Bis{μ-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}bis­[(thio­cyanato-κN)iron(III)]

Hao, L.; Mu, C.; Kong, B.

doi:10.1107/S1600536808021892

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1034

doi:10.1107/S1600536808021892

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RETRACTED ARTICLE

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Retracted: Bis{μ-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}bis[(thiocyanato-κN)iron(III)]

Lujiang Hao,^a ^* Chunhua Mu ^b and Binbin Kong ^a

^aCollege of Food and Biological Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China, and ^bMaize Research Insitute, Shandong Academy of Agricultural Science, Jinan 250100, People's Republic of China
^*Correspondence e-mail: lujianghao001@yahoo.com.cn

(Received 28 June 2008; accepted 14 July 2008; online 16 July 2008)

The title compound, [Fe₂(C₁₆H₁₄N₂O₂)₂(NCS)₂], is isostructural with the Mn^III-containing analogue. Each Fe^III atom is chelated by a tetradentate 2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate ligand and by the N atom of a thiocyanate anion, in a square-pyramidal arrangement. The complex molecules form centrosymmetric dimers, with an Fe—O contact of 2.549 (3) Å, trans to each thiocyanate anion, completing a distorted octahedral coordination geometry.

Related literature

For related literature, see: Garnovskii et al. (1993 ); Huang et al. (2002 ); Bhadbhade & Srinivas (1993 ); Bunce et al. (1998 ). For the isostructural Mn^III-containing compound, see: Wang et al. (2008 ).

Experimental

Crystal data

[Fe₂(C₁₆H₁₄N₂O₂)₂(NCS)₂]
M_r = 380.23
Monoclinic, P 2₁ /n
a = 8.9231 (10) Å
b = 14.0779 (10) Å
c = 14.9716 (10) Å
β = 106.844 (1)°
V = 1800.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 293 (2) K
0.12 × 0.11 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.893, T_max = 0.918
12796 measured reflections
3191 independent reflections
2535 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.180
S = 1.00
3191 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.33 e Å⁻³

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/S1600536808021892/bi2293sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021892/bi2293Isup2.hkl

checkCIF report

Comment top

The design of Schiff-base complexes has received long-lasting research interest not only because of their appealing structural and topological novelty but also due to their potential medical value derived from their antiviral and the inhibition of angiogenesis (Garnovskii et al., 1993; Huang et al., 2002). The related Fe complexes with multidentate Schiff-base ligands have aroused particular interest because this metal can exhibit several oxidation states and may provide the basis of models for active sites of biological systems (Bhadbhade & Srinivas, 1993; Bunce et al., 1998).

The title compound is isostructural with its Mn^III-containing analogue (Wang et al., 2008). Each Fe^III atom is chelated by a tetradentate 2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate ligand and by the N atom of a thiocyanate anion, in a square-pyramidal arrangement. The maximum atomic deviation from the least-square plane of the equatorially located atoms, Fe1, N1, N2, O1 and O2, is 0.077 Å. The Fe—N(isothiocyanato) bond length (2.178 (4) Å) is longer than the other two Fe—N bonds (1.985 (4) and 1.988 (4) Å). The complexes form centrosymmetric dimers, with an Fe—O contact of 2.549 (3)Å trans to each thiocyanate anion, completing a distorted octahedral coordination geometry.

Related literature top

For related literature, see: Garnovskii et al. (1993); Huang et al. (2002); Bhadbhade & Srinivas (1993); Bunce et al. (1998). For the isostructural Mn^III-containing compound, see: Wang et al. (2008).

Experimental top

A mixture of iron(III) 2,4-pentanedionate (0.5 mmol), N,N'-disalicylidene-ethylenediamine (0.5 mmoL), and sodium isothiocyanate (1 mmoL) in 20 ml methanol was refluxed for two hours. The resulting solution was cooled and filtered and the filtrate was evaporated naturally at room temperature to yield brown blocks after a few days with a yield of 11%. Elemental analysis calculated: C 53.65, H 3.68, N 11.05%; found: C 53.60, H 3.64, N 11.02%.

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 asymmetric unit drawn with 30% probability displacement ellipsoids for the non-H atoms.

