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

Wei, P.; Yuan, D.; Zhu, W.; Zhang, X.; Hu, B.

doi:10.1107/S1600536810002412

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m190-m191

https://doi.org/10.1107/S1600536810002412

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

Peihai Wei,^a Dong Yuan,^a Wencai Zhu,^a Xiutang Zhang ^a,^b ^* and Bo Hu ^a

^aAdvanced Material Institute of Research, Department of Chemistry and Chemical Engineering, ShanDong Institute of Education, Jinan 250013, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: xiutangzhang@yahoo.com.cn

(Received 12 January 2010; accepted 19 January 2010; online 23 January 2010)

The asymmetric unit of the title compound, [Fe(C₈H₇N₃)₃]₂[SiMo₁₄O₄₄], consists of a complex [Fe(C₈H₇N₃)₃]²⁺ cation and half of a derivative of an α-Keggin-type anion, [SiMo₁₄O₄₄]⁴⁻. In the mixed-valent Mo^V/VI anion, the α-Keggin type core is capped on two oppositely disposed tetragonal faces by additional (MoO₂) units. The [SiMo₁₄O₄₄]⁴⁻ anion shows disorder. Two O atoms of the central SiO₄ group ( $[\overline{1}]$ symmetry) are equally disordered about an inversion centre. Moreover, two of the outer bridging O atoms and the O atoms of the capping (MoO₂) unit are likewise disordered. The Fe²⁺ cation is surrounded in a slightly distorted octahedral coordination by six N atoms from three 3-(2-pyridyl)-1H-pyrazole ligands. N—H⋯O hydrogen bonding between the cations and anions 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, Shi et al. (2010a ,b ); Zhang, Wei, Sun et al. (2009 ); Zhang, Wei, Zhu et al. (2010 ); Zhang, Yuan et al. (2010 ). For another structure containing the α-Keggin-type derivative [SiMo₁₄O₄₄]⁴⁻, see: Dolbecq et al. (1999 ). For background to the bond-valence method, see: Brese & O'Keeffe (1991 ). For the role of amines in hydrothermal synthesis, see: Yang et al. (2003 ).

Experimental

Crystal data

[Fe(C₈H₇N₃)₃]₂[SiMo₁₄O₄₄]
M_r = 3057.95
Monoclinic, P 2₁ /c
a = 13.055 (3) Å
b = 16.931 (3) Å
c = 18.562 (4) Å
β = 102.69 (3)°
V = 4002.6 (14) Å³
Z = 2
Mo Kα radiation
μ = 2.58 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 = 0.747, T_max = 0.820
27223 measured reflections
7026 independent reflections
4730 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.157
S = 1.00
7026 reflections
638 parameters
444 restraints
H-atom parameters constrained
Δρ_max = 1.47 e Å⁻³
Δρ_min = −1.52 e Å⁻³

Table 1
Selected bond lengths (Å)

Si1—O17A	1.606 (13)
Si1—O18A	1.648 (13)
Si1—O18B	1.670 (13)
Si1—O17B	1.684 (13)
Fe1—N2	2.105 (11)
Fe1—N8	2.119 (11)
Fe1—N5	2.153 (11)
Fe1—N3	2.173 (11)
Fe1—N9	2.186 (12)
Fe1—N6	2.206 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O13ⁱ	0.86	2.15	2.973 (17)	159
N1—H1A⋯O21Aⁱⁱ	0.86	2.17	2.96 (3)	152
N1—H1A⋯O21ⁱⁱ	0.86	2.05	2.844 (19)	153
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

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/S1600536810002412/wm2300sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002412/wm2300Isup2.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, Shi et al., 2010a,b; Zhang, Wei, Sun et al., 2009; Zhang, Wei, Zhu et al., 2010; Zhang, Yuan et al., 2010). Here, we describe the synthesis and structural characterization of the title compound.

As shown in Figure 1, the title compound consists of two subunits, viz. of a complex caion [Fe(C₈H₇N₃)₃]²⁺ and a derivative of the α-Keggin-type anion with overall composition [SiMo₁₄O₄₄]^4-. The iron(II) ion is in a distorted octahedral coordination by six N atoms from two 3-(2-pyridyl)pyrazole ligands. The Fe—N bond lengths are in the range of 2.105 (11)—2.206 (11) Å. The anion [SiMo₁₄O₄₄]^4- can be described as a derivative of an α-Keggin-type core capped on two oppositely disposed tetragonal faces by (MoO₂) subunits (Dolbecq et al., 1999). The molybdenum atoms of the disordered capping unit have a highly distorted coordination environment with short Mo—Ot bonds [1.70 (15)–1.84 (3) Å] and longer Mo—O bridging bonds [1.998 (16)–2.174 (15) Å].

The formula sum of the title compound reveals that the valence of some metal atoms in the title compound are (partly) reduced (part of Mo⁶⁺ to Mo⁵⁺; Fe³⁺ to Fe²⁺). 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). The oxidation states of the metals are confirmed by bond valence sum calculations (Brese & O'Keeffe, 1991). For the Mo and Fe atoms in the title compound the bond valence sums equal to 5.93, 4.95, 5.83, 6.17, 5.81, 6.18, 5.24, and 2.01.

N—H···O hydrogen bonding between the cations and anions 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, Shi et al. (2010a,b); Zhang, Wei, Sun et al. (2009); Zhang, Wei, Zhu et al. (2010); Zhang, Yuan et al. (2010). For another structure containing the α-Keggin-type derivative [SiMo₁₄O₄₄]^4-, see: Dolbecq et al. (1999). For background to the bond-valence method, see: Brese & O'Keeffe (1991). For the role of amines in hydrothermal synthesis, see: Yang et al. (2003).

Experimental top

A mixture of 3-(2-pyridyl)pyrazole (1 mmoL 0.14 g), sodium molybdate (2 mmoL, 0.48 g), sodium silicate nonahydrate (0.2 mmoL, 0.05 g) and iron(III) chloride hexahydrate (0.25 mmol, 0.06 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. Anal. C₄₈H₄₂Fe₂Mo₁₄N₁₈O₄₄Si: C, 18.85; H, 1.38; N, 8.25. Found: C, 18.75; H, 1.12; N, 8.15%.

The TGA measure,ent shows that the release of organic liangds takes place above ca 623 K. The overall thermal decomposition process can be described by the following equation: C₄₈H₄₂Fe₂Mo₁₄N₁₈O₄₄Si + 84O₂ = 21H₂O + 48CO₂ + 9N₂O₅ + Fe₂O₃ + SiO₂ + 14MoO₃ Eq.(1). IR bands appear at the following wavelengths (cm^-1): 3303, 3117, 1697, 1604, 1550, 1485, 1355, 1300, 1171, 1088, 1051, 903, 765, 664, 507, 451, 414.

Structure description top

N—H···O hydrogen bonding between the cations and anions 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, Shi et al. (2010a,b); Zhang, Wei, Sun et al. (2009); Zhang, Wei, Zhu et al. (2010); Zhang, Yuan et al. (2010). For another structure containing the α-Keggin-type derivative [SiMo₁₄O₄₄]^4-, see: Dolbecq et al. (1999). For background to the bond-valence method, see: Brese & O'Keeffe (1991). 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 hydrogen bonds as dashed lines.

