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Acta Cryst. (2008). E64, m672    [ doi:10.1107/S1600536808009896 ]

Tris[tris(1,10-phenanthroline-[kappa]2N,N')iron(II)] dodecatungstoferrate dihydrate

F.-X. Ma, Y.-G. Chen and D.-M. Shi

Abstract top

The title compound, [Fe(C12H8N2)3]3[FeW12O40]·2H2O, was prepared under hydrothermal conditions. The discrete Keggin-type [FeW12O40]6- heteropolyoxoanion has threefold symmetry, with the FeII atom located on the threefold rotation axis. The central FeO4 tetrahedron in the anion shares its O atoms with four W3O13 trinuclear units, each of which is made up of three edge-shared WO6 octahedral units. The FeII atom in the complex cation, viz [Fe(phen)3]2+ (phen is 1,10-phenanthroline), shows a slightly distorted octahedral geometry defined by six N atoms from three phen ligands. The polyoxoanions pack together with the cations, with the disordered water molecules located in voids; the site occupancy factor for each water O atom is 0.33.

Comment top

Polyoxometalates (POMs) have attracted attention in recent years, not only because of their structural diversity but also because of their potential applications in medicine, material science, especially in catalysis (Misono, 1987; Pope, 1983).

The structure of the title compound is built up from three complex cations, [Fe(phen)3]2+ (phen = 1,10-phenanthroline), one Keggin-type anion, [FeW12O40]6-, and two disordered water molecules. The heteropolyoxoanion [FeW12O40]6- has threefold symmetry with the Fe1 atom located on the threefold rotation axis. The Fe2 atom in the cation is coordinated by six N atoms from three phen molecules, forming a distorted FeN6 octahedron with Fe—N bond distances ranging from 1.969 (11) to 2.001 (11)Å (Fig. 1; Table 1).

Results of bond valence sum (BVS) calculations (Brown, 2002) are in accordance with expected values for hexavalent tungsten (average 6.15 valence units for the 12 W atoms) and divalent iron (1.92 valence units for the Fe atom in the complex cation).

Related literature top

For related literature, see: Brown (2002); Misono (1987); Pope (1983).

Experimental top

A mixture of ammonium tungstate monohydrate (1.005 g, 0.6 mmol), FeCl3.6H2O (0.157 g, 0.6 mmol), phen.H2O (0.256 g, 1.3 mmol), NH4VO3(0.053 g, 0.5 mmol), oxalic acid dihydrate(0.205 g, 1.6 mmol) and H2O (10 ml) was adjusted to pH = 5.8 by addition of 2 mol L-1 NaOH under stirring for 30 min. The final solution was transferred into a 25 ml Teflon-lined autoclave and was heated at 453 K for 96 h. Then the autoclave was cooled in a rate of 10 K h-1 to room temperature. Red block-like crystals were filtered off, washed with distilled water, and dried at ambient temperature (40% yield on W).

