Tris[tris­(1,10-phenanthroline-κ2N,N′)iron(II)] dodeca­tungstoferrate dihydrate

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

doi:10.1107/S1600536808009896

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m672

doi:10.1107/S1600536808009896

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Tris[tris(1,10-phenanthroline-κ²N,N′)iron(II)] dodecatungstoferrate dihydrate

Feng-Xia Ma,^a,^b Ya-Guang Chen ^a ^* and Dong-Mei Shi ^a

^aDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China, and ^bBasic Science Department, Jilin Agricultural Science and Technology College, Jilin 132101, People's Republic of China
^*Correspondence e-mail: chenyg146@nenu.edu.cn

(Received 24 March 2008; accepted 10 April 2008; online 16 April 2008)

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 Fe^II 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 Fe^II 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.

Related literature

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

Experimental

Crystal data

[Fe(C₁₂H₈N₂)₃]₃[FeW₁₂O₄₀]·2H₂O
M_r = 4727.47
Trigonal, R 3
a = 25.088 (5) Å
c = 17.231 (5) Å
V = 9392 (4) Å³
Z = 3
Mo Kα radiation
μ = 11.51 mm⁻¹
T = 293 (2) K
0.24 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.075, T_max = 0.104
16084 measured reflections
6154 independent reflections
5557 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.093
S = 1.03
6154 reflections
560 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.62 e Å⁻³
Δρ_min = −1.55 e Å⁻³
Absolute structure: Flack (1983 ), 3713 Friedel pairs
Flack parameter: −0.006 (6)

Table 1
Selected bond lengths (Å)

Fe1—O13	1.826 (8)
Fe1—O1	1.833 (18)
Fe2—N6	1.969 (11)
Fe2—N3	1.971 (12)
Fe2—N1	1.972 (10)
Fe2—N5	1.979 (12)
Fe2—N2	1.986 (11)
Fe2—N4	2.001 (11)
W1—O3	1.692 (9)
W1—O4	1.898 (9)
W1—O7	1.943 (8)
W1—O12	1.950 (8)
W1—O1	2.230 (9)
W2—O5	1.702 (10)
W2—O7	1.858 (9)
W2—O9	1.940 (9)
W2—O14ⁱ	1.954 (9)
W2—O11ⁱ	1.963 (10)
W2—O13ⁱ	2.211 (8)
W3—O6	1.742 (11)
W3—O2ⁱ	1.903 (9)
W3—O2	1.911 (9)
W3—O11	1.951 (10)
W3—O10	1.961 (10)
W3—O13	2.229 (10)
W4—O8	1.678 (9)
W4—O9	1.896 (8)
W4—O4	1.904 (9)
W4—O10	1.944 (11)
W4—O14	2.001 (9)
W4—O13	2.221 (8)
Symmetry code: (i) -x+y+1, -x+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009896/hy2126sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808009896/hy2126Isup2.hkl

checkCIF report

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).

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

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]·2H₂O	D_x = 2.527 Mg m⁻³
M_r = 4727.47	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 5571 reflections
Hall symbol: R 3	θ = 1.5–25.1°
a = 25.088 (5) Å	µ = 11.51 mm⁻¹
c = 17.231 (5) Å	T = 293 K
V = 9392 (4) Å³	Block, red
Z = 3	0.24 × 0.21 × 0.20 mm
F(000) = 6593.7

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	6154 independent reflections
Radiation source: fine-focus sealed tube	5557 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→29
T_min = 0.075, T_max = 0.104	k = −29→29
16084 measured reflections	l = −20→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0566P)² + 7.5378P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
6154 reflections	Δρ_max = 1.62 e Å⁻³
560 parameters	Δρ_min = −1.55 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3713 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.006 (6)

Crystal data top

[Fe(C₁₂H₈N₂)₃]₃[FeW₁₂O₄₀]·2H₂O	Z = 3
M_r = 4727.47	Mo Kα radiation
Trigonal, R3	µ = 11.51 mm⁻¹
a = 25.088 (5) Å	T = 293 K
c = 17.231 (5) Å	0.24 × 0.21 × 0.20 mm
V = 9392 (4) Å³

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)
T_min = 0.075, T_max = 0.104	R_int = 0.034
16084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.093	Δρ_max = 1.62 e Å⁻³
S = 1.04	Δρ_min = −1.55 e Å⁻³
6154 reflections	Absolute structure: Flack (1983), 3713 Friedel pairs
560 parameters	Absolute structure parameter: −0.006 (6)
1 restraint

