Bis{tris-[3-(2-pyrid-yl)pyrazole]manganese(II)} dodeca-molybdosilicate hexa-hydrate.

The title compound, [Mn(C(8)H(7)N(3))(3)](2)[SiMo(12)O(40)]·6H(2)O, consists of an [SiMo(12)O(40)](4-) heteropolyanion, lying on a centre of inversion, and a complex [Mn(C(8)H(7)N(3))(3)](4+) cation. The Mn(II) atom of the cation is hexa-coordinated in a distorted octa-hedral geometry by six N atoms from three chelating 3-(2-pyrid-yl)pyrazole ligands. In the heteropolyanion, the four O atoms of the tetra-hedral SiO(4) group each half-occupy eight sites due to Si lying on the centre of inversion. N-H⋯O and O-H⋯O hydrogen bonding mediated by the water mol-ecules leads to a consolidation of the structure.

Related literature

For background to polyoxometalates, see: Pope & Müller (1991 ▶). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009 ▶); Zhang, Wei, Shi et al. (2010a ▶,b ▶); Zhang, Wei, Sun et al. (2009 ▶); Zhang, Wei, Zhu et al. (2010 ▶); Zhang, Yuan et al. (2010 ▶). For another dodeca­molybdosilicate, see: Wu et al. (2003 ▶).

Experimental

Crystal data

[Mn(C8H7N3)3]2[SiMo12O40]·6H2O

M = 2908.34

Monoclinic,

a = 18.907 (4) Å

b = 16.385 (3) Å

c = 27.552 (6) Å

β = 105.09 (3)°

V = 8241 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.17 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 = 0.780, T max = 0.845

27737 measured reflections

7045 independent reflections

5381 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.144

S = 1.01

7045 reflections

615 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.13 e Å−3

Δρmin = −0.63 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810001492/jh2123sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001492/jh2123Isup2.hkl

