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

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

doi:10.1107/S1600536810004861

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m283-m284

doi:10.1107/S1600536810004861

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Bis{tris[3-(2-pyridyl)-1H-pyrazole]iron(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 4 February 2010; accepted 8 February 2010; online 13 February 2010)

Crystals of the title compound, [Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O, prepared under hydrothermal conditions, are isotypic with the Mn²⁺ and Cd²⁺ analogues. The Fe²⁺ cation is in a distorted octahedral coordination by six N atoms from three chelating 3-(2-pyridyl)-1H-pyrazole ligands. The heteropolyanion [PMo₁₂O₄₀]⁴⁻ is a one-electron reduced species in which 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 make a contribution to the crystal packing. The Fe—N bond lengths [2.085 (19)—2.15 (2) Å] are somewhat shorter than the Mn—N and Cd—N bond lengths [2.224 (6)–2.283 (5) and 2.316 (7)–2.334 (6) Å, respectively]. All other bond lengths and angles and the hydrogen-bonding motifs are very similar in the isotypic structures.

Related literature

For the isotypic Mn²⁺ and Cd²⁺structures, see: Hao, Ma et al. (2010 ); Hao, Wang et al. (2010 ). 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 other structures containing the one-electron reduced heteropolyanion [PMo₁₂O₄₀]⁴⁻, see: Artero & Proust (2000 ); Kurmoo et al. (1998 ); Niu et al. (1999 ). For the role of amines in hydrothermal synthesis, see: Yang et al. (2003 ).

Experimental

Crystal data

[Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r = 2913.04
Monoclinic, C 2/c
a = 18.6816 (10) Å
b = 16.2224 (10) Å
c = 27.6405 (15) Å
β = 104.295 (1)°
V = 8117.4 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.26 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 = 0.773, T_max = 0.840
20565 measured reflections
7090 independent reflections
5550 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.142
S = 1.00
7090 reflections
592 parameters
H-atom parameters constrained
Δρ_max = 1.36 e Å⁻³
Δρ_min = −0.80 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—N8	2.085 (19)
Fe1—N5	2.08 (2)
Fe1—N2	2.11 (2)
Fe1—N1	2.129 (17)
Fe1—N4	2.13 (2)
Fe1—N7	2.15 (2)
P1—O21Aⁱ	1.49 (2)
P1—O21Bⁱ	1.52 (2)
P1—O19Bⁱ	1.54 (2)
P1—O19Aⁱ	1.56 (2)
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	2.03	2.82 (3)	153
N6—H6⋯O2W	0.86	1.98	2.82 (5)	167
N9—H9A⋯O1W	0.86	1.95	2.77 (3)	157
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/S1600536810004861/wm2304sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004861/wm2304Isup2.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)-1H-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 [Fe(C₈H₇N₃)₃]²⁺ cation, half of a a [PMo₁₂O₄₀]^4- heteropolyanion and of three uncoordinated water molecules. The Fe²⁺ 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 an one-electron reduced derivative of [PMo₁₂O₄₀]^3-, similar to anions with different counter cations as reported by Artero & Proust (2000); Kurmoo et al. (1998); Niu et al. (1999). The employed organic ligand appears to adjust the pH value, and additionally supplies reducing electrons, which is a commonly observed feature of hydrothermal syntheses when organic amines are used to prepare various hybrid materials, zeolites or metal phosphates (Yang et al., 2003).

In the Keggin-type heteropolyanion, each Mo atom is surrounded by six O atoms and the P atom is located at the center of the anion. There are four kinds of O atoms present in the anion according to their coordination environments: O_a (O atoms in the disordered PO₄ tetrahedron), O_b (bridging O atoms between two triplet groups of MoO₆ octahedra), O_c (bridging O atoms within one triplet group of MoO₆ octahedra) and O_d (terminal O atoms). The P—O bond distances are in the normal range of 1.49 (2)—1.56 (2) Å. The Mo—O bond distances vary widely from 1.636 (15) to 2.51 (2) Å. The shortest Mo—O bonds are in the range of 1.636 (2)—1.659 (15) Å for the terminal oxygen atoms. The longest Mo—O lengths are in the range of 2.43 (2)—2.51 (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 [(Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ is isotypic with the Mn²⁺ and Cd²⁺ analogues, [(Mn(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ (Hao, Ma et al., 2010) and [(Cd(C₈H₇N₃)₃]₂[PMo₁₂O₄₀](H₂O)₆ (Hao, Wang et al., 2010). In comparison with the Mn²⁺ and Cd²⁺ analogues, the Fe—N bond lengths (2.085 (19)—2.15 (2) Å) are somewhat shorter than the Mn—N and Cd—N bond lengths with 2.224 (6)—2.283 (5) Å and 2.316 (7)—2.334 (6) Å, respectively. All other bond lengths and angles and the hydrogen-bonding motifs are very similar in the isotypic structures.

Related literature top

For the isotypic Mn²⁺ and Cd²⁺structures, see: Hao, Ma et al. (2010); Hao, Wang et al. (2010). 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 other structures containing the one-electron reduced heteropolyanion [PMo₁₂O₄₀]^4-, see: Artero & Proust (2000); Kurmoo et al. (1998); Niu et al. (1999). For the role of amines in hydrothermal synthesis, see: Yang et al. (2003).

Experimental top

A mixture of 3-(2-pyridyl)-1H-pyrazole (0.5 mmoL 0.07 g), sodium molybdate (0.4 mmoL, 0.10 g), iron(III) chloride hexahydrate (0.25 mmol, 0.07 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. Brown crystals suitable for the X-ray experiment were obtained. IR(cm^-1): 3441, 3118, 2674, 2546, 1696, 1605, 1540, 1429, 1356, 1291, 1107, 1014, 931, 876, 802, 719, 562, 507.