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.6667	0.3333	0.3946 (2)	0.0268 (6)
Fe2	0.32586 (8)	0.15648 (8)	0.72949 (11)	0.0297 (4)
W1	0.58806 (3)	0.33016 (3)	0.22372 (4)	0.03811 (16)
W2	0.58842 (3)	0.41729 (3)	0.39586 (3)	0.04278 (17)
W3	0.58253 (3)	0.24702 (3)	0.55437 (4)	0.04819 (18)
W4	0.50462 (2)	0.24669 (3)	0.39934 (3)	0.04051 (16)
C1	0.2245 (6)	0.0581 (6)	0.8268 (8)	0.035 (3)
H1A	0.2201	0.0887	0.8513	0.043*
C2	0.1869 (6)	−0.0018 (6)	0.8499 (9)	0.040 (3)
H2A	0.1596	−0.0099	0.8907	0.048*
C3	0.1885 (6)	−0.0479 (6)	0.8161 (8)	0.042 (3)
H3A	0.1614	−0.0885	0.8298	0.050*
C4	0.2355 (6)	−0.0320 (5)	0.7551 (8)	0.035 (3)
C5	0.2712 (5)	0.0293 (5)	0.7356 (8)	0.035 (3)
C6	0.3150 (6)	0.0474 (6)	0.6755 (8)	0.044 (3)
C7	0.3259 (7)	0.0014 (6)	0.6414 (9)	0.052 (4)
C8	0.2083 (6)	0.1176 (7)	0.6442 (9)	0.048 (4)
H8A	0.1871	0.0856	0.6792	0.057*
C9	0.1760 (9)	0.1237 (9)	0.5801 (13)	0.079 (7)
H9A	0.1338	0.0965	0.5779	0.095*
C10	0.1990 (11)	0.1623 (11)	0.5263 (12)	0.080 (6)
H10A	0.1757	0.1626	0.4846	0.096*
C11	0.3893 (7)	0.1268 (7)	0.6061 (10)	0.062 (5)
H11A	0.4110	0.1683	0.5931	0.074*
C12	0.4027 (12)	0.0851 (9)	0.5665 (12)	0.095 (8)
H12A	0.4323	0.1003	0.5275	0.114*
C13	0.2444 (7)	−0.0784 (7)	0.7168 (11)	0.063 (5)
H13A	0.2185	−0.1201	0.7264	0.076*
C14	0.4425 (7)	0.2691 (7)	0.6851 (10)	0.054 (4)
H14A	0.4602	0.2610	0.7277	0.065*
C15	0.2629 (13)	0.2054 (10)	0.5327 (10)	0.085 (7)
C16	0.3002 (18)	0.2552 (15)	0.4770 (12)	0.140 (14)
H16A	0.2817	0.2599	0.4327	0.168*
C17	0.3649 (14)	0.2965 (12)	0.4905 (13)	0.094 (8)
H17A	0.3881	0.3268	0.4542	0.113*
C18	0.3929 (12)	0.2912 (8)	0.5584 (11)	0.081 (7)
C19	0.3567 (8)	0.2426 (6)	0.6103 (9)	0.051 (4)
C20	0.3430 (5)	0.2139 (5)	0.8739 (7)	0.033 (3)
C21	0.3882 (6)	0.1979 (6)	0.8721 (7)	0.038 (3)
C22	0.4287 (7)	0.2118 (7)	0.9329 (9)	0.054 (4)
C23	0.4718 (8)	0.1912 (9)	0.9277 (12)	0.070 (6)
H23A	0.5000	0.1999	0.9675	0.084*
C24	0.4291 (8)	0.1453 (9)	0.8025 (11)	0.072 (5)
H24A	0.4292	0.1232	0.7592	0.086*
C25	0.2933 (11)	−0.0580 (8)	0.6650 (11)	0.081 (7)
H25A	0.3040	−0.0861	0.6460	0.097*
C26	0.2600 (6)	0.2131 (6)	0.8112 (9)	0.042 (3)
H26A	0.2338	0.2023	0.7687	0.051*
C27	0.2488 (7)	0.2413 (7)	0.8753 (9)	0.045 (4)
H27A	0.2156	0.2482	0.8747	0.054*
C28	0.2852 (8)	0.2575 (7)	0.9352 (9)	0.059 (5)
H28A	0.2784	0.2772	0.9765	0.071*
C29	0.3371 (7)	0.2455 (6)	0.9392 (8)	0.045 (3)
C30	0.3740 (9)	0.2556 (8)	0.9998 (10)	0.068 (5)
H30A	0.3661	0.2705	1.0452	0.081*
C31	0.4232 (8)	0.2451 (7)	0.9995 (9)	0.063 (5)
H31A	0.4516	0.2587	1.0399	0.076*
C32	0.2986 (8)	0.2029 (6)	0.5974 (9)	0.054 (4)
C33	0.4560 (12)	0.3308 (9)	0.5740 (13)	0.088 (8)
H33A	0.4795	0.3637	0.5411	0.105*
C34	0.3739 (9)	0.0237 (9)	0.5835 (11)	0.083 (6)
H34A	0.3847	−0.0025	0.5589	0.100*
C35	0.4820 (8)	0.3208 (7)	0.6360 (13)	0.070 (6)
H35A	0.5236	0.3461	0.6471	0.084*
C36	0.4723 (8)	0.1583 (10)	0.8642 (13)	0.084 (6)
H36A	0.5005	0.1446	0.8613	0.101*
N1	0.2665 (4)	0.0749 (4)	0.7718 (6)	0.027 (2)
N2	0.3485 (5)	0.1086 (5)	0.6585 (7)	0.040 (3)
N3	0.2656 (6)	0.1551 (5)	0.6549 (6)	0.040 (3)
N4	0.3847 (6)	0.2337 (5)	0.6735 (7)	0.041 (3)
N5	0.3875 (5)	0.1656 (5)	0.8079 (7)	0.040 (3)
N6	0.3062 (5)	0.2008 (5)	0.8083 (6)	0.031 (2)
O1	0.6667	0.3333	0.2882 (10)	0.038 (4)
O2	0.6684 (4)	0.2746 (4)	0.5635 (6)	0.047 (2)
O3	0.5416 (5)	0.3302 (5)	0.1526 (6)	0.046 (2)
O4	0.5342 (4)	0.2705 (4)	0.2961 (5)	0.040 (2)
O5	0.5375 (5)	0.4431 (5)	0.3877 (7)	0.059 (3)
O6	0.5548 (5)	0.2172 (6)	0.6463 (6)	0.063 (3)
O7	0.5918 (4)	0.3915 (4)	0.2958 (5)	0.037 (2)
O8	0.4282 (4)	0.2170 (5)	0.3920 (7)	0.056 (3)
O9	0.5345 (4)	0.3311 (4)	0.4206 (5)	0.040 (2)
O10	0.5036 (4)	0.2295 (4)	0.5095 (6)	0.049 (3)
O11	0.5687 (4)	0.1702 (4)	0.5081 (6)	0.046 (2)
O12	0.6053 (4)	0.2694 (4)	0.1776 (6)	0.040 (2)
O13	0.5982 (4)	0.2633 (4)	0.4271 (6)	0.036 (2)
O14	0.5038 (4)	0.1676 (4)	0.3806 (6)	0.045 (2)
O1W	0.5848 (13)	0.3187 (15)	0.7626 (19)	0.053 (9)	0.33
O2W	0.5964 (9)	0.2622 (9)	1.0192 (12)	0.013 (4)*	0.33

