Bis{tris-[3-(2-pyrid-yl)-1H-pyrazole]nickel(II)} dodeca-molybdosilicate tetra-hydrate.

The asymmetric unit of the title compound, [Ni(C(8)H(7)N(3))(3)](2)[SiMo(12)O(40)]·4H(2)O, consists of a complex [Ni(C(8)H(7)N(3))(3)](2+) cation, half of a Keggin-type heteropolyanion [SiMo(12)O(40)](4-) and two uncoordinated water mol-ecules. The Ni(2+) cation is surrounded in a slightly distorted octa-hedral coordination by six N atoms from three chelating 3-(2-pyrid-yl)-1H-pyrazole ligands. In the heteropolyanion, two O atoms of the central SiO(4) group ( symmetry) are equally disordered about an inversion centre. N-H⋯O and O-H⋯O hydrogen bonding between the cations, anions and the uncoordinated water mol-ecules leads to a consolidation of the structure.

Related literature

For general background to polyoxometalates, see: Pope & Müller (1991 ▶). For n class="Chemical">polyoxometalates modified with amines, see: Zhang, Dou et al. (2009 ▶); Zhang, Wei, Sun et al. (2009 ▶; Zhang, Wei, Shi et al. (2010 ▶). For the related structure of the Zn analogue that crystallizes as the hexa­hydrate, see: Zhang, Wei, Zhu et al. (2010 ▶). For a further related structure, see: Wu et al. (2003 ▶).

Experimental

Crystal data

[Ni(C8n class="Species">H7N3)3]2[SiMo12O40]·4H2O

M = 2879.85

Monoclinic,

a = 18.687 (4) Å

b = 16.299 (3) Å

c = 27.604 (6) Å

β = 104.10 (3)°

V = 8154 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.35 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 = 0.766, T max = 0.835

28737 measured reflections

7188 independent reflections

3439 reflections with I > 2σ(I)

R int = 0.125

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.121

S = 1.00

7188 reflections

587 parameters

H-atom parameters constrained

Δρmax = 1.78 e Å−3

Δρmin = −0.66 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAIn class="Chemical">NT-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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810000978/wm2297sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000978/wm2297Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C8H7N3)3]2[SiMo12O40]·4H2O	F(000) = 5560
Mr = 2879.85	Dx = 2.346 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7031 reflections
a = 18.687 (4) Å	θ = 1.7–25.0°
b = 16.299 (3) Å	µ = 2.35 mm−1
c = 27.604 (6) Å	T = 293 K
β = 104.10 (3)°	Block, green
V = 8154 (3) Å3	0.12 × 0.10 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	7188 independent reflections
Radiation source: fine-focus sealed tube	3439 reflections with I > 2σ(I)
graphite	Rint = 0.125
phi and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→22
Tmin = 0.766, Tmax = 0.835	k = −19→19
28737 measured reflections	l = −32→32