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

[Mn(C8H7N3)3]2[SiMo12O40]·6H2O	F(000) = 5616
Mr = 2908.34	Dx = 2.344 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7045 reflections
a = 18.907 (4) Å	θ = 1.5–25.0°
b = 16.385 (3) Å	µ = 2.17 mm−1
c = 27.552 (6) Å	T = 293 K
β = 105.09 (3)°	Block, pink
V = 8241 (3) Å3	0.12 × 0.10 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	7045 independent reflections
Radiation source: fine-focus sealed tube	5381 reflections with I > 2σ(I)
graphite	Rint = 0.054
phi and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→22
Tmin = 0.780, Tmax = 0.845	k = −19→19
27737 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.060P)2 + 127.9076P] where P = (Fo2 + 2Fc2)/3
7045 reflections	(Δ/σ)max = 0.001
615 parameters	Δρmax = 1.13 e Å−3
9 restraints	Δρmin = −0.63 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Si1	0.2500	0.2500	0.0000	0.0238 (6)
Mn8	0.20275 (8)	0.32148 (10)	0.30305 (6)	0.0499 (4)
Mo1	0.35094 (4)	0.40389 (5)	0.07736 (3)	0.0410 (2)
Mo2	0.41814 (4)	0.31787 (6)	−0.01901 (3)	0.0438 (2)
Mo3	0.17562 (5)	0.34714 (6)	0.08913 (3)	0.0440 (2)
Mo4	0.41640 (4)	0.20104 (6)	0.08819 (3)	0.0469 (2)
Mo5	0.19369 (5)	0.45425 (5)	−0.01788 (4)	0.0468 (2)
Mo6	0.24655 (6)	0.14836 (6)	0.11242 (3)	0.0511 (3)
C1	0.0885 (6)	0.2487 (7)	0.2033 (5)	0.062 (3)
H1	0.0835	0.3029	0.1930	0.075*
C2	0.0494 (8)	0.1908 (11)	0.1719 (6)	0.088 (4)
H2	0.0188	0.2053	0.1408	0.106*
C3	0.0563 (8)	0.1110 (9)	0.1870 (6)	0.091 (5)
H3	0.0309	0.0697	0.1666	0.109*
C4	0.1015 (8)	0.0941 (9)	0.2331 (6)	0.088 (4)
H4	0.1056	0.0406	0.2448	0.105*
C5	0.1400 (6)	0.1527 (7)	0.2617 (4)	0.057 (3)
C6	0.1915 (6)	0.1368 (7)	0.3104 (4)	0.054 (3)
C7	0.2133 (8)	0.0644 (8)	0.3366 (5)	0.078 (4)
H7	0.1954	0.0124	0.3269	0.094*
C8	0.2654 (8)	0.0840 (8)	0.3787 (5)	0.080 (4)
H8	0.2904	0.0483	0.4036	0.096*
C9	0.1679 (7)	0.4862 (7)	0.2345 (5)	0.063 (3)
H9	0.1976	0.4650	0.2155	0.075*
C10	0.1422 (7)	0.5620 (8)	0.2259 (5)	0.068 (3)
H10	0.1555	0.5930	0.2014	0.082*
C11	0.0997 (9)	0.5939 (12)	0.2501 (7)	0.101 (5)
H11	0.0821	0.6466	0.2426	0.122*
C12	0.0815 (7)	0.5535 (10)	0.2844 (7)	0.090 (5)
H12	0.0508	0.5764	0.3021	0.109*
C13	0.1085 (6)	0.4732 (8)	0.2952 (5)	0.063 (3)
C14	0.0871 (6)	0.4282 (8)	0.3333 (4)	0.059 (3)
C15	0.0374 (8)	0.4441 (11)	0.3619 (6)	0.096 (5)
H15	0.0074	0.4894	0.3607	0.115*
C16	0.0447 (7)	0.3695 (14)	0.3953 (6)	0.113 (7)
H16	0.0194	0.3582	0.4192	0.135*
C17	0.2995 (6)	0.3995 (6)	0.4069 (4)	0.048 (2)
H17	0.2567	0.3938	0.4174	0.057*