Bis{tris[3-(2-pyridyl)-1H-pyrazole]iron(II)} tetradecamolybdo(V,VI)silicate top

Crystal data top

[Fe(C₈H₇N₃)₃]₂[SiMo₁₄O₄₄]	F(000) = 2924
M_r = 3057.95	D_x = 2.537 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7026 reflections
a = 13.055 (3) Å	θ = 1.7–25.0°
b = 16.931 (3) Å	µ = 2.58 mm⁻¹
c = 18.562 (4) Å	T = 293 K
β = 102.69 (3)°	Block, brown
V = 4002.6 (14) Å³	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	7026 independent reflections
Radiation source: fine-focus sealed tube	4730 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→15
T_min = 0.747, T_max = 0.820	k = −20→20
27223 measured reflections	l = −21→22

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.058P)² + 47.4341P] where P = (F_o² + 2F_c²)/3
7026 reflections	(Δ/σ)_max = 0.001
638 parameters	Δρ_max = 1.47 e Å⁻³
444 restraints	Δρ_min = −1.52 e Å⁻³

Crystal data top

[Fe(C₈H₇N₃)₃]₂[SiMo₁₄O₄₄]	V = 4002.6 (14) Å³
M_r = 3057.95	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.055 (3) Å	µ = 2.58 mm⁻¹
b = 16.931 (3) Å	T = 293 K
c = 18.562 (4) Å	0.12 × 0.10 × 0.08 mm
β = 102.69 (3)°