TGA curve shows a separation of lattice water molecules and the organic ligands above 352 and 655 K, respectively. The overall thermal decomposition process can be described by the followed equation: 4C₄₈H₅₄Fe₂Mo₁₂N₁₈O₄₆P + 327O₂ = 108H₂O + 192CO₂ + 36N₂O₅ + 4Fe₂O₃ + 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]iron(II)} dodecamolybdo(V,VI)phosphate hexahydrate top

Crystal data top

[(Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	F(000) = 5628
M_r = 2913.04	D_x = 2.384 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9828 reflections
a = 18.6816 (10) Å	θ = 2.4–28.2°
b = 16.2224 (10) Å	µ = 2.26 mm⁻¹
c = 27.6405 (15) Å	T = 293 K
β = 104.295 (1)°	Block, brown
V = 8117.4 (8) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7090 independent reflections
Radiation source: fine-focus sealed tube	5550 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
phi and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→17
T_min = 0.773, T_max = 0.840	k = −18→19
20565 measured reflections	l = −32→31

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 20.1545P] where P = (F_o² + 2F_c²)/3
7090 reflections	(Δ/σ)_max = 0.001
592 parameters	Δρ_max = 1.36 e Å⁻³
0 restraints	Δρ_min = −0.80 e Å⁻³

Crystal data top

[(Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O	V = 8117.4 (8) Å³
M_r = 2913.04	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.6816 (10) Å	µ = 2.26 mm⁻¹
b = 16.2224 (10) Å	T = 293 K
c = 27.6405 (15) Å	0.12 × 0.10 × 0.08 mm
β = 104.295 (1)°

