8481 (14)	0.2052 (8)	0.043 (6)
C7	0.0946 (16)	0.845 (2)	0.2344 (11)	0.074 (9)
H7	0.0455	0.8612	0.2257	0.089*
C8	0.135 (2)	0.813 (2)	0.2804 (11)	0.074 (9)
H8	0.1172	0.8038	0.3086	0.089*
C9	0.3232 (13)	0.9754 (14)	0.2567 (9)	0.047 (6)
H9	0.2895	0.9552	0.2735	0.056*
C10	0.3547 (16)	1.050 (2)	0.2699 (11)	0.061 (8)
H10	0.3434	1.0793	0.2959	0.073*
C11	0.4016 (19)	1.080 (2)	0.2455 (15)	0.090 (11)
H11	0.4226	1.1315	0.2542	0.108*
C12	0.4194 (14)	1.0371 (19)	0.2079 (10)	0.063 (7)
H12	0.4523	1.0577	0.1906	0.075*
C13	0.3872 (13)	0.9634 (16)	0.1968 (9)	0.052 (6)
C14	0.4049 (13)	0.9098 (17)	0.1581 (9)	0.051 (6)
C15	0.4550 (15)	0.919 (2)	0.1271 (12)	0.075 (10)
H15	0.4876	0.9621	0.1266	0.090*
C16	0.4433 (17)	0.848 (2)	0.0973 (12)	0.074 (9)
H16	0.4670	0.8339	0.0726	0.089*
C17	0.4107 (15)	0.7609 (19)	0.2864 (10)	0.060 (7)
H17	0.4164	0.8166	0.2938	0.072*
C18	0.4501 (18)	0.706 (2)	0.3200 (13)	0.082 (10)
H18	0.4809	0.7241	0.3496	0.099*
C19	0.443 (2)	0.625 (2)	0.3091 (14)	0.092 (11)
H19	0.4703	0.5868	0.3308	0.110*
C20	0.3948 (17)	0.5994 (19)	0.2644 (12)	0.078 (9)
H20	0.3882	0.5440	0.2564	0.094*
C21	0.3580 (14)	0.6586 (16)	0.2337 (10)	0.047 (6)
C22	0.3041 (14)	0.6382 (16)	0.1873 (9)	0.048 (6)
C23	0.2838 (17)	0.5645 (17)	0.1627 (10)	0.063 (8)
H23	0.3033	0.5127	0.1717	0.075*
C24	0.2287 (18)	0.5843 (17)	0.1221 (11)	0.069 (8)
H24	0.2030	0.5479	0.0984	0.083*
Ni1	0.29253 (16)	0.81664 (19)	0.19077 (11)	0.0411 (8)
Mo1	0.24269 (12)	0.14134 (13)	0.11084 (7)	0.0420 (6)
Mo2	0.19263 (12)	0.45800 (12)	−0.01469 (8)	0.0417 (6)
Mo3	0.42259 (10)	0.31668 (12)	−0.01927 (7)	0.0370 (6)
Mo4	0.35304 (11)	0.40513 (13)	0.07783 (7)	0.0388 (6)
Mo5	0.41654 (10)	0.19716 (13)	0.08814 (7)	0.0402 (6)
Mo6	0.17514 (11)	0.34583 (13)	0.09260 (7)	0.0385 (6)
N1	0.2031 (10)	0.8709 (11)	0.1392 (6)	0.038 (4)
N2	0.2102 (10)	0.8191 (12)	0.2297 (7)	0.043 (5)
N3	0.2020 (13)	0.7966 (15)	0.2756 (8)	0.056 (6)
H3A	0.2361	0.7749	0.2984	0.067*
N4	0.3392 (11)	0.9302 (13)	0.2204 (8)	0.049 (5)
N5	0.3682 (11)	0.8410 (13)	0.1487 (7)	0.048 (5)
N6	0.3924 (12)	0.8050 (16)	0.1113 (8)	0.066 (7)
H6	0.3760	0.7588	0.0981	0.079*
N7	0.3642 (10)	0.7388 (13)	0.2433 (7)	0.048 (5)
N8	0.2643 (11)	0.7011 (13)	0.1619 (7)	0.050 (5)
N9	0.2184 (12)	0.6674 (15)	0.1229 (8)	0.062 (6)
H9A	0.1865	0.6941	0.1011	0.074*
O1	0.4066 (11)	0.3947 (10)	0.0246 (6)	0.063 (5)
O2	0.1446 (9)	0.3914 (12)	0.1373 (6)	0.057 (5)
O3	0.2405 (9)	0.0897 (11)	0.1619 (6)	0.055 (5)
O4	0.3441 (11)	0.1729 (13)	0.1236 (8)	0.079 (7)
O5	0.4024 (11)	0.3112 (10)	0.1052 (7)	0.065 (6)
O6	0.2780 (9)	0.3874 (13)	0.1090 (7)	0.066 (5)
O7	0.4526 (11)	0.2417 (10)	0.0345 (6)	0.060 (5)
O8	0.4028 (11)	0.4785 (11)	0.1120 (7)	0.066 (5)
O9	0.4027 (11)	0.2166 (11)	−0.0602 (7)	0.082 (7)
O10	0.5030 (9)	0.3438 (11)	−0.0293 (7)	0.061 (5)