C18	0.3587 (7)	0.4342 (7)	0.4391 (4)	0.060 (3)
H18	0.3559	0.4531	0.4703	0.072*
C19	0.4236 (6)	0.4412 (7)	0.4246 (4)	0.054 (3)
H19	0.4651	0.4640	0.4460	0.065*
C20	0.4246 (5)	0.4140 (7)	0.3785 (4)	0.054 (3)
H20	0.4674	0.4182	0.3681	0.065*
C21	0.3615 (5)	0.3793 (6)	0.3461 (4)	0.042 (2)
C22	0.3585 (5)	0.3527 (6)	0.2960 (4)	0.045 (2)
C23	0.4141 (6)	0.3462 (9)	0.2710 (4)	0.068 (3)
H23	0.4635	0.3583	0.2835	0.082*
C24	0.3795 (7)	0.3180 (9)	0.2241 (5)	0.072 (4)
H24	0.4012	0.3088	0.1979	0.087*
N1	0.1336 (5)	0.2310 (6)	0.2482 (4)	0.054 (2)
N2	0.2303 (5)	0.1991 (6)	0.3359 (3)	0.056 (2)
N3	0.2743 (5)	0.1662 (7)	0.3777 (4)	0.064 (3)
N4	0.2995 (4)	0.3733 (5)	0.3613 (3)	0.0421 (19)
N5	0.2962 (5)	0.3277 (5)	0.2663 (3)	0.051 (2)
N6	0.3102 (5)	0.3063 (6)	0.2225 (3)	0.061 (3)
H6	0.2780	0.2875	0.1970	0.073*
N7	0.1515 (5)	0.4406 (6)	0.2700 (4)	0.064 (3)
N8	0.1227 (5)	0.3571 (6)	0.3462 (4)	0.060 (3)
N9	0.0967 (6)	0.3225 (8)	0.3825 (4)	0.084 (4)
H9A	0.1111	0.2761	0.3960	0.101*
O1	0.4018 (5)	0.2154 (5)	−0.0598 (4)	0.109 (4)
O2	0.3538 (5)	0.3658 (5)	−0.0743 (4)	0.106 (4)
O3	0.4979 (4)	0.3440 (5)	−0.0290 (3)	0.062 (2)
O4	0.4530 (5)	0.2433 (5)	0.0359 (3)	0.071 (2)
O5	0.4039 (5)	0.3952 (5)	0.0236 (3)	0.073 (2)
O6	0.4010 (4)	0.4783 (5)	0.1107 (3)	0.066 (2)
O7	0.4045 (5)	0.3127 (5)	0.1067 (3)	0.075 (2)
O8	0.4923 (4)	0.1803 (5)	0.1310 (3)	0.069 (2)
O9	0.3467 (5)	0.1770 (5)	0.1265 (4)	0.083 (3)
O10	0.2789 (4)	0.3891 (6)	0.1087 (3)	0.076 (2)
O11	0.3948 (5)	0.1018 (6)	0.0552 (4)	0.096 (4)
O12	0.2946 (6)	0.1829 (6)	0.0405 (4)	0.028 (2)	0.50
O13	0.3293 (6)	0.2834 (6)	0.0270 (4)	0.025 (2)	0.50
O14	0.2846 (4)	0.4671 (6)	0.0256 (3)	0.083 (3)
O15	0.2325 (5)	0.4385 (6)	−0.0712 (4)	0.103 (4)
O16	0.1658 (4)	0.5493 (4)	−0.0260 (3)	0.068 (2)
O17	0.2006 (6)	0.2371 (6)	0.0415 (4)	0.027 (2)	0.50
O18	0.1577 (4)	0.4246 (6)	0.0403 (3)	0.081 (3)
O19	0.1482 (4)	0.3937 (5)	0.1343 (3)	0.063 (2)
O20	0.2231 (5)	0.2542 (5)	0.1287 (3)	0.087 (3)
O21	0.2460 (4)	0.0986 (5)	0.1638 (2)	0.059 (2)
O22	0.2488 (6)	0.3354 (6)	0.0285 (4)	0.025 (2)	0.50
O1W	0.3845 (6)	0.2182 (8)	0.4579 (5)	0.114 (4)
O2W	0.4625 (13)	0.0738 (17)	0.4742 (14)	0.292 (16)
O3W	0.6311 (8)	0.3371 (13)	0.9351 (6)	0.195 (8)
H1W	0.407 (2)	0.175 (2)	0.465 (4)	0.180*
H2W	0.352 (5)	0.225 (6)	0.473 (4)	0.180*
H3W	0.483 (7)	0.059 (9)	0.453 (4)	0.380*
H3WB	0.420 (14)	0.07 (5)	0.48 (3)	0.380*
H5W	0.590 (2)	0.348 (7)	0.938 (3)	0.280*
H6W	0.636 (5)	0.343 (9)	0.9065 (17)	0.280*
H3A	0.312 (3)	0.203 (4)	0.396 (4)	0.07 (4)*