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0211 (7)	0.0211 (7)	0.0382 (16)	0.0105 (4)	0.000	0.000
Fe2	0.0294 (9)	0.0271 (10)	0.0303 (9)	0.0123 (8)	0.0027 (7)	−0.0021 (8)
W1	0.0322 (3)	0.0341 (3)	0.0487 (4)	0.0171 (2)	−0.0097 (3)	−0.0013 (3)
W2	0.0389 (3)	0.0400 (3)	0.0606 (5)	0.0282 (3)	−0.0024 (3)	−0.0043 (3)
W3	0.0459 (4)	0.0465 (4)	0.0512 (4)	0.0223 (3)	0.0143 (3)	0.0129 (3)
W4	0.0216 (3)	0.0361 (3)	0.0588 (4)	0.0107 (2)	0.0040 (2)	−0.0005 (3)
C1	0.038 (7)	0.033 (7)	0.039 (8)	0.020 (6)	0.012 (6)	0.008 (6)
C2	0.042 (8)	0.042 (8)	0.042 (9)	0.025 (7)	0.007 (6)	0.009 (7)
C3	0.038 (7)	0.035 (7)	0.055 (9)	0.020 (6)	−0.008 (6)	0.006 (6)
C4	0.039 (7)	0.020 (6)	0.047 (8)	0.016 (5)	0.005 (6)	0.000 (5)
C5	0.029 (6)	0.028 (7)	0.050 (8)	0.016 (5)	−0.003 (6)	0.001 (6)
C6	0.052 (8)	0.047 (8)	0.037 (8)	0.029 (7)	0.004 (7)	−0.020 (6)
C7	0.060 (9)	0.040 (8)	0.051 (10)	0.020 (7)	0.014 (7)	−0.008 (7)
C8	0.038 (8)	0.040 (7)	0.058 (10)	0.013 (6)	−0.024 (7)	−0.011 (6)
C9	0.082 (13)	0.064 (12)	0.106 (17)	0.048 (11)	−0.068 (13)	−0.046 (12)
C10	0.094 (16)	0.082 (15)	0.067 (14)	0.046 (13)	−0.038 (12)	−0.005 (11)
C11	0.061 (10)	0.033 (8)	0.082 (13)	0.017 (7)	0.034 (9)	0.010 (8)
C12	0.15 (2)	0.066 (13)	0.075 (15)	0.056 (14)	0.066 (15)	−0.001 (10)
C13	0.052 (10)	0.042 (9)	0.083 (13)	0.014 (8)	0.012 (9)	−0.012 (8)
C14	0.050 (9)	0.045 (9)	0.055 (10)	0.014 (8)	0.016 (8)	−0.010 (7)
C15	0.18 (2)	0.085 (14)	0.035 (10)	0.097 (17)	0.013 (12)	0.019 (9)
C16	0.31 (4)	0.18 (3)	0.044 (14)	0.21 (3)	0.06 (2)	0.056 (17)
C17	0.16 (2)	0.101 (19)	0.069 (16)	0.102 (19)	0.033 (16)	0.041 (13)
C18	0.15 (2)	0.056 (11)	0.056 (12)	0.067 (13)	0.049 (12)	0.015 (9)
C19	0.081 (12)	0.036 (8)	0.042 (9)	0.033 (8)	0.035 (8)	0.013 (7)
C20	0.028 (6)	0.023 (6)	0.035 (7)	0.003 (5)	0.005 (5)	0.006 (5)
C21	0.033 (7)	0.047 (8)	0.030 (7)	0.017 (6)	−0.010 (6)	−0.002 (6)
C22	0.043 (8)	0.045 (9)	0.058 (11)	0.009 (7)	0.001 (7)	0.010 (7)
C23	0.037 (9)	0.085 (13)	0.074 (14)	0.020 (9)	−0.029 (9)	0.010 (11)
C24	0.046 (9)	0.089 (13)	0.088 (14)	0.040 (10)	−0.014 (9)	−0.009 (11)
C25	0.139 (18)	0.048 (10)	0.075 (13)	0.062 (12)	0.032 (13)	−0.011 (9)