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3
7188 reflections	(Δ/σ)max < 0.001
587 parameters	Δρmax = 1.78 e Å−3
0 restraints	Δρmin = −0.66 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.35240 (6)	0.39842 (7)	0.08084 (4)	0.0443 (3)
Mo2	0.41863 (6)	0.32246 (7)	−0.01978 (4)	0.0435 (3)
Mo3	0.17276 (7)	0.34378 (8)	0.09029 (4)	0.0473 (4)
Mo4	0.41827 (6)	0.19458 (8)	0.08355 (4)	0.0465 (4)
Mo5	0.19742 (7)	0.45683 (7)	−0.01322 (5)	0.0504 (4)
Mo6	0.24752 (7)	0.14446 (8)	0.11101 (4)	0.0518 (4)
Ni1	0.20687 (9)	0.68505 (11)	0.80894 (6)	0.0483 (5)
Si1	0.2500	0.2500	0.0000	0.0298 (12)
C1	0.0571 (10)	0.6492 (14)	0.9038 (7)	0.094 (7)
H1	0.0339	0.6609	0.9292	0.112*
C2	0.0465 (9)	0.5804 (13)	0.8729 (7)	0.091 (7)
H2	0.0143	0.5370	0.8733	0.110*
C3	0.0961 (8)	0.5903 (10)	0.8402 (6)	0.054 (4)
C4	0.1117 (8)	0.5414 (11)	0.8024 (6)	0.054 (4)
C5	0.0818 (9)	0.4649 (14)	0.7921 (7)	0.087 (6)
H5	0.0509	0.4437	0.8108	0.105*
C6	0.0967 (10)	0.4219 (13)	0.7560 (8)	0.098 (7)
H6	0.0761	0.3701	0.7487	0.117*
C7	0.1423 (9)	0.4526 (11)	0.7292 (6)	0.068 (5)
H7	0.1521	0.4238	0.7025	0.082*
C8	0.1740 (8)	0.5294 (10)	0.7432 (5)	0.060 (4)
H8	0.2075	0.5497	0.7262	0.072*
C9	0.3644 (10)	0.6954 (10)	0.7209 (5)	0.075 (5)
H9	0.3831	0.7078	0.6935	0.090*
C10	0.4029 (8)	0.6601 (10)	0.7658 (6)	0.077 (5)
H10	0.4520	0.6436	0.7745	0.092*
C11	0.3521 (8)	0.6553 (8)	0.7941 (5)	0.049 (4)
C12	0.3576 (7)	0.6248 (7)	0.8444 (5)	0.038 (3)
C13	0.4223 (8)	0.5908 (9)	0.8744 (6)	0.068 (5)
H13	0.4653	0.5878	0.8633	0.081*
C14	0.4201 (8)	0.5628 (9)	0.9197 (6)	0.069 (5)
H14	0.4623	0.5394	0.9401	0.083*
C15	0.3569 (8)	0.5679 (8)	0.9368 (5)	0.051 (4)
H15	0.3562	0.5480	0.9682	0.061*
C16	0.2960 (7)	0.6023 (8)	0.9071 (5)	0.045 (4)
H16	0.2533	0.6064	0.9186	0.054*
C17	0.2717 (10)	0.9142 (11)	0.8778 (6)	0.077 (5)
H17	0.2973	0.9505	0.9019	0.092*
C18	0.2178 (9)	0.9341 (10)	0.8373 (6)	0.077 (5)
H18	0.1991	0.9863	0.8282	0.093*
C19	0.1958 (8)	0.8617 (9)	0.8119 (6)	0.057 (4)
C20	0.1435 (8)	0.8442 (11)	0.7662 (5)	0.059 (4)
C21	0.1056 (9)	0.9007 (10)	0.7363 (6)	0.082 (6)
H21	0.1121	0.9556	0.7454	0.098*
C22	0.0578 (10)	0.8808 (12)	0.6928 (8)	0.103 (7)
H22	0.0308	0.9203	0.6717	0.124*
C23	0.0516 (9)	0.8002 (14)	0.6820 (6)	0.095 (6)
H23	0.0210	0.7830	0.6519	0.114*
C24	0.0910 (8)	0.7415 (9)	0.7157 (6)	0.067 (5)
H24	0.0837	0.6861	0.7082	0.081*
N1	0.1099 (7)	0.6972 (8)	0.8887 (5)	0.076 (4)
H1A	0.1262	0.7435	0.9018	0.091*
N2	0.1317 (6)	0.6609 (8)	0.8510 (4)	0.057 (3)
N3	0.1596 (6)	0.5741 (7)	0.7786 (4)	0.055 (3)
N4	0.2975 (7)	0.7076 (7)	0.7250 (4)	0.063 (4)
H4	0.2633	0.7290	0.7019	0.075*
N5	0.2877 (6)	0.6839 (7)	0.7681 (4)	0.055 (3)
N6	0.2958 (6)	0.6311 (6)	0.8608 (4)	0.044 (3)
N7	0.2818 (6)	0.8333 (8)	0.8773 (4)	0.066 (4)
H7A	0.3136	0.8063	0.8993	0.080*
N8	0.2349 (6)	0.7999 (7)	0.8373 (4)	0.052 (3)
N9	0.1365 (6)	0.7627 (8)	0.7565 (4)	0.050 (3)
O1A	0.2482 (7)	0.3343 (8)	0.0309 (5)	0.027 (4)	0.50
O1B	0.2934 (7)	0.1816 (9)	0.0391 (5)	0.029 (4)	0.50
O2	0.2429 (5)	0.0914 (5)	0.1612 (3)	0.060 (3)
O3	0.3450 (5)	0.1717 (6)	0.1221 (3)	0.084 (3)
O4	0.3951 (5)	0.0981 (6)	0.0507 (4)	0.090 (3)
O5	0.4948 (4)	0.1706 (6)	0.1251 (3)	0.072 (3)
O6	0.4537 (5)	0.2423 (5)	0.0337 (3)	0.065 (3)
O7	0.5002 (5)	0.3493 (5)	−0.0291 (3)	0.064 (3)
O8	0.3538 (5)	0.3703 (5)	−0.0718 (3)	0.083 (3)
O9	0.4062 (5)	0.3955 (5)	0.0265 (3)	0.069 (3)
O10	0.4013 (5)	0.4725 (5)	0.1145 (3)	0.068 (3)
O11	0.2353 (5)	0.4438 (6)	−0.0677 (4)	0.087 (3)
O12A	0.2849 (9)	0.4501 (13)	0.0254 (7)	0.043 (6)	0.50
O12B	0.2927 (14)	0.4877 (14)	0.0385 (9)	0.057 (9)*	0.50
O13	0.1700 (5)	0.5541 (5)	−0.0185 (3)	0.064 (3)
O14	0.1565 (4)	0.4247 (6)	0.0429 (3)	0.079 (3)
O15	0.1428 (4)	0.3897 (5)	0.1359 (3)	0.061 (3)
O16	0.0955 (6)	0.2809 (6)	0.0605 (4)	0.097 (4)
O17	0.2229 (5)	0.2482 (6)	0.1281 (4)	0.090 (3)
O18A	0.1691 (8)	0.2190 (8)	−0.0272 (5)	0.029 (4)	0.50
O18B	0.1992 (7)	0.2358 (9)	0.0414 (5)	0.031 (4)	0.50
O19	0.4037 (5)	0.3075 (5)	0.1058 (3)	0.067 (3)
O20	0.2782 (4)	0.3836 (6)	0.1090 (3)	0.079 (3)
O21	0.3627 (7)	0.6467 (9)	0.0636 (5)	0.157 (5)
O22	0.6160 (6)	0.2176 (6)	0.0381 (4)	0.096 (4)

