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

Hao, L.; Ma, C.; Chen, J.; Zhang, X.; Zhang, X.

doi:10.1107/S160053681000320X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m231-m232

https://doi.org/10.1107/S160053681000320X

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

Lujiang Hao,^a Chunling Ma,^a Jianghui Chen,^a Xiaofei Zhang ^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 20 January 2010; accepted 25 January 2010; online 30 January 2010)

The asymmetric unit of the title compound, [Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O, consists of a complex [Mn(C₈H₇N₃)₃]²⁺ cation, half of a mixed-valent Mo^V,VI α-Keggin-type [PMo₁₂O₄₀]⁴⁻ heteropolyanion, and three uncoordinated water molecules. The Mn²⁺ cation is surrounded by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands in a distorted octahedral coordination. In the 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 bonding between the cations, anions and the uncoordinated water molecules leads to a consolidation of the structure.

Related literature

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

[Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r = 2911.22
Monoclinic, C 2/c
a = 18.897 (4) Å
b = 16.360 (3) Å
c = 27.615 (6) Å
β = 104.90 (3)°
V = 8250 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.18 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
15879 measured reflections
7042 independent reflections
5890 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.103
S = 1.00
7042 reflections
610 parameters
H-atom parameters constrained
Δρ_max = 1.52 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N8	2.224 (6)
Mn1—N5	2.224 (5)
Mn1—N2	2.250 (5)
Mn1—N4	2.259 (6)
Mn1—N1	2.260 (5)
Mn1—N7	2.283 (5)
P1—O21Aⁱ	1.495 (7)
P1—O21Bⁱ	1.519 (7)
P1—O19Bⁱ	1.531 (6)
P1—O19Aⁱ	1.562 (6)
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
N9—H9A⋯O1W	0.86	1.96	2.786 (9)	160
N6—H6⋯O2W	0.86	2.10	2.951 (13)	171
N3—H3A⋯O17ⁱⁱ	0.86	1.97	2.814 (7)	165
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: https://doi.org/10.1107/S160053681000320X/wm2301sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681000320X/wm2301Isup2.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 [Mn(C₈H₇N₃)₃]²⁺ cation, a heteropolyanion [PMo₁₂O₄₀]^4- and of three uncoordinated water molecules. The Mn(II) ion is distorted octahedrally coordinated by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands. The Mn—N bond lengths are in the range of 2.224 (6)—2.283 (5) Å.

The heteropolyanion [PMo₁₂O₄₀]^4- is an one electron-reduced derivative of [PMo₁₂O₄₀]^3-, similar to other reported representatives (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 centre 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 1.495 (7)—1.562 (6) Å. The Mo—O bond distances vary widely from 1.644 (4) to 2.517 (6) Å. The shortest Mo—O bonds are in the range of 1.644 (4)—1.666 (4) Å for the terminal oxygen atoms. The longest Mo—O lengths are in the range of 2.455 (7)—2.517 (6) 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).

Related literature top

For general background to polyoxometalates, see: Pope & Müller (1991). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei et al. (2009). For the structure and chemistry of 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), manganese(II) sulfate monohydrate (0.3 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. Pink crystals suitable for the X-ray experiment were obtained. Anal. C₄₈H₅₄Mn₂Mo₁₂N₁₈O₄₆P: C, 19.80; H, 1.82; N, 8.66. Found: C, 19.71; H, 1.74; N, 8.58 %. IR(cm-1): 3456, 1676, 1605, 1433, 1363, 1306, 1015, 959, 773, 739, 694, 942.

TGA curve shows that the lattice water molecules and the organic ligands seperate above 372 and 683 K, respectively. The overall thermal decomposition process can be described by the followed equation: 4C₄₈H₅₄Mn₂Mo₁₂N₁₈O₄₆P + 325O₂ = 108H₂O + 192CO₂ + 36N₂O₅ + 8MnO + 2P₂O₅ + 48MoO₃

Structure description top

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

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

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. Water molecules have been omitted for clarity.

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

Crystal data top

[Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	F(000) = 5620
M_r = 2911.22	D_x = 2.344 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7042 reflections
a = 18.897 (4) Å	θ = 2.9–25.0°
b = 16.360 (3) Å	µ = 2.18 mm⁻¹
c = 27.615 (6) Å	T = 293 K
β = 104.90 (3)°	Block, pink
V = 8250 (3) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7042 independent reflections
Radiation source: fine-focus sealed tube	5890 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −19→22
T_min = 0.780, T_max = 0.845	k = −19→18
15879 measured reflections	l = −32→15

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.058P)² + 43.0549P] where P = (F_o² + 2F_c²)/3
7042 reflections	(Δ/σ)_max = 0.001
610 parameters	Δρ_max = 1.52 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	V = 8250 (3) Å³
M_r = 2911.22	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.897 (4) Å	µ = 2.18 mm⁻¹
b = 16.360 (3) Å	T = 293 K
c = 27.615 (6) Å	0.12 × 0.10 × 0.08 mm
β = 104.90 (3)°