C26	0.030 (7)	0.035 (7)	0.056 (10)	0.012 (6)	−0.005 (6)	0.001 (6)
C27	0.055 (9)	0.055 (9)	0.037 (9)	0.035 (8)	−0.001 (7)	−0.006 (7)
C28	0.093 (13)	0.050 (9)	0.039 (10)	0.040 (9)	0.025 (9)	−0.008 (7)
C29	0.052 (9)	0.043 (8)	0.033 (8)	0.019 (7)	−0.011 (7)	−0.018 (6)
C30	0.085 (13)	0.059 (11)	0.059 (12)	0.036 (10)	−0.018 (10)	−0.021 (8)
C31	0.073 (12)	0.040 (8)	0.046 (10)	0.005 (8)	−0.026 (9)	−0.006 (7)
C32	0.090 (12)	0.030 (8)	0.047 (10)	0.034 (8)	0.019 (8)	0.007 (7)
C33	0.117 (19)	0.051 (11)	0.077 (16)	0.029 (13)	0.071 (14)	0.014 (11)
C34	0.083 (14)	0.073 (13)	0.095 (15)	0.039 (11)	0.026 (12)	−0.030 (11)
C35	0.046 (10)	0.035 (9)	0.101 (17)	0.000 (8)	0.047 (11)	0.002 (9)
C36	0.050 (11)	0.116 (17)	0.101 (18)	0.052 (12)	−0.006 (10)	0.006 (14)
N1	0.031 (5)	0.027 (5)	0.028 (6)	0.019 (5)	0.001 (4)	0.000 (4)
N2	0.041 (7)	0.039 (6)	0.037 (7)	0.019 (5)	0.009 (5)	−0.004 (5)
N3	0.061 (8)	0.039 (6)	0.028 (6)	0.031 (6)	−0.001 (6)	−0.006 (5)
N4	0.063 (8)	0.022 (5)	0.031 (7)	0.016 (6)	0.023 (6)	0.000 (5)
N5	0.023 (5)	0.037 (6)	0.049 (7)	0.008 (5)	0.004 (5)	−0.001 (5)
N6	0.030 (6)	0.026 (5)	0.024 (6)	0.006 (5)	−0.002 (4)	−0.003 (4)
O1	0.030 (5)	0.030 (5)	0.055 (11)	0.015 (2)	0.000	0.000
O2	0.046 (6)	0.043 (6)	0.054 (7)	0.025 (5)	0.003 (5)	0.008 (5)
O3	0.048 (6)	0.048 (6)	0.048 (6)	0.028 (5)	−0.022 (5)	−0.008 (5)
O4	0.040 (5)	0.028 (5)	0.049 (6)	0.013 (4)	0.005 (4)	−0.003 (4)
O5	0.054 (6)	0.038 (6)	0.096 (9)	0.030 (5)	−0.002 (6)	−0.010 (5)
O6	0.062 (7)	0.072 (8)	0.056 (8)	0.035 (6)	0.016 (6)	0.015 (6)
O7	0.041 (5)	0.028 (5)	0.050 (6)	0.022 (4)	−0.007 (4)	−0.009 (4)
O8	0.025 (5)	0.045 (6)	0.089 (9)	0.010 (4)	0.013 (5)	−0.003 (6)
O9	0.040 (5)	0.032 (5)	0.053 (6)	0.021 (4)	0.006 (4)	−0.002 (4)
O10	0.049 (6)	0.033 (5)	0.054 (7)	0.013 (5)	0.020 (5)	−0.004 (4)
O11	0.046 (6)	0.041 (5)	0.054 (7)	0.024 (5)	0.005 (5)	0.015 (5)
O12	0.034 (5)	0.032 (5)	0.054 (7)	0.016 (4)	0.000 (4)	0.001 (4)
O13	0.036 (5)	0.026 (4)	0.044 (6)	0.013 (4)	0.002 (4)	0.002 (4)
O14	0.039 (5)	0.041 (5)	0.058 (7)	0.022 (5)	0.003 (4)	−0.005 (4)
O1W	0.048 (18)	0.08 (2)	0.05 (2)	0.041 (17)	−0.010 (14)	−0.042 (16)