Bis{µ-2,2'-[ethane-1,2- diylbis(nitrilomethylidyne)]diphenolato}bis[(thiocyanato-κN)iron(III)] top

Crystal data top

[Fe₂(C₁₆H₁₄N₂O₂)₂(NCS)₂]	F(000) = 780
M_r = 380.23	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4497 reflections
a = 8.9231 (10) Å	θ = 2.4–24.4°
b = 14.0779 (10) Å	µ = 0.97 mm⁻¹
c = 14.9716 (10) Å	T = 293 K
β = 106.844 (1)°	Block, brown
V = 1800.0 (3) Å³	0.12 × 0.11 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3191 independent reflections
Radiation source: fine-focus sealed tube	2535 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.893, T_max = 0.918	k = −16→16
12796 measured reflections	l = −18→17

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.114P)² + 1.289P] where P = (F_o² + 2F_c²)/3
3191 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 1.12 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Fe₂(C₁₆H₁₄N₂O₂)₂(NCS)₂]	V = 1800.0 (3) Å³
M_r = 380.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9231 (10) Å	µ = 0.97 mm⁻¹
b = 14.0779 (10) Å	T = 293 K
c = 14.9716 (10) Å	0.12 × 0.11 × 0.09 mm
β = 106.844 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3191 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2535 reflections with I > 2σ(I)
T_min = 0.893, T_max = 0.918	R_int = 0.023
12796 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.180	H-atom parameters constrained
S = 1.00	Δρ_max = 1.12 e Å⁻³
3191 reflections	Δρ_min = −0.33 e Å⁻³
217 parameters