Refinement top

H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of the disordered water molecules were not located. In the final difference Fourier map, the highest peak is 2.83Å away from O2W and the deepest hole is 0.23 Å from Fe1.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms and disordered water molecules are omitted for clarity. [Symmetry codes: (i) -y + 1, x-y, z; (ii) -x + y+1, -x + 1, z.]
Tris[tris(1,10-phenanthroline-κ2N,N')iron(II)] dodecatungstoferrate dihydrate top
Crystal data top
[Fe(C12H8N2)3]3[FeW12O40]·2H2OZ = 3
Mr = 4727.47F000 = 6593.7
Trigonal, R3Dx = 2.527 Mg m−3
Hall symbol: R 3Mo Kα radiation
λ = 0.71073 Å
a = 25.088 (5) ÅCell parameters from 5571 reflections
b = 25.088 (5) Åθ = 1.5–25.1º
c = 17.231 (5) ŵ = 11.51 mm−1
α = 90ºT = 293 (2) K
β = 90ºBlock, red
γ = 120º0.24 × 0.21 × 0.20 mm
V = 9392 (4) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		6154 independent reflections
Radiation source: fine-focus sealed tube5557 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 293(2) Kθmax = 25.1º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −29→29
Tmin = 0.075, Tmax = 0.104k = −29→29
16084 measured reflectionsl = −20→12
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2) + (0.0566P)2 + 7.5378P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093(Δ/σ)max = 0.001
S = 1.04Δρmax = 1.62 e Å−3
6154 reflectionsΔρmin = −1.55 e Å−3
560 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 3713 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.006 (6)
Secondary atom site location: difference Fourier map
Crystal data top
[Fe(C12H8N2)3]3[FeW12O40]·2H2Oγ = 120º
Mr = 4727.47V = 9392 (4) Å3
Trigonal, R3Z = 3
a = 25.088 (5) ÅMo Kα
b = 25.088 (5) ŵ = 11.51 mm−1
c = 17.231 (5) ÅT = 293 (2) K
α = 90º0.24 × 0.21 × 0.20 mm
β = 90º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		6154 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		5557 reflections with I > 2σ(I)
Tmin = 0.075, Tmax = 0.104Rint = 0.034
16084 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.093Δρmax = 1.62 e Å−3
S = 1.04Δρmin = −1.55 e Å−3
6154 reflectionsAbsolute structure: Flack (1983), 3713 Friedel pairs
560 parametersFlack parameter: −0.006 (6)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.66670.33330.3946 (2)0.0268 (6)
Fe20.32586 (8)0.15648 (8)0.72949 (11)0.0297 (4)
W10.58806 (3)0.33016 (3)0.22372 (4)0.03811 (16)