	U11	U22	U33	U12	U13	U23
Mo1	0.0396 (8)	0.0504 (8)	0.0407 (8)	−0.0109 (6)	0.0055 (6)	−0.0107 (7)
Mo2	0.0335 (7)	0.0450 (8)	0.0510 (8)	−0.0066 (6)	0.0085 (6)	−0.0027 (7)
Mo3	0.0542 (9)	0.0530 (9)	0.0335 (7)	0.0146 (7)	0.0085 (6)	−0.0077 (7)
Mo4	0.0344 (7)	0.0582 (9)	0.0412 (8)	−0.0001 (6)	−0.0016 (6)	0.0041 (7)
Mo5	0.0592 (9)	0.0338 (7)	0.0639 (9)	0.0095 (7)	0.0260 (7)	0.0070 (7)
Mo6	0.0765 (10)	0.0469 (8)	0.0300 (7)	−0.0085 (7)	0.0094 (7)	0.0062 (6)
Ni1	0.0458 (11)	0.0548 (13)	0.0445 (11)	0.0074 (10)	0.0111 (9)	0.0094 (10)
Si1	0.031 (3)	0.032 (3)	0.022 (3)	0.001 (2)	−0.001 (2)	−0.001 (2)
C1	0.062 (13)	0.16 (2)	0.071 (14)	0.042 (14)	0.031 (11)	0.054 (14)
C2	0.050 (12)	0.14 (2)	0.074 (14)	0.007 (12)	−0.007 (11)	0.057 (13)
C3	0.035 (7)	0.063 (8)	0.058 (8)	0.000 (7)	0.001 (6)	0.021 (7)
C4	0.033 (9)	0.058 (12)	0.059 (11)	0.009 (8)	−0.011 (8)	0.002 (10)
C5	0.071 (13)	0.114 (19)	0.063 (14)	−0.017 (13)	−0.011 (11)	0.029 (13)
C6	0.078 (15)	0.112 (19)	0.084 (16)	−0.020 (13)	−0.017 (13)	0.009 (14)
C7	0.063 (12)	0.072 (13)	0.062 (12)	0.001 (10)	−0.001 (9)	0.005 (10)
C8	0.064 (11)	0.065 (12)	0.044 (10)	0.004 (10)	0.002 (9)	0.015 (9)
C9	0.080 (13)	0.110 (15)	0.040 (10)	−0.019 (12)	0.023 (10)	0.008 (10)
C10	0.063 (12)	0.092 (14)	0.077 (13)	0.005 (10)	0.020 (10)	0.003 (11)
C11	0.053 (10)	0.055 (10)	0.046 (10)	−0.010 (8)	0.023 (8)	−0.002 (8)
C12	0.038 (9)	0.034 (9)	0.042 (9)	−0.002 (7)	0.008 (7)	−0.002 (7)
C13	0.051 (11)	0.081 (13)	0.069 (12)	0.000 (9)	0.010 (9)	0.015 (10)
C14	0.061 (12)	0.078 (12)	0.054 (11)	−0.008 (9)	−0.015 (9)	0.006 (10)
C15	0.077 (12)	0.045 (9)	0.031 (9)	−0.014 (9)	0.012 (9)	0.008 (7)
C16	0.029 (8)	0.056 (10)	0.050 (9)	−0.002 (7)	0.009 (7)	0.015 (8)
C17	0.115 (16)	0.067 (13)	0.051 (12)	−0.015 (12)	0.024 (11)	−0.022 (10)
C18	0.095 (14)	0.072 (14)	0.066 (13)	0.036 (11)	0.023 (11)	0.009 (11)
C19	0.069 (12)	0.034 (10)	0.077 (13)	0.009 (9)	0.035 (10)	−0.004 (10)
C20	0.067 (11)	0.064 (12)	0.039 (10)	0.016 (10)	0.002 (8)	0.006 (9)
C21	0.080 (13)	0.070 (13)	0.076 (13)	−0.001 (11)	−0.019 (10)	0.019 (11)
C22	0.094 (16)	0.077 (15)	0.122 (19)	0.015 (13)	−0.006 (13)	0.029 (14)
C23	0.082 (14)	0.128 (19)	0.053 (12)	−0.002 (14)	−0.027 (10)	0.005 (13)