Data collection top

Bruker APEXII CCD diffractometer	7026 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4730 reflections with I > 2σ(I)
T_min = 0.747, T_max = 0.820	R_int = 0.076
27223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	444 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.058P)² + 47.4341P] where P = (F_o² + 2F_c²)/3
7026 reflections	Δρ_max = 1.47 e Å⁻³
638 parameters	Δρ_min = −1.52 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Si1	0.0000	0.5000	0.5000	0.0193 (8)
Fe1	0.36074 (14)	0.58896 (11)	0.17093 (11)	0.0497 (5)
Mo1	0.20889 (7)	0.55765 (6)	0.41647 (5)	0.0364 (3)
Mo2	−0.00697 (9)	0.46521 (7)	0.30342 (6)	0.0431 (3)
Mo3	0.33482 (8)	0.44820 (7)	0.54989 (6)	0.0464 (3)
Mo4	0.21554 (8)	0.59444 (6)	0.61448 (6)	0.0408 (3)
Mo5	0.05628 (8)	0.70722 (6)	0.47289 (6)	0.0389 (3)
Mo6	−0.16040 (7)	0.61555 (6)	0.35957 (6)	0.0378 (3)
Mo7	−0.14918 (7)	0.65270 (6)	0.55885 (5)	0.0339 (3)
C1	0.5226 (13)	0.7541 (10)	0.3320 (9)	0.080 (5)
H1	0.5807	0.7807	0.3592	0.096*
C2	0.4230 (13)	0.7709 (10)	0.3329 (9)	0.074 (4)
H2	0.3975	0.8084	0.3611	0.088*
C3	0.3659 (11)	0.7178 (8)	0.2806 (7)	0.055 (3)
C4	0.2536 (10)	0.7064 (8)	0.2539 (7)	0.048 (3)
C5	0.1772 (11)	0.7481 (9)	0.2789 (8)	0.060 (4)
H5	0.1956	0.7867	0.3151	0.072*
C6	0.0709 (12)	0.7310 (10)	0.2481 (9)	0.069 (4)
H6	0.0182	0.7576	0.2648	0.082*
C7	0.0462 (12)	0.6771 (10)	0.1956 (9)	0.070 (4)
H7	−0.0240	0.6661	0.1752	0.084*
C8	0.1236 (11)	0.6369 (9)	0.1708 (8)	0.063 (4)
H8	0.1044	0.5995	0.1336	0.076*
C9	0.4257 (14)	0.7723 (10)	0.0181 (9)	0.079 (5)
H9	0.4153	0.8194	−0.0084	0.095*
C10	0.5155 (13)	0.7282 (10)	0.0337 (8)	0.072 (4)
H10	0.5774	0.7377	0.0181	0.086*
C11	0.4943 (11)	0.6643 (8)	0.0791 (7)	0.053 (3)
C12	0.5598 (10)	0.6004 (8)	0.1139 (7)	0.048 (3)
C13	0.6664 (12)	0.5936 (10)	0.1094 (8)	0.072 (4)
H13	0.6971	0.6311	0.0843	0.087*
C14	0.7234 (15)	0.5302 (12)	0.1431 (10)	0.095 (6)
H14	0.7922	0.5218	0.1388	0.114*
C15	0.6750 (13)	0.4797 (10)	0.1834 (9)	0.076 (5)
H15	0.7126	0.4373	0.2077	0.091*
C16	0.5731 (12)	0.4904 (9)	0.1886 (8)	0.067 (4)
H16	0.5430	0.4553	0.2164	0.081*
C17	0.3580 (12)	0.3850 (9)	0.3102 (9)	0.065 (4)
H17	0.3773	0.3553	0.3532	0.078*
C18	0.2902 (12)	0.3614 (9)	0.2482 (8)	0.066 (4)
H18	0.2535	0.3141	0.2391	0.079*
C19	0.2886 (10)	0.4280 (8)	0.1993 (8)	0.054 (3)
C20	0.2335 (10)	0.4416 (8)	0.1235 (7)	0.052 (3)
C21	0.1621 (13)	0.3881 (10)	0.0809 (10)	0.081 (5)
H21	0.1494	0.3387	0.0989	0.098*
C22	0.1117 (13)	0.4130 (11)	0.0105 (9)	0.081 (5)
H22	0.0637	0.3795	−0.0191	0.097*
C23	0.1311 (13)	0.4857 (10)	−0.0161 (9)	0.075 (4)
H23	0.0938	0.5025	−0.0621	0.090*
C24	0.2060 (11)	0.5332 (9)	0.0258 (8)	0.059 (4)
H24	0.2231	0.5807	0.0062	0.070*
N1	0.3925 (9)	0.4562 (7)	0.3005 (6)	0.060 (3)
H1A	0.4368	0.4813	0.3338	0.072*
N2	0.3507 (8)	0.4859 (6)	0.2324 (6)	0.051 (3)
N3	0.2551 (9)	0.5129 (7)	0.0943 (6)	0.057 (3)
N4	0.3541 (10)	0.7337 (7)	0.0492 (7)	0.072 (4)
H4	0.2902	0.7490	0.0449	0.087*
N5	0.3958 (9)	0.6673 (6)	0.0883 (6)	0.055 (3)
N6	0.5155 (8)	0.5512 (6)	0.1541 (6)	0.052 (3)
N7	0.5271 (10)	0.6937 (8)	0.2864 (7)	0.072 (4)
H7A	0.5839	0.6725	0.2793	0.086*
N8	0.4298 (8)	0.6712 (7)	0.2534 (6)	0.052 (3)
N9	0.2279 (9)	0.6507 (7)	0.1994 (6)	0.058 (3)
O1	0.0848 (7)	0.8012 (5)	0.4612 (5)	0.058 (2)
O2	−0.2484 (7)	0.6655 (6)	0.2974 (5)	0.061 (2)
O3	0.3156 (7)	0.5797 (6)	0.3861 (5)	0.061 (2)
O4	0.3275 (6)	0.6295 (5)	0.6651 (5)	0.052 (2)
O5	−0.0141 (7)	0.4491 (5)	0.2150 (5)	0.054 (2)
O6	−0.0494 (8)	0.7163 (6)	0.5323 (5)	0.071 (3)
O7	0.1182 (8)	0.5280 (6)	0.3314 (5)	0.074 (3)
O8	−0.0581 (7)	0.6902 (6)	0.3890 (5)	0.071 (3)
O9	−0.2306 (7)	0.7206 (6)	0.5792 (5)	0.066 (3)
O10	0.2238 (9)	0.3640 (6)	0.5498 (5)	0.080 (3)
O11A	0.2488 (15)	0.5526 (11)	0.5273 (10)	0.040 (5)	0.50
O11B	0.2997 (13)	0.5646 (10)	0.5258 (9)	0.033 (4)	0.50
O12	−0.0731 (8)	0.6245 (6)	0.6494 (5)	0.076 (3)
O13	0.1592 (8)	0.6844 (6)	0.5658 (5)	0.077 (3)
O14	0.2189 (12)	0.4826 (9)	0.6113 (9)	0.033 (4)	0.50
O14A	0.2767 (14)	0.4726 (10)	0.6443 (9)	0.043 (4)	0.50
O15	−0.0919 (9)	0.5605 (6)	0.2994 (7)	0.090 (3)
O16	0.2659 (13)	0.4376 (10)	0.4430 (9)	0.036 (4)	0.50
O16B	0.2127 (12)	0.4516 (9)	0.4492 (8)	0.028 (4)	0.50
O17A	−0.0469 (10)	0.5874 (8)	0.4826 (7)	0.029 (3)	0.50
O17B	−0.0747 (10)	0.4992 (8)	0.4136 (7)	0.028 (3)	0.50
O18A	0.0684 (10)	0.4742 (8)	0.4390 (7)	0.027 (3)	0.50
O18B	−0.0905 (10)	0.4306 (8)	0.5014 (7)	0.028 (3)	0.50
O19	0.1508 (9)	0.6552 (7)	0.4225 (6)	0.087 (3)
O20	0.4195 (13)	0.4254 (10)	0.4906 (10)	0.104 (5)	0.75
O20A	0.412 (2)	0.3654 (19)	0.5690 (16)	0.041 (8)	0.25
O21A	0.449 (2)	0.5140 (17)	0.5616 (15)	0.034 (7)	0.25
O21	0.4286 (12)	0.4547 (10)	0.6293 (9)	0.100 (5)	0.75
O22	0.1328 (8)	0.5930 (6)	0.6805 (7)	0.085 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0201 (18)	0.0165 (19)	0.0221 (18)	0.0002 (15)	0.0064 (15)	−0.0006 (15)