W20.58842 (3)0.41729 (3)0.39586 (3)0.04278 (17)
W30.58253 (3)0.24702 (3)0.55437 (4)0.04819 (18)
W40.50462 (2)0.24669 (3)0.39934 (3)0.04051 (16)
C10.2245 (6)0.0581 (6)0.8268 (8)0.035 (3)
H1A0.22010.08870.85130.043*
C20.1869 (6)−0.0018 (6)0.8499 (9)0.040 (3)
H2A0.1596−0.00990.89070.048*
C30.1885 (6)−0.0479 (6)0.8161 (8)0.042 (3)
H3A0.1614−0.08850.82980.050*
C40.2355 (6)−0.0320 (5)0.7551 (8)0.035 (3)
C50.2712 (5)0.0293 (5)0.7356 (8)0.035 (3)
C60.3150 (6)0.0474 (6)0.6755 (8)0.044 (3)
C70.3259 (7)0.0014 (6)0.6414 (9)0.052 (4)
C80.2083 (6)0.1176 (7)0.6442 (9)0.048 (4)
H8A0.18710.08560.67920.057*
C90.1760 (9)0.1237 (9)0.5801 (13)0.079 (7)
H9A0.13380.09650.57790.095*
C100.1990 (11)0.1623 (11)0.5263 (12)0.080 (6)
H10A0.17570.16260.48460.096*
C110.3893 (7)0.1268 (7)0.6061 (10)0.062 (5)
H11A0.41100.16830.59310.074*
C120.4027 (12)0.0851 (9)0.5665 (12)0.095 (8)
H12A0.43230.10030.52750.114*
C130.2444 (7)−0.0784 (7)0.7168 (11)0.063 (5)
H13A0.2185−0.12010.72640.076*
C140.4425 (7)0.2691 (7)0.6851 (10)0.054 (4)
H14A0.46020.26100.72770.065*
C150.2629 (13)0.2054 (10)0.5327 (10)0.085 (7)
C160.3002 (18)0.2552 (15)0.4770 (12)0.140 (14)
H16A0.28170.25990.43270.168*
C170.3649 (14)0.2965 (12)0.4905 (13)0.094 (8)
H17A0.38810.32680.45420.113*
C180.3929 (12)0.2912 (8)0.5584 (11)0.081 (7)
C190.3567 (8)0.2426 (6)0.6103 (9)0.051 (4)
C200.3430 (5)0.2139 (5)0.8739 (7)0.033 (3)
C210.3882 (6)0.1979 (6)0.8721 (7)0.038 (3)
C220.4287 (7)0.2118 (7)0.9329 (9)0.054 (4)
C230.4718 (8)0.1912 (9)0.9277 (12)0.070 (6)
H23A0.50000.19990.96750.084*
C240.4291 (8)0.1453 (9)0.8025 (11)0.072 (5)
H24A0.42920.12320.75920.086*
C250.2933 (11)−0.0580 (8)0.6650 (11)0.081 (7)
H25A0.3040−0.08610.64600.097*
C260.2600 (6)0.2131 (6)0.8112 (9)0.042 (3)
H26A0.23380.20230.76870.051*
C270.2488 (7)0.2413 (7)0.8753 (9)0.045 (4)
H27A0.21560.24820.87470.054*
C280.2852 (8)0.2575 (7)0.9352 (9)0.059 (5)
H28A0.27840.27720.97650.071*
C290.3371 (7)0.2455 (6)0.9392 (8)0.045 (3)
C300.3740 (9)0.2556 (8)0.9998 (10)0.068 (5)
H30A0.36610.27051.04520.081*
C310.4232 (8)0.2451 (7)0.9995 (9)0.063 (5)
H31A0.45160.25871.03990.076*
C320.2986 (8)0.2029 (6)0.5974 (9)0.054 (4)
C330.4560 (12)0.3308 (9)0.5740 (13)0.088 (8)
H33A0.47950.36370.54110.105*
C340.3739 (9)0.0237 (9)0.5835 (11)0.083 (6)
H34A0.3847−0.00250.55890.100*
C350.4820 (8)0.3208 (7)0.6360 (13)0.070 (6)
H35A0.52360.34610.64710.084*
C360.4723 (8)0.1583 (10)0.8642 (13)0.084 (6)