Data collection top

Bruker APEXII CCD diffractometer	7090 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	5550 reflections with I > 2σ(I)
T_min = 0.773, T_max = 0.840	R_int = 0.042
20565 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 20.1545P] where P = (F_o² + 2F_c²)/3
7090 reflections	Δρ_max = 1.36 e Å⁻³
592 parameters	Δρ_min = −0.80 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	0.2037 (13)	0.8989 (13)	0.0951 (8)	0.049 (5)
H1	0.2470	0.8948	0.0844	0.059*
C2	0.1427 (14)	0.9335 (14)	0.0638 (8)	0.054 (6)
H2	0.1446	0.9517	0.0323	0.065*
C3	0.0793 (13)	0.9410 (15)	0.0791 (8)	0.055 (6)
H3	0.0379	0.9660	0.0588	0.065*
C4	0.0780 (13)	0.9107 (15)	0.1252 (9)	0.055 (6)
H4	0.0345	0.9123	0.1359	0.066*
C5	0.1406 (12)	0.8781 (12)	0.1553 (7)	0.042 (5)
C6	0.1448 (12)	0.8483 (13)	0.2053 (8)	0.045 (5)
C7	0.0917 (16)	0.845 (2)	0.2338 (10)	0.076 (8)
H7	0.0423	0.8603	0.2244	0.091*
C8	0.1307 (19)	0.814 (2)	0.2788 (9)	0.079 (9)
H8	0.1119	0.8047	0.3065	0.095*
C9	0.3237 (16)	0.9793 (18)	0.2596 (11)	0.071 (7)
H9	0.2903	0.9589	0.2766	0.085*
C10	0.3526 (18)	1.0535 (19)	0.2716 (12)	0.076 (8)
H10	0.3402	1.0833	0.2971	0.091*
C11	0.400 (2)	1.086 (3)	0.2472 (15)	0.098 (11)
H11	0.4198	1.1378	0.2557	0.118*
C12	0.4175 (17)	1.043 (2)	0.2108 (14)	0.090 (10)
H12	0.4493	1.0655	0.1931	0.108*
C13	0.3882 (13)	0.9665 (18)	0.2001 (11)	0.066 (7)
C14	0.4075 (15)	0.915 (2)	0.1621 (11)	0.074 (8)
C15	0.4577 (19)	0.926 (3)	0.1312 (14)	0.101 (11)
H15	0.4894	0.9699	0.1306	0.121*
C16	0.4475 (19)	0.853 (2)	0.1010 (13)	0.091 (10)
H16	0.4719	0.8392	0.0766	0.109*
C17	0.4084 (15)	0.758 (2)	0.2901 (12)	0.077 (8)
H17	0.4135	0.8138	0.2988	0.093*
C18	0.4475 (19)	0.701 (2)	0.3232 (13)	0.097 (11)
H18	0.4766	0.7174	0.3540	0.116*
C19	0.443 (2)	0.622 (2)	0.3106 (14)	0.103 (12)
H19	0.4709	0.5832	0.3319	0.123*
C20	0.3977 (17)	0.5978 (18)	0.2657 (11)	0.078 (8)
H20	0.3943	0.5426	0.2563	0.093*
C21	0.3579 (13)	0.6562 (15)	0.2356 (9)	0.054 (6)
C22	0.3055 (13)	0.6380 (14)	0.1877 (9)	0.054 (6)
C23	0.2857 (17)	0.5644 (17)	0.1626 (10)	0.069 (7)
H23	0.3049	0.5122	0.1716	0.083*
C24	0.2312 (19)	0.5861 (18)	0.1213 (11)	0.077 (8)
H24	0.2051	0.5507	0.0968	0.092*
Fe1	0.29393 (17)	0.8180 (2)	0.19341 (13)	0.0479 (8)
Mo1	0.24259 (11)	0.14187 (11)	0.11115 (6)	0.0414 (5)
Mo2	0.19058 (10)	0.45820 (10)	−0.01680 (7)	0.0420 (5)
Mo3	0.42269 (9)	0.31452 (11)	−0.01975 (7)	0.0386 (5)
Mo4	0.35343 (9)	0.40933 (11)	0.07504 (6)	0.0398 (5)
Mo5	0.41686 (9)	0.20224 (11)	0.09088 (6)	0.0405 (5)
Mo6	0.17783 (10)	0.34811 (12)	0.09231 (6)	0.0420 (5)
N1	0.2034 (9)	0.8711 (11)	0.1403 (6)	0.042 (4)
N2	0.2095 (10)	0.8208 (12)	0.2318 (7)	0.051 (5)
N3	0.1991 (13)	0.7990 (14)	0.2763 (7)	0.068 (6)
H3A	0.2327	0.7779	0.3001	0.081*
N4	0.3407 (12)	0.9323 (13)	0.2238 (8)	0.064 (6)
N5	0.3703 (13)	0.8449 (17)	0.1521 (8)	0.072 (7)
N6	0.3958 (16)	0.8079 (19)	0.1153 (10)	0.093 (9)
H6	0.3805	0.7608	0.1026	0.112*
N7	0.3639 (11)	0.7377 (13)	0.2466 (8)	0.057 (5)
N8	0.2677 (11)	0.7008 (11)	0.1633 (7)	0.052 (5)
N9	0.2227 (12)	0.6693 (13)	0.1233 (8)	0.061 (5)
H9A	0.1918	0.6975	0.1013	0.073*
O1	0.4070 (10)	0.3947 (9)	0.0244 (6)	0.062 (5)
O2	0.1470 (9)	0.3952 (11)	0.1364 (6)	0.059 (4)
O3	0.2402 (9)	0.0913 (10)	0.1620 (5)	0.056 (4)
O4	0.3455 (11)	0.1738 (12)	0.1246 (7)	0.077 (6)
O5	0.4049 (11)	0.3141 (10)	0.1060 (6)	0.065 (5)
O6	0.2789 (8)	0.3892 (13)	0.1084 (7)	0.071 (5)
O7	0.4527 (11)	0.2401 (10)	0.0354 (6)	0.065 (5)
O8	0.4029 (10)	0.4828 (10)	0.1090 (6)	0.062 (4)
O9	0.4022 (12)	0.2143 (10)	−0.0602 (7)	0.085 (7)
O10	0.5038 (9)	0.3410 (10)	−0.0293 (7)	0.062 (4)
O11	0.2853 (9)	0.4702 (15)	0.0264 (7)	0.083 (7)
O12	0.1036 (11)	0.4003 (12)	−0.0543 (7)	0.083 (7)
O13	0.1436 (12)	0.1335 (10)	0.0730 (8)	0.088 (7)
O14	0.1569 (9)	0.4260 (15)	0.0409 (7)	0.084 (6)
O15	0.1641 (9)	0.5548 (9)	−0.0236 (7)	0.064 (5)
O16	0.2690 (11)	0.0585 (13)	0.0706 (8)	0.087 (7)
O17	0.2216 (10)	0.2520 (10)	0.1270 (7)	0.078 (6)
O18	0.4938 (9)	0.1788 (12)	0.1315 (6)	0.066 (5)
O19A	0.2032 (13)	0.2368 (14)	0.0391 (8)	0.030 (5)	0.50
O21A	0.3250 (13)	0.2802 (15)	0.0252 (9)	0.030 (5)	0.50
O19B	0.2909 (13)	0.1861 (14)	0.0380 (8)	0.028 (5)	0.50
O21B	0.2480 (14)	0.3317 (15)	0.0266 (9)	0.032 (5)	0.50
O1W	0.1172 (13)	0.7180 (15)	0.0392 (9)	0.096 (7)
O2W	0.362 (3)	0.657 (2)	0.0638 (17)	0.186 (11)
O3W	0.534 (2)	0.071 (3)	0.0275 (19)	0.199 (13)
P1	0.2500	0.2500	0.0000	0.0217 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.047 (12)	0.048 (12)	0.051 (13)	−0.004 (10)	0.012 (10)	0.016 (10)