O11	0.2863 (9)	0.4671 (14)	0.0283 (7)	0.080 (7)
O12	0.1059 (11)	0.4001 (13)	−0.0525 (7)	0.081 (7)
O13	0.1431 (12)	0.1324 (11)	0.0721 (8)	0.086 (8)
O14	0.1575 (9)	0.4236 (14)	0.0422 (7)	0.071 (6)
O15	0.1673 (10)	0.5557 (10)	−0.0206 (7)	0.062 (5)
O16	0.2676 (12)	0.0575 (14)	0.0694 (8)	0.090 (7)
O17	0.2203 (11)	0.2506 (11)	0.1275 (7)	0.074 (6)
O18	0.4935 (9)	0.1738 (12)	0.1293 (6)	0.064 (5)
O19A	0.2028 (14)	0.2368 (16)	0.0390 (10)	0.029 (6)	0.50
O21A	0.3246 (13)	0.2799 (16)	0.0253 (10)	0.028 (6)	0.50
O19B	0.2904 (15)	0.1847 (16)	0.0376 (9)	0.031 (6)	0.50
O21B	0.2482 (14)	0.3299 (17)	0.0264 (9)	0.032 (6)	0.50
O1W	0.1158 (13)	0.7172 (16)	0.0399 (9)	0.099 (8)
O2W	0.358 (2)	0.653 (2)	0.0612 (15)	0.163 (12)
O3W	0.534 (3)	0.072 (3)	0.027 (2)	0.27 (2)
P1	0.2500	0.2500	0.0000	0.0252 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.054 (15)	0.049 (15)	0.045 (15)	0.001 (12)	0.013 (12)	0.011 (12)
C2	0.058 (17)	0.055 (15)	0.035 (12)	−0.005 (13)	0.000 (12)	0.017 (11)
C3	0.045 (16)	0.075 (19)	0.047 (15)	−0.005 (14)	−0.005 (12)	0.010 (14)
C4	0.037 (15)	0.09 (2)	0.055 (16)	0.006 (14)	0.003 (12)	0.004 (15)
C5	0.032 (12)	0.038 (13)	0.048 (14)	−0.011 (10)	0.007 (10)	0.003 (11)
C6	0.042 (14)	0.049 (14)	0.041 (13)	−0.002 (11)	0.013 (11)	0.006 (11)
C7	0.047 (17)	0.11 (3)	0.07 (2)	0.013 (17)	0.020 (15)	0.014 (19)
C8	0.09 (2)	0.09 (2)	0.053 (19)	−0.016 (19)	0.028 (18)	0.012 (16)
C9	0.052 (15)	0.043 (14)	0.045 (14)	−0.003 (11)	0.009 (11)	0.000 (11)
C10	0.065 (19)	0.06 (2)	0.053 (17)	−0.003 (16)	0.003 (14)	−0.001 (16)
C11	0.08 (2)	0.09 (2)	0.09 (3)	−0.001 (19)	−0.01 (2)	0.02 (2)
C12	0.055 (16)	0.08 (2)	0.051 (16)	−0.007 (15)	0.005 (13)	0.019 (15)
C13	0.034 (13)	0.062 (17)	0.054 (15)	−0.010 (12)	−0.003 (11)	0.016 (13)
C14	0.038 (13)	0.061 (17)	0.053 (15)	0.002 (12)	0.008 (11)	0.016 (13)
C15	0.040 (16)	0.10 (3)	0.08 (2)	0.005 (16)	0.010 (15)	0.05 (2)
C16	0.06 (2)	0.10 (2)	0.07 (2)	0.017 (17)	0.039 (16)	0.033 (18)
C17	0.057 (17)	0.06 (2)	0.057 (17)	−0.006 (15)	0.006 (14)	−0.005 (15)
C18	0.08 (2)	0.08 (2)	0.07 (2)	0.009 (19)	−0.025 (18)	0.012 (19)
C19	0.10 (3)	0.08 (3)	0.09 (3)	0.03 (2)	0.00 (2)	0.03 (2)
C20	0.07 (2)	0.07 (2)	0.08 (2)	0.008 (16)	−0.015 (17)	0.004 (17)
C21	0.046 (15)	0.054 (16)	0.042 (17)	0.008 (12)	0.010 (12)	0.005 (13)
C22	0.049 (15)	0.049 (16)	0.046 (14)	0.017 (13)	0.016 (12)	0.000 (13)
C23	0.08 (2)	0.052 (17)	0.052 (16)	0.023 (15)	0.014 (15)	−0.005 (13)
C24	0.09 (2)	0.053 (17)	0.061 (19)	−0.007 (16)	0.023 (17)	−0.034 (14)
Ni1	0.0353 (16)	0.0469 (18)	0.0408 (17)	0.0041 (13)	0.0083 (13)	0.0042 (14)
Mo1	0.0552 (13)	0.0425 (12)	0.0281 (10)	−0.0059 (10)	0.0094 (9)	0.0041 (9)
Mo2	0.0455 (12)	0.0313 (11)	0.0521 (13)	0.0059 (9)	0.0190 (10)	0.0026 (9)