Geometric parameters (Å, º) top

Fe1—O13ⁱ	1.826 (8)	C11—C12	1.42 (2)
Fe1—O13	1.826 (8)	C11—H11A	0.9300
Fe1—O13ⁱⁱ	1.826 (8)	C12—C34	1.37 (2)
Fe1—O1	1.833 (18)	C12—H12A	0.9300
Fe2—N6	1.969 (11)	C13—C25	1.39 (2)
Fe2—N3	1.971 (12)	C13—H13A	0.9300
Fe2—N1	1.972 (10)	C14—N4	1.283 (19)
Fe2—N5	1.979 (12)	C14—C35	1.45 (2)
Fe2—N2	1.986 (11)	C14—H14A	0.9300
Fe2—N4	2.001 (11)	C15—C32	1.45 (3)
W1—O3	1.692 (9)	C15—C16	1.48 (3)
W1—O4	1.898 (9)	C16—C17	1.44 (4)
W1—O7	1.943 (8)	C16—H16A	0.9300
W1—O12ⁱⁱ	1.950 (9)	C17—C18	1.41 (3)
W1—O12	1.950 (8)	C17—H17A	0.9300
W1—O1	2.230 (9)	C18—C33	1.41 (3)
W2—O5	1.702 (10)	C18—C19	1.42 (2)
W2—O7	1.858 (9)	C19—C32	1.31 (2)
W2—O9	1.940 (9)	C19—N4	1.37 (2)
W2—O14ⁱⁱ	1.954 (9)	C20—C21	1.380 (17)
W2—O11ⁱⁱ	1.963 (10)	C20—N6	1.390 (16)
W2—O13ⁱⁱ	2.211 (8)	C20—C29	1.425 (18)
W3—O6	1.742 (11)	C21—N5	1.367 (17)
W3—O2ⁱⁱ	1.903 (9)	C21—C22	1.377 (19)
W3—O2	1.911 (9)	C22—C23	1.42 (2)
W3—O11	1.951 (10)	C22—C31	1.47 (2)
W3—O10	1.961 (10)	C23—C36	1.37 (3)
W3—O13	2.229 (10)	C23—H23A	0.9300
W4—O8	1.678 (9)	C24—N5	1.373 (19)
W4—O9	1.896 (8)	C24—C36	1.44 (2)
W4—O4	1.904 (9)	C24—H24A	0.9300
W4—O10	1.944 (11)	C25—H25A	0.9300
W4—O14	2.001 (9)	C26—N6	1.341 (16)
W4—O13	2.221 (8)	C26—C27	1.41 (2)
C1—N1	1.319 (15)	C26—H26A	0.9300
C1—C2	1.375 (18)	C27—C28	1.30 (2)
C1—H1A	0.9300	C27—H27A	0.9300
C2—C3	1.313 (18)	C28—C29	1.48 (2)
C2—H2A	0.9300	C28—H28A	0.9300
C3—C4	1.477 (18)	C29—C30	1.33 (2)
C3—H3A	0.9300	C30—C31	1.39 (2)
C4—C5	1.378 (16)	C30—H30A	0.9300
C4—C13	1.451 (18)	C31—H31A	0.9300
C5—N1	1.360 (15)	C32—N3	1.455 (18)
C5—C6	1.409 (18)	C33—C35	1.34 (3)
C6—N2	1.363 (17)	C33—H33A	0.9300
C6—C7	1.440 (18)	C34—H34A	0.9300
C7—C25	1.36 (2)	C35—H35A	0.9300
C7—C34	1.44 (2)	C36—H36A	0.9300
C8—N3	1.279 (17)	O1—W1ⁱ	2.230 (9)
C8—C9	1.42 (2)	O1—W1ⁱⁱ	2.230 (9)
C8—H8A	0.9300	O2—W3ⁱ	1.903 (9)
C9—C10	1.25 (3)	O11—W2ⁱ	1.963 (10)
C9—H9A	0.9300	O12—W1ⁱ	1.950 (8)
C10—C15	1.42 (3)	O13—W2ⁱ	2.211 (8)
C10—H10A	0.9300	O14—W2ⁱ	1.954 (9)
C11—N2	1.267 (17)