Data collection top

Bruker APEXII CCD diffractometer	7042 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	5890 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.845	R_int = 0.019
15879 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.058P)² + 43.0549P] where P = (F_o² + 2F_c²)/3
7042 reflections	Δρ_max = 1.52 e Å⁻³
610 parameters	Δρ_min = −0.59 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	0.2008 (4)	0.9012 (4)	0.0945 (2)	0.0468 (15)
H1	0.2435	0.8957	0.0840	0.056*
C2	0.1413 (4)	0.9354 (4)	0.0625 (2)	0.0514 (16)
H2	0.1441	0.9547	0.0314	0.062*
C3	0.0778 (4)	0.9412 (4)	0.0766 (2)	0.0520 (16)
H3	0.0364	0.9640	0.0551	0.062*
C4	0.0755 (3)	0.9131 (4)	0.1228 (2)	0.0484 (15)
H4	0.0322	0.9158	0.1328	0.058*
C5	0.1377 (3)	0.8807 (3)	0.1543 (2)	0.0365 (12)
C6	0.1409 (3)	0.8535 (4)	0.2053 (2)	0.0404 (13)
C7	0.0856 (4)	0.8496 (5)	0.2303 (2)	0.064 (2)
H7	0.0365	0.8635	0.2181	0.076*
C8	0.1203 (4)	0.8206 (5)	0.2770 (2)	0.067 (2)
H8	0.0985	0.8115	0.3032	0.080*
C9	0.3304 (4)	0.9890 (4)	0.2657 (3)	0.0570 (17)
H9	0.2996	0.9679	0.2840	0.068*
C10	0.3564 (5)	1.0653 (5)	0.2751 (3)	0.069 (2)
H10	0.3428	1.0958	0.2997	0.083*
C11	0.3992 (6)	1.0970 (7)	0.2513 (4)	0.098 (3)
H11	0.4173	1.1495	0.2591	0.118*
C12	0.4172 (5)	1.0565 (6)	0.2166 (4)	0.082 (3)
H12	0.4473	1.0801	0.1986	0.098*
C13	0.3917 (3)	0.9775 (4)	0.2058 (3)	0.0552 (17)
C14	0.4124 (3)	0.9290 (5)	0.1680 (3)	0.0552 (17)
C15	0.4646 (5)	0.9425 (7)	0.1395 (4)	0.091 (3)
H15	0.4956	0.9871	0.1408	0.109*
C16	0.4578 (4)	0.8683 (7)	0.1073 (3)	0.088 (3)
H16	0.4837	0.8562	0.0838	0.105*
C17	0.4104 (4)	0.7489 (5)	0.2977 (3)	0.0660 (19)
H17	0.4144	0.8031	0.3083	0.079*
C18	0.4495 (5)	0.6912 (6)	0.3289 (3)	0.079 (2)
H18	0.4794	0.7057	0.3601	0.095*
C19	0.4441 (6)	0.6112 (6)	0.3136 (4)	0.092 (3)
H19	0.4704	0.5709	0.3343	0.111*
C20	0.3994 (5)	0.5909 (5)	0.2674 (3)	0.079 (2)
H20	0.3955	0.5372	0.2560	0.095*
C21	0.3607 (4)	0.6534 (4)	0.2384 (2)	0.0487 (15)
C22	0.3089 (4)	0.6366 (4)	0.1895 (2)	0.0505 (15)
C23	0.2897 (5)	0.5646 (5)	0.1635 (3)	0.070 (2)
H23	0.3090	0.5128	0.1727	0.083*
C24	0.2363 (5)	0.5851 (5)	0.1211 (3)	0.073 (2)
H24	0.2118	0.5498	0.0959	0.088*
Mn1	0.29740 (5)	0.82270 (6)	0.19825 (4)	0.0462 (2)
Mo1	0.24323 (3)	0.14506 (3)	0.112281 (17)	0.03994 (14)
Mo2	0.18961 (3)	0.45615 (3)	−0.01922 (2)	0.04104 (14)
Mo3	0.42154 (2)	0.31322 (3)	−0.019107 (18)	0.03646 (13)
Mo4	0.35196 (3)	0.41058 (3)	0.074082 (17)	0.03616 (13)
Mo5	0.41597 (3)	0.20430 (3)	0.092200 (17)	0.03748 (14)
Mo6	0.17852 (3)	0.34986 (3)	0.091187 (17)	0.03910 (14)
N1	0.2007 (3)	0.8748 (3)	0.14048 (17)	0.0390 (11)
N2	0.2040 (3)	0.8284 (3)	0.23478 (17)	0.0415 (11)
N3	0.1895 (3)	0.8080 (3)	0.27848 (18)	0.0526 (14)
H3A	0.2215	0.7891	0.3041	0.063*
N4	0.3478 (3)	0.9425 (3)	0.2304 (2)	0.0534 (13)
N5	0.3778 (3)	0.8576 (4)	0.1555 (2)	0.0570 (14)
N6	0.4054 (4)	0.8223 (4)	0.1200 (3)	0.0742 (18)
H6	0.3912	0.7755	0.1067	0.089*
N7	0.3668 (3)	0.7316 (3)	0.2531 (2)	0.0497 (13)
N8	0.2709 (3)	0.6996 (3)	0.1642 (2)	0.0524 (13)
N9	0.2268 (3)	0.6667 (4)	0.1234 (2)	0.0609 (15)
H9A	0.1958	0.6942	0.1011	0.073*
O1	0.4056 (3)	0.3944 (3)	0.02306 (16)	0.0595 (12)
O2	0.1489 (2)	0.3974 (3)	0.13557 (15)	0.0558 (12)
O3	0.2416 (3)	0.0967 (3)	0.16414 (14)	0.0567 (12)
O4	0.3463 (3)	0.1779 (3)	0.12631 (19)	0.0705 (15)
O5	0.4037 (3)	0.3167 (3)	0.10546 (17)	0.0636 (13)
O6	0.2797 (2)	0.3910 (3)	0.10699 (17)	0.0666 (14)
O7	0.4517 (3)	0.2416 (3)	0.03601 (16)	0.0601 (12)
O8	0.4019 (3)	0.4847 (3)	0.10750 (16)	0.0588 (12)
O9	0.4004 (3)	0.2128 (3)	−0.0597 (2)	0.086 (2)
O10	0.5010 (2)	0.3399 (3)	−0.02956 (19)	0.0588 (12)
O11	0.2847 (2)	0.4701 (4)	0.02450 (18)	0.0755 (16)
O12	0.1037 (3)	0.3971 (3)	−0.0559 (2)	0.0782 (17)
O13	0.1456 (3)	0.1368 (3)	0.0741 (2)	0.086 (2)
O14	0.1576 (2)	0.4261 (4)	0.03989 (18)	0.0736 (16)
O15	0.1624 (3)	0.5528 (3)	−0.0271 (2)	0.0646 (13)
O16	0.2695 (3)	0.0609 (4)	0.0729 (2)	0.0851 (19)
O17	0.2240 (3)	0.2553 (3)	0.1280 (2)	0.0731 (15)
O18	0.4931 (2)	0.1832 (3)	0.13411 (16)	0.0629 (13)
O19A	0.2040 (4)	0.2382 (4)	0.0391 (2)	0.0276 (14)	0.50
O21A	0.3249 (4)	0.2805 (4)	0.0255 (2)	0.0273 (14)	0.50
O19B	0.2906 (4)	0.1881 (4)	0.0389 (2)	0.0281 (14)	0.50
O21B	0.2470 (4)	0.3319 (4)	0.0253 (2)	0.0287 (15)	0.50
O1W	0.1174 (4)	0.7183 (5)	0.0408 (3)	0.107 (2)
O2W	0.3674 (7)	0.6650 (7)	0.0673 (5)	0.193 (6)
O3W	0.5347 (7)	0.0708 (9)	0.0266 (7)	0.232 (7)