Mo3	0.0258 (10)	0.0433 (12)	0.0418 (12)	−0.0038 (8)	0.0081 (8)	−0.0004 (9)
Mo4	0.0324 (11)	0.0423 (12)	0.0400 (11)	−0.0070 (9)	0.0055 (8)	−0.0093 (9)
Mo5	0.0286 (11)	0.0528 (13)	0.0353 (11)	0.0018 (9)	0.0003 (8)	0.0032 (9)
Mo6	0.0400 (12)	0.0457 (12)	0.0304 (10)	0.0085 (9)	0.0095 (8)	−0.0063 (9)
N1	0.035 (10)	0.043 (11)	0.037 (10)	0.002 (8)	0.009 (8)	0.009 (8)
N2	0.040 (11)	0.054 (12)	0.034 (10)	0.004 (9)	0.008 (9)	0.005 (9)
N3	0.049 (14)	0.074 (17)	0.043 (13)	−0.003 (12)	0.010 (11)	0.015 (12)
N4	0.041 (12)	0.047 (13)	0.058 (13)	0.000 (10)	0.009 (10)	0.014 (11)
N5	0.041 (12)	0.061 (14)	0.048 (12)	0.009 (10)	0.021 (10)	0.015 (10)
N6	0.053 (14)	0.084 (18)	0.061 (14)	0.029 (13)	0.014 (12)	0.010 (13)
N7	0.037 (11)	0.058 (14)	0.047 (12)	0.004 (10)	0.008 (9)	0.006 (10)
N8	0.054 (13)	0.056 (13)	0.036 (11)	0.008 (10)	0.003 (10)	−0.006 (10)
N9	0.059 (15)	0.075 (18)	0.047 (13)	0.006 (12)	0.004 (11)	0.005 (12)
O1	0.100 (15)	0.048 (11)	0.055 (11)	0.024 (10)	0.045 (10)	0.010 (9)
O2	0.050 (10)	0.078 (14)	0.045 (10)	0.003 (9)	0.018 (8)	−0.018 (9)
O3	0.058 (11)	0.069 (12)	0.035 (9)	−0.003 (9)	0.005 (8)	0.018 (8)
O4	0.073 (14)	0.094 (16)	0.087 (15)	−0.045 (12)	0.052 (12)	−0.053 (12)
O5	0.104 (16)	0.049 (11)	0.055 (11)	0.026 (10)	0.044 (11)	0.012 (9)
O6	0.028 (9)	0.102 (15)	0.067 (12)	0.007 (9)	0.008 (8)	0.041 (11)
O7	0.095 (14)	0.045 (10)	0.050 (10)	0.022 (10)	0.041 (10)	0.008 (8)
O8	0.077 (13)	0.056 (12)	0.060 (13)	−0.024 (10)	0.009 (10)	−0.021 (10)
O9	0.091 (15)	0.043 (11)	0.077 (13)	0.018 (10)	−0.048 (11)	−0.013 (10)
O10	0.043 (10)	0.061 (12)	0.091 (14)	−0.010 (9)	0.038 (10)	−0.002 (10)
O11	0.038 (10)	0.129 (18)	0.077 (14)	0.007 (11)	0.021 (9)	0.057 (13)
O12	0.079 (14)	0.096 (16)	0.087 (14)	−0.047 (12)	0.058 (12)	−0.060 (12)
O13	0.095 (15)	0.036 (10)	0.089 (15)	0.017 (10)	−0.051 (12)	−0.014 (10)
O14	0.027 (9)	0.118 (17)	0.067 (13)	0.004 (10)	0.012 (9)	0.050 (12)
O15	0.064 (12)	0.031 (9)	0.090 (15)	0.011 (8)	0.015 (11)	0.012 (10)
O16	0.082 (13)	0.102 (15)	0.102 (14)	−0.047 (12)	0.052 (11)	−0.059 (12)
O17	0.078 (13)	0.044 (11)	0.075 (13)	−0.002 (10)	−0.033 (10)	−0.003 (9)
O18	0.049 (11)	0.089 (15)	0.044 (10)	0.026 (10)	−0.007 (8)	0.011 (10)
O19A	0.023 (14)	0.030 (15)	0.036 (15)	−0.003 (11)	0.007 (11)	−0.007 (12)
O21A	0.018 (13)	0.035 (15)	0.030 (15)	0.002 (11)	0.007 (11)	0.004 (12)
O19B	0.042 (16)	0.029 (15)	0.019 (14)	0.002 (12)	0.000 (12)	0.002 (11)
O21B	0.029 (15)	0.049 (17)	0.021 (13)	0.001 (12)	0.011 (11)	−0.009 (12)
O1W	0.077 (15)	0.12 (2)	0.084 (16)	0.024 (14)	−0.011 (12)	−0.006 (14)
O2W	0.165 (13)	0.164 (13)	0.191 (13)	−0.005 (3)	0.102 (4)	−0.017 (3)
O3W	0.22 (2)	0.23 (2)	0.39 (2)	0.000 (3)	0.151 (6)	−0.045 (3)
P1	0.026 (4)	0.026 (4)	0.023 (4)	0.001 (3)	0.004 (3)	0.000 (3)