C2	0.064 (15)	0.048 (12)	0.046 (12)	−0.015 (12)	0.007 (11)	0.009 (10)
C3	0.041 (12)	0.062 (14)	0.047 (13)	−0.004 (11)	−0.014 (10)	0.011 (11)
C4	0.039 (12)	0.070 (15)	0.055 (14)	0.001 (11)	0.008 (10)	0.004 (12)
C5	0.043 (11)	0.040 (11)	0.040 (11)	−0.002 (9)	0.005 (9)	0.002 (9)
C6	0.037 (11)	0.053 (12)	0.044 (12)	−0.006 (10)	0.006 (9)	0.003 (10)
C7	0.063 (17)	0.11 (2)	0.067 (17)	0.011 (16)	0.035 (14)	0.013 (16)
C8	0.09 (2)	0.11 (2)	0.037 (13)	−0.009 (19)	0.020 (14)	0.018 (14)
C9	0.070 (18)	0.070 (17)	0.080 (19)	0.018 (15)	0.033 (15)	0.027 (15)
C10	0.08 (2)	0.071 (19)	0.076 (19)	0.009 (16)	0.014 (15)	0.006 (15)
C11	0.08 (2)	0.10 (3)	0.10 (3)	0.01 (2)	0.00 (2)	0.02 (2)
C12	0.051 (17)	0.11 (3)	0.10 (2)	−0.010 (18)	−0.005 (17)	0.02 (2)
C13	0.036 (12)	0.077 (18)	0.076 (17)	0.007 (12)	−0.001 (12)	0.032 (14)
C14	0.049 (15)	0.10 (2)	0.070 (18)	0.022 (16)	0.016 (13)	0.038 (17)
C15	0.068 (17)	0.13 (2)	0.11 (2)	0.018 (17)	0.018 (16)	0.051 (19)
C16	0.082 (18)	0.12 (2)	0.082 (18)	0.038 (17)	0.050 (15)	0.028 (17)
C17	0.053 (16)	0.08 (2)	0.09 (2)	−0.001 (15)	0.006 (15)	−0.021 (17)
C18	0.07 (2)	0.10 (3)	0.09 (2)	−0.006 (19)	−0.027 (18)	0.00 (2)
C19	0.09 (3)	0.09 (2)	0.10 (3)	0.02 (2)	−0.02 (2)	0.01 (2)
C20	0.074 (19)	0.065 (17)	0.08 (2)	0.012 (14)	−0.002 (16)	0.008 (15)
C21	0.044 (12)	0.054 (14)	0.064 (15)	0.003 (11)	0.016 (11)	0.000 (11)
C22	0.054 (14)	0.049 (13)	0.061 (14)	0.010 (11)	0.021 (11)	−0.004 (11)
C23	0.09 (2)	0.053 (14)	0.066 (17)	0.008 (14)	0.018 (15)	−0.002 (13)
C24	0.10 (2)	0.067 (18)	0.063 (17)	0.006 (16)	0.015 (16)	−0.017 (13)
Fe1	0.0393 (17)	0.0462 (18)	0.060 (2)	0.0076 (14)	0.0151 (14)	0.0097 (14)
Mo1	0.0516 (11)	0.0396 (10)	0.0317 (9)	−0.0035 (8)	0.0077 (8)	0.0034 (7)
Mo2	0.0421 (10)	0.0313 (9)	0.0549 (11)	0.0073 (7)	0.0165 (8)	0.0039 (7)
Mo3	0.0257 (9)	0.0415 (10)	0.0474 (11)	−0.0038 (7)	0.0068 (7)	−0.0020 (8)
Mo4	0.0308 (9)	0.0425 (10)	0.0436 (10)	−0.0059 (7)	0.0044 (7)	−0.0096 (7)
Mo5	0.0281 (9)	0.0501 (11)	0.0394 (10)	0.0028 (7)	0.0006 (7)	0.0023 (8)
Mo6	0.0423 (10)	0.0483 (11)	0.0350 (10)	0.0105 (8)	0.0087 (8)	−0.0084 (7)
N1	0.036 (9)	0.047 (10)	0.043 (10)	−0.002 (8)	0.010 (7)	0.005 (8)
N2	0.043 (10)	0.056 (11)	0.044 (10)	−0.007 (9)	−0.005 (8)	0.010 (8)
N3	0.073 (16)	0.082 (15)	0.040 (11)	−0.016 (12)	−0.001 (10)	0.020 (10)
N4	0.058 (13)	0.063 (13)	0.078 (14)	0.019 (11)	0.029 (11)	0.027 (11)
N5	0.062 (14)	0.098 (18)	0.063 (14)	0.034 (14)	0.027 (11)	0.022 (13)
N6	0.09 (2)	0.12 (2)	0.074 (16)	0.054 (18)	0.024 (15)	0.018 (15)
N7	0.040 (10)	0.067 (13)	0.064 (13)	−0.002 (9)	0.010 (9)	−0.007 (10)
N8	0.051 (11)	0.051 (11)	0.050 (11)	0.007 (9)	0.006 (9)	−0.004 (9)
N9	0.071 (14)	0.056 (12)	0.051 (12)	0.003 (10)	0.007 (10)	−0.006 (9)
O1	0.094 (13)	0.045 (9)	0.059 (10)	0.024 (9)	0.042 (9)	0.009 (7)
O2	0.048 (9)	0.081 (12)	0.048 (9)	0.008 (8)	0.013 (7)	−0.022 (8)
O3	0.057 (10)	0.069 (10)	0.042 (8)	−0.010 (8)	0.009 (7)	0.012 (7)
O4	0.071 (12)	0.086 (13)	0.089 (13)	−0.046 (10)	0.049 (11)	−0.049 (11)
O5	0.101 (14)	0.048 (9)	0.062 (10)	0.026 (9)	0.049 (10)	0.012 (8)
O6	0.030 (8)	0.114 (15)	0.067 (11)	0.004 (9)	0.010 (7)	0.040 (10)
O7	0.099 (14)	0.051 (9)	0.055 (10)	0.025 (9)	0.040 (9)	0.011 (8)
O8	0.075 (12)	0.049 (9)	0.058 (10)	−0.020 (9)	0.009 (8)	−0.014 (8)
O9	0.092 (13)	0.039 (8)	0.087 (12)	0.007 (9)	−0.046 (10)	−0.015 (8)
O10	0.047 (9)	0.065 (10)	0.085 (12)	−0.003 (8)	0.038 (9)	−0.001 (9)
O11	0.038 (9)	0.146 (19)	0.068 (11)	0.010 (11)	0.015 (8)	0.052 (12)
O12	0.078 (13)	0.092 (14)	0.096 (14)	−0.049 (11)	0.055 (11)	−0.052 (11)
O13	0.086 (14)	0.043 (9)	0.096 (14)	0.018 (9)	−0.053 (11)	−0.021 (9)
O14	0.037 (9)	0.137 (18)	0.074 (12)	−0.004 (10)	0.007 (8)	0.054 (12)
O15	0.052 (10)	0.036 (8)	0.101 (13)	0.014 (7)	0.012 (9)	0.006 (8)
O16	0.079 (13)	0.097 (14)	0.105 (14)	−0.053 (12)	0.060 (12)	−0.062 (12)
O17	0.069 (12)	0.046 (9)	0.088 (13)	0.007 (8)	−0.038 (10)	−0.013 (9)
O18	0.051 (10)	0.094 (13)	0.043 (9)	0.029 (9)	−0.007 (7)	0.004 (8)
O19A	0.023 (12)	0.037 (13)	0.028 (12)	0.002 (10)	0.004 (10)	−0.005 (10)
O21A	0.022 (12)	0.033 (13)	0.036 (13)	−0.001 (10)	0.008 (10)	−0.001 (10)
O19B	0.032 (13)	0.025 (11)	0.025 (12)	0.001 (10)	0.003 (10)	−0.003 (9)
O21B	0.035 (14)	0.032 (13)	0.029 (13)	0.000 (11)	0.006 (10)	−0.001 (10)
O1W	0.077 (14)	0.102 (16)	0.095 (16)	0.019 (13)	−0.005 (12)	0.004 (13)
O2W	0.231 (11)	0.150 (11)	0.239 (11)	−0.014 (3)	0.179 (4)	−0.011 (3)
O3W	0.166 (13)	0.165 (13)	0.311 (13)	0.000 (3)	0.140 (5)	−0.042 (3)
P1	0.022 (3)	0.020 (3)	0.022 (3)	0.002 (2)	0.004 (2)	−0.001 (2)