	U11	U22	U33	U12	U13	U23
Si1	0.0229 (15)	0.0222 (16)	0.0245 (16)	−0.0009 (13)	0.0027 (12)	0.0004 (12)
Mn8	0.0404 (8)	0.0423 (9)	0.0661 (11)	−0.0054 (7)	0.0121 (8)	−0.0092 (8)
Mo1	0.0326 (4)	0.0433 (5)	0.0447 (5)	−0.0086 (4)	0.0061 (4)	−0.0126 (4)
Mo2	0.0284 (4)	0.0507 (5)	0.0529 (5)	−0.0092 (4)	0.0119 (4)	−0.0028 (4)
Mo3	0.0469 (5)	0.0486 (5)	0.0361 (5)	0.0103 (4)	0.0103 (4)	−0.0108 (4)
Mo4	0.0301 (4)	0.0578 (6)	0.0447 (5)	−0.0007 (4)	−0.0046 (4)	0.0053 (4)
Mo5	0.0527 (5)	0.0300 (4)	0.0614 (6)	0.0079 (4)	0.0214 (4)	0.0026 (4)
Mo6	0.0720 (6)	0.0474 (5)	0.0323 (5)	−0.0099 (5)	0.0104 (4)	0.0065 (4)
C1	0.056 (7)	0.057 (7)	0.066 (8)	0.000 (6)	0.002 (6)	−0.010 (6)
C2	0.075 (9)	0.111 (13)	0.072 (9)	0.009 (9)	0.006 (7)	−0.018 (9)
C3	0.090 (10)	0.068 (10)	0.102 (12)	−0.022 (8)	0.000 (9)	−0.038 (9)
C4	0.088 (8)	0.070 (7)	0.091 (8)	−0.016 (6)	−0.002 (6)	−0.009 (6)
C5	0.055 (7)	0.053 (7)	0.066 (7)	−0.010 (5)	0.019 (6)	−0.016 (6)
C6	0.063 (7)	0.045 (6)	0.060 (7)	−0.010 (5)	0.028 (6)	−0.005 (5)
C7	0.098 (10)	0.063 (9)	0.077 (9)	−0.015 (7)	0.029 (8)	0.000 (7)
C8	0.111 (12)	0.049 (8)	0.077 (9)	0.004 (7)	0.021 (8)	0.019 (7)
C9	0.073 (8)	0.050 (7)	0.073 (8)	−0.003 (6)	0.033 (7)	−0.018 (6)
C10	0.077 (7)	0.062 (7)	0.059 (6)	−0.004 (6)	0.007 (5)	0.000 (5)
C11	0.099 (9)	0.102 (9)	0.098 (9)	0.008 (7)	0.016 (7)	−0.019 (8)
C12	0.051 (8)	0.101 (12)	0.102 (12)	0.009 (8)	−0.009 (8)	−0.036 (10)
C13	0.041 (6)	0.062 (8)	0.076 (8)	0.009 (6)	−0.005 (6)	−0.025 (6)
C14	0.042 (5)	0.074 (7)	0.060 (6)	−0.003 (5)	0.009 (5)	−0.017 (5)
C15	0.072 (7)	0.112 (9)	0.097 (8)	0.009 (7)	0.010 (6)	−0.041 (7)
C16	0.041 (7)	0.23 (2)	0.075 (10)	−0.066 (10)	0.036 (7)	−0.070 (12)
C17	0.054 (6)	0.047 (6)	0.048 (6)	−0.007 (5)	0.021 (5)	−0.017 (5)
C18	0.077 (8)	0.047 (6)	0.049 (6)	0.015 (6)	0.003 (6)	−0.013 (5)
C19	0.050 (6)	0.058 (7)	0.042 (6)	0.014 (5)	−0.010 (5)	−0.011 (5)
C20	0.031 (5)	0.079 (8)	0.046 (6)	−0.001 (5)	−0.001 (4)	0.002 (6)
C21	0.040 (5)	0.038 (5)	0.048 (6)	0.003 (4)	0.011 (4)	0.002 (4)
C22	0.044 (6)	0.048 (6)	0.040 (5)	0.001 (5)	0.007 (4)	−0.002 (5)
C23	0.044 (6)	0.114 (11)	0.052 (7)	0.000 (7)	0.022 (5)	−0.016 (7)
C24	0.067 (8)	0.103 (11)	0.049 (7)	0.000 (7)	0.021 (6)	−0.004 (7)
N1	0.042 (5)	0.054 (6)	0.065 (6)	−0.007 (4)	0.010 (4)	−0.008 (5)
N2	0.050 (5)	0.054 (6)	0.061 (6)	−0.005 (4)	0.007 (5)	−0.002 (5)
N3	0.062 (6)	0.075 (7)	0.052 (6)	−0.014 (5)	0.012 (5)	0.002 (5)
N4	0.039 (4)	0.040 (5)	0.050 (5)	−0.007 (4)	0.016 (4)	−0.011 (4)
N5	0.046 (5)	0.062 (6)	0.041 (5)	0.000 (4)	0.005 (4)	−0.007 (4)
N6	0.066 (6)	0.079 (7)	0.033 (5)	0.004 (5)	0.005 (4)	−0.012 (5)
N7	0.042 (5)	0.056 (6)	0.089 (7)	0.000 (5)	0.009 (5)	−0.010 (6)
N8	0.041 (5)	0.073 (7)	0.071 (6)	−0.018 (5)	0.019 (5)	−0.016 (5)
N9	0.066 (7)	0.092 (9)	0.088 (8)	−0.042 (6)	0.008 (6)	−0.009 (7)
O1	0.101 (7)	0.039 (5)	0.129 (8)	0.015 (5)	−0.075 (6)	−0.013 (5)
O2	0.108 (7)	0.042 (5)	0.116 (8)	0.028 (5)	−0.066 (6)	−0.027 (5)
O3	0.048 (4)	0.063 (5)	0.088 (6)	−0.005 (4)	0.041 (4)	−0.003 (4)
O4	0.108 (6)	0.058 (4)	0.060 (4)	0.031 (4)	0.044 (4)	0.012 (4)
O5	0.107 (6)	0.062 (5)	0.061 (5)	0.042 (4)	0.043 (4)	0.013 (4)
O6	0.077 (5)	0.060 (5)	0.057 (5)	−0.024 (4)	0.013 (4)	−0.024 (4)
O7	0.111 (6)	0.065 (5)	0.068 (5)	0.023 (4)	0.058 (4)	0.010 (4)
O8	0.054 (5)	0.092 (6)	0.049 (5)	0.023 (4)	−0.007 (4)	−0.003 (4)
O9	0.091 (5)	0.083 (5)	0.095 (6)	−0.043 (4)	0.059 (5)	−0.042 (5)
O10	0.042 (4)	0.113 (6)	0.072 (5)	0.012 (4)	0.016 (4)	0.039 (5)
O11	0.103 (7)	0.113 (8)	0.099 (7)	−0.067 (6)	0.073 (6)	−0.068 (6)
O12	0.032 (6)	0.019 (6)	0.033 (6)	0.003 (5)	0.007 (5)	−0.008 (5)
O13	0.025 (6)	0.020 (6)	0.029 (6)	−0.006 (4)	0.008 (5)	0.002 (4)
O14	0.049 (4)	0.127 (7)	0.074 (5)	0.019 (4)	0.021 (4)	0.051 (5)
O15	0.081 (6)	0.133 (8)	0.126 (8)	−0.073 (6)	0.080 (6)	−0.085 (7)
O16	0.055 (5)	0.035 (4)	0.110 (7)	0.012 (3)	0.013 (4)	0.017 (4)
O17	0.022 (5)	0.030 (6)	0.024 (6)	0.000 (5)	0.000 (4)	0.003 (5)
O18	0.040 (4)	0.123 (6)	0.075 (5)	0.006 (4)	0.010 (4)	0.038 (5)
O19	0.050 (4)	0.087 (6)	0.056 (5)	−0.002 (4)	0.023 (4)	−0.030 (4)
O20	0.084 (5)	0.050 (4)	0.091 (6)	0.001 (4)	−0.040 (4)	−0.007 (4)
O21	0.072 (5)	0.071 (5)	0.034 (4)	−0.009 (4)	0.013 (3)	0.011 (4)
O22	0.031 (6)	0.026 (6)	0.020 (5)	−0.006 (5)	0.008 (5)	−0.005 (4)
O1W	0.079 (8)	0.144 (11)	0.106 (9)	−0.012 (7)	0.003 (6)	0.000 (8)
O2W	0.22 (2)	0.23 (2)	0.51 (5)	−0.002 (18)	0.26 (3)	0.08 (3)
O3W	0.207 (17)	0.226 (19)	0.208 (18)	−0.037 (15)	0.153 (15)	−0.054 (15)