O13ⁱ—Fe1—O13	111.0 (3)	C34—C12—C11	122.6 (17)
O13ⁱ—Fe1—O13ⁱⁱ	111.0 (3)	C34—C12—H12A	118.7
O13—Fe1—O13ⁱⁱ	111.0 (3)	C11—C12—H12A	118.7
O13ⁱ—Fe1—O1	107.9 (3)	C25—C13—C4	117.4 (14)
O13—Fe1—O1	107.9 (3)	C25—C13—H13A	121.3
O13ⁱⁱ—Fe1—O1	107.9 (3)	C4—C13—H13A	121.3
N6—Fe2—N3	93.0 (4)	N4—C14—C35	124.1 (18)
N6—Fe2—N1	93.4 (4)	N4—C14—H14A	118.0
N3—Fe2—N1	92.8 (4)	C35—C14—H14A	118.0
N6—Fe2—N5	82.3 (5)	C10—C15—C32	120.9 (16)
N3—Fe2—N5	174.4 (5)	C10—C15—C16	126 (2)
N1—Fe2—N5	90.5 (4)	C32—C15—C16	113 (2)
N6—Fe2—N2	174.4 (5)	C17—C16—C15	121 (2)
N3—Fe2—N2	92.1 (5)	C17—C16—H16A	119.7
N1—Fe2—N2	84.0 (4)	C15—C16—H16A	119.7
N5—Fe2—N2	92.7 (5)	C18—C17—C16	120 (2)
N6—Fe2—N4	93.3 (4)	C18—C17—H17A	119.9
N3—Fe2—N4	83.7 (5)	C16—C17—H17A	119.9
N1—Fe2—N4	172.6 (4)	C17—C18—C33	122 (2)
N5—Fe2—N4	93.5 (5)	C17—C18—C19	118 (2)
N2—Fe2—N4	89.6 (4)	C33—C18—C19	120 (2)
O3—W1—O4	104.9 (5)	C32—C19—N4	118.5 (13)
O3—W1—O7	102.9 (4)	C32—C19—C18	122.6 (18)
O4—W1—O7	86.4 (4)	N4—C19—C18	118.7 (17)
O3—W1—O12ⁱⁱ	95.3 (5)	C21—C20—N6	117.3 (11)
O4—W1—O12ⁱⁱ	159.7 (4)	C21—C20—C29	120.5 (12)
O7—W1—O12ⁱⁱ	87.9 (4)	N6—C20—C29	122.1 (11)
O3—W1—O12	97.3 (4)	N5—C21—C22	123.7 (13)
O4—W1—O12	90.0 (4)	N5—C21—C20	115.0 (11)
O7—W1—O12	159.7 (4)	C22—C21—C20	121.3 (13)
O12ⁱⁱ—W1—O12	88.6 (5)	C21—C22—C23	117.4 (16)
O3—W1—O1	163.4 (5)	C21—C22—C31	118.1 (15)
O4—W1—O1	88.2 (4)	C23—C22—C31	124.4 (16)
O7—W1—O1	87.8 (4)	C36—C23—C22	120.5 (15)
O12ⁱⁱ—W1—O1	72.1 (4)	C36—C23—H23A	119.7
O12—W1—O1	72.1 (4)	C22—C23—H23A	119.7
O5—W2—O7	103.3 (5)	N5—C24—C36	119.5 (17)
O5—W2—O9	101.8 (4)	N5—C24—H24A	120.3
O7—W2—O9	86.7 (4)	C36—C24—H24A	120.3
O5—W2—O14ⁱⁱ	97.7 (5)	C7—C25—C13	122.2 (14)
O7—W2—O14ⁱⁱ	92.2 (4)	C7—C25—H25A	118.9
O9—W2—O14ⁱⁱ	160.2 (4)	C13—C25—H25A	118.9
O5—W2—O11ⁱⁱ	95.9 (5)	N6—C26—C27	123.7 (13)
O7—W2—O11ⁱⁱ	160.7 (4)	N6—C26—H26A	118.2
O9—W2—O11ⁱⁱ	86.8 (4)	C27—C26—H26A	118.2
O14ⁱⁱ—W2—O11ⁱⁱ	87.8 (4)	C28—C27—C26	119.4 (15)
O5—W2—O13ⁱⁱ	166.2 (5)	C28—C27—H27A	120.3
O7—W2—O13ⁱⁱ	88.3 (4)	C26—C27—H27A	120.3
O9—W2—O13ⁱⁱ	86.2 (3)	C27—C28—C29	121.8 (13)
O14ⁱⁱ—W2—O13ⁱⁱ	74.0 (3)	C27—C28—H28A	119.1
O11ⁱⁱ—W2—O13ⁱⁱ	73.1 (3)	C29—C28—H28A	119.1
O6—W3—O2ⁱⁱ	103.8 (5)	C30—C29—C20	118.0 (14)
O6—W3—O2	102.5 (5)	C30—C29—C28	126.6 (14)
O2ⁱⁱ—W3—O2	85.6 (5)	C20—C29—C28	115.0 (12)
O6—W3—O11	96.5 (5)	C29—C30—C31	124.1 (16)
O2ⁱⁱ—W3—O11	159.7 (4)	C29—C30—H30A	117.9