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
Fe1	0.64494 (7)	0.01030 (4)	0.10343 (4)	0.0586 (3)
C1	0.9422 (5)	−0.0874 (3)	0.2499 (3)	0.0612 (10)
C2	0.5250 (4)	−0.1763 (3)	0.0554 (3)	0.0563 (9)
C3	0.5503 (5)	−0.2621 (3)	0.0151 (4)	0.0690 (11)
H3	0.6005	−0.2622	−0.0314	0.083*
C4	0.5012 (7)	−0.3464 (4)	0.0441 (5)	0.0905 (15)
H4	0.5190	−0.4032	0.0171	0.109*
C5	0.4258 (7)	−0.3475 (4)	0.1126 (5)	0.103 (2)
H5	0.3939	−0.4049	0.1318	0.124*
C6	0.3974 (7)	−0.2631 (4)	0.1529 (4)	0.0895 (16)
H6	0.3438	−0.2638	0.1977	0.107*
C7	0.4493 (5)	−0.1778 (3)	0.1262 (3)	0.0665 (11)
C8	0.4150 (6)	−0.0914 (4)	0.1685 (3)	0.0757 (13)
H8	0.3416	−0.0948	0.2016	0.091*
C9	0.4311 (10)	0.0777 (5)	0.2043 (5)	0.117 (2)
H9A	0.3827	0.0625	0.2528	0.141*
H9B	0.3577	0.1145	0.1563	0.141*
C10	0.5833 (10)	0.1335 (4)	0.2450 (4)	0.109 (2)
H10A	0.5603	0.1986	0.2577	0.130*
H10B	0.6451	0.1046	0.3027	0.130*
C11	0.7504 (8)	0.2036 (4)	0.1629 (4)	0.0936 (18)
H11	0.7469	0.2578	0.1977	0.112*
C12	0.8444 (6)	0.2076 (3)	0.1012 (4)	0.0801 (13)
C13	0.8633 (5)	0.1309 (3)	0.0459 (3)	0.0684 (11)
C14	0.9632 (6)	0.1410 (4)	−0.0104 (4)	0.0900 (16)
H14	0.9784	0.0901	−0.0464	0.108*
C15	1.0394 (7)	0.2261 (6)	−0.0128 (7)	0.125 (3)
H15	1.1052	0.2319	−0.0507	0.150*
C16	1.0191 (9)	0.3026 (6)	0.0405 (7)	0.136 (3)
H16	1.0706	0.3596	0.0382	0.163*
C17	0.9219 (9)	0.2942 (5)	0.0971 (5)	0.123 (3)
H17	0.9076	0.3457	0.1326	0.148*
N1	0.8171 (5)	−0.0695 (3)	0.2098 (3)	0.0785 (10)
N2	0.6685 (6)	0.1309 (3)	0.1752 (3)	0.0796 (11)
N3	0.4771 (5)	−0.0113 (3)	0.1639 (3)	0.0721 (10)
O1	0.5684 (3)	−0.09420 (17)	0.02262 (18)	0.0553 (6)
O2	0.7880 (3)	0.0489 (2)	0.0418 (2)	0.0660 (7)
S1	1.11963 (15)	−0.11760 (11)	0.30804 (10)	0.0858 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0672 (4)	0.0522 (4)	0.0613 (4)	0.0061 (2)	0.0262 (3)	−0.0013 (2)
C1	0.075 (3)	0.048 (2)	0.065 (2)	0.0050 (19)	0.028 (2)	0.0093 (17)
C2	0.053 (2)	0.050 (2)	0.066 (2)	0.0008 (16)	0.0163 (17)	0.0063 (17)
C3	0.064 (2)	0.051 (2)	0.090 (3)	0.0037 (18)	0.020 (2)	0.005 (2)
C4	0.087 (3)	0.055 (3)	0.120 (4)	0.000 (2)	0.016 (3)	0.011 (3)
C5	0.104 (4)	0.074 (4)	0.120 (5)	−0.018 (3)	0.014 (4)	0.040 (3)
C6	0.084 (3)	0.096 (4)	0.087 (3)	−0.019 (3)	0.023 (3)	0.034 (3)
C7	0.056 (2)	0.079 (3)	0.064 (2)	−0.002 (2)	0.0153 (19)	0.021 (2)
C8	0.075 (3)	0.095 (4)	0.068 (3)	0.011 (3)	0.038 (2)	0.021 (2)
C9	0.149 (6)	0.116 (5)	0.122 (5)	0.046 (5)	0.093 (5)	−0.003 (4)
C10	0.177 (7)	0.081 (4)	0.078 (3)	0.032 (4)	0.052 (4)	−0.008 (3)
C11	0.127 (5)	0.056 (3)	0.070 (3)	0.007 (3)	−0.015 (3)	−0.014 (2)
C12	0.084 (3)	0.067 (3)	0.071 (3)	−0.011 (2)	−0.006 (2)	−0.001 (2)
C13	0.051 (2)	0.065 (3)	0.079 (3)	−0.0061 (18)	0.002 (2)	0.012 (2)
C14	0.059 (3)	0.089 (4)	0.120 (4)	−0.006 (2)	0.023 (3)	0.024 (3)
C15	0.075 (4)	0.118 (6)	0.164 (7)	−0.038 (4)	0.006 (4)	0.045 (5)
C16	0.104 (5)	0.109 (6)	0.156 (7)	−0.057 (5)	−0.024 (5)	0.032 (5)
C17	0.129 (6)	0.082 (4)	0.117 (5)	−0.037 (4)	−0.032 (4)	−0.001 (3)
N1	0.077 (3)	0.075 (2)	0.082 (3)	0.017 (2)	0.020 (2)	0.012 (2)
N2	0.113 (3)	0.063 (2)	0.057 (2)	0.019 (2)	0.015 (2)	−0.0085 (16)
N3	0.080 (2)	0.079 (3)	0.069 (2)	0.0157 (19)	0.040 (2)	0.0052 (17)
O1	0.0636 (15)	0.0482 (13)	0.0608 (14)	0.0017 (11)	0.0284 (12)	0.0024 (11)
O2	0.0625 (16)	0.0566 (16)	0.084 (2)	−0.0024 (13)	0.0289 (14)	−0.0006 (14)
S1	0.0658 (7)	0.0956 (9)	0.0968 (9)	0.0082 (6)	0.0248 (6)	0.0267 (7)