Si1—O13	1.587 (10)	C4—C5	1.332 (16)
Si1—O13i	1.587 (10)	C4—H4	0.9300
Si1—O22i	1.607 (10)	C5—N1	1.332 (14)
Si1—O22	1.607 (10)	C5—C6	1.462 (16)
Si1—O12i	1.635 (11)	C6—N2	1.343 (13)
Si1—O12	1.635 (11)	C6—C7	1.395 (17)
Si1—O17i	1.667 (11)	C7—C8	1.352 (18)
Si1—O17	1.667 (11)	C7—H7	0.9300
Mn8—N2	2.207 (9)	C8—N3	1.358 (15)
Mn8—N8	2.232 (9)	C8—H8	0.9300
Mn8—N5	2.255 (9)	C9—N7	1.330 (15)
Mn8—N7	2.262 (10)	C9—C10	1.333 (16)
Mn8—N4	2.262 (8)	C9—H9	0.9300
Mn8—N1	2.272 (9)	C10—C11	1.281 (19)
Mo1—O6	1.665 (7)	C10—H10	0.9300
Mo1—O10	1.809 (7)	C11—C12	1.27 (2)
Mo1—O7	1.866 (8)	C11—H11	0.9300
Mo1—O14	1.935 (8)	C12—C13	1.414 (19)
Mo1—O5	1.998 (7)	C12—H12	0.9300
Mo1—O22	2.334 (10)	C13—N7	1.312 (15)
Mo1—O13	2.386 (10)	C13—C14	1.426 (18)
Mo2—O3	1.659 (7)	C14—N8	1.347 (15)
Mo2—O5	1.794 (7)	C14—C15	1.398 (19)
Mo2—O2	1.858 (8)	C15—C16	1.51 (2)
Mo2—O4	1.922 (8)	C15—H15	0.9300
Mo2—O1	1.999 (8)	C16—N9	1.364 (19)
Mo2—O17i	2.348 (10)	C16—H16	0.9300
Mo2—O13	2.421 (10)	C17—N4	1.328 (12)
Mo3—O19	1.655 (7)	C17—C18	1.359 (15)
Mo3—O1i	1.797 (8)	C17—H17	0.9300
Mo3—O18	1.816 (8)	C18—C19	1.390 (16)
Mo3—O20	1.950 (8)	C18—H18	0.9300
Mo3—O10	2.007 (8)	C19—C20	1.349 (14)
Mo3—O17	2.349 (11)	C19—H19	0.9300
Mo3—O22	2.439 (10)	C20—C21	1.410 (13)
Mo4—O8	1.639 (7)	C20—H20	0.9300
Mo4—O11	1.856 (8)	C21—N4	1.348 (11)
Mo4—O4	1.886 (8)	C21—C22	1.435 (13)
Mo4—O7	1.928 (8)	C22—N5	1.313 (12)
Mo4—O9	1.932 (8)	C22—C23	1.403 (14)
Mo4—O12	2.355 (10)	C23—C24	1.367 (16)
Mo4—O13	2.434 (10)	C23—H23	0.9300
Mo5—O16	1.641 (7)	C24—N6	1.315 (15)
Mo5—O15	1.825 (8)	C24—H24	0.9300
Mo5—O14	1.834 (8)	N2—N3	1.344 (12)
Mo5—O11i	1.951 (8)	N3—H3A	0.97 (8)
Mo5—O18	1.960 (8)	N5—N6	1.346 (11)
Mo5—O12i	2.359 (10)	N6—H6	0.8600
Mo5—O22	2.413 (11)	N8—N9	1.348 (14)
Mo6—O21	1.637 (7)	N9—H9A	0.8600
Mo6—O20	1.873 (8)	O1—Mo3i	1.797 (8)
Mo6—O9	1.890 (8)	O2—Mo6i	1.929 (8)
Mo6—O2i	1.929 (8)	O11—Mo5i	1.951 (8)
Mo6—O15i	1.925 (8)	O12—Mo5i	2.359 (10)
Mo6—O17	2.409 (10)	O13—O22	1.753 (15)
Mo6—O12	2.451 (11)	O15—Mo6i	1.925 (8)
C1—N1	1.340 (14)	O17—Mo2i	2.348 (10)
C1—C2	1.364 (17)	O1W—H1W	0.82 (5)
C1—H1	0.9300	O1W—H2W	0.83 (10)
C2—C3	1.37 (2)	O2W—H3W	0.82 (13)
C2—H2	0.9300	O2W—H3WB	0.9 (6)
C3—C4	1.361 (19)	O3W—H5W	0.82 (6)
C3—H3	0.9300	O3W—H6W	0.82 (7)
O13—Si1—O13i	180.0 (12)	O21—Mo6—O17	157.0 (4)
O13—Si1—O22i	113.4 (5)	O20—Mo6—O17	65.0 (4)
O13i—Si1—O22i	66.6 (5)	O9—Mo6—O17	98.5 (4)