O2—W3—O11	90.1 (4)	C31—C30—H30A	117.9
O6—W3—O10	96.9 (5)	C30—C31—C22	117.2 (14)
O2ⁱⁱ—W3—O10	90.0 (4)	C30—C31—H31A	121.4
O2—W3—O10	160.6 (4)	C22—C31—H31A	121.4
O11—W3—O10	87.5 (4)	C19—C32—C15	125.1 (16)
O6—W3—O13	165.8 (5)	C19—C32—N3	118.0 (15)
O2ⁱⁱ—W3—O13	87.1 (4)	C15—C32—N3	116.7 (16)
O2—W3—O13	87.2 (4)	C35—C33—C18	120.0 (17)
O11—W3—O13	73.0 (3)	C35—C33—H33A	120.0
O10—W3—O13	73.7 (4)	C18—C33—H33A	120.0
O8—W4—O9	103.7 (4)	C12—C34—C7	117.0 (15)
O8—W4—O4	104.3 (5)	C12—C34—H34A	121.5
O9—W4—O4	87.5 (4)	C7—C34—H34A	121.5
O8—W4—O10	95.1 (5)	C33—C35—C14	117.1 (18)
O9—W4—O10	90.8 (4)	C33—C35—H35A	121.5
O4—W4—O10	160.3 (4)	C14—C35—H35A	121.5
O8—W4—O14	96.0 (4)	C23—C36—C24	119.6 (17)
O9—W4—O14	160.3 (4)	C23—C36—H36A	120.2
O4—W4—O14	88.3 (4)	C24—C36—H36A	120.2
O10—W4—O14	86.8 (4)	C1—N1—C5	116.9 (10)
O8—W4—O13	164.7 (4)	C1—N1—Fe2	131.6 (8)
O9—W4—O13	87.6 (3)	C5—N1—Fe2	111.5 (8)
O4—W4—O13	86.2 (4)	C11—N2—C6	119.4 (12)
O10—W4—O13	74.2 (4)	C11—N2—Fe2	130.2 (10)
O14—W4—O13	72.9 (3)	C6—N2—Fe2	110.2 (8)
N1—C1—C2	124.0 (12)	C8—N3—C32	118.3 (13)
N1—C1—H1A	118.0	C8—N3—Fe2	132.7 (10)
C2—C1—H1A	118.0	C32—N3—Fe2	108.4 (10)
C3—C2—C1	121.8 (14)	C14—N4—C19	120.3 (13)
C3—C2—H2A	119.1	C14—N4—Fe2	128.8 (12)
C1—C2—H2A	119.1	C19—N4—Fe2	110.5 (10)
C2—C3—C4	116.7 (12)	C21—N5—C24	119.2 (13)
C2—C3—H3A	121.7	C21—N5—Fe2	113.5 (9)
C4—C3—H3A	121.7	C24—N5—Fe2	127.2 (11)
C5—C4—C13	120.5 (13)	C26—N6—C20	117.7 (11)
C5—C4—C3	117.5 (11)	C26—N6—Fe2	130.1 (9)
C13—C4—C3	122.0 (12)	C20—N6—Fe2	111.7 (8)
N1—C5—C4	123.0 (12)	Fe1—O1—W1ⁱ	119.9 (4)
N1—C5—C6	116.5 (11)	Fe1—O1—W1ⁱⁱ	119.9 (4)
C4—C5—C6	120.5 (12)	W1ⁱ—O1—W1ⁱⁱ	97.4 (5)
N2—C6—C5	117.7 (11)	Fe1—O1—W1	119.9 (4)
N2—C6—C7	123.9 (13)	W1ⁱ—O1—W1	97.4 (5)
C5—C6—C7	118.1 (13)	W1ⁱⁱ—O1—W1	97.4 (5)
C25—C7—C6	120.5 (14)	W3ⁱ—O2—W3	152.4 (5)
C25—C7—C34	124.2 (15)	W1—O4—W4	150.8 (5)
C6—C7—C34	115.3 (14)	W2—O7—W1	151.3 (5)
N3—C8—C9	121.7 (16)	W4—O9—W2	150.3 (5)
N3—C8—H8A	119.2	W4—O10—W3	115.8 (4)
C9—C8—H8A	119.2	W3—O11—W2ⁱ	116.6 (4)
C10—C9—C8	126.2 (19)	W1ⁱ—O12—W1	118.3 (5)
C10—C9—H9A	116.9	Fe1—O13—W2ⁱ	121.3 (4)
C8—C9—H9A	116.9	Fe1—O13—W4	120.8 (4)
C9—C10—C15	116.0 (18)	W2ⁱ—O13—W4	97.7 (3)
C9—C10—H10A	122.0	Fe1—O13—W3	118.3 (5)
C15—C10—H10A	122.0	W2ⁱ—O13—W3	97.2 (3)
N2—C11—C12	121.5 (14)	W4—O13—W3	96.0 (3)
N2—C11—H11A	119.2	W2ⁱ—O14—W4	115.2 (4)
C12—C11—H11A	119.2