Fe1	0.0472 (11)	0.0411 (11)	0.0604 (12)	−0.0018 (9)	0.0109 (9)	−0.0033 (9)
Mo1	0.0292 (5)	0.0435 (6)	0.0374 (6)	−0.0003 (4)	0.0090 (4)	0.0018 (5)
Mo2	0.0549 (7)	0.0418 (7)	0.0353 (6)	−0.0056 (5)	0.0162 (5)	−0.0055 (5)
Mo3	0.0418 (6)	0.0427 (7)	0.0500 (7)	0.0061 (5)	−0.0001 (5)	−0.0015 (5)
Mo4	0.0297 (5)	0.0392 (6)	0.0513 (7)	−0.0034 (4)	0.0043 (4)	−0.0140 (5)
Mo5	0.0460 (6)	0.0235 (5)	0.0442 (6)	0.0013 (4)	0.0036 (5)	0.0015 (5)
Mo6	0.0300 (5)	0.0322 (6)	0.0487 (6)	0.0053 (4)	0.0030 (4)	0.0082 (5)
Mo7	0.0296 (5)	0.0275 (5)	0.0440 (6)	0.0044 (4)	0.0071 (4)	−0.0050 (4)
C1	0.075 (8)	0.079 (8)	0.079 (8)	−0.011 (7)	0.001 (7)	−0.005 (7)
C2	0.080 (8)	0.072 (8)	0.072 (8)	−0.004 (7)	0.024 (7)	−0.010 (7)
C3	0.053 (7)	0.053 (7)	0.058 (7)	0.000 (6)	0.007 (6)	0.011 (6)
C4	0.051 (6)	0.045 (6)	0.051 (6)	0.010 (5)	0.017 (5)	0.015 (5)
C5	0.072 (7)	0.053 (7)	0.056 (7)	0.005 (6)	0.019 (6)	0.015 (6)
C6	0.064 (7)	0.072 (8)	0.074 (8)	0.014 (6)	0.025 (6)	0.023 (7)
C7	0.060 (7)	0.078 (8)	0.071 (8)	0.003 (7)	0.013 (6)	0.024 (7)
C8	0.055 (7)	0.068 (8)	0.064 (7)	0.000 (6)	0.006 (6)	0.006 (6)
C9	0.093 (8)	0.062 (8)	0.080 (8)	−0.006 (7)	0.012 (7)	0.019 (7)
C10	0.067 (8)	0.075 (8)	0.069 (7)	−0.003 (7)	0.008 (6)	0.005 (7)
C11	0.059 (7)	0.046 (7)	0.049 (6)	−0.007 (6)	0.003 (5)	−0.001 (5)
C12	0.048 (6)	0.051 (7)	0.046 (6)	0.004 (5)	0.010 (5)	−0.001 (5)
C13	0.070 (8)	0.080 (8)	0.067 (8)	0.002 (7)	0.015 (6)	0.014 (7)
C14	0.090 (9)	0.108 (10)	0.093 (9)	0.014 (8)	0.035 (8)	0.011 (8)
C15	0.081 (8)	0.077 (8)	0.072 (8)	0.022 (7)	0.023 (7)	0.005 (7)
C16	0.076 (8)	0.063 (8)	0.066 (7)	0.015 (6)	0.023 (6)	0.016 (6)
C17	0.072 (7)	0.061 (8)	0.063 (7)	0.011 (6)	0.016 (6)	0.008 (6)
C18	0.075 (8)	0.059 (7)	0.067 (7)	−0.008 (6)	0.022 (6)	0.000 (6)
C19	0.053 (7)	0.053 (7)	0.057 (7)	−0.010 (6)	0.015 (6)	−0.006 (6)
C20	0.040 (6)	0.058 (7)	0.059 (7)	−0.007 (5)	0.016 (5)	−0.010 (6)
C21	0.078 (8)	0.074 (8)	0.090 (9)	−0.024 (7)	0.013 (7)	−0.005 (7)
C22	0.078 (8)	0.087 (9)	0.071 (8)	−0.022 (7)	0.004 (7)	−0.007 (7)
C23	0.076 (8)	0.084 (8)	0.067 (8)	−0.005 (7)	0.018 (6)	0.004 (7)
C24	0.055 (7)	0.062 (7)	0.058 (7)	−0.006 (6)	0.010 (6)	0.001 (6)
N1	0.055 (6)	0.062 (7)	0.063 (6)	−0.004 (5)	0.014 (5)	−0.004 (5)
N2	0.050 (5)	0.050 (6)	0.052 (6)	0.000 (5)	0.011 (5)	0.007 (5)
N3	0.062 (6)	0.055 (6)	0.055 (6)	−0.006 (5)	0.016 (5)	−0.002 (5)
N4	0.073 (7)	0.058 (7)	0.077 (7)	0.015 (6)	−0.002 (6)	−0.007 (6)
N5	0.059 (6)	0.046 (6)	0.056 (6)	0.010 (5)	0.000 (5)	0.003 (5)
N6	0.057 (6)	0.042 (6)	0.055 (6)	0.010 (5)	0.011 (5)	0.004 (5)
N7	0.060 (6)	0.078 (7)	0.075 (7)	−0.001 (6)	0.010 (6)	0.006 (6)
N8	0.040 (5)	0.061 (6)	0.053 (6)	−0.004 (5)	0.004 (5)	0.006 (5)
N9	0.056 (6)	0.058 (6)	0.060 (6)	−0.003 (5)	0.012 (5)	0.010 (5)
O1	0.058 (3)	0.057 (3)	0.058 (3)	−0.0004 (10)	0.0125 (11)	0.0000 (10)
O2	0.061 (3)	0.062 (3)	0.061 (3)	0.0006 (10)	0.0132 (11)	0.0009 (10)
O3	0.061 (3)	0.061 (3)	0.062 (3)	−0.0001 (10)	0.0139 (11)	0.0009 (10)
O4	0.051 (2)	0.052 (2)	0.052 (2)	0.0003 (10)	0.0108 (11)	−0.0007 (10)
O5	0.055 (2)	0.054 (2)	0.053 (2)	−0.0001 (10)	0.0118 (11)	−0.0002 (10)
O6	0.072 (6)	0.092 (6)	0.053 (5)	−0.038 (5)	0.019 (4)	−0.017 (5)
O7	0.086 (6)	0.056 (5)	0.061 (5)	−0.020 (5)	−0.026 (5)	0.019 (4)
O8	0.070 (5)	0.101 (6)	0.044 (5)	−0.038 (5)	0.017 (4)	−0.002 (5)
O9	0.066 (3)	0.066 (3)	0.067 (3)	0.0009 (10)	0.0142 (11)	−0.0014 (10)
O10	0.105 (7)	0.073 (6)	0.062 (6)	−0.049 (5)	0.018 (5)	−0.014 (5)
O11A	0.041 (8)	0.035 (8)	0.043 (8)	−0.001 (7)	0.010 (7)	0.005 (6)
O11B	0.028 (7)	0.030 (7)	0.038 (7)	0.003 (6)	0.000 (6)	0.002 (6)
O12	0.087 (6)	0.052 (5)	0.070 (6)	−0.028 (5)	−0.026 (5)	0.013 (5)
O13	0.092 (6)	0.076 (6)	0.053 (5)	0.050 (5)	−0.005 (5)	−0.017 (5)
O14	0.033 (7)	0.031 (7)	0.036 (7)	−0.003 (6)	0.007 (6)	0.007 (6)
O14A	0.042 (7)	0.039 (8)	0.044 (8)	0.003 (6)	0.002 (6)	−0.003 (6)
O15	0.093 (6)	0.059 (6)	0.138 (8)	0.002 (5)	0.069 (6)	−0.010 (6)
O16	0.035 (7)	0.038 (8)	0.036 (7)	0.008 (7)	0.009 (6)	0.000 (6)
O16B	0.023 (7)	0.033 (7)	0.029 (7)	0.004 (6)	0.008 (6)	−0.008 (6)
O17A	0.025 (6)	0.028 (6)	0.033 (6)	0.003 (5)	0.004 (5)	0.000 (5)
O17B	0.030 (6)	0.024 (6)	0.034 (6)	0.008 (5)	0.013 (5)	0.005 (5)
O18A	0.027 (6)	0.027 (6)	0.023 (6)	0.003 (5)	0.000 (5)	−0.003 (5)
O18B	0.030 (6)	0.023 (6)	0.028 (6)	0.001 (5)	0.001 (5)	−0.011 (5)
O19	0.101 (6)	0.094 (6)	0.060 (5)	0.044 (5)	0.006 (5)	0.001 (5)
O20	0.096 (8)	0.105 (9)	0.114 (9)	0.008 (7)	0.031 (7)	−0.007 (7)
O20A	0.040 (11)	0.048 (11)	0.036 (11)	0.020 (9)	0.007 (8)	0.000 (9)
O21A	0.024 (9)	0.043 (10)	0.031 (10)	−0.008 (8)	0.001 (8)	0.005 (8)
O21	0.079 (8)	0.096 (9)	0.111 (9)	0.003 (7)	−0.008 (7)	−0.001 (7)
O22	0.086 (6)	0.051 (6)	0.136 (7)	−0.005 (5)	0.062 (6)	−0.020 (5)