O13—Si1—O22	66.6 (5)	O2i—Mo6—O17	62.3 (4)
O13i—Si1—O22	113.4 (5)	O15i—Mo6—O17	93.1 (5)
O22i—Si1—O22	180.0 (9)	O21—Mo6—O12	154.4 (4)
O13—Si1—O12i	110.2 (5)	O20—Mo6—O12	98.0 (4)
O13i—Si1—O12i	69.8 (5)	O9—Mo6—O12	63.1 (4)
O22i—Si1—O12i	108.7 (5)	O2i—Mo6—O12	96.1 (4)
O22—Si1—O12i	71.3 (5)	O15i—Mo6—O12	61.2 (4)
O13—Si1—O12	69.8 (5)	O17—Mo6—O12	48.4 (4)
O13i—Si1—O12	110.2 (5)	N1—C1—C2	123.1 (12)
O22i—Si1—O12	71.3 (5)	N1—C1—H1	118.5
O22—Si1—O12	108.7 (5)	C2—C1—H1	118.5
O12i—Si1—O12	180.0 (12)	C1—C2—C3	118.5 (14)
O13—Si1—O17i	69.5 (5)	C1—C2—H2	120.7
O13i—Si1—O17i	110.5 (5)	C3—C2—H2	120.7
O22i—Si1—O17i	72.1 (5)	C4—C3—C2	117.7 (13)
O22—Si1—O17i	107.9 (5)	C4—C3—H3	121.2
O12i—Si1—O17i	74.2 (5)	C2—C3—H3	121.2
O12—Si1—O17i	105.8 (5)	C5—C4—C3	121.3 (14)
O13—Si1—O17	110.5 (5)	C5—C4—H4	119.4
O13i—Si1—O17	69.5 (5)	C3—C4—H4	119.4
O22i—Si1—O17	107.9 (5)	N1—C5—C4	122.2 (12)
O22—Si1—O17	72.1 (5)	N1—C5—C6	114.7 (9)
O12i—Si1—O17	105.8 (5)	C4—C5—C6	123.1 (12)
O12—Si1—O17	74.2 (5)	N2—C6—C7	109.1 (11)
O17i—Si1—O17	180.0 (9)	N2—C6—C5	119.2 (10)
N2—Mn8—N8	98.0 (4)	C7—C6—C5	131.5 (11)
N2—Mn8—N5	95.6 (3)	C8—C7—C6	107.0 (12)
N8—Mn8—N5	161.1 (3)	C8—C7—H7	126.5
N2—Mn8—N7	168.5 (3)	C6—C7—H7	126.5
N8—Mn8—N7	73.2 (4)	C7—C8—N3	106.5 (12)
N5—Mn8—N7	94.8 (3)	C7—C8—H8	126.8
N2—Mn8—N4	89.4 (3)	N3—C8—H8	126.8
N8—Mn8—N4	93.4 (3)	N7—C9—C10	120.7 (11)
N5—Mn8—N4	73.6 (3)	N7—C9—H9	119.6
N7—Mn8—N4	98.3 (3)	C10—C9—H9	119.6
N2—Mn8—N1	73.3 (3)	C11—C10—C9	122.4 (15)
N8—Mn8—N1	100.0 (3)	C11—C10—H10	118.8
N5—Mn8—N1	96.5 (3)	C9—C10—H10	118.8
N7—Mn8—N1	100.6 (3)	C12—C11—C10	120.1 (19)
N4—Mn8—N1	159.4 (3)	C12—C11—H11	119.9
O6—Mo1—O10	103.1 (4)	C10—C11—H11	119.9
O6—Mo1—O7	100.4 (4)	C11—C12—C13	119.2 (16)
O10—Mo1—O7	94.4 (4)	C11—C12—H12	120.4
O6—Mo1—O14	100.4 (4)	C13—C12—H12	120.4
O10—Mo1—O14	89.9 (3)	N7—C13—C12	120.4 (14)
O7—Mo1—O14	157.2 (4)	N7—C13—C14	120.9 (11)
O6—Mo1—O5	97.9 (4)	C12—C13—C14	118.7 (13)
O10—Mo1—O5	158.4 (4)	N8—C14—C15	112.1 (13)
O7—Mo1—O5	86.8 (3)	N8—C14—C13	115.1 (10)
O14—Mo1—O5	81.2 (3)	C15—C14—C13	132.8 (14)
O6—Mo1—O22	159.5 (4)	C14—C15—C16	102.9 (13)
O10—Mo1—O22	66.3 (4)	C14—C15—H15	128.6
O7—Mo1—O22	98.0 (4)	C16—C15—H15	128.6
O14—Mo1—O22	63.4 (4)	N9—C16—C15	104.9 (12)
O5—Mo1—O22	92.1 (4)	N9—C16—H16	127.6
O6—Mo1—O13	155.9 (4)	C15—C16—H16	127.5
O10—Mo1—O13	97.4 (4)	N4—C17—C18	123.3 (10)
O7—Mo1—O13	65.2 (4)	N4—C17—H17	118.4
O14—Mo1—O13	92.0 (4)	C18—C17—H17	118.4