Geometric parameters (Å, º) top

Fe1—O2	1.860 (3)	C9—N3	1.500 (7)
Fe1—O1	1.902 (3)	C9—C10	1.534 (11)
Fe1—N3	1.985 (4)	C9—H9A	0.970
Fe1—N2	1.988 (4)	C9—H9B	0.970
Fe1—N1	2.178 (4)	C10—N2	1.459 (7)
C1—N1	1.132 (5)	C10—H10A	0.970
C1—S1	1.627 (5)	C10—H10B	0.970
C2—O1	1.355 (4)	C11—N2	1.302 (7)
C2—C7	1.412 (6)	C11—C12	1.418 (8)
C2—C3	1.397 (6)	C11—H11	0.930
C3—C4	1.378 (7)	C12—C13	1.401 (7)
C3—H3	0.930	C12—C17	1.412 (8)
C4—C5	1.380 (9)	C13—O2	1.328 (5)
C4—H4	0.930	C13—C14	1.400 (7)
C5—C6	1.388 (9)	C14—C15	1.383 (9)
C5—H5	0.930	C14—H14	0.930
C6—C7	1.387 (7)	C15—C16	1.384 (13)
C6—H6	0.930	C15—H15	0.930
C7—C8	1.445 (7)	C16—C17	1.382 (12)
C8—N3	1.267 (6)	C16—H16	0.930
C8—H8	0.930	C17—H17	0.930

O2—Fe1—O1	94.72 (12)	H9A—C9—H9B	108.7
O2—Fe1—N3	171.11 (14)	N2—C10—C9	106.7 (5)
O1—Fe1—N3	89.55 (14)	N2—C10—H10A	110.4
O2—Fe1—N2	92.21 (17)	C9—C10—H10A	110.4
O1—Fe1—N2	165.26 (15)	N2—C10—H10B	110.4
N3—Fe1—N2	81.92 (19)	C9—C10—H10B	110.4
O2—Fe1—N1	94.22 (14)	H10A—C10—H10B	108.6
O1—Fe1—N1	96.51 (14)	N2—C11—C12	125.9 (5)
N3—Fe1—N1	93.03 (16)	N2—C11—H11	117.0
N2—Fe1—N1	95.94 (16)	C12—C11—H11	117.0
N1—C1—S1	177.6 (4)	C13—C12—C17	119.7 (6)
O1—C2—C7	122.3 (4)	C13—C12—C11	123.4 (4)
O1—C2—C3	118.8 (4)	C17—C12—C11	116.9 (6)
C7—C2—C3	118.9 (4)	O2—C13—C14	117.6 (5)
C2—C3—C4	120.2 (5)	O2—C13—C12	123.4 (4)
C2—C3—H3	119.9	C14—C13—C12	119.0 (5)
C4—C3—H3	119.9	C13—C14—C15	120.5 (7)
C5—C4—C3	120.7 (5)	C13—C14—H14	119.8
C5—C4—H4	119.6	C15—C14—H14	119.7
C3—C4—H4	119.6	C16—C15—C14	120.8 (8)
C4—C5—C6	120.2 (5)	C16—C15—H15	119.6
C4—C5—H5	119.9	C14—C15—H15	119.6
C6—C5—H5	119.9	C17—C16—C15	119.8 (6)
C7—C6—C5	119.8 (5)	C17—C16—H16	120.1
C7—C6—H6	120.1	C15—C16—H16	120.1
C5—C6—H6	120.1	C16—C17—C12	120.2 (8)
C2—C7—C6	120.1 (5)	C16—C17—H17	119.9
C2—C7—C8	121.6 (4)	C12—C17—H17	119.9
C6—C7—C8	118.2 (4)	C1—N1—Fe1	151.7 (4)
N3—C8—C7	125.0 (4)	C11—N2—C10	120.8 (5)
N3—C8—H8	117.5	C11—N2—Fe1	124.8 (4)
C7—C8—H8	117.5	C10—N2—Fe1	114.4 (4)
N3—C9—C10	105.9 (5)	C8—N3—C9	123.1 (5)
N3—C9—H9A	110.6	C8—N3—Fe1	124.1 (3)
C10—C9—H9A	110.6	C9—N3—Fe1	112.8 (4)
N3—C9—H9B	110.6	C2—O1—Fe1	121.1 (2)
C10—C9—H9B	110.6	C13—O2—Fe1	130.0 (3)

Experimental details

Crystal data
Chemical formula	[Fe₂(C₁₆H₁₄N₂O₂)₂(NCS)₂]
M_r	380.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.9231 (10), 14.0779 (10), 14.9716 (10)
β (°)	106.844 (1)
V (Å³)	1800.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.12 × 0.11 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.893, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	12796, 3191, 2535
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.180, 1.00
No. of reflections	3191
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.33

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

Acknowledgements

This work is supported by the Natural Science Foundation of Shandong Province (grant No. Y2007D39).

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