Geometric parameters (Å, º) top

C1—N1	1.33 (3)	Mo1—O19B	2.51 (2)
C1—C2	1.37 (3)	Mo2—O15	1.641 (14)
C1—H1	0.9300	Mo2—O16ⁱ	1.847 (17)
C2—C3	1.36 (3)	Mo2—O11	1.884 (18)
C2—H2	0.9300	Mo2—O14	1.925 (17)
C3—C4	1.37 (3)	Mo2—O12	1.941 (18)
C3—H3	0.9300	Mo2—O19Bⁱ	2.46 (2)
C4—C5	1.36 (3)	Mo2—O21B	2.48 (2)
C4—H4	0.9300	Mo3—O10	1.659 (15)
C5—N1	1.34 (3)	Mo3—O1	1.855 (15)
C5—C6	1.45 (3)	Mo3—O13ⁱ	1.875 (16)
C6—N2	1.33 (3)	Mo3—O7	1.916 (15)
C6—C7	1.41 (3)	Mo3—O9	1.958 (16)
C7—C8	1.37 (4)	Mo3—O19Aⁱ	2.43 (2)
C7—H7	0.9300	Mo3—O21A	2.51 (2)
C8—N3	1.32 (4)	Mo4—O8	1.652 (15)
C8—H8	0.9300	Mo4—O6	1.878 (16)
C9—C10	1.33 (4)	Mo4—O11	1.887 (17)
C9—N4	1.35 (3)	Mo4—O5	1.907 (16)
C9—H9	0.9300	Mo4—O1	1.926 (15)
C10—C11	1.34 (5)	Mo4—O21B	2.44 (2)
C10—H10	0.9300	Mo4—O21A	2.49 (2)
C11—C12	1.33 (5)	Mo5—O18	1.636 (15)
C11—H11	0.9300	Mo5—O4	1.864 (16)
C12—C13	1.36 (4)	Mo5—O5	1.888 (15)
C12—H12	0.9300	Mo5—O7	1.920 (15)
C13—N4	1.35 (3)	Mo5—O12ⁱ	1.935 (17)
C13—C14	1.45 (4)	Mo5—O19B	2.46 (2)
C14—N5	1.33 (4)	Mo5—O21A	2.51 (2)
C14—C15	1.43 (4)	Mo6—O2	1.657 (14)
C15—C16	1.43 (5)	Mo6—O9ⁱ	1.841 (17)
C15—H15	0.9300	Mo6—O14	1.870 (17)
C16—N6	1.34 (4)	Mo6—O17	1.907 (17)
C16—H16	0.9300	Mo6—O6	1.948 (16)
C17—N7	1.33 (3)	Mo6—O19A	2.45 (2)
C17—C18	1.38 (4)	Mo6—O21B	2.50 (2)
C17—H17	0.9300	N2—N3	1.34 (3)
C18—C19	1.32 (5)	N3—H3A	0.8600
C18—H18	0.9300	N5—N6	1.37 (3)
C19—C20	1.38 (4)	N6—H6	0.8600
C19—H19	0.9300	N8—N9	1.32 (3)
C20—C21	1.36 (3)	N9—H9A	0.8600
C20—H20	0.9300	O9—Mo6ⁱ	1.841 (17)
C21—N7	1.36 (3)	O12—Mo5ⁱ	1.935 (17)
C21—C22	1.47 (4)	O13—Mo3ⁱ	1.875 (16)
C22—N8	1.33 (3)	O16—Mo2ⁱ	1.847 (17)
C22—C23	1.38 (3)	O19A—P1	1.56 (2)
C23—C24	1.37 (4)	O19A—O21Aⁱ	1.75 (3)
C23—H23	0.9300	O19A—Mo3ⁱ	2.43 (2)
C24—N9	1.36 (3)	O21A—P1	1.49 (2)
C24—H24	0.9300	O21A—O21B	1.67 (3)
Fe1—N8	2.085 (19)	O21A—O19B	1.72 (3)
Fe1—N5	2.08 (2)	O21A—O19Aⁱ	1.75 (3)
Fe1—N2	2.11 (2)	O19B—P1	1.54 (2)
Fe1—N1	2.129 (17)	O19B—O21Bⁱ	1.78 (3)
Fe1—N4	2.13 (2)	O19B—Mo2ⁱ	2.46 (2)
Fe1—N7	2.15 (2)	O21B—P1	1.52 (2)
Mo1—O3	1.639 (14)	O21B—O19Bⁱ	1.78 (3)
Mo1—O13	1.893 (18)	P1—O21Aⁱ	1.49 (2)
Mo1—O16	1.898 (17)	P1—O21Bⁱ	1.52 (2)
Mo1—O17	1.903 (17)	P1—O19Bⁱ	1.54 (2)
Mo1—O4	1.937 (17)	P1—O19Aⁱ	1.56 (2)
Mo1—O19A	2.48 (2)