Geometric parameters (Å, º) top

Si1—O17Aⁱ	1.606 (13)	C1—H1	0.9300
Si1—O17A	1.606 (13)	C2—C3	1.410 (19)
Si1—O18A	1.648 (13)	C2—H2	0.9300
Si1—O18Aⁱ	1.648 (13)	C3—N8	1.325 (16)
Si1—O18B	1.670 (13)	C3—C4	1.455 (18)
Si1—O18Bⁱ	1.670 (13)	C4—N9	1.370 (16)
Si1—O17B	1.684 (13)	C4—C5	1.383 (18)
Si1—O17Bⁱ	1.684 (13)	C5—C6	1.409 (19)
Fe1—N2	2.105 (11)	C5—H5	0.9300
Fe1—N8	2.119 (11)	C6—C7	1.32 (2)
Fe1—N5	2.153 (11)	C6—H6	0.9300
Fe1—N3	2.173 (11)	C7—C8	1.38 (2)
Fe1—N9	2.186 (12)	C7—H7	0.9300
Fe1—N6	2.206 (11)	C8—N9	1.369 (17)
Mo1—O3	1.657 (9)	C8—H8	0.9300
Mo1—O7	1.823 (9)	C9—C10	1.37 (2)
Mo1—O19	1.832 (11)	C9—N4	1.368 (19)
Mo1—O16B	1.892 (16)	C9—H9	0.9300
Mo1—O11A	2.010 (19)	C10—C11	1.435 (19)
Mo1—O11B	2.117 (17)	C10—H10	0.9300
Mo1—O16	2.183 (17)	C11—N5	1.335 (16)
Mo1—O18Bⁱ	2.406 (13)	C11—C12	1.440 (18)
Mo1—O18A	2.423 (13)	C12—N6	1.332 (16)
Mo2—O5	1.646 (9)	C12—C13	1.417 (19)
Mo2—O7	1.923 (9)	C13—C14	1.38 (2)
Mo2—O12ⁱ	1.940 (10)	C13—H13	0.9300
Mo2—O15	1.950 (11)	C14—C15	1.38 (2)
Mo2—O22ⁱ	1.993 (10)	C14—H14	0.9300
Mo2—O17B	2.468 (13)	C15—C16	1.37 (2)
Mo2—O18A	2.498 (12)	C15—H15	0.9300
Mo3—O21	1.700 (15)	C16—N6	1.351 (17)
Mo3—O20A	1.72 (3)	C16—H16	0.9300
Mo3—O20	1.765 (17)	C17—N1	1.313 (17)
Mo3—O21A	1.84 (3)	C17—C18	1.349 (19)
Mo3—O16	1.998 (16)	C17—H17	0.9300
Mo3—O10	2.033 (9)	C18—C19	1.444 (19)
Mo3—O11B	2.051 (17)	C18—H18	0.9300
Mo3—O11A	2.086 (19)	C19—N2	1.333 (16)
Mo3—O14A	2.099 (16)	C19—C20	1.452 (18)
Mo3—O14	2.164 (15)	C20—N3	1.378 (16)
Mo3—O16B	2.174 (15)	C20—C21	1.411 (19)
Mo4—O4	1.663 (8)	C21—C22	1.39 (2)
Mo4—O22	1.803 (10)	C21—H21	0.9300
Mo4—O13	1.839 (9)	C22—C23	1.37 (2)
Mo4—O14	1.895 (15)	C22—H22	0.9300
Mo4—O11A	1.903 (19)	C23—C24	1.37 (2)
Mo4—O11B	2.228 (18)	C23—H23	0.9300
Mo4—O14A	2.237 (17)	C24—N3	1.335 (16)
Mo4—O17Bⁱ	2.397 (14)	C24—H24	0.9300
Mo4—O18Bⁱ	2.435 (13)	N1—N2	1.359 (14)
Mo5—O1	1.659 (9)	N1—H1A	0.8600
Mo5—O19	1.918 (11)	N4—N5	1.382 (15)
Mo5—O8	1.928 (9)	N4—H4	0.8600
Mo5—O6	1.952 (9)	N7—N8	1.339 (14)
Mo5—O13	1.978 (9)	N7—H7A	0.8600
Mo5—O18Bⁱ	2.404 (13)	O10—Mo7ⁱ	2.058 (10)
Mo5—O17A	2.463 (14)	O10—Mo6ⁱ	2.061 (11)
Mo6—O2	1.668 (9)	O11A—O11B	0.701 (18)
Mo6—O8	1.833 (9)	O12—Mo2ⁱ	1.940 (10)
Mo6—O15	1.832 (10)	O14—O14A	0.878 (17)
Mo6—O14ⁱ	1.954 (15)	O14—Mo6ⁱ	1.954 (15)
Mo6—O10ⁱ	2.061 (11)	O14A—Mo6ⁱ	2.119 (17)
Mo6—O14Aⁱ	2.119 (17)	O16—O16B	0.766 (16)
Mo6—O17B	2.375 (13)	O16—Mo7ⁱ	2.154 (17)
Mo6—O17A	2.480 (13)	O16B—Mo7ⁱ	1.943 (16)
Mo7—O9	1.664 (10)	O17A—O18Bⁱ	1.778 (18)
Mo7—O12	1.818 (9)	O17B—Mo4ⁱ	2.397 (14)
Mo7—O6	1.840 (9)	O18A—Mo7ⁱ	2.389 (13)
Mo7—O16Bⁱ	1.943 (16)	O18B—O17Aⁱ	1.778 (18)
Mo7—O10ⁱ	2.058 (10)	O18B—Mo5ⁱ	2.404 (13)
Mo7—O16ⁱ	2.154 (17)	O18B—Mo1ⁱ	2.406 (13)
Mo7—O18Aⁱ	2.389 (13)	O18B—Mo4ⁱ	2.435 (13)
Mo7—O17A	2.417 (13)	O20—O20A	1.79 (4)
C1—C2	1.34 (2)	O21A—O21	1.68 (3)
C1—N7	1.337 (19)	O22—Mo2ⁱ	1.993 (10)