H36A0.50050.14460.86130.101*
N10.2665 (4)0.0749 (4)0.7718 (6)0.027 (2)
N20.3485 (5)0.1086 (5)0.6585 (7)0.040 (3)
N30.2656 (6)0.1551 (5)0.6549 (6)0.040 (3)
N40.3847 (6)0.2337 (5)0.6735 (7)0.041 (3)
N50.3875 (5)0.1656 (5)0.8079 (7)0.040 (3)
N60.3062 (5)0.2008 (5)0.8083 (6)0.031 (2)
O10.66670.33330.2882 (10)0.038 (4)
O20.6684 (4)0.2746 (4)0.5635 (6)0.047 (2)
O30.5416 (5)0.3302 (5)0.1526 (6)0.046 (2)
O40.5342 (4)0.2705 (4)0.2961 (5)0.040 (2)
O50.5375 (5)0.4431 (5)0.3877 (7)0.059 (3)
O60.5548 (5)0.2172 (6)0.6463 (6)0.063 (3)
O70.5918 (4)0.3915 (4)0.2958 (5)0.037 (2)
O80.4282 (4)0.2170 (5)0.3920 (7)0.056 (3)
O90.5345 (4)0.3311 (4)0.4206 (5)0.040 (2)
O100.5036 (4)0.2295 (4)0.5095 (6)0.049 (3)
O110.5687 (4)0.1702 (4)0.5081 (6)0.046 (2)
O120.6053 (4)0.2694 (4)0.1776 (6)0.040 (2)
O130.5982 (4)0.2633 (4)0.4271 (6)0.036 (2)
O140.5038 (4)0.1676 (4)0.3806 (6)0.045 (2)
O1W0.5848 (13)0.3187 (15)0.7626 (19)0.053 (9)0.33
O2W0.5964 (9)0.2622 (9)1.0192 (12)0.013 (4)*0.33
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0211 (7)0.0211 (7)0.0382 (16)0.0105 (4)0.0000.000
Fe20.0294 (9)0.0271 (10)0.0303 (9)0.0123 (8)0.0027 (7)−0.0021 (8)
W10.0322 (3)0.0341 (3)0.0487 (4)0.0171 (2)−0.0097 (3)−0.0013 (3)
W20.0389 (3)0.0400 (3)0.0606 (5)0.0282 (3)−0.0024 (3)−0.0043 (3)
W30.0459 (4)0.0465 (4)0.0512 (4)0.0223 (3)0.0143 (3)0.0129 (3)
W40.0216 (3)0.0361 (3)0.0588 (4)0.0107 (2)0.0040 (2)−0.0005 (3)
C10.038 (7)0.033 (7)0.039 (8)0.020 (6)0.012 (6)0.008 (6)
C20.042 (8)0.042 (8)0.042 (9)0.025 (7)0.007 (6)0.009 (7)
C30.038 (7)0.035 (7)0.055 (9)0.020 (6)−0.008 (6)0.006 (6)
C40.039 (7)0.020 (6)0.047 (8)0.016 (5)0.005 (6)0.000 (5)
C50.029 (6)0.028 (7)0.050 (8)0.016 (5)−0.003 (6)0.001 (6)
C60.052 (8)0.047 (8)0.037 (8)0.029 (7)0.004 (7)−0.020 (6)
C70.060 (9)0.040 (8)0.051 (10)0.020 (7)0.014 (7)−0.008 (7)
C80.038 (8)0.040 (7)0.058 (10)0.013 (6)−0.024 (7)−0.011 (6)
C90.082 (13)0.064 (12)0.106 (17)0.048 (11)−0.068 (13)−0.046 (12)
C100.094 (16)0.082 (15)0.067 (14)0.046 (13)−0.038 (12)−0.005 (11)
C110.061 (10)0.033 (8)0.082 (13)0.017 (7)0.034 (9)0.010 (8)
C120.15 (2)0.066 (13)0.075 (15)0.056 (14)0.066 (15)−0.001 (10)
C130.052 (10)0.042 (9)0.083 (13)0.014 (8)0.012 (9)−0.012 (8)
C140.050 (9)0.045 (9)0.055 (10)0.014 (8)0.016 (8)−0.010 (7)
C150.18 (2)0.085 (14)0.035 (10)0.097 (17)0.013 (12)0.019 (9)
C160.31 (4)0.18 (3)0.044 (14)0.21 (3)0.06 (2)0.056 (17)
C170.16 (2)0.101 (19)0.069 (16)0.102 (19)0.033 (16)0.041 (13)