N1—C1—C2	122 (2)	O18—Mo5—O4	102.4 (10)
N1—C1—H1	118.8	O18—Mo5—O5	101.7 (9)
C2—C1—H1	118.8	O4—Mo5—O5	89.4 (8)
C1—C2—C3	120 (2)	O18—Mo5—O7	101.6 (9)
C1—C2—H2	120.2	O4—Mo5—O7	155.9 (9)
C3—C2—H2	120.2	O5—Mo5—O7	87.3 (7)
C2—C3—C4	118 (2)	O18—Mo5—O12ⁱ	100.7 (10)
C2—C3—H3	120.8	O4—Mo5—O12ⁱ	88.6 (7)
C4—C3—H3	120.9	O5—Mo5—O12ⁱ	157.4 (9)
C5—C4—C3	120 (2)	O7—Mo5—O12ⁱ	85.4 (7)
C5—C4—H4	120.2	O18—Mo5—O19B	159.0 (9)
C3—C4—H4	120.2	O4—Mo5—O19B	64.8 (8)
N1—C5—C4	122 (2)	O5—Mo5—O19B	94.9 (8)
N1—C5—C6	114.9 (18)	O7—Mo5—O19B	91.7 (8)
C4—C5—C6	123 (2)	O12ⁱ—Mo5—O19B	64.0 (8)
N2—C6—C7	110 (2)	O18—Mo5—O21A	160.3 (9)
N2—C6—C5	117.8 (19)	O4—Mo5—O21A	92.4 (9)
C7—C6—C5	132 (2)	O5—Mo5—O21A	65.1 (8)
C8—C7—C6	103 (3)	O7—Mo5—O21A	64.6 (8)
C8—C7—H7	128.3	O12ⁱ—Mo5—O21A	92.5 (9)
C6—C7—H7	128.3	O19B—Mo5—O21A	40.6 (7)
N3—C8—C7	109 (2)	O2—Mo6—O9ⁱ	102.7 (9)
N3—C8—H8	125.6	O2—Mo6—O14	101.7 (9)
C7—C8—H8	125.6	O9ⁱ—Mo6—O14	90.7 (9)
C10—C9—N4	123 (3)	O2—Mo6—O17	101.0 (9)
C10—C9—H9	118.7	O9ⁱ—Mo6—O17	89.4 (7)
N4—C9—H9	118.6	O14—Mo6—O17	156.7 (10)
C9—C10—C11	120 (3)	O2—Mo6—O6	99.7 (8)
C9—C10—H10	119.8	O9ⁱ—Mo6—O6	157.5 (10)
C11—C10—H10	119.8	O14—Mo6—O6	87.2 (7)
C12—C11—C10	120 (4)	O17—Mo6—O6	83.9 (8)
C12—C11—H11	120.0	O2—Mo6—O19A	159.3 (8)
C10—C11—H11	120.1	O9ⁱ—Mo6—O19A	63.9 (9)
C11—C12—C13	118 (4)	O14—Mo6—O19A	94.4 (9)
C11—C12—H12	120.8	O17—Mo6—O19A	64.9 (8)
C13—C12—H12	120.8	O6—Mo6—O19A	94.0 (8)
N4—C13—C12	123 (3)	O2—Mo6—O21B	157.2 (8)
N4—C13—C14	115 (3)	O9ⁱ—Mo6—O21B	95.8 (9)
C12—C13—C14	121 (3)	O14—Mo6—O21B	64.5 (9)
N5—C14—C15	111 (3)	O17—Mo6—O21B	92.4 (9)
N5—C14—C13	116 (2)	O6—Mo6—O21B	63.2 (8)
C15—C14—C13	133 (3)	O19A—Mo6—O21B	43.3 (8)
C14—C15—C16	104 (3)	C1—N1—C5	117.9 (18)
C14—C15—H15	128.1	C1—N1—Fe1	126.7 (15)
C16—C15—H15	128.2	C5—N1—Fe1	115.4 (13)
N6—C16—C15	106 (3)	C6—N2—N3	106 (2)
N6—C16—H16	126.9	C6—N2—Fe1	115.0 (14)
C15—C16—H16	126.8	N3—N2—Fe1	138.8 (16)
N7—C17—C18	123 (3)	C8—N3—N2	111 (2)
N7—C17—H17	118.6	C8—N3—H3A	124.4
C18—C17—H17	118.6	N2—N3—H3A	124.4
C19—C18—C17	119 (3)	C9—N4—C13	115 (3)
C19—C18—H18	120.3	C9—N4—Fe1	129.3 (19)
C17—C18—H18	120.3	C13—N4—Fe1	115 (2)
C18—C19—C20	120 (3)	C14—N5—N6	106 (3)
C18—C19—H19	120.0	C14—N5—Fe1	117.3 (19)
C20—C19—H19	120.1	N6—N5—Fe1	137 (2)
C21—C20—C19	118 (3)	N5—N6—C16	113 (3)
C21—C20—H20	120.8	N5—N6—H6	123.6
C19—C20—H20	120.8	C16—N6—H6	123.5
N7—C21—C20	123 (2)	C17—N7—C21	117 (2)
N7—C21—C22	113 (2)	C17—N7—Fe1	127.5 (19)
C20—C21—C22	124 (2)	C21—N7—Fe1	115.8 (16)
N8—C22—C23	111 (2)	N9—N8—C22	106.2 (19)
N8—C22—C21	117 (2)	N9—N8—Fe1	136.8 (15)
C23—C22—C21	131 (2)	C22—N8—Fe1	117.0 (16)
C24—C23—C22	104 (2)	N8—N9—C24	111 (2)
C24—C23—H23	127.8	N8—N9—H9A	124.4
C22—C23—H23	127.8	C24—N9—H9A	124.4
N9—C24—C23	107 (3)	Mo3—O1—Mo4	139.4 (10)
N9—C24—H24	126.6	Mo5—O4—Mo1	140.2 (11)
C23—C24—H24	126.5	Mo5—O5—Mo4	138.8 (11)
N8—Fe1—N5	95.6 (10)	Mo4—O6—Mo6	137.9 (11)
N8—Fe1—N2	95.1 (8)	Mo3—O7—Mo5	138.2 (10)
N5—Fe1—N2	166.1 (9)	Mo6ⁱ—O9—Mo3	138.8 (13)
N8—Fe1—N1	91.4 (7)	Mo2—O11—Mo4	139.5 (13)
N5—Fe1—N1	94.2 (7)	Mo5ⁱ—O12—Mo2	136.6 (12)
N2—Fe1—N1	76.8 (6)	Mo3ⁱ—O13—Mo1	140.3 (13)
N8—Fe1—N4	169.6 (8)	Mo6—O14—Mo2	139.8 (12)
N5—Fe1—N4	76.3 (10)	Mo2ⁱ—O16—Mo1	142.9 (12)
N2—Fe1—N4	93.9 (7)	Mo1—O17—Mo6	137.6 (11)
N1—Fe1—N4	95.7 (7)	P1—O19A—O21Aⁱ	53.0 (10)
N8—Fe1—N7	76.4 (8)	P1—O19A—Mo3ⁱ	124.8 (12)
N5—Fe1—N7	96.8 (8)	O21Aⁱ—O19A—Mo3ⁱ	71.9 (11)
N2—Fe1—N7	94.2 (7)	P1—O19A—Mo6	122.6 (13)
N1—Fe1—N7	164.3 (7)	O21Aⁱ—O19A—Mo6	132.3 (14)
N4—Fe1—N7	97.8 (8)	Mo3ⁱ—O19A—Mo6	93.7 (8)
O3—Mo1—O13	102.2 (9)	P1—O19A—Mo1	122.3 (12)
O3—Mo1—O16	102.5 (9)	O21Aⁱ—O19A—Mo1	132.4 (14)
O13—Mo1—O16	88.9 (9)	Mo3ⁱ—O19A—Mo1	92.5 (8)
O3—Mo1—O17	102.8 (9)	Mo6—O19A—Mo1	92.2 (8)
O13—Mo1—O17	88.2 (7)	P1—O21A—O21B	57.2 (12)