P1	0.2500	0.2500	0.0000	0.0222 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.049 (4)	0.047 (4)	0.047 (3)	−0.001 (3)	0.017 (3)	0.013 (3)
C2	0.062 (4)	0.049 (4)	0.040 (3)	−0.014 (3)	0.008 (3)	0.011 (3)
C3	0.040 (4)	0.058 (4)	0.046 (3)	−0.004 (3)	−0.010 (3)	0.009 (3)
C4	0.038 (3)	0.061 (4)	0.044 (3)	−0.002 (3)	0.007 (3)	0.003 (3)
C5	0.033 (3)	0.038 (3)	0.035 (3)	−0.002 (2)	0.002 (2)	0.000 (2)
C6	0.035 (3)	0.046 (3)	0.039 (3)	0.000 (3)	0.009 (3)	0.003 (3)
C7	0.043 (4)	0.101 (6)	0.051 (4)	0.013 (4)	0.019 (3)	0.018 (4)
C8	0.067 (5)	0.096 (6)	0.041 (3)	−0.001 (4)	0.022 (3)	0.014 (4)
C9	0.063 (4)	0.054 (4)	0.059 (4)	0.003 (4)	0.025 (4)	0.014 (3)
C10	0.080 (6)	0.063 (5)	0.055 (4)	0.001 (4)	0.001 (4)	0.005 (4)
C11	0.092 (6)	0.096 (6)	0.095 (6)	−0.001 (5)	0.001 (5)	0.004 (6)
C12	0.063 (5)	0.075 (6)	0.088 (6)	−0.017 (5)	−0.016 (5)	0.024 (5)
C13	0.031 (3)	0.058 (4)	0.064 (4)	−0.005 (3)	−0.012 (3)	0.023 (3)
C14	0.033 (3)	0.070 (5)	0.059 (4)	−0.001 (3)	0.004 (3)	0.025 (4)
C15	0.055 (4)	0.115 (6)	0.095 (5)	−0.009 (5)	0.006 (4)	0.040 (5)
C16	0.048 (4)	0.159 (10)	0.063 (5)	0.046 (5)	0.026 (4)	0.033 (6)
C17	0.068 (5)	0.059 (5)	0.062 (4)	0.004 (4)	0.000 (4)	0.001 (4)
C18	0.075 (6)	0.079 (6)	0.071 (5)	0.001 (5)	−0.004 (4)	0.011 (5)
C19	0.097 (6)	0.075 (5)	0.086 (5)	0.013 (5)	−0.011 (5)	0.027 (5)
C20	0.085 (6)	0.050 (4)	0.090 (6)	0.014 (4)	0.000 (5)	0.007 (4)
C21	0.046 (4)	0.046 (4)	0.055 (4)	0.009 (3)	0.015 (3)	0.008 (3)
C22	0.050 (4)	0.046 (4)	0.059 (4)	0.007 (3)	0.021 (3)	0.002 (3)
C23	0.094 (6)	0.051 (4)	0.068 (5)	0.015 (4)	0.028 (5)	−0.003 (4)
C24	0.097 (6)	0.060 (5)	0.063 (5)	0.003 (5)	0.022 (5)	−0.018 (4)
Mn1	0.0361 (5)	0.0403 (5)	0.0618 (6)	0.0050 (4)	0.0118 (4)	0.0090 (4)
Mo1	0.0514 (3)	0.0399 (3)	0.0269 (2)	−0.0058 (2)	0.0069 (2)	0.0034 (2)
Mo2	0.0427 (3)	0.0312 (3)	0.0513 (3)	0.0064 (2)	0.0160 (2)	0.0036 (2)
Mo3	0.0249 (3)	0.0423 (3)	0.0419 (3)	−0.0054 (2)	0.0080 (2)	−0.0026 (2)
Mo4	0.0297 (3)	0.0395 (3)	0.0371 (2)	−0.0073 (2)	0.0047 (2)	−0.0095 (2)
Mo5	0.0265 (3)	0.0484 (3)	0.0336 (2)	0.0016 (2)	0.0004 (2)	0.0013 (2)
Mo6	0.0401 (3)	0.0467 (3)	0.0304 (2)	0.0085 (2)	0.0088 (2)	−0.0092 (2)
N1	0.037 (3)	0.038 (3)	0.042 (2)	0.001 (2)	0.010 (2)	0.008 (2)
N2	0.038 (3)	0.047 (3)	0.037 (2)	−0.001 (2)	0.006 (2)	0.006 (2)
N3	0.054 (3)	0.063 (4)	0.036 (2)	−0.003 (3)	0.003 (2)	0.014 (2)
N4	0.044 (3)	0.046 (3)	0.068 (3)	−0.002 (3)	0.010 (3)	0.010 (3)
N5	0.042 (3)	0.067 (4)	0.067 (3)	0.010 (3)	0.021 (3)	0.013 (3)
N6	0.057 (4)	0.082 (5)	0.082 (4)	0.020 (4)	0.014 (4)	0.006 (4)
N7	0.045 (3)	0.045 (3)	0.058 (3)	0.006 (2)	0.011 (3)	0.003 (3)
N8	0.048 (3)	0.051 (3)	0.056 (3)	0.005 (3)	0.008 (3)	−0.001 (3)
N9	0.062 (4)	0.062 (4)	0.053 (3)	0.005 (3)	0.004 (3)	−0.003 (3)
O1	0.092 (3)	0.048 (2)	0.050 (2)	0.022 (2)	0.038 (2)	0.010 (2)
O2	0.048 (3)	0.076 (3)	0.047 (2)	0.002 (2)	0.017 (2)	−0.024 (2)
O3	0.060 (3)	0.073 (3)	0.034 (2)	−0.014 (2)	0.006 (2)	0.016 (2)
O4	0.064 (3)	0.079 (3)	0.083 (3)	−0.037 (3)	0.046 (3)	−0.041 (3)
O5	0.097 (4)	0.052 (3)	0.056 (3)	0.024 (3)	0.045 (3)	0.012 (2)
O6	0.036 (2)	0.105 (4)	0.059 (3)	0.001 (2)	0.012 (2)	0.033 (3)
O7	0.093 (3)	0.050 (3)	0.049 (2)	0.022 (2)	0.039 (2)	0.008 (2)
O8	0.075 (3)	0.049 (3)	0.051 (2)	−0.021 (2)	0.013 (2)	−0.016 (2)
O9	0.087 (4)	0.040 (3)	0.089 (4)	0.011 (3)	−0.053 (3)	−0.015 (3)
O10	0.044 (3)	0.061 (3)	0.080 (3)	−0.005 (2)	0.033 (2)	0.002 (3)
O11	0.041 (3)	0.124 (4)	0.063 (3)	0.008 (3)	0.016 (2)	0.045 (3)
O12	0.076 (3)	0.083 (4)	0.093 (4)	−0.044 (3)	0.054 (3)	−0.048 (3)
O13	0.082 (4)	0.042 (3)	0.092 (4)	0.014 (3)	−0.053 (3)	−0.020 (3)
O14	0.031 (2)	0.126 (4)	0.061 (3)	0.000 (3)	0.007 (2)	0.041 (3)
O15	0.053 (3)	0.042 (3)	0.094 (4)	0.010 (2)	0.010 (3)	0.012 (2)
O16	0.073 (3)	0.096 (4)	0.107 (4)	−0.053 (3)	0.059 (3)	−0.066 (4)
O17	0.065 (3)	0.043 (3)	0.079 (3)	0.003 (2)	−0.038 (3)	−0.013 (2)
O18	0.044 (3)	0.089 (4)	0.043 (2)	0.023 (3)	−0.010 (2)	−0.001 (2)
O19A	0.029 (4)	0.030 (4)	0.023 (3)	−0.002 (3)	0.005 (3)	−0.004 (3)
O21A	0.024 (3)	0.029 (4)	0.029 (3)	−0.002 (3)	0.007 (3)	−0.001 (3)
O19B	0.029 (4)	0.030 (4)	0.023 (3)	0.002 (3)	0.002 (3)	0.001 (3)
O21B	0.027 (4)	0.028 (4)	0.031 (3)	−0.001 (3)	0.007 (3)	−0.002 (3)
O1W	0.086 (5)	0.107 (5)	0.108 (5)	0.011 (4)	−0.012 (4)	−0.006 (4)
O2W	0.207 (11)	0.137 (8)	0.301 (15)	−0.038 (8)	0.187 (12)	−0.053 (9)
O3W	0.169 (11)	0.183 (13)	0.41 (2)	0.001 (9)	0.190 (14)	−0.068 (13)
P1	0.0213 (9)	0.0235 (9)	0.0209 (7)	−0.0005 (7)	0.0036 (7)	−0.0016 (7)