C180.15 (2)0.056 (11)0.056 (12)0.067 (13)0.049 (12)0.015 (9)
C190.081 (12)0.036 (8)0.042 (9)0.033 (8)0.035 (8)0.013 (7)
C200.028 (6)0.023 (6)0.035 (7)0.003 (5)0.005 (5)0.006 (5)
C210.033 (7)0.047 (8)0.030 (7)0.017 (6)−0.010 (6)−0.002 (6)
C220.043 (8)0.045 (9)0.058 (11)0.009 (7)0.001 (7)0.010 (7)
C230.037 (9)0.085 (13)0.074 (14)0.020 (9)−0.029 (9)0.010 (11)
C240.046 (9)0.089 (13)0.088 (14)0.040 (10)−0.014 (9)−0.009 (11)
C250.139 (18)0.048 (10)0.075 (13)0.062 (12)0.032 (13)−0.011 (9)
C260.030 (7)0.035 (7)0.056 (10)0.012 (6)−0.005 (6)0.001 (6)
C270.055 (9)0.055 (9)0.037 (9)0.035 (8)−0.001 (7)−0.006 (7)
C280.093 (13)0.050 (9)0.039 (10)0.040 (9)0.025 (9)−0.008 (7)
C290.052 (9)0.043 (8)0.033 (8)0.019 (7)−0.011 (7)−0.018 (6)
C300.085 (13)0.059 (11)0.059 (12)0.036 (10)−0.018 (10)−0.021 (8)
C310.073 (12)0.040 (8)0.046 (10)0.005 (8)−0.026 (9)−0.006 (7)
C320.090 (12)0.030 (8)0.047 (10)0.034 (8)0.019 (8)0.007 (7)
C330.117 (19)0.051 (11)0.077 (16)0.029 (13)0.071 (14)0.014 (11)
C340.083 (14)0.073 (13)0.095 (15)0.039 (11)0.026 (12)−0.030 (11)
C350.046 (10)0.035 (9)0.101 (17)0.000 (8)0.047 (11)0.002 (9)
C360.050 (11)0.116 (17)0.101 (18)0.052 (12)−0.006 (10)0.006 (14)
N10.031 (5)0.027 (5)0.028 (6)0.019 (5)0.001 (4)0.000 (4)
N20.041 (7)0.039 (6)0.037 (7)0.019 (5)0.009 (5)−0.004 (5)
N30.061 (8)0.039 (6)0.028 (6)0.031 (6)−0.001 (6)−0.006 (5)
N40.063 (8)0.022 (5)0.031 (7)0.016 (6)0.023 (6)0.000 (5)
N50.023 (5)0.037 (6)0.049 (7)0.008 (5)0.004 (5)−0.001 (5)
N60.030 (6)0.026 (5)0.024 (6)0.006 (5)−0.002 (4)−0.003 (4)
O10.030 (5)0.030 (5)0.055 (11)0.015 (2)0.0000.000
O20.046 (6)0.043 (6)0.054 (7)0.025 (5)0.003 (5)0.008 (5)
O30.048 (6)0.048 (6)0.048 (6)0.028 (5)−0.022 (5)−0.008 (5)
O40.040 (5)0.028 (5)0.049 (6)0.013 (4)0.005 (4)−0.003 (4)
O50.054 (6)0.038 (6)0.096 (9)0.030 (5)−0.002 (6)−0.010 (5)
O60.062 (7)0.072 (8)0.056 (8)0.035 (6)0.016 (6)0.015 (6)
O70.041 (5)0.028 (5)0.050 (6)0.022 (4)−0.007 (4)−0.009 (4)
O80.025 (5)0.045 (6)0.089 (9)0.010 (4)0.013 (5)−0.003 (6)
O90.040 (5)0.032 (5)0.053 (6)0.021 (4)0.006 (4)−0.002 (4)
O100.049 (6)0.033 (5)0.054 (7)0.013 (5)0.020 (5)−0.004 (4)
O110.046 (6)0.041 (5)0.054 (7)0.024 (5)0.005 (5)0.015 (5)
O120.034 (5)0.032 (5)0.054 (7)0.016 (4)0.000 (4)0.001 (4)
O130.036 (5)0.026 (4)0.044 (6)0.013 (4)0.002 (4)0.002 (4)
O140.039 (5)0.041 (5)0.058 (7)0.022 (5)0.003 (4)−0.005 (4)
O1W0.048 (18)0.08 (2)0.05 (2)0.041 (17)−0.010 (14)−0.042 (16)