C24	0.063 (12)	0.066 (12)	0.067 (12)	0.001 (9)	0.005 (9)	0.013 (10)
N1	0.070 (10)	0.086 (11)	0.064 (10)	0.027 (8)	0.002 (8)	0.003 (9)
N2	0.050 (8)	0.078 (10)	0.041 (8)	0.021 (7)	0.011 (6)	−0.002 (7)
N3	0.048 (8)	0.070 (10)	0.047 (8)	0.006 (7)	0.014 (7)	0.001 (7)
N4	0.071 (10)	0.083 (10)	0.035 (8)	0.002 (8)	0.014 (7)	0.020 (7)
N5	0.048 (8)	0.064 (9)	0.049 (8)	−0.001 (7)	0.003 (7)	0.013 (7)
N6	0.049 (8)	0.032 (7)	0.051 (8)	0.009 (5)	0.014 (6)	0.010 (6)
N7	0.069 (9)	0.073 (10)	0.056 (9)	0.005 (8)	0.014 (7)	0.002 (8)
N8	0.058 (8)	0.057 (9)	0.042 (8)	−0.001 (7)	0.015 (6)	−0.008 (7)
N9	0.040 (8)	0.064 (9)	0.041 (8)	0.007 (7)	0.002 (6)	−0.003 (7)
O1A	0.032 (7)	0.031 (7)	0.020 (7)	0.002 (6)	0.008 (6)	0.003 (6)
O1B	0.022 (7)	0.036 (8)	0.029 (7)	−0.001 (6)	0.006 (6)	0.006 (6)
O2	0.063 (6)	0.070 (7)	0.043 (6)	−0.003 (5)	0.002 (5)	0.023 (5)
O3	0.089 (7)	0.087 (7)	0.092 (7)	−0.045 (5)	0.051 (5)	−0.039 (5)
O4	0.094 (7)	0.101 (7)	0.088 (7)	−0.046 (6)	0.050 (5)	−0.038 (6)
O5	0.049 (6)	0.105 (9)	0.050 (6)	0.027 (6)	−0.009 (5)	−0.002 (6)
O6	0.111 (9)	0.049 (6)	0.047 (6)	0.023 (6)	0.042 (6)	0.010 (5)
O7	0.060 (7)	0.063 (7)	0.077 (7)	−0.012 (5)	0.033 (5)	0.006 (6)
O8	0.088 (6)	0.041 (5)	0.087 (6)	0.010 (5)	−0.046 (5)	−0.010 (5)
O9	0.108 (8)	0.063 (7)	0.052 (6)	0.044 (6)	0.051 (6)	0.026 (5)
O10	0.094 (8)	0.063 (7)	0.047 (6)	−0.031 (6)	0.019 (5)	−0.023 (5)
O11	0.080 (6)	0.101 (7)	0.093 (7)	−0.047 (5)	0.049 (5)	−0.054 (6)
O12A	0.012 (10)	0.064 (17)	0.047 (14)	−0.011 (11)	−0.002 (9)	0.013 (13)
O13	0.065 (7)	0.034 (6)	0.089 (8)	0.013 (5)	0.008 (6)	0.006 (5)
O14	0.040 (6)	0.131 (10)	0.067 (7)	0.003 (6)	0.015 (5)	0.049 (7)
O15	0.056 (6)	0.078 (7)	0.054 (6)	0.004 (5)	0.025 (5)	−0.014 (5)
O16	0.104 (7)	0.066 (6)	0.085 (7)	0.006 (6)	−0.048 (5)	−0.005 (5)
O17	0.091 (7)	0.053 (6)	0.094 (7)	0.013 (5)	−0.037 (5)	−0.011 (5)
O18A	0.032 (10)	0.027 (10)	0.025 (9)	0.002 (8)	0.000 (8)	0.010 (7)
O18B	0.014 (8)	0.040 (11)	0.043 (11)	0.010 (7)	0.015 (8)	0.000 (8)
O19	0.106 (8)	0.056 (7)	0.054 (6)	0.025 (6)	0.048 (6)	0.010 (5)
O20	0.031 (6)	0.132 (10)	0.073 (7)	0.012 (6)	0.011 (5)	0.059 (7)
O21	0.157 (5)	0.157 (5)	0.157 (5)	−0.0005 (11)	0.0390 (16)	−0.0004 (11)
O22	0.096 (4)	0.096 (4)	0.096 (4)	0.0005 (10)	0.0228 (13)	−0.0002 (11)