Geometric parameters (Å, º) top

C1—N1	1.37 (3)	Mo2—O15	1.657 (16)
C1—C2	1.34 (3)	Mo2—O16ⁱ	1.86 (2)
C1—H1	0.9300	Mo2—O11	1.876 (18)
C2—C3	1.35 (4)	Mo2—O14	1.930 (18)
C2—H2	0.9300	Mo2—O12	1.952 (18)
C3—C4	1.36 (4)	Mo2—O19Bⁱ	2.45 (3)
C3—H3	0.9300	Mo2—O21B	2.48 (3)
C4—C5	1.37 (3)	Mo3—O10	1.655 (16)
C4—H4	0.9300	Mo3—O1	1.831 (17)
C5—N1	1.33 (3)	Mo3—O7	1.903 (16)
C5—C6	1.45 (3)	Mo3—O13ⁱ	1.866 (17)
C6—N2	1.31 (3)	Mo3—O9	1.969 (18)
C6—C7	1.41 (3)	Mo3—O19Aⁱ	2.44 (2)
C7—C8	1.42 (4)	Mo3—O21A	2.52 (3)
C7—H7	0.9300	Mo4—O8	1.665 (16)
C8—N3	1.32 (4)	Mo4—O6	1.840 (17)
C8—H8	0.9300	Mo4—O11	1.910 (18)
C9—N4	1.34 (3)	Mo4—O5	1.853 (17)
C9—C10	1.36 (4)	Mo4—O1	1.979 (17)
C9—H9	0.9300	Mo4—O21B	2.46 (3)
C10—C11	1.33 (4)	Mo4—O21A	2.49 (3)
C10—H10	0.9300	Mo5—O18	1.655 (15)
C11—C12	1.36 (4)	Mo5—O4	1.897 (18)
C11—H11	0.9300	Mo5—O5	1.950 (17)
C12—C13	1.35 (4)	Mo5—O12ⁱ	1.860 (17)
C12—H12	0.9300	Mo5—O7	1.915 (16)
C13—N4	1.34 (3)	Mo5—O19B	2.45 (3)
C13—C14	1.48 (4)	Mo5—O21A	2.52 (2)
C14—N5	1.31 (3)	Mo6—O2	1.658 (16)
C14—C15	1.42 (4)	Mo6—O9ⁱ	1.828 (18)
C15—C16	1.41 (5)	Mo6—O14	1.854 (17)
C15—H15	0.9300	Mo6—O17	1.914 (17)
C16—N6	1.31 (3)	Mo6—O6	1.990 (17)
C16—H16	0.9300	Mo6—O19A	2.45 (3)
C17—N7	1.35 (3)	Mo6—O21B	2.55 (2)
C17—C18	1.37 (4)	N2—N3	1.37 (3)
C17—H17	0.9300	N3—H3A	0.8600
C18—C19	1.35 (4)	N5—N6	1.36 (3)
C18—H18	0.9300	N6—H6	0.8600
C19—C20	1.41 (4)	N8—N9	1.33 (3)
C19—H19	0.9300	N9—H9A	0.8600
C20—C21	1.36 (4)	O9—Mo6ⁱ	1.828 (18)
C20—H20	0.9300	O12—Mo5ⁱ	1.860 (17)
C21—N7	1.33 (3)	O13—Mo3ⁱ	1.866 (17)
C21—C22	1.47 (3)	O16—Mo2ⁱ	1.86 (2)
C22—N8	1.36 (3)	O19A—P1	1.57 (3)
C22—C23	1.39 (4)	O19A—O21Aⁱ	1.75 (4)
C23—C24	1.37 (4)	O19A—O21B	1.81 (4)
C23—H23	0.9300	O19A—O19B	1.86 (4)
C24—N9	1.37 (3)	O19A—Mo3ⁱ	2.44 (2)
C24—H24	0.9300	O21A—P1	1.49 (2)
Ni1—N5	2.077 (19)	O21A—O21B	1.65 (4)
Ni1—N8	2.06 (2)	O21A—O19B	1.74 (4)
Ni1—N2	2.084 (19)	O21A—O19Aⁱ	1.75 (4)
Ni1—N4	2.13 (2)	O19B—P1	1.55 (3)
Ni1—N1	2.118 (17)	O19B—O21Bⁱ	1.76 (3)
Ni1—N7	2.14 (2)	O19B—Mo2ⁱ	2.45 (3)
Mo1—O3	1.653 (15)	O21B—P1	1.50 (3)
Mo1—O13	1.923 (19)	O21B—O19Bⁱ	1.76 (3)
Mo1—O16	1.91 (2)	P1—O21Aⁱ	1.49 (2)
Mo1—O17	1.911 (18)	P1—O21Bⁱ	1.50 (3)
Mo1—O4	1.919 (19)	P1—O19Bⁱ	1.55 (3)
Mo1—O19A	2.49 (3)	P1—O19Aⁱ	1.57 (3)
Mo1—O19B	2.50 (3)