O16—Mo1—O17	154.6 (10)	P1—O21A—O19B	56.7 (11)
O3—Mo1—O4	101.8 (8)	O21B—O21A—O19B	94.2 (16)
O13—Mo1—O4	155.9 (10)	P1—O21A—O19Aⁱ	57.2 (11)
O16—Mo1—O4	85.1 (7)	O21B—O21A—O19Aⁱ	93.2 (16)
O17—Mo1—O4	87.5 (8)	O19B—O21A—O19Aⁱ	92.0 (16)
O3—Mo1—O19A	159.1 (8)	P1—O21A—Mo4	125.7 (13)
O13—Mo1—O19A	62.8 (9)	O21B—O21A—Mo4	68.6 (11)
O16—Mo1—O19A	92.1 (9)	O19B—O21A—Mo4	132.1 (14)
O17—Mo1—O19A	64.2 (8)	O19Aⁱ—O21A—Mo4	131.7 (15)
O4—Mo1—O19A	94.2 (8)	P1—O21A—Mo5	124.8 (13)
O3—Mo1—O19B	157.6 (8)	O21B—O21A—Mo5	132.4 (15)
O13—Mo1—O19B	93.9 (9)	O19B—O21A—Mo5	68.1 (11)
O16—Mo1—O19B	62.0 (8)	O19Aⁱ—O21A—Mo5	129.6 (14)
O17—Mo1—O19B	93.0 (9)	Mo4—O21A—Mo5	90.6 (8)
O4—Mo1—O19B	62.7 (8)	P1—O21A—Mo3	123.9 (13)
O19A—Mo1—O19B	43.3 (7)	O21B—O21A—Mo3	129.4 (15)
O15—Mo2—O16ⁱ	102.7 (10)	O19B—O21A—Mo3	130.4 (14)
O15—Mo2—O11	100.6 (9)	O19Aⁱ—O21A—Mo3	66.7 (10)
O16ⁱ—Mo2—O11	91.0 (9)	Mo4—O21A—Mo3	90.3 (8)
O15—Mo2—O14	101.7 (10)	Mo5—O21A—Mo3	91.1 (8)
O16ⁱ—Mo2—O14	155.4 (10)	P1—O19B—O21A	53.8 (11)
O11—Mo2—O14	87.2 (7)	P1—O19B—O21Bⁱ	54.0 (10)
O15—Mo2—O12	102.3 (9)	O21A—O19B—O21Bⁱ	91.1 (15)
O16ⁱ—Mo2—O12	87.4 (7)	P1—O19B—Mo2ⁱ	123.7 (12)
O11—Mo2—O12	156.9 (10)	O21A—O19B—Mo2ⁱ	135.5 (14)
O14—Mo2—O12	84.8 (8)	O21Bⁱ—O19B—Mo2ⁱ	69.7 (10)
O15—Mo2—O19Bⁱ	159.9 (8)	P1—O19B—Mo5	125.1 (12)
O16ⁱ—Mo2—O19Bⁱ	63.8 (8)	O21A—O19B—Mo5	71.3 (11)
O11—Mo2—O19Bⁱ	94.8 (9)	O21Bⁱ—O19B—Mo5	135.2 (15)
O14—Mo2—O19Bⁱ	91.9 (9)	Mo2ⁱ—O19B—Mo5	94.2 (8)
O12—Mo2—O19Bⁱ	63.9 (8)	P1—O19B—Mo1	121.7 (12)
O15—Mo2—O21B	158.0 (9)	O21A—O19B—Mo1	129.9 (13)
O16ⁱ—Mo2—O21B	93.0 (10)	O21Bⁱ—O19B—Mo1	128.5 (14)
O11—Mo2—O21B	63.5 (9)	Mo2ⁱ—O19B—Mo1	91.1 (7)
O14—Mo2—O21B	64.3 (9)	Mo5—O19B—Mo1	91.9 (7)
O12—Mo2—O21B	93.6 (9)	P1—O21B—O21A	55.3 (11)
O19Bⁱ—Mo2—O21B	42.1 (8)	P1—O21B—O19Bⁱ	55.0 (11)
O10—Mo3—O1	102.8 (8)	O21A—O21B—O19Bⁱ	92.2 (16)
O10—Mo3—O13ⁱ	102.2 (10)	P1—O21B—Mo4	127.1 (14)
O1—Mo3—O13ⁱ	91.1 (8)	O21A—O21B—Mo4	71.8 (12)
O10—Mo3—O7	101.0 (9)	O19Bⁱ—O21B—Mo4	135.2 (15)
O1—Mo3—O7	89.0 (7)	P1—O21B—Mo2	123.1 (13)
O13ⁱ—Mo3—O7	156.2 (10)	O21A—O21B—Mo2	132.4 (15)
O10—Mo3—O9	100.5 (10)	O19Bⁱ—O21B—Mo2	68.2 (10)
O1—Mo3—O9	156.6 (9)	Mo4—O21B—Mo2	91.9 (8)
O13ⁱ—Mo3—O9	85.8 (7)	P1—O21B—Mo6	121.5 (13)
O7—Mo3—O9	84.8 (8)	O21A—O21B—Mo6	132.6 (15)
O10—Mo3—O19Aⁱ	158.1 (8)	O19Bⁱ—O21B—Mo6	126.0 (15)
O1—Mo3—O19Aⁱ	94.8 (8)	Mo4—O21B—Mo6	92.4 (8)
O13ⁱ—Mo3—O19Aⁱ	64.2 (9)	Mo2—O21B—Mo6	91.2 (8)
O7—Mo3—O19Aⁱ	92.1 (8)	O21Aⁱ—P1—O21A	180 (3)
O9—Mo3—O19Aⁱ	63.0 (9)	O21Aⁱ—P1—O21Bⁱ	67.6 (13)
O10—Mo3—O21A	160.2 (8)	O21A—P1—O21Bⁱ	112.4 (13)
O1—Mo3—O21A	65.0 (8)	O21Aⁱ—P1—O21B	112.4 (13)
O13ⁱ—Mo3—O21A	93.9 (10)	O21A—P1—O21B	67.6 (13)
O7—Mo3—O21A	64.7 (8)	O21Bⁱ—P1—O21B	180 (2)
O9—Mo3—O21A	92.0 (9)	O21Aⁱ—P1—O19B	110.5 (12)
O19Aⁱ—Mo3—O21A	41.4 (8)	O21A—P1—O19B	69.5 (12)
O8—Mo4—O6	103.0 (9)	O21Bⁱ—P1—O19B	71.0 (12)
O8—Mo4—O11	102.3 (10)	O21B—P1—O19B	109.0 (12)
O6—Mo4—O11	89.4 (7)	O21Aⁱ—P1—O19Bⁱ	69.5 (12)
O8—Mo4—O5	100.3 (9)	O21A—P1—O19Bⁱ	110.5 (12)
O6—Mo4—O5	89.5 (7)	O21Bⁱ—P1—O19Bⁱ	109.0 (12)
O11—Mo4—O5	157.0 (10)	O21B—P1—O19Bⁱ	71.0 (12)
O8—Mo4—O1	100.6 (8)	O19B—P1—O19Bⁱ	180 (3)
O6—Mo4—O1	156.4 (9)	O21Aⁱ—P1—O19Aⁱ	110.1 (12)
O11—Mo4—O1	85.8 (7)	O21A—P1—O19Aⁱ	69.9 (12)
O5—Mo4—O1	86.1 (6)	O21Bⁱ—P1—O19Aⁱ	72.6 (13)
O8—Mo4—O21B	161.3 (9)	O21B—P1—O19Aⁱ	107.4 (13)
O6—Mo4—O21B	65.4 (8)	O19B—P1—O19Aⁱ	107.2 (12)
O11—Mo4—O21B	64.4 (9)	O19Bⁱ—P1—O19Aⁱ	72.8 (12)
O5—Mo4—O21B	94.5 (8)	O21Aⁱ—P1—O19A	69.9 (12)
O1—Mo4—O21B	91.8 (8)	O21A—P1—O19A	110.1 (12)
O8—Mo4—O21A	159.1 (8)	O21Bⁱ—P1—O19A	107.4 (13)
O6—Mo4—O21A	92.4 (9)	O21B—P1—O19A	72.6 (13)
O11—Mo4—O21A	91.8 (9)	O19B—P1—O19A	72.8 (12)
O5—Mo4—O21A	65.3 (8)	O19Bⁱ—P1—O19A	107.2 (12)
O1—Mo4—O21A	64.7 (7)	O19Aⁱ—P1—O19A	180 (2)
O21B—Mo4—O21A	39.6 (8)