Mo1—O10	1.657 (8)	C3—C4	1.397 (18)
Mo1—O20	1.763 (8)	C4—N3	1.344 (17)
Mo1—O19	1.808 (8)	C4—C5	1.37 (2)
Mo1—O12A	1.924 (18)	C5—C6	1.30 (2)
Mo1—O9	2.000 (8)	C5—H5	0.9300
Mo1—O12B	2.02 (3)	C6—C7	1.35 (2)
Mo1—O1A	2.340 (13)	C6—H6	0.9300
Mo1—O18Ai	2.394 (14)	C7—C8	1.398 (18)
Mo2—O7	1.666 (8)	C7—H7	0.9300
Mo2—O9	1.802 (8)	C8—N3	1.298 (16)
Mo2—O8	1.813 (8)	C8—H8	0.9300
Mo2—O6	1.961 (8)	C9—N4	1.298 (16)
Mo2—O16i	2.006 (9)	C9—C10	1.395 (18)
Mo2—O18Bi	2.337 (13)	C9—H9	0.9300
Mo2—O18Ai	2.420 (14)	C10—C11	1.372 (17)
Mo3—O15	1.673 (8)	C10—H10	0.9300
Mo3—O16	1.798 (9)	C11—N5	1.326 (15)
Mo3—O14	1.830 (9)	C11—C12	1.455 (16)
Mo3—O17	1.979 (9)	C12—N6	1.342 (14)
Mo3—O20	2.019 (8)	C12—C13	1.404 (16)
Mo3—O18B	2.343 (14)	C13—C14	1.340 (17)
Mo3—O1A	2.414 (13)	C13—H13	0.9300
Mo4—O5	1.647 (8)	C14—C15	1.376 (17)
Mo4—O4	1.814 (9)	C14—H14	0.9300
Mo4—O6	1.838 (8)	C15—C16	1.351 (16)
Mo4—O3	1.964 (9)	C15—H15	0.9300
Mo4—O19	1.981 (9)	C16—N6	1.359 (14)
Mo4—O1B	2.366 (13)	C16—H16	0.9300
Mo4—O18Ai	2.415 (13)	C17—N7	1.332 (17)
Mo5—O13	1.662 (8)	C17—C18	1.352 (18)
Mo5—O12A	1.724 (17)	C17—H17	0.9300
Mo5—O11	1.824 (9)	C18—C19	1.383 (18)
Mo5—O14	1.958 (8)	C18—H18	0.9300
Mo5—O4i	1.997 (9)	C19—N8	1.337 (16)
Mo5—O12B	2.06 (2)	C19—C20	1.426 (18)
Mo5—O1Bi	2.385 (14)	C20—C21	1.321 (18)
Mo5—O1A	2.411 (13)	C20—N9	1.355 (17)
Mo6—O2	1.653 (8)	C21—C22	1.35 (2)
Mo6—O17	1.844 (9)	C21—H21	0.9300
Mo6—O3	1.827 (9)	C22—C23	1.35 (2)
Mo6—O11i	1.946 (9)	C22—H22	0.9300
Mo6—O8i	1.954 (9)	C23—C24	1.410 (19)
Mo6—O1B	2.422 (13)	C23—H23	0.9300
Mo6—O18B	2.426 (14)	C24—N9	1.282 (15)
Ni1—N8	2.047 (11)	C24—H24	0.9300
Ni1—N5	2.093 (11)	N1—N2	1.345 (14)
Ni1—N2	2.066 (11)	N1—H1A	0.8600
Ni1—N6	2.104 (10)	N4—N5	1.305 (13)
Ni1—N3	2.096 (12)	N4—H4	0.8600
Ni1—N9	2.121 (11)	N7—N8	1.345 (13)
Si1—O18A	1.597 (13)	N7—H7A	0.8600
Si1—O18Ai	1.597 (13)	O1A—O18Ai	1.798 (18)
Si1—O18Bi	1.670 (13)	O1B—Mo5i	2.385 (14)
Si1—O18B	1.670 (13)	O4—Mo5i	1.997 (9)
Si1—O1Ai	1.622 (14)	O8—Mo6i	1.954 (9)
Si1—O1A	1.622 (14)	O11—Mo6i	1.946 (9)
Si1—O1Bi	1.625 (13)	O12A—O12B	0.71 (3)
Si1—O1B	1.625 (13)	O16—Mo2i	2.006 (9)
C1—N1	1.399 (19)	O18A—O18B	1.858 (19)
C1—C2	1.39 (2)	O18A—O1Ai	1.798 (18)
C1—H1	0.9300	O18A—Mo2i	2.420 (14)
C2—C3	1.45 (2)	O18A—Mo1i	2.394 (14)
C2—H2	0.9300	O18A—Mo4i	2.415 (13)
C3—N2	1.327 (16)	O18B—Mo2i	2.337 (13)
O10—Mo1—O20	103.7 (4)	O18A—Si1—O1Bi	69.1 (6)
O10—Mo1—O19	102.4 (4)	O18Ai—Si1—O1Bi	110.9 (6)
O20—Mo1—O19	96.9 (4)	O18Bi—Si1—O1Bi	74.1 (6)
O10—Mo1—O12A	107.0 (7)	O18B—Si1—O1Bi	105.9 (6)
O20—Mo1—O12A	88.7 (6)	O1Ai—Si1—O1Bi	107.6 (7)