O5—Mo1—O13	63.5 (4)	C17—C18—C19	119.1 (10)
O22—Mo1—O13	43.6 (4)	C17—C18—H18	120.5
O3—Mo2—O5	102.9 (4)	C19—C18—H18	120.5
O3—Mo2—O2	100.6 (5)	C20—C19—C18	118.2 (10)
O5—Mo2—O2	93.5 (4)	C20—C19—H19	120.9
O3—Mo2—O4	98.9 (4)	C18—C19—H19	120.9
O5—Mo2—O4	90.8 (3)	C19—C20—C21	120.8 (10)
O2—Mo2—O4	158.6 (5)	C19—C20—H20	119.6
O3—Mo2—O1	97.9 (4)	C21—C20—H20	119.6
O5—Mo2—O1	158.9 (5)	N4—C21—C20	119.6 (9)
O2—Mo2—O1	85.5 (3)	N4—C21—C22	117.2 (9)
O4—Mo2—O1	83.1 (4)	C20—C21—C22	123.2 (9)
O3—Mo2—O17i	154.7 (4)	N5—C22—C23	109.6 (9)
O5—Mo2—O17i	98.5 (4)	N5—C22—C21	119.9 (9)
O2—Mo2—O17i	64.5 (4)	C23—C22—C21	130.5 (9)
O4—Mo2—O17i	94.2 (4)	C24—C23—C22	104.8 (10)
O1—Mo2—O17i	62.1 (4)	C24—C23—H23	127.6
O3—Mo2—O13	158.8 (4)	C22—C23—H23	127.6
O5—Mo2—O13	65.2 (4)	N6—C24—C23	107.8 (11)
O2—Mo2—O13	97.7 (5)	N6—C24—H24	126.1
O4—Mo2—O13	65.3 (4)	C23—C24—H24	126.1
O1—Mo2—O13	94.1 (5)	C5—N1—C1	117.1 (10)
O17i—Mo2—O13	45.8 (4)	C5—N1—Mn8	116.6 (7)
O19—Mo3—O1i	102.9 (5)	C1—N1—Mn8	126.3 (8)
O19—Mo3—O18	101.6 (4)	C6—N2—N3	106.0 (9)
O1i—Mo3—O18	95.3 (4)	C6—N2—Mn8	115.9 (7)
O19—Mo3—O20	97.4 (4)	N3—N2—Mn8	138.0 (7)
O1i—Mo3—O20	90.5 (4)	N2—N3—C8	111.4 (10)
O18—Mo3—O20	158.4 (4)	N2—N3—H3A	114 (7)
O19—Mo3—O10	96.5 (4)	C8—N3—H3A	133 (6)
O1i—Mo3—O10	159.6 (5)	C17—N4—C21	119.0 (8)
O18—Mo3—O10	86.6 (3)	C17—N4—Mn8	126.4 (6)
O20—Mo3—O10	80.9 (4)	C21—N4—Mn8	114.5 (6)
O19—Mo3—O17	157.3 (4)	C22—N5—N6	106.6 (8)
O1i—Mo3—O17	64.5 (4)	C22—N5—Mn8	114.5 (7)
O18—Mo3—O17	98.6 (4)	N6—N5—Mn8	138.6 (7)
O20—Mo3—O17	65.3 (4)	C24—N6—N5	111.1 (9)
O10—Mo3—O17	95.1 (4)	C24—N6—H6	124.4
O19—Mo3—O22	153.8 (4)	N5—N6—H6	124.4
O1i—Mo3—O22	100.8 (5)	C13—N7—C9	117.1 (11)
O18—Mo3—O22	65.0 (4)	C13—N7—Mn8	113.4 (9)
O20—Mo3—O22	93.4 (4)	C9—N7—Mn8	128.6 (8)
O10—Mo3—O22	61.6 (3)	C14—N8—N9	107.8 (10)
O17—Mo3—O22	47.5 (4)	C14—N8—Mn8	116.6 (8)
O8—Mo4—O11	102.2 (5)	N9—N8—Mn8	135.6 (9)
O8—Mo4—O4	101.5 (4)	N8—N9—C16	112.4 (13)
O11—Mo4—O4	91.5 (4)	N8—N9—H9A	123.8
O8—Mo4—O7	98.4 (4)	C16—N9—H9A	123.8
O11—Mo4—O7	159.2 (5)	Mo3i—O1—Mo2	136.1 (6)
O4—Mo4—O7	86.8 (3)	Mo2—O2—Mo6i	137.5 (7)
O8—Mo4—O9	99.1 (4)	Mo4—O4—Mo2	135.7 (5)
O11—Mo4—O9	89.7 (3)	Mo2—O5—Mo1	136.4 (5)
O4—Mo4—O9	158.6 (4)	Mo1—O7—Mo4	137.1 (5)
O7—Mo4—O9	84.6 (3)	Mo6—O9—Mo4	136.7 (5)
O8—Mo4—O12	157.2 (4)	Mo1—O10—Mo3	135.9 (5)
O11—Mo4—O12	63.8 (4)	Mo4—O11—Mo5i	136.0 (6)
O4—Mo4—O12	96.9 (4)	Si1—O12—Mo4	123.5 (6)