Geometric parameters (Å, °) top
Fe1—O13i1.826 (8)C11—C121.42 (2)
Fe1—O131.826 (8)C11—H11A0.9300
Fe1—O13ii1.826 (8)C12—C341.37 (2)
Fe1—O11.833 (18)C12—H12A0.9300
Fe2—N61.969 (11)C13—C251.39 (2)
Fe2—N31.971 (12)C13—H13A0.9300
Fe2—N11.972 (10)C14—N41.283 (19)
Fe2—N51.979 (12)C14—C351.45 (2)
Fe2—N21.986 (11)C14—H14A0.9300
Fe2—N42.001 (11)C15—C321.45 (3)
W1—O31.692 (9)C15—C161.48 (3)
W1—O41.898 (9)C16—C171.44 (4)
W1—O71.943 (8)C16—H16A0.9300
W1—O12ii1.950 (9)C17—C181.41 (3)
W1—O121.950 (8)C17—H17A0.9300
W1—O12.230 (9)C18—C331.41 (3)
W2—O51.702 (10)C18—C191.42 (2)
W2—O71.858 (9)C19—C321.31 (2)
W2—O91.940 (9)C19—N41.37 (2)
W2—O14ii1.954 (9)C20—C211.380 (17)
W2—O11ii1.963 (10)C20—N61.390 (16)
W2—O13ii2.211 (8)C20—C291.425 (18)
W3—O61.742 (11)C21—N51.367 (17)
W3—O2ii1.903 (9)C21—C221.377 (19)
W3—O21.911 (9)C22—C231.42 (2)
W3—O111.951 (10)C22—C311.47 (2)
W3—O101.961 (10)C23—C361.37 (3)
W3—O132.229 (10)C23—H23A0.9300
W4—O81.678 (9)C24—N51.373 (19)
W4—O91.896 (8)C24—C361.44 (2)
W4—O41.904 (9)C24—H24A0.9300
W4—O101.944 (11)C25—H25A0.9300
W4—O142.001 (9)C26—N61.341 (16)
W4—O132.221 (8)C26—C271.41 (2)
C1—N11.319 (15)C26—H26A0.9300
C1—C21.375 (18)C27—C281.30 (2)
C1—H1A0.9300C27—H27A0.9300
C2—C31.313 (18)C28—C291.48 (2)
C2—H2A0.9300C28—H28A0.9300
C3—C41.477 (18)C29—C301.33 (2)
C3—H3A0.9300C30—C311.39 (2)
C4—C51.378 (16)C30—H30A0.9300
C4—C131.451 (18)C31—H31A0.9300
C5—N11.360 (15)C32—N31.455 (18)
C5—C61.409 (18)C33—C351.34 (3)
C6—N21.363 (17)C33—H33A0.9300
C6—C71.440 (18)C34—H34A0.9300
C7—C251.36 (2)C35—H35A0.9300
C7—C341.44 (2)C36—H36A0.9300
C8—N31.279 (17)O1—W1i2.230 (9)
C8—C91.42 (2)O1—W1ii2.230 (9)
C8—H8A0.9300O2—W3i1.903 (9)
C9—C101.25 (3)O11—W2i1.963 (10)
C9—H9A0.9300O12—W1i1.950 (8)
C10—C151.42 (3)O13—W2i2.211 (8)
C10—H10A0.9300O14—W2i1.954 (9)
C11—N21.267 (17)
O13i—Fe1—O13111.0 (3)C34—C12—C11122.6 (17)
O13i—Fe1—O13ii111.0 (3)C34—C12—H12A118.7
O13—Fe1—O13ii111.0 (3)C11—C12—H12A118.7
O13i—Fe1—O1107.9 (3)C25—C13—C4117.4 (14)
O13—Fe1—O1107.9 (3)C25—C13—H13A121.3
O13ii—Fe1—O1107.9 (3)C4—C13—H13A121.3
N6—Fe2—N393.0 (4)N4—C14—C35124.1 (18)
N6—Fe2—N193.4 (4)N4—C14—H14A118.0
N3—Fe2—N192.8 (4)C35—C14—H14A118.0
N6—Fe2—N582.3 (5)C10—C15—C32120.9 (16)
N3—Fe2—N5174.4 (5)C10—C15—C16126 (2)
N1—Fe2—N590.5 (4)C32—C15—C16113 (2)
N6—Fe2—N2174.4 (5)C17—C16—C15121 (2)
N3—Fe2—N292.1 (5)C17—C16—H16A119.7
N1—Fe2—N284.0 (4)C15—C16—H16A119.7
N5—Fe2—N292.7 (5)C18—C17—C16120 (2)