N1—C1—C2	121 (2)	O4—Mo5—O19B	64.3 (9)
N1—C1—H1	119.2	O5—Mo5—O19B	92.8 (9)
C2—C1—H1	119.6	O12ⁱ—Mo5—O19B	64.0 (9)
C3—C2—C1	120 (2)	O7—Mo5—O19B	93.4 (9)
C3—C2—H2	120.0	O18—Mo5—O21A	159.4 (9)
C1—C2—H2	119.7	O4—Mo5—O21A	90.7 (10)
C2—C3—C4	120 (2)	O5—Mo5—O21A	63.2 (8)
C2—C3—H3	120.3	O12ⁱ—Mo5—O21A	93.3 (10)
C4—C3—H3	120.1	O7—Mo5—O21A	64.7 (8)
C3—C4—C5	119 (3)	O19B—Mo5—O21A	41.0 (8)
C3—C4—H4	120.6	O2—Mo6—O9ⁱ	103.8 (10)
C5—C4—H4	120.5	O2—Mo6—O14	103.0 (10)
N1—C5—C4	122 (2)	O9ⁱ—Mo6—O14	91.9 (9)
N1—C5—C6	115.1 (19)	O2—Mo6—O17	100.1 (10)
C4—C5—C6	123 (2)	O9ⁱ—Mo6—O17	90.1 (7)
N2—C6—C7	111 (2)	O14—Mo6—O17	155.6 (10)
N2—C6—C5	117 (2)	O2—Mo6—O6	99.5 (9)
C7—C6—C5	132 (2)	O9ⁱ—Mo6—O6	156.5 (10)
C6—C7—C8	104 (3)	O14—Mo6—O6	85.9 (7)
C6—C7—H7	128.3	O17—Mo6—O6	82.7 (8)
C8—C7—H7	128.1	O2—Mo6—O19A	159.8 (9)
N3—C8—C7	107 (3)	O9ⁱ—Mo6—O19A	63.8 (9)
N3—C8—H8	126.4	O14—Mo6—O19A	93.7 (10)
C7—C8—H8	126.1	O17—Mo6—O19A	65.6 (9)
N4—C9—C10	122 (3)	O6—Mo6—O19A	92.9 (8)
N4—C9—H9	118.5	O2—Mo6—O21B	157.3 (9)
C10—C9—H9	119.4	O9ⁱ—Mo6—O21B	95.4 (10)
C11—C10—C9	120 (3)	O14—Mo6—O21B	63.8 (9)
C11—C10—H10	120.2	O17—Mo6—O21B	91.8 (10)
C9—C10—H10	120.2	O6—Mo6—O21B	62.7 (8)
C10—C11—C12	121 (3)	O19A—Mo6—O21B	42.5 (9)
C10—C11—H11	119.00	C5—N1—C1	117.9 (19)
C12—C11—H11	119.0	C5—N1—Ni1	114.9 (14)
C11—C12—C13	117 (3)	C1—N1—Ni1	127.2 (15)
C11—C12—H12	121.4	C6—N2—N3	106.7 (19)
C13—C12—H12	121.5	C6—N2—Ni1	115.7 (15)
N4—C13—C12	124 (3)	N3—N2—Ni1	137.5 (16)
N4—C13—C14	114 (2)	C8—N3—N2	111 (2)
C12—C13—C14	122 (2)	C8—N3—H3A	125.00
N5—C14—C15	111 (3)	N2—N3—H3A	124.9
N5—C14—C13	117 (2)	C13—N4—C9	116 (2)
C15—C14—C13	132 (3)	C13—N4—Ni1	115.1 (18)
C14—C15—C16	103 (3)	C9—N4—Ni1	128.6 (17)
C14—C15—H15	128.7	C14—N5—N6	105 (2)
C16—C15—H15	128.1	C14—N5—Ni1	116.7 (18)
N6—C16—C15	107 (3)	N6—N5—Ni1	137.8 (19)
N6—C16—H16	126.0	N5—N6—C16	113 (3)
C15—C16—H16	127.2	N5—N6—H6	123.1
N7—C17—C18	124 (3)	C16—N6—H6	123.7
N7—C17—H17	118.2	C21—N7—C17	117 (2)
C18—C17—H17	118.0	C21—N7—Ni1	115.7 (16)
C19—C18—C17	119 (3)	C17—N7—Ni1	127.6 (19)
C19—C18—H18	120.8	C22—N8—N9	106 (2)
C17—C18—H18	120.7	C22—N8—Ni1	115.4 (16)
C18—C19—C20	120 (3)	N9—N8—Ni1	138.5 (17)
C18—C19—H19	120.9	C24—N9—N8	111 (2)
C20—C19—H19	121.00	C24—N9—H9A	124.5
C21—C20—C19	117 (3)	N8—N9—H9A	124.7
C21—C20—H20	120.8	Mo3—O1—Mo4	138.2 (11)
C19—C20—H20	121.8	Mo5—O4—Mo1	139.5 (12)
N7—C21—C20	124 (3)	Mo5—O5—Mo4	140.4 (11)
N7—C21—C22	114 (2)	Mo4—O6—Mo6	138.9 (11)
C20—C21—C22	122 (3)	Mo3—O7—Mo5	139.2 (10)
N8—C22—C23	110 (2)	Mo6ⁱ—O9—Mo3	139.6 (13)
N8—C22—C21	117 (2)	Mo4—O11—Mo2	140.0 (12)
C23—C22—C21	133 (2)	Mo5ⁱ—O12—Mo2	138.5 (12)
C22—C23—C24	105 (2)	Mo1—O13—Mo3ⁱ	140.7 (13)
C22—C23—H23	127.8	Mo6—O14—Mo2	141.1 (11)