Geometric parameters (Å, º) top

C1—N1	1.342 (7)	Mo1—O19B	2.517 (6)
C1—C2	1.358 (9)	Mo2—O15	1.660 (4)
C1—H1	0.9300	Mo2—O16ⁱ	1.860 (5)
C2—C3	1.356 (9)	Mo2—O11	1.903 (5)
C2—H2	0.9300	Mo2—O12	1.936 (5)
C3—C4	1.366 (9)	Mo2—O14	1.944 (4)
C3—H3	0.9300	Mo2—O19Bⁱ	2.471 (7)
C4—C5	1.376 (8)	Mo2—O21B	2.478 (7)
C4—H4	0.9300	Mo3—O10	1.658 (4)
C5—N1	1.344 (7)	Mo3—O1	1.841 (4)
C5—C6	1.463 (7)	Mo3—O7	1.889 (4)
C6—N2	1.324 (7)	Mo3—O13ⁱ	1.895 (5)
C6—C7	1.394 (8)	Mo3—O9	1.971 (5)
C7—C8	1.375 (9)	Mo3—O19Aⁱ	2.443 (7)
C7—H7	0.9300	Mo3—O21A	2.510 (6)
C8—N3	1.315 (9)	Mo4—O8	1.662 (4)
C8—H8	0.9300	Mo4—O6	1.852 (4)
C9—N4	1.341 (9)	Mo4—O11	1.882 (5)
C9—C10	1.341 (10)	Mo4—O5	1.906 (5)
C9—H9	0.9300	Mo4—O1	1.954 (4)
C10—C11	1.278 (13)	Mo4—O21B	2.455 (7)
C10—H10	0.9300	Mo4—O21A	2.498 (7)
C11—C12	1.281 (13)	Mo5—O18	1.647 (4)
C11—H11	0.9300	Mo5—O4	1.857 (4)
C12—C13	1.384 (11)	Mo5—O5	1.900 (5)
C12—H12	0.9300	Mo5—O12ⁱ	1.924 (5)
C13—N4	1.330 (8)	Mo5—O7	1.943 (4)
C13—C14	1.445 (10)	Mo5—O19B	2.461 (7)
C14—N5	1.339 (9)	Mo5—O21A	2.506 (7)
C14—C15	1.428 (11)	Mo6—O2	1.666 (4)
C15—C16	1.490 (14)	Mo6—O9ⁱ	1.834 (5)
C15—H15	0.9300	Mo6—O14	1.852 (5)
C16—N6	1.360 (11)	Mo6—O17	1.928 (5)
C16—H16	0.9300	Mo6—O6	1.967 (5)
C17—N7	1.325 (9)	Mo6—O19A	2.449 (6)
C17—C18	1.361 (11)	Mo6—O21B	2.506 (6)
C17—H17	0.9300	N2—N3	1.346 (7)
C18—C19	1.370 (12)	N3—H3A	0.8600
C18—H18	0.9300	N5—N6	1.354 (8)
C19—C20	1.377 (12)	N6—H6	0.8600
C19—H19	0.9300	N8—N9	1.331 (8)
C20—C21	1.386 (10)	N9—H9A	0.8600
C20—H20	0.9300	O9—Mo6ⁱ	1.834 (5)
C21—N7	1.337 (8)	O12—Mo5ⁱ	1.924 (5)
C21—C22	1.477 (10)	O13—Mo3ⁱ	1.895 (5)
C22—N8	1.345 (8)	O16—Mo2ⁱ	1.860 (5)
C22—C23	1.380 (10)	O19A—P1	1.562 (6)
C23—C24	1.376 (11)	O19A—O21Aⁱ	1.752 (9)
C23—H23	0.9300	O19A—Mo3ⁱ	2.443 (7)
C24—N9	1.352 (9)	O21A—P1	1.495 (7)
C24—H24	0.9300	O21A—O21B	1.693 (9)
Mn1—N8	2.224 (6)	O21A—O19B	1.723 (9)
Mn1—N5	2.224 (5)	O21A—O19Aⁱ	1.752 (9)
Mn1—N2	2.250 (5)	O19B—P1	1.531 (6)
Mn1—N4	2.259 (6)	O19B—O21Bⁱ	1.764 (9)
Mn1—N1	2.260 (5)	O19B—Mo2ⁱ	2.471 (7)
Mn1—N7	2.283 (5)	O21B—P1	1.519 (7)
Mo1—O3	1.644 (4)	O21B—O19Bⁱ	1.764 (9)
Mo1—O13	1.880 (5)	P1—O21Aⁱ	1.495 (7)
Mo1—O16	1.899 (5)	P1—O21Bⁱ	1.519 (7)
Mo1—O17	1.911 (5)	P1—O19Bⁱ	1.531 (6)
Mo1—O4	1.960 (5)	P1—O19Aⁱ	1.562 (6)
Mo1—O19A	2.488 (6)