O17Aⁱ—Si1—O17A	180.0 (10)	O14ⁱ—Mo6—O14Aⁱ	24.5 (5)
O17Aⁱ—Si1—O18A	69.8 (7)	O10ⁱ—Mo6—O14Aⁱ	74.5 (5)
O17A—Si1—O18A	110.2 (7)	O2—Mo6—O17B	154.3 (5)
O17Aⁱ—Si1—O18Aⁱ	110.2 (7)	O8—Mo6—O17B	101.6 (5)
O17A—Si1—O18Aⁱ	69.8 (7)	O15—Mo6—O17B	65.6 (5)
O18A—Si1—O18Aⁱ	180.000 (3)	O14ⁱ—Mo6—O17B	49.8 (6)
O17Aⁱ—Si1—O18B	65.7 (6)	O10ⁱ—Mo6—O17B	91.8 (4)
O17A—Si1—O18B	114.3 (6)	O14Aⁱ—Mo6—O17B	72.4 (6)
O18A—Si1—O18B	108.4 (6)	O2—Mo6—O17A	156.3 (4)
O18Aⁱ—Si1—O18B	71.6 (6)	O8—Mo6—O17A	67.0 (4)
O17Aⁱ—Si1—O18Bⁱ	114.3 (6)	O15—Mo6—O17A	101.0 (5)
O17A—Si1—O18Bⁱ	65.7 (6)	O14ⁱ—Mo6—O17A	76.8 (6)
O18A—Si1—O18Bⁱ	71.6 (6)	O10ⁱ—Mo6—O17A	63.1 (4)
O18Aⁱ—Si1—O18Bⁱ	108.4 (6)	O14Aⁱ—Mo6—O17A	100.1 (6)
O18B—Si1—O18Bⁱ	180.0 (6)	O17B—Mo6—O17A	47.2 (5)
O17Aⁱ—Si1—O17B	107.4 (7)	O9—Mo7—O12	102.6 (5)
O17A—Si1—O17B	72.6 (7)	O9—Mo7—O6	100.4 (5)
O18A—Si1—O17B	68.4 (6)	O12—Mo7—O6	97.2 (4)
O18Aⁱ—Si1—O17B	111.6 (6)	O9—Mo7—O16Bⁱ	111.2 (6)
O18B—Si1—O17B	75.3 (6)	O12—Mo7—O16Bⁱ	88.3 (5)
O18Bⁱ—Si1—O17B	104.7 (6)	O6—Mo7—O16Bⁱ	145.8 (6)
O17Aⁱ—Si1—O17Bⁱ	72.6 (7)	O9—Mo7—O10ⁱ	97.4 (5)
O17A—Si1—O17Bⁱ	107.4 (7)	O12—Mo7—O10ⁱ	156.2 (5)
O18A—Si1—O17Bⁱ	111.6 (6)	O6—Mo7—O10ⁱ	91.6 (4)
O18Aⁱ—Si1—O17Bⁱ	68.4 (6)	O16Bⁱ—Mo7—O10ⁱ	72.4 (5)
O18B—Si1—O17Bⁱ	104.7 (6)	O9—Mo7—O16ⁱ	90.5 (6)
O18Bⁱ—Si1—O17Bⁱ	75.3 (6)	O12—Mo7—O16ⁱ	94.0 (5)
O17B—Si1—O17Bⁱ	180.000 (3)	O6—Mo7—O16ⁱ	162.2 (5)
N2—Fe1—N8	102.7 (4)	O16Bⁱ—Mo7—O16ⁱ	20.7 (5)
N2—Fe1—N5	161.1 (4)	O10ⁱ—Mo7—O16ⁱ	72.9 (5)
N8—Fe1—N5	89.3 (4)	O9—Mo7—O18Aⁱ	156.7 (5)
N2—Fe1—N3	76.0 (4)	O12—Mo7—O18Aⁱ	66.4 (5)
N8—Fe1—N3	166.1 (4)	O6—Mo7—O18Aⁱ	101.3 (5)
N5—Fe1—N3	95.8 (4)	O16Bⁱ—Mo7—O18Aⁱ	50.4 (6)
N2—Fe1—N9	96.8 (4)	O10ⁱ—Mo7—O18Aⁱ	90.3 (4)
N8—Fe1—N9	75.2 (4)	O16ⁱ—Mo7—O18Aⁱ	70.7 (5)
N5—Fe1—N9	100.5 (4)	O9—Mo7—O17A	155.7 (5)
N3—Fe1—N9	91.1 (4)	O12—Mo7—O17A	99.3 (5)
N2—Fe1—N6	90.3 (4)	O6—Mo7—O17A	66.2 (5)
N8—Fe1—N6	92.0 (4)	O16Bⁱ—Mo7—O17A	79.6 (6)
N5—Fe1—N6	74.5 (4)	O10ⁱ—Mo7—O17A	64.3 (5)
N3—Fe1—N6	101.8 (4)	O16ⁱ—Mo7—O17A	98.4 (6)
N9—Fe1—N6	166.5 (4)	O18Aⁱ—Mo7—O17A	45.6 (4)
O3—Mo1—O7	101.6 (5)	C2—C1—N7	110.5 (15)
O3—Mo1—O19	102.0 (5)	C2—C1—H1	124.7
O7—Mo1—O19	95.9 (5)	N7—C1—H1	124.8
O3—Mo1—O16B	111.0 (6)	C1—C2—C3	102.9 (15)
O7—Mo1—O16B	89.0 (5)	C1—C2—H2	128.5
O19—Mo1—O16B	144.9 (6)	C3—C2—H2	128.6
O3—Mo1—O11A	108.1 (6)	N8—C3—C2	111.1 (13)
O7—Mo1—O11A	147.9 (6)	N8—C3—C4	117.5 (13)
O19—Mo1—O11A	89.7 (6)	C2—C3—C4	131.4 (14)
O16B—Mo1—O11A	69.4 (7)	N9—C4—C5	121.5 (13)
O3—Mo1—O11B	88.8 (6)	N9—C4—C3	114.1 (12)
O7—Mo1—O11B	165.0 (6)	C5—C4—C3	124.4 (13)
O19—Mo1—O11B	92.5 (6)	C4—C5—C6	118.5 (14)
O16B—Mo1—O11B	77.0 (6)	C4—C5—H5	120.7
O11A—Mo1—O11B	19.3 (5)	C6—C5—H5	120.8
O3—Mo1—O16	90.9 (6)	C7—C6—C5	119.9 (15)
O7—Mo1—O16	93.6 (5)	C7—C6—H6	120.1
O19—Mo1—O16	162.0 (6)	C5—C6—H6	120.0
O16B—Mo1—O16	20.1 (5)	C6—C7—C8	120.6 (16)
O11A—Mo1—O16	74.4 (7)	C6—C7—H7	119.6
O11B—Mo1—O16	75.2 (6)	C8—C7—H7	119.8
O3—Mo1—O18Bⁱ	154.5 (4)	N9—C8—C7	121.8 (15)
O7—Mo1—O18Bⁱ	100.7 (5)	N9—C8—H8	119.1
O19—Mo1—O18Bⁱ	63.6 (5)	C7—C8—H8	119.1
O16B—Mo1—O18Bⁱ	81.4 (6)	C10—C9—N4	106.4 (14)
O11A—Mo1—O18Bⁱ	54.1 (6)	C10—C9—H9	126.8
O11B—Mo1—O18Bⁱ	71.9 (6)	N4—C9—H9	126.7
O16—Mo1—O18Bⁱ	99.7 (5)	C9—C10—C11	105.6 (14)
O3—Mo1—O18A	156.2 (5)	C9—C10—H10	127.1
O7—Mo1—O18A	67.5 (4)	C11—C10—H10	127.2
O19—Mo1—O18A	100.2 (5)	N5—C11—C10	111.2 (13)
O16B—Mo1—O18A	50.1 (6)	N5—C11—C12	117.7 (12)
O11A—Mo1—O18A	80.4 (6)	C10—C11—C12	131.1 (13)
O11B—Mo1—O18A	98.8 (6)	N6—C12—C13	122.3 (13)
O16—Mo1—O18A	69.6 (5)	N6—C12—C11	115.7 (11)
O18Bⁱ—Mo1—O18A	47.4 (4)	C13—C12—C11	121.9 (13)
O5—Mo2—O7	102.7 (4)	C14—C13—C12	118.5 (16)
O5—Mo2—O12ⁱ	103.1 (4)	C14—C13—H13	120.7
O7—Mo2—O12ⁱ	88.3 (4)	C12—C13—H13	120.7
O5—Mo2—O15	101.1 (5)	C13—C14—C15	117.6 (17)
O7—Mo2—O15	89.7 (5)	C13—C14—H14	121.1
O12ⁱ—Mo2—O15	155.6 (5)	C15—C14—H14	121.3
O5—Mo2—O22ⁱ	101.5 (5)	C16—C15—C14	121.8 (17)
O7—Mo2—O22ⁱ	155.8 (5)	C16—C15—H15	119.2
O12ⁱ—Mo2—O22ⁱ	85.7 (4)	C14—C15—H15	119.1
O15—Mo2—O22ⁱ	86.2 (4)	N6—C16—C15	121.1 (15)
O5—Mo2—O17B	155.9 (4)	N6—C16—H16	119.5
O7—Mo2—O17B	94.9 (5)	C15—C16—H16	119.4
O12ⁱ—Mo2—O17B	93.7 (4)	N1—C17—C18	109.6 (14)
O15—Mo2—O17B	62.2 (5)	N1—C17—H17	125.2
O22ⁱ—Mo2—O17B	62.2 (4)	C18—C17—H17	125.2
O5—Mo2—O18A	159.8 (4)	C17—C18—C19	102.8 (14)
O7—Mo2—O18A	64.6 (4)	C17—C18—H18	128.7
O12ⁱ—Mo2—O18A	62.6 (4)	C19—C18—H18	128.5
O15—Mo2—O18A	94.8 (5)	N2—C19—C18	111.2 (12)
O22ⁱ—Mo2—O18A	92.0 (5)	N2—C19—C20	116.9 (12)
O17B—Mo2—O18A	44.3 (4)	C18—C19—C20	131.9 (13)
O21—Mo3—O20A	66.1 (11)	N3—C20—C21	120.6 (13)
O21—Mo3—O20	97.1 (8)	N3—C20—C19	114.9 (11)
O20A—Mo3—O20	61.9 (12)	C21—C20—C19	124.5 (14)
O21—Mo3—O21A	56.4 (10)	C22—C21—C20	116.7 (16)
O20A—Mo3—O21A	92.6 (14)	C22—C21—H21	121.6
O20—Mo3—O21A	66.6 (11)	C20—C21—H21	121.8
O21—Mo3—O16	161.4 (8)	C23—C22—C21	121.5 (16)
O20A—Mo3—O16	104.3 (11)	C23—C22—H22	119.2
O20—Mo3—O16	64.5 (7)	C21—C22—H22	119.2
O21A—Mo3—O16	110.4 (10)	C24—C23—C22	119.2 (16)
O21—Mo3—O10	115.0 (7)	C24—C23—H23	120.4
O20A—Mo3—O10	79.4 (11)	C22—C23—H23	120.4
O20—Mo3—O10	113.0 (7)	N3—C24—C23	121.5 (14)
O21A—Mo3—O10	170.5 (9)	N3—C24—H24	119.2
O16—Mo3—O10	76.8 (6)	C23—C24—H24	119.2
O21—Mo3—O11B	102.1 (7)	C17—N1—N2	112.8 (12)
O20A—Mo3—O11B	157.2 (12)	C17—N1—H1A	123.5