C24—C23—H23	126.9	Mo2ⁱ—O16—Mo1	142.1 (13)
N9—C24—C23	108 (2)	Mo1—O17—Mo6	136.8 (11)
N9—C24—H24	127.0	P1—O19A—O21Aⁱ	53.0 (11)
C23—C24—H24	125.4	P1—O19A—O21B	52.0 (11)
N5—Ni1—N8	95.9 (9)	O21Aⁱ—O19A—O21B	88.4 (17)
N5—Ni1—N2	167.4 (8)	P1—O19A—O19B	53.1 (11)
N8—Ni1—N2	93.7 (8)	O21Aⁱ—O19A—O19B	87.3 (16)
N5—Ni1—N4	77.1 (9)	O21B—O19A—O19B	85.4 (16)
N8—Ni1—N4	170.8 (8)	P1—O19A—Mo3ⁱ	124.6 (14)
N2—Ni1—N4	94.1 (8)	O21Aⁱ—O19A—Mo3ⁱ	71.6 (12)
N5—Ni1—N1	94.5 (7)	O21B—O19A—Mo3ⁱ	136.6 (16)
N8—Ni1—N1	91.8 (7)	O19B—O19A—Mo3ⁱ	129.8 (15)
N2—Ni1—N1	77.1 (7)	P1—O19A—Mo6	123.7 (14)
N4—Ni1—N1	94.8 (7)	O21Aⁱ—O19A—Mo6	132.5 (16)
N5—Ni1—N7	95.3 (7)	O21B—O19A—Mo6	71.7 (11)
N8—Ni1—N7	77.6 (8)	O19B—O19A—Mo6	131.4 (14)
N2—Ni1—N7	94.7 (7)	Mo3ⁱ—O19A—Mo6	93.6 (9)
N4—Ni1—N7	96.9 (8)	P1—O19A—Mo1	121.6 (13)
N1—Ni1—N7	166.2 (7)	O21Aⁱ—O19A—Mo1	132.3 (16)
O3—Mo1—O13	102.6 (10)	O21B—O19A—Mo1	127.5 (15)
O3—Mo1—O16	102.1 (10)	O19B—O19A—Mo1	68.5 (11)
O13—Mo1—O16	87.4 (9)	Mo3ⁱ—O19A—Mo1	92.6 (9)
O3—Mo1—O17	102.4 (9)	Mo6—O19A—Mo1	92.0 (9)
O13—Mo1—O17	88.0 (7)	P1—O21A—O21B	56.6 (12)
O16—Mo1—O17	155.5 (10)	P1—O21A—O19B	56.8 (12)
O3—Mo1—O4	101.8 (9)	O21B—O21A—O19B	94.2 (18)
O13—Mo1—O4	155.5 (10)	P1—O21A—O19Aⁱ	57.1 (12)
O16—Mo1—O4	85.9 (8)	O21B—O21A—O19Aⁱ	92.9 (17)
O17—Mo1—O4	88.3 (9)	O19B—O21A—O19Aⁱ	91.6 (17)
O3—Mo1—O19A	159.1 (9)	P1—O21A—Mo3	124.1 (14)
O13—Mo1—O19A	62.4 (9)	O21B—O21A—Mo3	128.9 (16)
O16—Mo1—O19A	92.1 (10)	O19B—O21A—Mo3	130.8 (16)
O17—Mo1—O19A	64.6 (8)	O19Aⁱ—O21A—Mo3	67.1 (12)
O4—Mo1—O19A	94.3 (9)	P1—O21A—Mo4	126.1 (14)
O3—Mo1—O19B	157.2 (9)	O21B—O21A—Mo4	69.5 (13)
O13—Mo1—O19B	93.2 (10)	O19B—O21A—Mo4	130.8 (16)
O16—Mo1—O19B	62.0 (9)	O19Aⁱ—O21A—Mo4	133.7 (16)
O17—Mo1—O19B	94.3 (9)	Mo3—O21A—Mo4	90.7 (8)
O4—Mo1—O19B	62.9 (9)	P1—O21A—Mo5	124.0 (14)
O19A—Mo1—O19B	43.6 (8)	O21B—O21A—Mo5	134.5 (16)
O15—Mo2—O16ⁱ	102.2 (10)	O19B—O21A—Mo5	67.3 (12)
O15—Mo2—O11	100.8 (10)	O19Aⁱ—O21A—Mo5	127.1 (15)
O16ⁱ—Mo2—O11	91.7 (9)	Mo3—O21A—Mo5	90.4 (8)
O15—Mo2—O14	102.3 (9)	Mo4—O21A—Mo5	91.1 (8)
O16ⁱ—Mo2—O14	155.2 (10)	P1—O19B—O21A	53.3 (12)
O11—Mo2—O14	87.5 (8)	P1—O19B—O21Bⁱ	53.3 (12)
O15—Mo2—O12	103.3 (10)	O21A—O19B—O21Bⁱ	90.3 (17)
O16ⁱ—Mo2—O12	86.7 (8)	P1—O19B—O19A	53.8 (12)
O11—Mo2—O12	155.6 (10)	O21A—O19B—O19A	88.1 (16)
O14—Mo2—O12	83.9 (8)	O21Bⁱ—O19B—O19A	86.0 (16)
O15—Mo2—O19Bⁱ	159.6 (9)	P1—O19B—Mo2ⁱ	123.3 (13)
O16ⁱ—Mo2—O19Bⁱ	63.8 (10)	O21A—O19B—Mo2ⁱ	135.8 (17)
O11—Mo2—O19Bⁱ	94.5 (10)	O21Bⁱ—O19B—Mo2ⁱ	70.1 (12)
O14—Mo2—O19Bⁱ	91.5 (9)	O19A—O19B—Mo2ⁱ	127.6 (15)
O12—Mo2—O19Bⁱ	63.0 (9)	P1—O19B—Mo5	125.1 (14)
O15—Mo2—O21B	158.5 (9)	O21A—O19B—Mo5	71.8 (12)
O16ⁱ—Mo2—O21B	93.1 (10)	O21Bⁱ—O19B—Mo5	133.9 (17)