N1—C1—C2	123.0 (6)	O18—Mo5—O4	102.1 (3)
N1—C1—H1	118.5	O18—Mo5—O5	101.3 (2)
C2—C1—H1	118.5	O4—Mo5—O5	89.4 (2)
C3—C2—C1	119.2 (6)	O18—Mo5—O12ⁱ	101.7 (3)
C3—C2—H2	120.4	O4—Mo5—O12ⁱ	89.8 (2)
C1—C2—H2	120.4	O5—Mo5—O12ⁱ	156.6 (3)
C2—C3—C4	119.1 (6)	O18—Mo5—O7	101.6 (2)
C2—C3—H3	120.5	O4—Mo5—O7	156.3 (2)
C4—C3—H3	120.5	O5—Mo5—O7	86.25 (18)
C3—C4—C5	119.5 (6)	O12ⁱ—Mo5—O7	85.1 (2)
C3—C4—H4	120.2	O18—Mo5—O19B	159.9 (2)
C5—C4—H4	120.2	O4—Mo5—O19B	65.1 (2)
N1—C5—C4	121.6 (5)	O5—Mo5—O19B	94.2 (2)
N1—C5—C6	115.5 (5)	O12ⁱ—Mo5—O19B	64.4 (2)
C4—C5—C6	122.9 (5)	O7—Mo5—O19B	92.0 (2)
N2—C6—C7	110.6 (5)	O18—Mo5—O21A	159.5 (2)
N2—C6—C5	119.7 (5)	O4—Mo5—O21A	92.6 (2)
C7—C6—C5	129.8 (6)	O5—Mo5—O21A	64.3 (2)
C8—C7—C6	104.1 (6)	O12ⁱ—Mo5—O21A	92.4 (3)
C8—C7—H7	127.9	O7—Mo5—O21A	64.6 (2)
C6—C7—H7	127.9	O19B—Mo5—O21A	40.6 (2)
N3—C8—C7	108.2 (6)	O2—Mo6—O9ⁱ	102.9 (3)
N3—C8—H8	125.9	O2—Mo6—O14	101.7 (3)
C7—C8—H8	125.9	O9ⁱ—Mo6—O14	91.5 (2)
N4—C9—C10	121.5 (7)	O2—Mo6—O17	100.2 (2)
N4—C9—H9	119.2	O9ⁱ—Mo6—O17	90.0 (2)
C10—C9—H9	119.2	O14—Mo6—O17	157.2 (2)
C11—C10—C9	121.8 (9)	O2—Mo6—O6	99.7 (2)
C11—C10—H10	119.1	O9ⁱ—Mo6—O6	157.2 (3)
C9—C10—H10	119.1	O14—Mo6—O6	86.7 (2)
C10—C11—C12	120.1 (11)	O17—Mo6—O6	83.2 (2)
C10—C11—H11	120.0	O2—Mo6—O19A	159.3 (2)
C12—C11—H11	120.0	O9ⁱ—Mo6—O19A	64.1 (3)
C11—C12—C13	119.9 (10)	O14—Mo6—O19A	95.1 (2)
C11—C12—H12	120.1	O17—Mo6—O19A	65.3 (2)
C13—C12—H12	120.1	O6—Mo6—O19A	93.4 (2)
N4—C13—C12	121.4 (8)	O2—Mo6—O21B	157.4 (2)
N4—C13—C14	117.0 (6)	O9ⁱ—Mo6—O21B	95.7 (3)
C12—C13—C14	121.6 (7)	O14—Mo6—O21B	64.7 (2)
N5—C14—C15	110.8 (8)	O17—Mo6—O21B	92.5 (2)
N5—C14—C13	117.4 (6)	O6—Mo6—O21B	63.1 (2)
C15—C14—C13	131.8 (8)	O19A—Mo6—O21B	43.1 (2)
C14—C15—C16	103.7 (8)	C1—N1—C5	117.5 (5)
C14—C15—H15	128.2	C1—N1—Mn1	126.3 (4)
C16—C15—H15	128.2	C5—N1—Mn1	116.2 (3)
N6—C16—C15	104.8 (7)	C6—N2—N3	105.7 (5)
N6—C16—H16	127.6	C6—N2—Mn1	115.0 (4)
C15—C16—H16	127.6	N3—N2—Mn1	139.1 (4)
N7—C17—C18	123.2 (7)	C8—N3—N2	111.3 (5)
N7—C17—H17	118.4	C8—N3—H3A	124.3
C18—C17—H17	118.4	N2—N3—H3A	124.3
C17—C18—C19	118.8 (8)	C13—N4—C9	115.3 (6)
C17—C18—H18	120.6	C13—N4—Mn1	115.3 (5)
C19—C18—H18	120.6	C9—N4—Mn1	128.4 (4)
C18—C19—C20	119.7 (8)	C14—N5—N6	107.7 (6)
C18—C19—H19	120.1	C14—N5—Mn1	116.3 (5)
C20—C19—H19	120.1	N6—N5—Mn1	135.9 (5)
C19—C20—C21	117.6 (8)	N5—N6—C16	113.1 (7)
C19—C20—H20	121.2	N5—N6—H6	123.5
C21—C20—H20	121.2	C16—N6—H6	123.5
N7—C21—C20	122.6 (7)	C17—N7—C21	118.1 (6)
N7—C21—C22	116.1 (6)	C17—N7—Mn1	126.2 (5)
C20—C21—C22	121.2 (6)	C21—N7—Mn1	115.7 (4)