O19—Mo1—O12A	147.9 (7)	O1A—Si1—O1Bi	72.4 (7)
O10—Mo1—O9	97.4 (4)	O18A—Si1—O1B	110.9 (6)
O20—Mo1—O9	157.0 (4)	O18Ai—Si1—O1B	69.1 (6)
O19—Mo1—O9	87.2 (3)	O18Bi—Si1—O1B	105.9 (6)
O12A—Mo1—O9	76.5 (6)	O18B—Si1—O1B	74.1 (6)
O10—Mo1—O12B	87.2 (7)	O1Ai—Si1—O1B	72.4 (7)
O20—Mo1—O12B	88.3 (8)	O1A—Si1—O1B	107.6 (7)
O19—Mo1—O12B	167.6 (7)	O1Bi—Si1—O1B	180.0 (11)
O12A—Mo1—O12B	20.5 (8)	N1—C1—C2	105.9 (17)
O9—Mo1—O12B	83.7 (8)	N1—C1—H1	127.0
O10—Mo1—O1A	157.3 (5)	C2—C1—H1	127.0
O20—Mo1—O1A	64.4 (4)	C1—C2—C3	105.9 (18)
O19—Mo1—O1A	98.4 (5)	C1—C2—H2	127.1
O12A—Mo1—O1A	55.7 (7)	C3—C2—H2	127.1
O9—Mo1—O1A	92.6 (4)	N2—C3—C4	118.6 (16)
O12B—Mo1—O1A	73.7 (7)	N2—C3—C2	108.4 (16)
O10—Mo1—O18Ai	156.5 (5)	C4—C3—C2	133.0 (18)
O20—Mo1—O18Ai	97.6 (5)	N3—C4—C5	123.1 (16)
O19—Mo1—O18Ai	64.8 (4)	N3—C4—C3	115.1 (16)
O12A—Mo1—O18Ai	83.1 (7)	C5—C4—C3	121.8 (19)
O9—Mo1—O18Ai	63.6 (4)	C6—C5—C4	120 (2)
O12B—Mo1—O18Ai	103.4 (7)	C6—C5—H5	120.1
O1A—Mo1—O18Ai	44.6 (4)	C4—C5—H5	120.1
O7—Mo2—O9	102.5 (4)	C5—C6—C7	120 (2)
O7—Mo2—O8	103.0 (5)	C5—C6—H6	120.0
O9—Mo2—O8	95.8 (4)	C7—C6—H6	120.0
O7—Mo2—O6	98.1 (4)	C6—C7—C8	117.4 (17)
O9—Mo2—O6	89.1 (3)	C6—C7—H7	121.3
O8—Mo2—O6	156.8 (4)	C8—C7—H7	121.3
O7—Mo2—O16i	97.7 (4)	N3—C8—C7	123.9 (15)
O9—Mo2—O16i	158.4 (4)	N3—C8—H8	118.0
O8—Mo2—O16i	86.9 (4)	C7—C8—H8	118.0
O6—Mo2—O16i	80.6 (4)	N4—C9—C10	106.6 (14)
O7—Mo2—O18Bi	155.2 (5)	N4—C9—H9	126.7
O9—Mo2—O18Bi	100.0 (5)	C10—C9—H9	126.7
O8—Mo2—O18Bi	64.3 (5)	C11—C10—C9	104.5 (14)
O6—Mo2—O18Bi	92.4 (4)	C11—C10—H10	127.8
O16i—Mo2—O18Bi	61.9 (4)	C9—C10—H10	127.8
O7—Mo2—O18Ai	157.1 (4)	N5—C11—C10	109.6 (13)
O9—Mo2—O18Ai	65.4 (4)	N5—C11—C12	118.7 (13)
O8—Mo2—O18Ai	97.8 (5)	C10—C11—C12	131.8 (15)
O6—Mo2—O18Ai	63.6 (4)	N6—C12—C13	121.3 (13)
O16i—Mo2—O18Ai	92.9 (5)	N6—C12—C11	115.5 (12)
O18Bi—Mo2—O18Ai	45.9 (4)	C13—C12—C11	123.3 (14)
O15—Mo3—O16	102.8 (5)	C14—C13—C12	117.9 (15)
O15—Mo3—O14	100.8 (4)	C14—C13—H13	121.1
O16—Mo3—O14	96.3 (4)	C12—C13—H13	121.1
O15—Mo3—O17	99.0 (4)	C13—C14—C15	121.5 (15)
O16—Mo3—O17	91.0 (4)	C13—C14—H14	119.3
O14—Mo3—O17	156.8 (4)	C15—C14—H14	119.3
O15—Mo3—O20	98.5 (4)	C16—C15—C14	118.9 (13)
O16—Mo3—O20	157.7 (5)	C16—C15—H15	120.5
O14—Mo3—O20	86.1 (4)	C14—C15—H15	120.5
O17—Mo3—O20	79.1 (4)	C15—C16—N6	121.5 (12)
O15—Mo3—O18B	157.7 (5)	C15—C16—H16	119.3
O16—Mo3—O18B	64.3 (5)	N6—C16—H16	119.3
O14—Mo3—O18B	98.7 (5)	N7—C17—C18	107.9 (15)
O17—Mo3—O18B	64.8 (4)	N7—C17—H17	126.1
O20—Mo3—O18B	93.4 (4)	C18—C17—H17	126.1
O15—Mo3—O1A	153.8 (4)	C17—C18—C19	106.4 (15)
O16—Mo3—O1A	100.9 (5)	C17—C18—H18	126.8
O14—Mo3—O1A	65.4 (4)	C19—C18—H18	126.8