O7—Mo4—O12	95.9 (4)	Si1—O12—Mo5i	121.8 (5)
O9—Mo4—O12	64.6 (4)	Mo4—O12—Mo5i	97.0 (4)
O8—Mo4—O13	157.1 (4)	Si1—O12—Mo6	118.3 (5)
O11—Mo4—O13	97.1 (4)	Mo4—O12—Mo6	95.3 (4)
O4—Mo4—O13	65.4 (3)	Mo5i—O12—Mo6	94.2 (4)
O7—Mo4—O13	63.4 (4)	Si1—O13—O22	57.3 (5)
O9—Mo4—O13	93.2 (4)	Si1—O13—Mo1	123.8 (6)
O12—Mo4—O13	45.3 (3)	O22—O13—Mo1	66.6 (5)
O16—Mo5—O15	101.9 (5)	Si1—O13—Mo2	122.3 (5)
O16—Mo5—O14	101.2 (4)	O22—O13—Mo2	128.5 (6)
O15—Mo5—O14	92.2 (4)	Mo1—O13—Mo2	94.2 (3)
O16—Mo5—O11i	100.0 (4)	Si1—O13—Mo4	121.4 (5)
O15—Mo5—O11i	88.8 (3)	O22—O13—Mo4	133.5 (6)
O14—Mo5—O11i	158.1 (5)	Mo1—O13—Mo4	94.2 (4)
O16—Mo5—O18	100.3 (4)	Mo2—O13—Mo4	93.2 (4)
O15—Mo5—O18	157.4 (5)	Mo5—O14—Mo1	137.5 (5)
O14—Mo5—O18	87.7 (3)	Mo5—O15—Mo6i	140.1 (6)
O11i—Mo5—O18	83.2 (4)	Si1—O17—Mo3	121.1 (5)
O16—Mo5—O12i	156.5 (4)	Si1—O17—Mo2i	122.3 (5)
O15—Mo5—O12i	64.4 (4)	Mo3—O17—Mo2i	97.1 (4)
O14—Mo5—O12i	98.4 (4)	Si1—O17—Mo6	119.0 (5)
O11i—Mo5—O12i	62.5 (4)	Mo3—O17—Mo6	95.3 (4)
O18—Mo5—O12i	93.3 (4)	Mo2i—O17—Mo6	95.8 (4)
O16—Mo5—O22	156.6 (4)	Mo3—O18—Mo5	137.9 (5)
O15—Mo5—O22	96.0 (5)	Mo6—O20—Mo3	133.8 (5)
O14—Mo5—O22	62.9 (4)	Si1—O22—O13	56.2 (5)
O11i—Mo5—O22	95.3 (4)	Si1—O22—Mo1	125.9 (6)
O18—Mo5—O22	63.9 (4)	O13—O22—Mo1	69.8 (5)
O12i—Mo5—O22	46.6 (4)	Si1—O22—Mo5	120.2 (5)
O21—Mo6—O20	101.5 (4)	O13—O22—Mo5	129.6 (6)
O21—Mo6—O9	100.2 (4)	Mo1—O22—Mo5	95.5 (4)
O20—Mo6—O9	90.4 (4)	Si1—O22—Mo3	119.1 (5)
O21—Mo6—O2i	100.6 (4)	O13—O22—Mo3	134.8 (6)
O20—Mo6—O2i	88.9 (3)	Mo1—O22—Mo3	95.7 (3)
O9—Mo6—O2i	158.9 (5)	Mo5—O22—Mo3	93.1 (4)
O21—Mo6—O15i	100.9 (4)	H1W—O1W—H2W	114 (9)
O20—Mo6—O15i	157.5 (5)	H3W—O2W—H3WB	139.00
O9—Mo6—O15i	87.5 (3)	H5W—O3W—H6W	114 (9)
O2i—Mo6—O15i	85.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O20	0.86	1.97	2.812 (12)	165
O1W—H1W···O2W	0.82 (5)	1.94 (3)	2.76 (3)	174 (12)
N9—H9A···O3Wii	0.86	2.13	2.98 (2)	170
O3W—H5W···O3iii	0.82 (6)	2.16 (4)	2.937 (15)	157 (10)
O2W—H3W···O11iv	0.82 (13)	2.48 (12)	3.046 (19)	127 (12)
O2W—H3WB···O16v	0.9 (6)	2.4 (4)	3.14 (2)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯O20	0.86	1.97	2.812 (12)	165
O1W—H1W⋯O2W	0.82 (5)	1.94 (3)	2.76 (3)	174 (12)
N9—H9A⋯O3Wi	0.86	2.13	2.98 (2)	170
O3W—H5W⋯O3ii	0.82 (6)	2.16 (4)	2.937 (15)	157 (10)
O2W—H3W⋯O11iii	0.82 (13)	2.48 (12)	3.046 (19)	127 (12)
O2W—H3WB⋯O16iv	0.9 (6)	2.4 (4)	3.14 (2)	158

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