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

Experimental details

Crystal data
Chemical formula	[Fe(C₁₂H₈N₂)₃]₃[FeW₁₂O₄₀]·2H₂O
M_r	4727.47
Crystal system, space group	Trigonal, R3
Temperature (K)	293
a, c (Å)	25.088 (5), 17.231 (5)
V (Å³)	9392 (4)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	11.51
Crystal size (mm)	0.24 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.075, 0.104
No. of measured, independent and observed [I > 2σ(I)] reflections	16084, 6154, 5557
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 1.04
No. of reflections	6154
No. of parameters	560
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.62, −1.55
Absolute structure	Flack (1983), 3713 Friedel pairs
Absolute structure parameter	−0.006 (6)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Selected bond lengths (Å) top

Fe1—O13	1.826 (8)	W2—O14ⁱ	1.954 (9)
Fe1—O1	1.833 (18)	W2—O11ⁱ	1.963 (10)
Fe2—N6	1.969 (11)	W2—O13ⁱ	2.211 (8)
Fe2—N3	1.971 (12)	W3—O6	1.742 (11)
Fe2—N1	1.972 (10)	W3—O2ⁱ	1.903 (9)
Fe2—N5	1.979 (12)	W3—O2	1.911 (9)
Fe2—N2	1.986 (11)	W3—O11	1.951 (10)
Fe2—N4	2.001 (11)	W3—O10	1.961 (10)
W1—O3	1.692 (9)	W3—O13	2.229 (10)
W1—O4	1.898 (9)	W4—O8	1.678 (9)
W1—O7	1.943 (8)	W4—O9	1.896 (8)
W1—O12	1.950 (8)	W4—O4	1.904 (9)
W1—O1	2.230 (9)	W4—O10	1.944 (11)
W2—O5	1.702 (10)	W4—O14	2.001 (9)
W2—O7	1.858 (9)	W4—O13	2.221 (8)
W2—O9	1.940 (9)

Symmetry code: (i) −x+y+1, −x+1, z.

Acknowledgements

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

References

Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry: the Bond Valence Model. Oxford University Press. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Misono, M. (1987). Cat. Rev. Sci. Eng. 29, 269–321. CrossRef CAS Web of Science Google Scholar
Pope, M. T. (1983). Heteropoly and Isopoly Oxometalates. Berlin: Springer. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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