O17—Mo3—O1A	91.6 (5)	N8—C19—C20	118.9 (15)
O20—Mo3—O1A	59.9 (4)	N8—C19—C18	108.7 (15)
O18B—Mo3—O1A	47.2 (5)	C20—C19—C18	132.3 (16)
O5—Mo4—O4	101.8 (5)	C21—C20—N9	123.3 (15)
O5—Mo4—O6	102.2 (4)	C21—C20—C19	124.2 (17)
O4—Mo4—O6	94.5 (4)	N9—C20—C19	112.5 (13)
O5—Mo4—O3	100.3 (4)	C20—C21—C22	121.8 (18)
O4—Mo4—O3	89.6 (4)	C20—C21—H21	119.1
O6—Mo4—O3	155.7 (4)	C22—C21—H21	119.1
O5—Mo4—O19	99.5 (4)	C23—C22—C21	115.7 (18)
O4—Mo4—O19	157.9 (4)	C23—C22—H22	122.1
O6—Mo4—O19	86.6 (3)	C21—C22—H22	122.1
O3—Mo4—O19	80.9 (4)	C22—C23—C24	120.8 (17)
O5—Mo4—O1B	156.7 (5)	C22—C23—H23	119.6
O4—Mo4—O1B	65.0 (5)	C24—C23—H23	119.6
O6—Mo4—O1B	98.0 (4)	N9—C24—C23	121.7 (16)
O3—Mo4—O1B	62.2 (4)	N9—C24—H24	119.2
O19—Mo4—O1B	93.0 (4)	C23—C24—H24	119.2
O5—Mo4—O18Ai	157.3 (5)	N2—N1—C1	110.7 (15)
O4—Mo4—O18Ai	98.1 (5)	N2—N1—H1A	124.7
O6—Mo4—O18Ai	65.2 (4)	C1—N1—H1A	124.7
O3—Mo4—O18Ai	90.5 (5)	N1—N2—C3	109.0 (14)
O19—Mo4—O18Ai	62.4 (4)	N1—N2—Ni1	136.7 (12)
O1B—Mo4—O18Ai	44.9 (5)	C3—N2—Ni1	114.3 (11)
O13—Mo5—O12A	109.9 (8)	C8—N3—C4	115.6 (14)
O13—Mo5—O11	102.2 (5)	C8—N3—Ni1	129.8 (12)
O12A—Mo5—O11	90.2 (7)	C4—N3—Ni1	114.4 (11)
O13—Mo5—O14	98.8 (4)	C9—N4—N5	112.7 (12)
O12A—Mo5—O14	89.3 (7)	C9—N4—H4	123.7
O11—Mo5—O14	157.8 (4)	N5—N4—H4	123.7
O13—Mo5—O4i	99.9 (4)	C11—N5—N4	106.7 (12)
O12A—Mo5—O4i	149.6 (8)	C11—N5—Ni1	113.0 (10)
O11—Mo5—O4i	88.9 (4)	N4—N5—Ni1	140.1 (10)
O14—Mo5—O4i	80.5 (4)	C12—N6—C16	119.0 (11)
O13—Mo5—O12B	91.4 (7)	C12—N6—Ni1	113.8 (9)
O12A—Mo5—O12B	19.1 (10)	C16—N6—Ni1	127.2 (9)
O11—Mo5—O12B	99.0 (8)	C17—N7—N8	110.1 (13)
O14—Mo5—O12B	87.4 (8)	C17—N7—H7A	124.9
O4i—Mo5—O12B	164.5 (8)	N8—N7—H7A	124.9
O13—Mo5—O1Bi	156.8 (4)	N7—N8—C19	106.8 (12)
O12A—Mo5—O1Bi	90.0 (8)	N7—N8—Ni1	137.6 (11)
O11—Mo5—O1Bi	64.7 (4)	C19—N8—Ni1	115.6 (11)
O14—Mo5—O1Bi	93.1 (4)	C24—N9—C20	116.6 (13)
O4i—Mo5—O1Bi	62.4 (4)	C24—N9—Ni1	127.4 (11)
O12B—Mo5—O1Bi	109.0 (7)	C20—N9—Ni1	115.8 (9)
O13—Mo5—O1A	155.5 (4)	Si1—O1A—O18Ai	55.4 (6)
O12A—Mo5—O1A	55.8 (8)	Si1—O1A—Mo1	124.6 (7)
O11—Mo5—O1A	97.8 (5)	O18Ai—O1A—Mo1	69.3 (6)
O14—Mo5—O1A	63.9 (4)	Si1—O1A—Mo5	119.5 (7)
O4i—Mo5—O1A	94.3 (4)	O18Ai—O1A—Mo5	127.6 (8)
O12B—Mo5—O1A	71.6 (7)	Mo1—O1A—Mo5	95.5 (5)
O1Bi—Mo5—O1A	47.1 (4)	Si1—O1A—Mo3	120.1 (7)
O2—Mo6—O17	101.4 (5)	O18Ai—O1A—Mo3	136.3 (8)
O2—Mo6—O3	103.9 (4)	Mo1—O1A—Mo3	96.4 (5)
O17—Mo6—O3	92.0 (4)	Mo5—O1A—Mo3	93.8 (5)
O2—Mo6—O11i	100.3 (4)	Si1—O1B—Mo4	123.5 (7)
O17—Mo6—O11i	157.5 (4)	Si1—O1B—Mo5i	120.7 (7)
O3—Mo6—O11i	88.6 (4)	Mo4—O1B—Mo5i	96.1 (5)
O2—Mo6—O8i	99.1 (4)	Si1—O1B—Mo6	119.8 (7)
O17—Mo6—O8i	89.2 (4)	Mo4—O1B—Mo6	95.7 (5)