N6—Fe2—N493.3 (4)C18—C17—H17A119.9
N3—Fe2—N483.7 (5)C16—C17—H17A119.9
N1—Fe2—N4172.6 (4)C17—C18—C33122 (2)
N5—Fe2—N493.5 (5)C17—C18—C19118 (2)
N2—Fe2—N489.6 (4)C33—C18—C19120 (2)
O3—W1—O4104.9 (5)C32—C19—N4118.5 (13)
O3—W1—O7102.9 (4)C32—C19—C18122.6 (18)
O4—W1—O786.4 (4)N4—C19—C18118.7 (17)
O3—W1—O12ii95.3 (5)C21—C20—N6117.3 (11)
O4—W1—O12ii159.7 (4)C21—C20—C29120.5 (12)
O7—W1—O12ii87.9 (4)N6—C20—C29122.1 (11)
O3—W1—O1297.3 (4)N5—C21—C22123.7 (13)
O4—W1—O1290.0 (4)N5—C21—C20115.0 (11)
O7—W1—O12159.7 (4)C22—C21—C20121.3 (13)
O12ii—W1—O1288.6 (5)C21—C22—C23117.4 (16)
O3—W1—O1163.4 (5)C21—C22—C31118.1 (15)
O4—W1—O188.2 (4)C23—C22—C31124.4 (16)
O7—W1—O187.8 (4)C36—C23—C22120.5 (15)
O12ii—W1—O172.1 (4)C36—C23—H23A119.7
O12—W1—O172.1 (4)C22—C23—H23A119.7
O5—W2—O7103.3 (5)N5—C24—C36119.5 (17)
O5—W2—O9101.8 (4)N5—C24—H24A120.3
O7—W2—O986.7 (4)C36—C24—H24A120.3
O5—W2—O14ii97.7 (5)C7—C25—C13122.2 (14)
O7—W2—O14ii92.2 (4)C7—C25—H25A118.9
O9—W2—O14ii160.2 (4)C13—C25—H25A118.9
O5—W2—O11ii95.9 (5)N6—C26—C27123.7 (13)
O7—W2—O11ii160.7 (4)N6—C26—H26A118.2
O9—W2—O11ii86.8 (4)C27—C26—H26A118.2
O14ii—W2—O11ii87.8 (4)C28—C27—C26119.4 (15)
O5—W2—O13ii166.2 (5)C28—C27—H27A120.3
O7—W2—O13ii88.3 (4)C26—C27—H27A120.3
O9—W2—O13ii86.2 (3)C27—C28—C29121.8 (13)
O14ii—W2—O13ii74.0 (3)C27—C28—H28A119.1
O11ii—W2—O13ii73.1 (3)C29—C28—H28A119.1
O6—W3—O2ii103.8 (5)C30—C29—C20118.0 (14)
O6—W3—O2102.5 (5)C30—C29—C28126.6 (14)
O2ii—W3—O285.6 (5)C20—C29—C28115.0 (12)
O6—W3—O1196.5 (5)C29—C30—C31124.1 (16)
O2ii—W3—O11159.7 (4)C29—C30—H30A117.9
O2—W3—O1190.1 (4)C31—C30—H30A117.9
O6—W3—O1096.9 (5)C30—C31—C22117.2 (14)
O2ii—W3—O1090.0 (4)C30—C31—H31A121.4
O2—W3—O10160.6 (4)C22—C31—H31A121.4
O11—W3—O1087.5 (4)C19—C32—C15125.1 (16)
O6—W3—O13165.8 (5)C19—C32—N3118.0 (15)
O2ii—W3—O1387.1 (4)C15—C32—N3116.7 (16)
O2—W3—O1387.2 (4)C35—C33—C18120.0 (17)
O11—W3—O1373.0 (3)C35—C33—H33A120.0
O10—W3—O1373.7 (4)C18—C33—H33A120.0
O8—W4—O9103.7 (4)C12—C34—C7117.0 (15)
O8—W4—O4104.3 (5)C12—C34—H34A121.5
O9—W4—O487.5 (4)C7—C34—H34A121.5
O8—W4—O1095.1 (5)C33—C35—C14117.1 (18)
O9—W4—O1090.8 (4)C33—C35—H35A121.5
O4—W4—O10160.3 (4)C14—C35—H35A121.5
O8—W4—O1496.0 (4)C23—C36—C24119.6 (17)
O9—W4—O14160.3 (4)C23—C36—H36A120.2
O4—W4—O1488.3 (4)C24—C36—H36A120.2
O10—W4—O1486.8 (4)C1—N1—C5116.9 (10)
O8—W4—O13164.7 (4)C1—N1—Fe2131.6 (8)
O9—W4—O1387.6 (3)C5—N1—Fe2111.5 (8)
O4—W4—O1386.2 (4)C11—N2—C6119.4 (12)