O11—Mo2—O21B	63.2 (9)	O19A—O19B—Mo5	133.4 (15)
O14—Mo2—O21B	64.5 (8)	Mo2ⁱ—O19B—Mo5	93.4 (9)
O12—Mo2—O21B	92.5 (10)	P1—O19B—Mo1	121.6 (15)
O19Bⁱ—Mo2—O21B	41.9 (8)	O21A—O19B—Mo1	128.9 (15)
O10—Mo3—O1	103.0 (9)	O21Bⁱ—O19B—Mo1	129.5 (16)
O10—Mo3—O7	101.0 (9)	O19A—O19B—Mo1	67.9 (12)
O1—Mo3—O7	89.5 (7)	Mo2ⁱ—O19B—Mo1	92.1 (9)
O10—Mo3—O13ⁱ	101.9 (11)	Mo5—O19B—Mo1	92.5 (8)
O1—Mo3—O13ⁱ	91.7 (8)	P1—O21B—O21A	56.1 (13)
O7—Mo3—O13ⁱ	156.1 (10)	P1—O21B—O19Bⁱ	56.2 (12)
O10—Mo3—O9	100.3 (10)	O21A—O21B—O19Bⁱ	93.6 (17)
O1—Mo3—O9	156.6 (10)	P1—O21B—O19A	55.5 (12)
O7—Mo3—O9	84.2 (7)	O21A—O21B—O19A	92.3 (18)
O13ⁱ—Mo3—O9	85.3 (7)	O19Bⁱ—O21B—O19A	88.9 (17)
O10—Mo3—O19Aⁱ	157.4 (9)	P1—O21B—Mo4	127.4 (15)
O1—Mo3—O19Aⁱ	95.4 (9)	O21A—O21B—Mo4	71.4 (13)
O7—Mo3—O19Aⁱ	92.0 (9)	O19Bⁱ—O21B—Mo4	136.7 (17)
O13ⁱ—Mo3—O19Aⁱ	64.2 (10)	O19A—O21B—Mo4	130.8 (15)
O9—Mo3—O19Aⁱ	62.4 (9)	P1—O21B—Mo2	124.2 (14)
O10—Mo3—O21A	160.9 (9)	O21A—O21B—Mo2	132.5 (17)
O1—Mo3—O21A	65.6 (8)	O19Bⁱ—O21B—Mo2	68.0 (12)
O7—Mo3—O21A	65.0 (8)	O19A—O21B—Mo2	128.7 (15)
O13ⁱ—Mo3—O21A	93.9 (10)	Mo4—O21B—Mo2	92.1 (9)
O9—Mo3—O21A	91.4 (10)	P1—O21B—Mo6	121.2 (15)
O19Aⁱ—Mo3—O21A	41.3 (8)	O21A—O21B—Mo6	132.8 (16)
O8—Mo4—O6	103.5 (10)	O19Bⁱ—O21B—Mo6	125.1 (16)
O8—Mo4—O11	102.2 (10)	O19A—O21B—Mo6	65.8 (11)
O6—Mo4—O11	88.7 (7)	Mo4—O21B—Mo6	91.5 (8)
O8—Mo4—O5	101.7 (10)	Mo2—O21B—Mo6	90.3 (9)
O6—Mo4—O5	92.4 (8)	O21A—P1—O21Aⁱ	180 (3)
O11—Mo4—O5	155.2 (10)	O21A—P1—O21B	67.3 (14)
O8—Mo4—O1	99.8 (9)	O21Aⁱ—P1—O21B	112.7 (14)
O6—Mo4—O1	156.4 (9)	O21A—P1—O21Bⁱ	112.7 (14)
O11—Mo4—O1	82.6 (8)	O21Aⁱ—P1—O21Bⁱ	67.3 (14)
O5—Mo4—O1	86.6 (7)	O21B—P1—O21Bⁱ	180.0 (19)
O8—Mo4—O21B	161.4 (9)	O21A—P1—O19B	69.9 (14)
O6—Mo4—O21B	66.3 (8)	O21Aⁱ—P1—O19B	110.1 (14)
O11—Mo4—O21B	63.4 (9)	O21B—P1—O19B	109.4 (14)
O5—Mo4—O21B	94.4 (9)	O21Bⁱ—P1—O19B	70.6 (14)
O1—Mo4—O21B	90.2 (8)	O21A—P1—O19Bⁱ	110.1 (14)
O8—Mo4—O21A	159.0 (9)	O21Aⁱ—P1—O19Bⁱ	69.9 (14)
O6—Mo4—O21A	93.7 (9)	O21B—P1—O19Bⁱ	70.6 (14)
O11—Mo4—O21A	90.1 (9)	O21Bⁱ—P1—O19Bⁱ	109.4 (14)
O5—Mo4—O21A	65.1 (8)	O19B—P1—O19Bⁱ	180 (2)
O1—Mo4—O21A	64.6 (8)	O21A—P1—O19A	110.1 (13)
O21B—Mo4—O21A	39.1 (8)	O21Aⁱ—P1—O19A	69.9 (13)
O18—Mo5—O4	102.1 (10)	O21B—P1—O19A	72.5 (14)
O18—Mo5—O5	101.5 (9)	O21Bⁱ—P1—O19A	107.5 (14)
O4—Mo5—O5	85.3 (8)	O19B—P1—O19A	73.1 (14)
O18—Mo5—O12ⁱ	102.6 (10)	O19Bⁱ—P1—O19A	106.9 (14)
O4—Mo5—O12ⁱ	89.9 (8)	O21A—P1—O19Aⁱ	69.9 (13)
O5—Mo5—O12ⁱ	155.9 (10)	O21Aⁱ—P1—O19Aⁱ	110.1 (13)
O18—Mo5—O7	102.1 (9)	O21B—P1—O19Aⁱ	107.5 (14)
O4—Mo5—O7	155.3 (9)	O21Bⁱ—P1—O19Aⁱ	72.5 (14)
O5—Mo5—O7	85.4 (7)	O19B—P1—O19Aⁱ	106.9 (14)
O12ⁱ—Mo5—O7	89.3 (8)	O19Bⁱ—P1—O19Aⁱ	73.1 (14)
O18—Mo5—O19B	159.6 (10)	O19A—P1—O19Aⁱ	180 (2)