O20—Mo3—O11B	102.4 (8)	N2—N1—H1A	123.7
O21A—Mo3—O11B	65.1 (10)	C19—N2—N1	103.6 (11)
O16—Mo3—O11B	80.8 (7)	C19—N2—Fe1	117.6 (9)
O10—Mo3—O11B	123.3 (6)	N1—N2—Fe1	138.7 (9)
O21—Mo3—O11A	111.9 (8)	C24—N3—C20	120.2 (12)
O20A—Mo3—O11A	176.6 (12)	C24—N3—Fe1	125.0 (10)
O20—Mo3—O11A	116.3 (8)	C20—N3—Fe1	114.6 (8)
O21A—Mo3—O11A	84.1 (10)	C9—N4—N5	112.5 (13)
O16—Mo3—O11A	76.8 (7)	C9—N4—H4	123.8
O10—Mo3—O11A	104.0 (6)	N5—N4—H4	123.7
O11B—Mo3—O11A	19.5 (5)	C11—N5—N4	104.1 (12)
O21—Mo3—O14A	65.6 (8)	C11—N5—Fe1	115.4 (9)
O20A—Mo3—O14A	107.0 (11)	N4—N5—Fe1	138.9 (10)
O20—Mo3—O14A	162.7 (7)	C12—N6—C16	118.5 (12)
O21A—Mo3—O14A	102.4 (10)	C12—N6—Fe1	114.9 (8)
O16—Mo3—O14A	132.9 (7)	C16—N6—Fe1	125.8 (10)
O10—Mo3—O14A	75.5 (5)	C1—N7—N8	109.7 (13)
O11B—Mo3—O14A	83.6 (7)	C1—N7—H7A	125.1
O11A—Mo3—O14A	74.0 (7)	N8—N7—H7A	125.2
O21—Mo3—O14	88.8 (7)	C3—N8—N7	105.7 (12)
O20A—Mo3—O14	124.0 (11)	C3—N8—Fe1	117.6 (9)
O20—Mo3—O14	173.2 (7)	N7—N8—Fe1	136.6 (10)
O21A—Mo3—O14	114.7 (10)	C8—N9—C4	117.6 (12)
O16—Mo3—O14	109.4 (7)	C8—N9—Fe1	126.9 (10)
O10—Mo3—O14	66.9 (5)	C4—N9—Fe1	115.4 (8)
O11B—Mo3—O14	73.0 (6)	Mo7—O6—Mo5	137.3 (6)
O11A—Mo3—O14	58.0 (6)	Mo1—O7—Mo2	137.5 (6)
O14A—Mo3—O14	23.7 (5)	Mo6—O8—Mo5	136.7 (5)
O21—Mo3—O16B	174.7 (7)	Mo3—O10—Mo7ⁱ	106.3 (4)
O20A—Mo3—O16B	119.1 (11)	Mo3—O10—Mo6ⁱ	107.2 (4)
O20—Mo3—O16B	84.9 (7)	Mo7ⁱ—O10—Mo6ⁱ	129.4 (6)
O21A—Mo3—O16B	120.5 (9)	O11B—O11A—Mo4	109 (3)
O16—Mo3—O16B	20.6 (5)	O11B—O11A—Mo1	89 (3)
O10—Mo3—O16B	68.3 (5)	Mo4—O11A—Mo1	143.0 (10)
O11B—Mo3—O16B	72.6 (6)	O11B—O11A—Mo3	77 (2)
O11A—Mo3—O16B	62.9 (7)	Mo4—O11A—Mo3	111.0 (9)
O14A—Mo3—O16B	112.4 (6)	Mo1—O11A—Mo3	104.4 (8)
O14—Mo3—O16B	88.8 (6)	O11A—O11B—Mo3	83 (2)
O4—Mo4—O22	101.8 (5)	O11A—O11B—Mo1	72 (2)
O4—Mo4—O13	100.9 (5)	Mo3—O11B—Mo1	101.9 (7)
O22—Mo4—O13	96.4 (5)	O11A—O11B—Mo4	54 (2)
O4—Mo4—O14	110.5 (6)	Mo3—O11B—Mo4	100.4 (7)
O22—Mo4—O14	91.7 (6)	Mo1—O11B—Mo4	117.2 (7)
O13—Mo4—O14	145.2 (6)	Mo7—O12—Mo2ⁱ	138.9 (6)
O4—Mo4—O11A	106.1 (6)	Mo4—O13—Mo5	135.4 (6)
O22—Mo4—O11A	148.9 (7)	O14A—O14—Mo4	101.1 (17)
O13—Mo4—O11A	91.8 (6)	O14A—O14—Mo6ⁱ	88.3 (16)
O14—Mo4—O11A	65.8 (7)	Mo4—O14—Mo6ⁱ	145.8 (9)
O4—Mo4—O11B	89.0 (5)	O14A—O14—Mo3	73.9 (15)
O22—Mo4—O11B	164.8 (6)	Mo4—O14—Mo3	108.0 (7)
O13—Mo4—O11B	91.9 (5)	Mo6ⁱ—O14—Mo3	106.1 (7)
O14—Mo4—O11B	74.4 (6)	O14—O14A—Mo3	82.4 (16)
O11A—Mo4—O11B	17.4 (6)	O14—O14A—Mo6ⁱ	67.2 (15)
O4—Mo4—O14A	88.1 (5)	Mo3—O14A—Mo6ⁱ	102.7 (7)
O22—Mo4—O14A	93.1 (5)	O14—O14A—Mo4	56.2 (15)
O13—Mo4—O14A	165.3 (5)	Mo3—O14A—Mo4	98.6 (7)
O14—Mo4—O14A	22.7 (5)	Mo6ⁱ—O14A—Mo4	115.3 (8)
O11A—Mo4—O14A	74.4 (7)	Mo6—O15—Mo2	138.4 (7)
O11B—Mo4—O14A	76.5 (6)	O16B—O16—Mo3	92.8 (19)
O4—Mo4—O17Bⁱ	153.6 (4)	O16B—O16—Mo7ⁱ	63.9 (19)
O22—Mo4—O17Bⁱ	66.0 (5)	Mo3—O16—Mo7ⁱ	104.0 (7)
O13—Mo4—O17Bⁱ	103.7 (5)	O16B—O16—Mo1	58.0 (18)
O14—Mo4—O17Bⁱ	49.8 (6)	Mo3—O16—Mo1	101.4 (7)
O11A—Mo4—O17Bⁱ	82.9 (6)	Mo7ⁱ—O16—Mo1	116.9 (8)
O11B—Mo4—O17Bⁱ	99.7 (5)	O16—O16B—Mo1	102 (2)
O14A—Mo4—O17Bⁱ	70.0 (5)	O16—O16B—Mo7ⁱ	95 (2)
O4—Mo4—O18Bⁱ	153.7 (4)	Mo1—O16B—Mo7ⁱ	149.0 (9)
O22—Mo4—O18Bⁱ	102.3 (5)	O16—O16B—Mo3	66.6 (18)
O13—Mo4—O18Bⁱ	66.0 (4)	Mo1—O16B—Mo3	105.3 (7)
O14—Mo4—O18Bⁱ	79.3 (6)	Mo7ⁱ—O16B—Mo3	105.2 (7)
O11A—Mo4—O18Bⁱ	54.4 (6)	Si1—O17A—O18Bⁱ	58.9 (6)
O11B—Mo4—O18Bⁱ	69.6 (5)	Si1—O17A—Mo7	122.6 (7)
O14A—Mo4—O18Bⁱ	101.0 (5)	O18Bⁱ—O17A—Mo7	130.3 (8)
O17Bⁱ—Mo4—O18Bⁱ	50.1 (5)	Si1—O17A—Mo5	125.7 (7)
O1—Mo5—O19	100.9 (5)	O18Bⁱ—O17A—Mo5	66.8 (6)
O1—Mo5—O8	101.2 (4)	Mo7—O17A—Mo5	92.7 (5)
O19—Mo5—O8	90.3 (4)	Si1—O17A—Mo6	119.1 (7)
O1—Mo5—O6	101.8 (4)	O18Bⁱ—O17A—Mo6	124.3 (8)
O19—Mo5—O6	157.2 (5)	Mo7—O17A—Mo6	99.0 (5)
O8—Mo5—O6	87.2 (4)	Mo5—O17A—Mo6	90.0 (4)
O1—Mo5—O13	99.9 (4)	Si1—O17B—Mo6	121.1 (7)
O19—Mo5—O13	87.1 (4)	Si1—O17B—Mo4ⁱ	117.9 (6)
O8—Mo5—O13	158.8 (4)	Mo6—O17B—Mo4ⁱ	100.9 (5)
O6—Mo5—O13	87.2 (4)	Si1—O17B—Mo2	123.6 (6)
O1—Mo5—O18Bⁱ	156.9 (4)	Mo6—O17B—Mo2	93.7 (4)
O19—Mo5—O18Bⁱ	62.6 (5)	Mo4ⁱ—O17B—Mo2	93.6 (5)
O8—Mo5—O18Bⁱ	95.3 (4)	Si1—O18A—Mo7ⁱ	122.1 (7)
O6—Mo5—O18Bⁱ	95.0 (5)	Si1—O18A—Mo1	120.6 (7)
O13—Mo5—O18Bⁱ	64.9 (4)	Mo7ⁱ—O18A—Mo1	100.3 (5)
O1—Mo5—O17A	160.3 (4)	Si1—O18A—Mo2	123.7 (6)
O19—Mo5—O17A	94.5 (5)	Mo7ⁱ—O18A—Mo2	92.1 (4)
O8—Mo5—O17A	66.2 (4)	Mo1—O18A—Mo2	90.4 (4)
O6—Mo5—O17A	63.8 (4)	Si1—O18B—O17Aⁱ	55.4 (6)
O13—Mo5—O17A	93.0 (5)	Si1—O18B—Mo5ⁱ	125.8 (7)
O18Bⁱ—Mo5—O17A	42.8 (4)	O17Aⁱ—O18B—Mo5ⁱ	70.4 (6)
O2—Mo6—O8	101.7 (5)	Si1—O18B—Mo1ⁱ	120.5 (6)
O2—Mo6—O15	101.0 (5)	O17Aⁱ—O18B—Mo1ⁱ	132.3 (8)
O8—Mo6—O15	96.4 (5)	Mo5ⁱ—O18B—Mo1ⁱ	94.1 (5)
O2—Mo6—O14ⁱ	111.8 (6)	Si1—O18B—Mo4ⁱ	116.6 (7)
O8—Mo6—O14ⁱ	143.8 (6)	O17Aⁱ—O18B—Mo4ⁱ	125.0 (8)
O15—Mo6—O14ⁱ	90.5 (6)	Mo5ⁱ—O18B—Mo4ⁱ	93.7 (4)
O2—Mo6—O10ⁱ	98.0 (5)	Mo1ⁱ—O18B—Mo4ⁱ	100.1 (5)
O8—Mo6—O10ⁱ	92.2 (4)	Mo1—O19—Mo5	139.7 (7)
O15—Mo6—O10ⁱ	157.0 (5)	Mo3—O20—O20A	57.8 (11)
O14ⁱ—Mo6—O10ⁱ	70.5 (5)	Mo3—O20A—O20	60.3 (11)
O2—Mo6—O14Aⁱ	87.4 (6)	O21—O21A—Mo3	57.7 (10)
O8—Mo6—O14Aⁱ	165.0 (5)	O21A—O21—Mo3	65.9 (11)
O15—Mo6—O14Aⁱ	93.6 (6)	Mo4—O22—Mo2ⁱ	138.2 (6)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O13ⁱⁱ	0.86	2.15	2.973 (17)	159
N1—H1A···O21Aⁱⁱⁱ	0.86	2.17	2.96 (3)	152
N1—H1A···O21ⁱⁱⁱ	0.86	2.05	2.844 (19)	153

Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Fe(C₈H₇N₃)₃]₂[SiMo₁₄O₄₄]
M_r	3057.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.055 (3), 16.931 (3), 18.562 (4)
β (°)	102.69 (3)
V (Å³)	4002.6 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.58
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	0.747, 0.820
No. of measured, independent and observed [I > 2σ(I)] reflections	27223, 7026, 4730
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.157, 1.00
No. of reflections	7026
No. of parameters	638
No. of restraints	444
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.058P)² + 47.4341P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.47, −1.52

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

Selected bond lengths (Å) top

Si1—O17A	1.606 (13)	Fe1—N8	2.119 (11)
Si1—O18A	1.648 (13)	Fe1—N5	2.153 (11)
Si1—O18B	1.670 (13)	Fe1—N3	2.173 (11)
Si1—O17B	1.684 (13)	Fe1—N9	2.186 (12)
Fe1—N2	2.105 (11)	Fe1—N6	2.206 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O13ⁱ	0.86	2.15	2.973 (17)	159.0
N1—H1A···O21Aⁱⁱ	0.86	2.17	2.96 (3)	151.7
N1—H1A···O21ⁱⁱ	0.86	2.05	2.844 (19)	153.3

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+1.

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

Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolbecq, A., Cadot, E., Eisner, D. & Secheresse, F. (1999). Inorg. Chem. 38, 4127–4134. Web of Science CSD CrossRef Google Scholar
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Volume 66| Part 2| February 2010| Pages m190-m191

https://doi.org/10.1107/S1600536810002412

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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)} tetra­deca­molybdo(V,VI)silicate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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