N8—C22—C23	110.6 (6)	N9—N8—C22	105.3 (5)
N8—C22—C21	118.2 (6)	N9—N8—Mn1	138.4 (4)
C23—C22—C21	131.3 (6)	C22—N8—Mn1	116.3 (4)
C24—C23—C22	105.8 (7)	N8—N9—C24	112.2 (6)
C24—C23—H23	127.1	N8—N9—H9A	123.9
C22—C23—H23	127.1	C24—N9—H9A	123.9
N9—C24—C23	106.1 (7)	Mo3—O1—Mo4	138.9 (3)
N9—C24—H24	126.9	Mo5—O4—Mo1	139.6 (3)
C23—C24—H24	126.9	Mo5—O5—Mo4	140.0 (3)
N8—Mn1—N5	96.8 (2)	Mo4—O6—Mo6	138.4 (3)
N8—Mn1—N2	96.26 (19)	Mo3—O7—Mo5	138.0 (3)
N5—Mn1—N2	161.7 (2)	Mo6ⁱ—O9—Mo3	139.2 (4)
N8—Mn1—N4	168.0 (2)	Mo4—O11—Mo2	138.7 (3)
N5—Mn1—N4	73.1 (2)	Mo5ⁱ—O12—Mo2	136.6 (3)
N2—Mn1—N4	95.04 (19)	Mo1—O13—Mo3ⁱ	140.9 (4)
N8—Mn1—N1	89.41 (19)	Mo6—O14—Mo2	139.6 (3)
N5—Mn1—N1	93.85 (18)	Mo2ⁱ—O16—Mo1	142.1 (3)
N2—Mn1—N1	73.49 (17)	Mo1—O17—Mo6	136.3 (3)
N4—Mn1—N1	97.64 (19)	P1—O19A—O21Aⁱ	53.2 (3)
N8—Mn1—N7	73.6 (2)	P1—O19A—Mo3ⁱ	124.6 (3)
N5—Mn1—N7	99.5 (2)	O21Aⁱ—O19A—Mo3ⁱ	71.3 (3)
N2—Mn1—N7	96.45 (18)	P1—O19A—Mo6	122.9 (4)
N4—Mn1—N7	101.2 (2)	O21Aⁱ—O19A—Mo6	132.2 (4)
N1—Mn1—N7	159.42 (19)	Mo3ⁱ—O19A—Mo6	93.6 (2)
O3—Mo1—O13	102.6 (3)	P1—O19A—Mo1	122.3 (4)
O3—Mo1—O16	102.5 (3)	O21Aⁱ—O19A—Mo1	132.0 (4)
O13—Mo1—O16	89.5 (2)	Mo3ⁱ—O19A—Mo1	92.4 (2)
O3—Mo1—O17	102.1 (2)	Mo6—O19A—Mo1	92.4 (2)
O13—Mo1—O17	88.8 (2)	P1—O21A—O21B	56.5 (3)
O16—Mo1—O17	155.1 (3)	P1—O21A—O19B	56.3 (3)
O3—Mo1—O4	101.5 (2)	O21B—O21A—O19B	93.5 (4)
O13—Mo1—O4	155.9 (3)	P1—O21A—O19Aⁱ	56.9 (3)
O16—Mo1—O4	85.4 (2)	O21B—O21A—O19Aⁱ	92.4 (4)
O17—Mo1—O4	86.2 (2)	O19B—O21A—O19Aⁱ	91.7 (4)
O3—Mo1—O19A	159.2 (2)	P1—O21A—Mo4	125.2 (4)
O13—Mo1—O19A	62.9 (2)	O21B—O21A—Mo4	68.7 (3)
O16—Mo1—O19A	92.6 (3)	O19B—O21A—Mo4	132.0 (4)
O17—Mo1—O19A	64.6 (2)	O19Aⁱ—O21A—Mo4	131.5 (4)
O4—Mo1—O19A	93.8 (2)	P1—O21A—Mo5	124.6 (4)
O3—Mo1—O19B	157.9 (2)	O21B—O21A—Mo5	132.9 (4)
O13—Mo1—O19B	94.0 (3)	O19B—O21A—Mo5	68.3 (3)
O16—Mo1—O19B	62.7 (2)	O19Aⁱ—O21A—Mo5	129.5 (4)
O17—Mo1—O19B	92.6 (2)	Mo4—O21A—Mo5	91.2 (2)
O4—Mo1—O19B	62.7 (2)	P1—O21A—Mo3	124.1 (3)
O19A—Mo1—O19B	42.9 (2)	O21B—O21A—Mo3	129.4 (4)
O15—Mo2—O16ⁱ	102.5 (3)	O19B—O21A—Mo3	130.9 (4)
O15—Mo2—O11	100.3 (3)	O19Aⁱ—O21A—Mo3	67.3 (3)
O16ⁱ—Mo2—O11	90.3 (2)	Mo4—O21A—Mo3	90.4 (2)
O15—Mo2—O12	102.5 (3)	Mo5—O21A—Mo3	91.0 (2)
O16ⁱ—Mo2—O12	88.4 (2)	P1—O19B—O21A	54.3 (3)
O11—Mo2—O12	156.8 (3)	P1—O19B—O21Bⁱ	54.3 (3)
O15—Mo2—O14	101.4 (3)	O21A—O19B—O21Bⁱ	91.3 (4)
O16ⁱ—Mo2—O14	156.0 (3)	P1—O19B—Mo5	125.4 (4)
O11—Mo2—O14	86.80 (19)	O21A—O19B—Mo5	71.1 (3)
O12—Mo2—O14	85.0 (2)	O21Bⁱ—O19B—Mo5	134.3 (4)
O15—Mo2—O19Bⁱ	160.1 (2)	P1—O19B—Mo2ⁱ	123.7 (3)