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	2.05	2.83 (3)	149
N6—H6···O2W	0.86	1.99	2.84 (5)	166
N9—H9A···O1W	0.86	1.92	2.74 (3)	160

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

Experimental details

Crystal data
Chemical formula	[Ni(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r	2918.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.741 (4), 16.285 (3), 27.678 (6)
β (°)	103.83 (3)
V (Å³)	8202 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.34
Crystal size (mm)	0.42 × 0.27 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.440, 0.652
No. of measured, independent and observed [I > 2σ(I)] reflections	22802, 7216, 5310
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.155, 1.00
No. of reflections	7216
No. of parameters	592
No. of restraints	18
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.088P)² + 10.3967P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.58, −0.67

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

Selected bond lengths (Å) top

Ni1—N5	2.077 (19)	Ni1—N7	2.14 (2)
Ni1—N8	2.06 (2)	P1—O21Aⁱ	1.49 (2)
Ni1—N2	2.084 (19)	P1—O21Bⁱ	1.50 (3)
Ni1—N4	2.13 (2)	P1—O19Bⁱ	1.55 (3)
Ni1—N1	2.118 (17)	P1—O19Aⁱ	1.57 (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	2.05	2.83 (3)	149.3
N6—H6···O2W	0.86	1.99	2.84 (5)	166.4
N9—H9A···O1W	0.86	1.92	2.74 (3)	159.8

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

Acknowledgements

Financial support from the International Cooperation Program for Excellent Lecturers of 2008 from Shandong Provincial Education Department, the Research Award Fund for Outstanding Young and Middle-aged Scientists of Shandong Province (2008BS04022), Shandong Provincial Education Department and Shandong Institute of Education are gratefully acknowledged.

References

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Volume 66| Part 3| March 2010| Pages m319-m320

doi:10.1107/S1600536810005945

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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]nickel(II)} dodeca­molybdo(V,VI)phosphate hexa­hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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