O3—Mo6—O8i	156.2 (4)	Mo5i—O1B—Mo6	94.3 (5)
O11i—Mo6—O8i	81.5 (4)	Mo6—O3—Mo4	138.9 (5)
O2—Mo6—O1B	156.7 (4)	Mo4—O4—Mo5i	136.0 (6)
O17—Mo6—O1B	98.1 (5)	Mo4—O6—Mo2	136.9 (5)
O3—Mo6—O1B	62.5 (4)	Mo2—O8—Mo6i	139.1 (6)
O11i—Mo6—O1B	62.4 (4)	Mo2—O9—Mo1	136.3 (5)
O8i—Mo6—O1B	93.8 (4)	Mo5—O11—Mo6i	138.4 (6)
O2—Mo6—O18B	154.1 (4)	O12B—O12A—Mo5	108 (3)
O17—Mo6—O18B	64.7 (4)	O12B—O12A—Mo1	88 (3)
O3—Mo6—O18B	98.5 (5)	Mo5—O12A—Mo1	149.2 (11)
O11i—Mo6—O18B	93.0 (5)	O12A—O12B—Mo5	53 (3)
O8i—Mo6—O18B	60.8 (4)	O12A—O12B—Mo1	72 (3)
O1B—Mo6—O18B	48.4 (4)	Mo5—O12B—Mo1	119.2 (11)
N8—Ni1—N5	93.6 (4)	Mo3—O14—Mo5	136.8 (5)
N8—Ni1—N2	96.0 (5)	Mo3—O16—Mo2i	135.8 (6)
N5—Ni1—N2	168.3 (5)	Mo6—O17—Mo3	134.6 (5)
N8—Ni1—N6	92.0 (4)	Si1—O18A—O18B	57.2 (6)
N5—Ni1—N6	79.0 (4)	Si1—O18A—O1Ai	56.7 (6)
N2—Ni1—N6	94.0 (4)	O18B—O18A—O1Ai	94.5 (8)
N8—Ni1—N3	170.2 (5)	Si1—O18A—Mo2i	121.6 (7)
N5—Ni1—N3	93.8 (5)	O18B—O18A—Mo2i	64.7 (6)
N2—Ni1—N3	77.4 (5)	O1Ai—O18A—Mo2i	126.8 (8)
N6—Ni1—N3	95.6 (4)	Si1—O18A—Mo1i	122.7 (7)
N8—Ni1—N9	77.0 (5)	O18B—O18A—Mo1i	135.4 (8)
N5—Ni1—N9	92.6 (4)	O1Ai—O18A—Mo1i	66.1 (6)
N2—Ni1—N9	96.0 (4)	Mo2i—O18A—Mo1i	94.3 (5)
N6—Ni1—N9	165.8 (4)	Si1—O18A—Mo4i	122.2 (7)
N3—Ni1—N9	96.3 (5)	O18B—O18A—Mo4i	124.0 (8)
O18A—Si1—O18Ai	180.0 (15)	O1Ai—O18A—Mo4i	134.5 (8)
O18A—Si1—O18Bi	110.7 (7)	Mo2i—O18A—Mo4i	93.9 (5)
O18Ai—Si1—O18Bi	69.3 (7)	Mo1i—O18A—Mo4i	94.7 (5)
O18A—Si1—O18B	69.3 (7)	Si1—O18B—O18A	53.5 (6)
O18Ai—Si1—O18B	110.7 (7)	Si1—O18B—Mo2i	122.6 (7)
O18Bi—Si1—O18B	180.0 (12)	O18A—O18B—Mo2i	69.4 (6)
O18A—Si1—O1Ai	67.9 (7)	Si1—O18B—Mo3	121.7 (7)
O18Ai—Si1—O1Ai	112.1 (7)	O18A—O18B—Mo3	130.1 (8)
O18Bi—Si1—O1Ai	70.7 (7)	Mo2i—O18B—Mo3	97.7 (5)
O18B—Si1—O1Ai	109.3 (7)	Si1—O18B—Mo6	117.6 (6)
O18A—Si1—O1A	112.1 (7)	O18A—O18B—Mo6	132.7 (8)
O18Ai—Si1—O1A	67.9 (7)	Mo2i—O18B—Mo6	95.6 (5)
O18Bi—Si1—O1A	109.3 (7)	Mo3—O18B—Mo6	95.4 (5)
O18B—Si1—O1A	70.7 (7)	Mo1—O19—Mo4	138.0 (5)
O1Ai—Si1—O1A	180.0 (12)	Mo1—O20—Mo3	139.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O21ii	0.86	2.01	2.850 (19)	165
N4—H4···O17iii	0.86	2.02	2.786 (13)	148
N7—H7A···O22iv	0.86	1.94	2.760 (16)	159

Table 1

Selected bond lengths (Å)

Ni1—N8	2.047 (11)
Ni1—N5	2.093 (11)
Ni1—N2	2.066 (11)
Ni1—N6	2.104 (10)
Ni1—N3	2.096 (12)
Ni1—N9	2.121 (11)
Si1—O18A	1.597 (13)
Si1—O18B	1.670 (13)
Si1—O1A	1.622 (14)
Si1—O1B	1.625 (13)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O21i	0.86	2.01	2.850 (19)	165
N4—H4⋯O17ii	0.86	2.02	2.786 (13)	148
N7—H7A⋯O22iii	0.86	1.94	2.760 (16)	159

Symmetry codes: (i) ; (ii) ; (iii) .