O16ⁱ—Mo2—O19Bⁱ	64.2 (2)	O21A—O19B—Mo2ⁱ	134.8 (4)
O11—Mo2—O19Bⁱ	94.7 (2)	O21Bⁱ—O19B—Mo2ⁱ	69.3 (3)
O12—Mo2—O19Bⁱ	64.1 (2)	Mo5—O19B—Mo2ⁱ	93.3 (2)
O14—Mo2—O19Bⁱ	92.3 (2)	P1—O19B—Mo1	122.2 (3)
O15—Mo2—O21B	158.2 (2)	O21A—O19B—Mo1	130.5 (4)
O16ⁱ—Mo2—O21B	93.1 (3)	O21Bⁱ—O19B—Mo1	128.6 (4)
O11—Mo2—O21B	64.0 (2)	Mo5—O19B—Mo1	92.0 (2)
O12—Mo2—O21B	93.0 (2)	Mo2ⁱ—O19B—Mo1	90.9 (2)
O14—Mo2—O21B	64.3 (2)	P1—O21B—O21A	55.1 (3)
O19Bⁱ—Mo2—O21B	41.8 (2)	P1—O21B—O19Bⁱ	55.0 (3)
O10—Mo3—O1	102.9 (2)	O21A—O21B—O19Bⁱ	92.0 (4)
O10—Mo3—O7	101.8 (2)	P1—O21B—Mo4	126.5 (4)
O1—Mo3—O7	90.13 (18)	O21A—O21B—Mo4	71.4 (3)
O10—Mo3—O13ⁱ	101.3 (3)	O19Bⁱ—O21B—Mo4	135.1 (4)
O1—Mo3—O13ⁱ	90.7 (2)	P1—O21B—Mo2	123.9 (4)
O7—Mo3—O13ⁱ	156.1 (3)	O21A—O21B—Mo2	132.7 (4)
O10—Mo3—O9	100.4 (3)	O19Bⁱ—O21B—Mo2	68.9 (3)
O1—Mo3—O9	156.7 (3)	Mo4—O21B—Mo2	91.7 (2)
O7—Mo3—O9	85.2 (2)	P1—O21B—Mo6	121.7 (3)
O13ⁱ—Mo3—O9	84.7 (2)	O21A—O21B—Mo6	131.9 (4)
O10—Mo3—O19Aⁱ	157.1 (2)	O19Bⁱ—O21B—Mo6	127.0 (4)
O1—Mo3—O19Aⁱ	94.8 (2)	Mo4—O21B—Mo6	92.0 (2)
O7—Mo3—O19Aⁱ	92.4 (2)	Mo2—O21B—Mo6	91.3 (2)
O13ⁱ—Mo3—O19Aⁱ	63.7 (2)	O21A—P1—O21Aⁱ	180.0 (8)
O9—Mo3—O19Aⁱ	62.7 (2)	O21A—P1—O21B	68.4 (4)
O10—Mo3—O21A	161.3 (2)	O21Aⁱ—P1—O21B	111.6 (4)
O1—Mo3—O21A	65.5 (2)	O21A—P1—O21Bⁱ	111.6 (4)
O7—Mo3—O21A	65.1 (2)	O21Aⁱ—P1—O21Bⁱ	68.4 (4)
O13ⁱ—Mo3—O21A	93.7 (3)	O21B—P1—O21Bⁱ	180.0 (5)
O9—Mo3—O21A	92.0 (3)	O21A—P1—O19Bⁱ	110.6 (4)
O19Aⁱ—Mo3—O21A	41.4 (2)	O21Aⁱ—P1—O19Bⁱ	69.4 (4)
O8—Mo4—O6	103.8 (2)	O21B—P1—O19Bⁱ	70.6 (3)
O8—Mo4—O11	102.0 (3)	O21Bⁱ—P1—O19Bⁱ	109.4 (3)
O6—Mo4—O11	90.04 (19)	O21A—P1—O19B	69.4 (4)
O8—Mo4—O5	100.6 (2)	O21Aⁱ—P1—O19B	110.6 (4)
O6—Mo4—O5	89.7 (2)	O21B—P1—O19B	109.4 (3)
O11—Mo4—O5	156.8 (3)	O21Bⁱ—P1—O19B	70.6 (3)
O8—Mo4—O1	100.0 (2)	O19Bⁱ—P1—O19B	180.0 (8)
O6—Mo4—O1	156.2 (2)	O21A—P1—O19Aⁱ	69.9 (3)
O11—Mo4—O1	85.7 (2)	O21Aⁱ—P1—O19Aⁱ	110.1 (3)
O5—Mo4—O1	85.27 (18)	O21B—P1—O19Aⁱ	107.6 (3)
O8—Mo4—O21B	161.8 (2)	O21Bⁱ—P1—O19Aⁱ	72.4 (3)
O6—Mo4—O21B	65.5 (2)	O19Bⁱ—P1—O19Aⁱ	72.6 (3)
O11—Mo4—O21B	64.7 (2)	O19B—P1—O19Aⁱ	107.4 (3)
O5—Mo4—O21B	94.2 (2)	O21A—P1—O19A	110.1 (3)
O1—Mo4—O21B	91.7 (2)	O21Aⁱ—P1—O19A	69.9 (3)
O8—Mo4—O21A	158.2 (2)	O21B—P1—O19A	72.4 (3)
O6—Mo4—O21A	92.4 (2)	O21Bⁱ—P1—O19A	107.6 (3)
O11—Mo4—O21A	92.5 (3)	O19Bⁱ—P1—O19A	107.4 (3)
O5—Mo4—O21A	64.4 (2)	O19B—P1—O19A	72.6 (3)
O1—Mo4—O21A	64.5 (2)	O19Aⁱ—P1—O19A	180.0 (4)
O21B—Mo4—O21A	40.0 (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
N9—H9A···O1W	0.86	1.96	2.786 (9)	160
N6—H6···O2W	0.86	2.10	2.951 (13)	171
N3—H3A···O17ⁱⁱ	0.86	1.97	2.814 (7)	165