O10—W4—O1374.2 (4)C11—N2—Fe2130.2 (10)
O14—W4—O1372.9 (3)C6—N2—Fe2110.2 (8)
N1—C1—C2124.0 (12)C8—N3—C32118.3 (13)
N1—C1—H1A118.0C8—N3—Fe2132.7 (10)
C2—C1—H1A118.0C32—N3—Fe2108.4 (10)
C3—C2—C1121.8 (14)C14—N4—C19120.3 (13)
C3—C2—H2A119.1C14—N4—Fe2128.8 (12)
C1—C2—H2A119.1C19—N4—Fe2110.5 (10)
C2—C3—C4116.7 (12)C21—N5—C24119.2 (13)
C2—C3—H3A121.7C21—N5—Fe2113.5 (9)
C4—C3—H3A121.7C24—N5—Fe2127.2 (11)
C5—C4—C13120.5 (13)C26—N6—C20117.7 (11)
C5—C4—C3117.5 (11)C26—N6—Fe2130.1 (9)
C13—C4—C3122.0 (12)C20—N6—Fe2111.7 (8)
N1—C5—C4123.0 (12)Fe1—O1—W1i119.9 (4)
N1—C5—C6116.5 (11)Fe1—O1—W1ii119.9 (4)
C4—C5—C6120.5 (12)W1i—O1—W1ii97.4 (5)
N2—C6—C5117.7 (11)Fe1—O1—W1119.9 (4)
N2—C6—C7123.9 (13)W1i—O1—W197.4 (5)
C5—C6—C7118.1 (13)W1ii—O1—W197.4 (5)
C25—C7—C6120.5 (14)W3i—O2—W3152.4 (5)
C25—C7—C34124.2 (15)W1—O4—W4150.8 (5)
C6—C7—C34115.3 (14)W2—O7—W1151.3 (5)
N3—C8—C9121.7 (16)W4—O9—W2150.3 (5)
N3—C8—H8A119.2W4—O10—W3115.8 (4)
C9—C8—H8A119.2W3—O11—W2i116.6 (4)
C10—C9—C8126.2 (19)W1i—O12—W1118.3 (5)
C10—C9—H9A116.9Fe1—O13—W2i121.3 (4)
C8—C9—H9A116.9Fe1—O13—W4120.8 (4)
C9—C10—C15116.0 (18)W2i—O13—W497.7 (3)
C9—C10—H10A122.0Fe1—O13—W3118.3 (5)
C15—C10—H10A122.0W2i—O13—W397.2 (3)
N2—C11—C12121.5 (14)W4—O13—W396.0 (3)
N2—C11—H11A119.2W2i—O14—W4115.2 (4)
C12—C11—H11A119.2
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z.
Table 1
Selected geometric parameters (Å) top
Fe1—O131.826 (8)W2—O14i1.954 (9)
Fe1—O11.833 (18)W2—O11i1.963 (10)
Fe2—N61.969 (11)W2—O13i2.211 (8)
Fe2—N31.971 (12)W3—O61.742 (11)
Fe2—N11.972 (10)W3—O2i1.903 (9)
Fe2—N51.979 (12)W3—O21.911 (9)
Fe2—N21.986 (11)W3—O111.951 (10)
Fe2—N42.001 (11)W3—O101.961 (10)
W1—O31.692 (9)W3—O132.229 (10)
W1—O41.898 (9)W4—O81.678 (9)
W1—O71.943 (8)W4—O91.896 (8)
W1—O121.950 (8)W4—O41.904 (9)
W1—O12.230 (9)W4—O101.944 (11)
W2—O51.702 (10)W4—O142.001 (9)
W2—O71.858 (9)W4—O132.221 (8)
W2—O91.940 (9)
Symmetry codes: (i) −x+y+1, −x+1, z.
Acknowledgements top

This work was supported by the Analysis and Testing Foundation of Northeast Normal University, Changchun, China.

references
References top

Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry: the Bond Valence Model. Oxford University Press.

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Misono, M. (1987). Cat. Rev. Sci. Eng. 29, 269–321.

Pope, M. T. (1983). Heteropoly and Isopoly Oxometalates. Berlin: Springer.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.