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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1034.
Published online 2008 July 16. doi:  10.1107/S1600536808021892
PMCID: PMC2961955

This article has been retractedRetraction in: Acta Crystallogr Sect E Struct Rep Online. 2012 April 01; 68(Pt 4): e10    See also: PMC Retraction Policy

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

Abstract

The title compound, [Fe2(C16H14N2O2)2(NCS)2], is isostructural with the MnIII-containing analogue. Each FeIII 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 [triangle]); Huang et al. (2002 [triangle]); Bhadbhade & Srinivas (1993 [triangle]); Bunce et al. (1998 [triangle]). For the isostructural MnIII-containing compound, see: Wang et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1034-scheme1.jpg

Experimental

Crystal data

  • [Fe2(C16H14N2O2)2(NCS)2]
  • M r = 380.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1034-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.180
  • S = 1.00
  • 3191 reflections
  • 217 parameters
  • H-atom parameters constrained
  • Δρmax = 1.12 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021892/bi2293sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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 MnIII-containing analogue (Wang et al., 2008). Each FeIII 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.

Experimental

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%.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93 Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The asymmetric unit drawn with 30% probability displacement ellipsoids for the non-H atoms.

Crystal data

[Fe2(C16H14N2O2)2(NCS)2]F000 = 780
Mr = 380.23Dx = 1.403 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4497 reflections
a = 8.9231 (10) Åθ = 2.4–24.4º
b = 14.0779 (10) ŵ = 0.97 mm1
c = 14.9716 (10) ÅT = 293 (2) K
β = 106.844 (1)ºBlock, brown
V = 1800.0 (3) Å30.12 × 0.11 × 0.09 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer3191 independent reflections
Radiation source: fine-focus sealed tube2535 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 293(2) Kθmax = 25.3º
[var phi] and ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Bruker, 2001)h = −10→10
Tmin = 0.893, Tmax = 0.918k = −16→16
12796 measured reflectionsl = −18→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.180  w = 1/[σ2(Fo2) + (0.114P)2 + 1.289P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
3191 reflectionsΔρmax = 1.12 e Å3
217 parametersΔρmin = −0.33 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Fe10.64494 (7)0.01030 (4)0.10343 (4)0.0586 (3)
C10.9422 (5)−0.0874 (3)0.2499 (3)0.0612 (10)
C20.5250 (4)−0.1763 (3)0.0554 (3)0.0563 (9)
C30.5503 (5)−0.2621 (3)0.0151 (4)0.0690 (11)
H30.6005−0.2622−0.03140.083*
C40.5012 (7)−0.3464 (4)0.0441 (5)0.0905 (15)
H40.5190−0.40320.01710.109*
C50.4258 (7)−0.3475 (4)0.1126 (5)0.103 (2)
H50.3939−0.40490.13180.124*
C60.3974 (7)−0.2631 (4)0.1529 (4)0.0895 (16)
H60.3438−0.26380.19770.107*
C70.4493 (5)−0.1778 (3)0.1262 (3)0.0665 (11)
C80.4150 (6)−0.0914 (4)0.1685 (3)0.0757 (13)
H80.3416−0.09480.20160.091*
C90.4311 (10)0.0777 (5)0.2043 (5)0.117 (2)
H9A0.38270.06250.25280.141*
H9B0.35770.11450.15630.141*
C100.5833 (10)0.1335 (4)0.2450 (4)0.109 (2)
H10A0.56030.19860.25770.130*
H10B0.64510.10460.30270.130*
C110.7504 (8)0.2036 (4)0.1629 (4)0.0936 (18)
H110.74690.25780.19770.112*
C120.8444 (6)0.2076 (3)0.1012 (4)0.0801 (13)
C130.8633 (5)0.1309 (3)0.0459 (3)0.0684 (11)
C140.9632 (6)0.1410 (4)−0.0104 (4)0.0900 (16)
H140.97840.0901−0.04640.108*
C151.0394 (7)0.2261 (6)−0.0128 (7)0.125 (3)
H151.10520.2319−0.05070.150*
C161.0191 (9)0.3026 (6)0.0405 (7)0.136 (3)
H161.07060.35960.03820.163*
C170.9219 (9)0.2942 (5)0.0971 (5)0.123 (3)
H170.90760.34570.13260.148*
N10.8171 (5)−0.0695 (3)0.2098 (3)0.0785 (10)
N20.6685 (6)0.1309 (3)0.1752 (3)0.0796 (11)
N30.4771 (5)−0.0113 (3)0.1639 (3)0.0721 (10)
O10.5684 (3)−0.09420 (17)0.02262 (18)0.0553 (6)
O20.7880 (3)0.0489 (2)0.0418 (2)0.0660 (7)
S11.11963 (15)−0.11760 (11)0.30804 (10)0.0858 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Fe10.0672 (4)0.0522 (4)0.0613 (4)0.0061 (2)0.0262 (3)−0.0013 (2)
C10.075 (3)0.048 (2)0.065 (2)0.0050 (19)0.028 (2)0.0093 (17)
C20.053 (2)0.050 (2)0.066 (2)0.0008 (16)0.0163 (17)0.0063 (17)
C30.064 (2)0.051 (2)0.090 (3)0.0037 (18)0.020 (2)0.005 (2)
C40.087 (3)0.055 (3)0.120 (4)0.000 (2)0.016 (3)0.011 (3)
C50.104 (4)0.074 (4)0.120 (5)−0.018 (3)0.014 (4)0.040 (3)
C60.084 (3)0.096 (4)0.087 (3)−0.019 (3)0.023 (3)0.034 (3)
C70.056 (2)0.079 (3)0.064 (2)−0.002 (2)0.0153 (19)0.021 (2)
C80.075 (3)0.095 (4)0.068 (3)0.011 (3)0.038 (2)0.021 (2)
C90.149 (6)0.116 (5)0.122 (5)0.046 (5)0.093 (5)−0.003 (4)
C100.177 (7)0.081 (4)0.078 (3)0.032 (4)0.052 (4)−0.008 (3)
C110.127 (5)0.056 (3)0.070 (3)0.007 (3)−0.015 (3)−0.014 (2)
C120.084 (3)0.067 (3)0.071 (3)−0.011 (2)−0.006 (2)−0.001 (2)
C130.051 (2)0.065 (3)0.079 (3)−0.0061 (18)0.002 (2)0.012 (2)
C140.059 (3)0.089 (4)0.120 (4)−0.006 (2)0.023 (3)0.024 (3)
C150.075 (4)0.118 (6)0.164 (7)−0.038 (4)0.006 (4)0.045 (5)
C160.104 (5)0.109 (6)0.156 (7)−0.057 (5)−0.024 (5)0.032 (5)
C170.129 (6)0.082 (4)0.117 (5)−0.037 (4)−0.032 (4)−0.001 (3)
N10.077 (3)0.075 (2)0.082 (3)0.017 (2)0.020 (2)0.012 (2)
N20.113 (3)0.063 (2)0.057 (2)0.019 (2)0.015 (2)−0.0085 (16)
N30.080 (2)0.079 (3)0.069 (2)0.0157 (19)0.040 (2)0.0052 (17)
O10.0636 (15)0.0482 (13)0.0608 (14)0.0017 (11)0.0284 (12)0.0024 (11)
O20.0625 (16)0.0566 (16)0.084 (2)−0.0024 (13)0.0289 (14)−0.0006 (14)
S10.0658 (7)0.0956 (9)0.0968 (9)0.0082 (6)0.0248 (6)0.0267 (7)