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	2.03	2.82 (3)	153
N6—H6···O2W	0.86	1.98	2.82 (5)	167
N9—H9A···O1W	0.86	1.95	2.77 (3)	157

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

Experimental details

Crystal data
Chemical formula	[(Fe(C₈H₇N₃)₃]₂[PMo₁₂O₄₀]·6H₂O
M_r	2913.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.6816 (10), 16.2224 (10), 27.6405 (15)
β (°)	104.295 (1)
V (Å³)	8117.4 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.26
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.773, 0.840
No. of measured, independent and observed [I > 2σ(I)] reflections	20565, 7090, 5550
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.142, 1.00
No. of reflections	7090
No. of parameters	592
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1P)² + 20.1545P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.36, −0.80

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

Selected bond lengths (Å) top

Fe1—N8	2.085 (19)	Fe1—N7	2.15 (2)
Fe1—N5	2.08 (2)	P1—O21Aⁱ	1.49 (2)
Fe1—N2	2.11 (2)	P1—O21Bⁱ	1.52 (2)
Fe1—N1	2.129 (17)	P1—O19Bⁱ	1.54 (2)
Fe1—N4	2.13 (2)	P1—O19Aⁱ	1.56 (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	2.03	2.82 (3)	153.1
N6—H6···O2W	0.86	1.98	2.82 (5)	166.6
N9—H9A···O1W	0.86	1.95	2.77 (3)	157.0

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 of 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 m283-m284

doi:10.1107/S1600536810004861

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