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

Experimental details

Crystal data
Chemical formula	[Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r	2911.22
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.897 (4), 16.360 (3), 27.615 (6)
β (°)	104.90 (3)
V (Å³)	8250 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.18
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.780, 0.845
No. of measured, independent and observed [I > 2σ(I)] reflections	15879, 7042, 5890
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.103, 1.00
No. of reflections	7042
No. of parameters	610
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.058P)² + 43.0549P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.52, −0.59

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

Selected bond lengths (Å) top

Mn1—N8	2.224 (6)	Mn1—N7	2.283 (5)
Mn1—N5	2.224 (5)	P1—O21Aⁱ	1.495 (7)
Mn1—N2	2.250 (5)	P1—O21Bⁱ	1.519 (7)
Mn1—N4	2.259 (6)	P1—O19Bⁱ	1.531 (6)
Mn1—N1	2.260 (5)	P1—O19Aⁱ	1.562 (6)

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
N9—H9A···O1W	0.86	1.96	2.786 (9)	159.9
N6—H6···O2W	0.86	2.10	2.951 (13)	171.2
N3—H3A···O17ⁱⁱ	0.86	1.97	2.814 (7)	165.0

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

Acknowledgements

Financial support from the Chinese Academy of Sciences (`Hundred Talents Program') and the Ministry of Science and Technology of China (grant No. 2007CB607608), Shandong Provincial Education Department and Shandong Institute of Education are gratefully acknowledged.

References

Artero, V. & Proust, A. (2000). Eur. J. Inorg. Chem. pp. 2393–2400 CrossRef Google Scholar
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Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kurmoo, M., Bonamico, M., Bellitto, C., Fares, V., Federici, F., Guionneau, P., Ducasse, L., Kitagawa, H. & Day, P. (1998). Adv. Mater. 7, 545–550. CrossRef Google Scholar
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Volume 66| Part 2| February 2010| Pages m231-m232

https://doi.org/10.1107/S160053681000320X

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