Geometric parameters (Å, °)

Fe1—O21.860 (3)C9—N31.500 (7)
Fe1—O11.902 (3)C9—C101.534 (11)
Fe1—N31.985 (4)C9—H9A0.970
Fe1—N21.988 (4)C9—H9B0.970
Fe1—N12.178 (4)C10—N21.459 (7)
C1—N11.132 (5)C10—H10A0.970
C1—S11.627 (5)C10—H10B0.970
C2—O11.355 (4)C11—N21.302 (7)
C2—C71.412 (6)C11—C121.418 (8)
C2—C31.397 (6)C11—H110.930
C3—C41.378 (7)C12—C131.401 (7)
C3—H30.930C12—C171.412 (8)
C4—C51.380 (9)C13—O21.328 (5)
C4—H40.930C13—C141.400 (7)
C5—C61.388 (9)C14—C151.383 (9)
C5—H50.930C14—H140.930
C6—C71.387 (7)C15—C161.384 (13)
C6—H60.930C15—H150.930
C7—C81.445 (7)C16—C171.382 (12)
C8—N31.267 (6)C16—H160.930
C8—H80.930C17—H170.930
O2—Fe1—O194.72 (12)H9A—C9—H9B108.7
O2—Fe1—N3171.11 (14)N2—C10—C9106.7 (5)
O1—Fe1—N389.55 (14)N2—C10—H10A110.4
O2—Fe1—N292.21 (17)C9—C10—H10A110.4
O1—Fe1—N2165.26 (15)N2—C10—H10B110.4
N3—Fe1—N281.92 (19)C9—C10—H10B110.4
O2—Fe1—N194.22 (14)H10A—C10—H10B108.6
O1—Fe1—N196.51 (14)N2—C11—C12125.9 (5)
N3—Fe1—N193.03 (16)N2—C11—H11117.0
N2—Fe1—N195.94 (16)C12—C11—H11117.0
N1—C1—S1177.6 (4)C13—C12—C17119.7 (6)
O1—C2—C7122.3 (4)C13—C12—C11123.4 (4)
O1—C2—C3118.8 (4)C17—C12—C11116.9 (6)
C7—C2—C3118.9 (4)O2—C13—C14117.6 (5)
C2—C3—C4120.2 (5)O2—C13—C12123.4 (4)
C2—C3—H3119.9C14—C13—C12119.0 (5)
C4—C3—H3119.9C13—C14—C15120.5 (7)
C5—C4—C3120.7 (5)C13—C14—H14119.8
C5—C4—H4119.6C15—C14—H14119.7
C3—C4—H4119.6C16—C15—C14120.8 (8)
C4—C5—C6120.2 (5)C16—C15—H15119.6
C4—C5—H5119.9C14—C15—H15119.6
C6—C5—H5119.9C17—C16—C15119.8 (6)
C7—C6—C5119.8 (5)C17—C16—H16120.1
C7—C6—H6120.1C15—C16—H16120.1
C5—C6—H6120.1C16—C17—C12120.2 (8)
C2—C7—C6120.1 (5)C16—C17—H17119.9
C2—C7—C8121.6 (4)C12—C17—H17119.9
C6—C7—C8118.2 (4)C1—N1—Fe1151.7 (4)
N3—C8—C7125.0 (4)C11—N2—C10120.8 (5)
N3—C8—H8117.5C11—N2—Fe1124.8 (4)
C7—C8—H8117.5C10—N2—Fe1114.4 (4)
N3—C9—C10105.9 (5)C8—N3—C9123.1 (5)
N3—C9—H9A110.6C8—N3—Fe1124.1 (3)
C10—C9—H9A110.6C9—N3—Fe1112.8 (4)
N3—C9—H9B110.6C2—O1—Fe1121.1 (2)
C10—C9—H9B110.6C13—O2—Fe1130.0 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2293).

References

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