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Acta Cryst. (2007). E63, m1963    [ doi:10.1107/S1600536807029601 ]

[N,N'-Bis(salicylidene)benzene-1,2-diaminato]iron(II)

Y.-H. Ye, Y. Han, T.-T. Chen and C.-H. Liu

Abstract top

The title complex (systematic name; {2,2'-[o-phenylenebis(nitrilomethylidyne)]diphenolato}iron(II)), [Fe(C20H14N2O2)], is a mononuclear iron(II) complex with a distorted square-planar coordination geometry. The central Fe2+ ion is four-coordinated by two O and two N atoms from a Schiff base ligand, which is obtained by condensing 1,2-diaminobenzene and two equivalents of salicylaldehyde in acetonitrile.

Comment top

Because of their interesting physical and biological properties, many iron complexes with amines or imines have structurally been studied (Liu, et al. 2004, You, et al. 2004a, 2004b, You, et al. 2005, Zhu, 2003a). When trying to synthesize iron(II) complexes with a Schiff base, condensed from salicylaldehyde and N-1,2-diaminobenzene, we isolated the title Fe(II) complex.

The title complex is a discrete iron(II) complex. The central iron(II) atom is four-coordinated by two oxygen atoms and two nitrogen atoms from a Schiff base ligand. The Schiff base acts as a tetradentate ligand. The iron(II) atom is in a distorted planar square coordination geometry.

Interestingly, all the atoms, including the hydrogen atoms, are in a plane with the mean deviation of 0.100 (2) /%A.

Related literature top

For related literature, see: Liu et al. (2004); You & Zhu (2004); You et al. (2004, 2005); Zhu et al. (2003).

Experimental top

All the solvents and chemicals were used as bought from Shanghai Chmical Company, Shanghai China, without further purification. 1,2-diaminobenzene and two equivalents of salicylaldehyde were dissolved in acetonitrile at room temperature with stirring. Five minutes later, equimolar Fe(ClO4)2·6H2O in methanol was added to the above solution, giving a clear dark green solution. Large green crystals precipitated after the solution was stood still in air for three days. These crystals were filtered, washed with acetonitrile/methanol (v:v = 1:1) for three times, and dried in air. Yield: 93%.

When using FeCl2·4H2O, Fe(NO3)2·6H2O, FeSO4·7H2O, or Fe(CH3COO)2·2H2O replaced Fe(ClO4)2·6H2O in the above reaction, the same product was isolated with the yields 65%, 46%, 70%, and 41%, respectively.

Refinement top

C-bound H atoms were included in the riding model approximation with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
{2,2'-[o-phenylenebis(nitrilomethylidyne)]diphenolato}iron(II) top
Crystal data top
Fe(C20H14N2O2)]F000 = 760
Mr = 370.18Dx = 1.564 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1882 reflections
a = 5.4675 (10) Åθ = 2.2–24.8º
b = 16.616 (4) ŵ = 0.98 mm−1
c = 17.310 (3) ÅT = 298 (2) K
V = 1572.6 (5) Å3Block, green
Z = 40.30 × 0.20 × 0.20 mm
Data collection top
Bruker APEX area-detector
diffractometer		3106 independent reflections
Radiation source: fine-focus sealed tube2404 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.069
T = 298(2) Kθmax = 26.0º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→6
Tmin = 0.759, Tmax = 0.829k = −20→20
11948 measured reflectionsl = −21→21
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054  w = 1/[σ2(Fo2) + (0.1483P)2 + 4.4994P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.170(Δ/σ)max = 0.003
S = 0.69Δρmax = 0.45 e Å−3
3106 reflectionsΔρmin = −0.27 e Å−3
226 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1279 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.09 (4)
Crystal data top
Fe(C20H14N2O2)]V = 1572.6 (5) Å3
Mr = 370.18Z = 4
Orthorhombic, P212121Mo Kα
a = 5.4675 (10) ŵ = 0.98 mm−1
b = 16.616 (4) ÅT = 298 (2) K
c = 17.310 (3) Å0.30 × 0.20 × 0.20 mm
Data collection top
Bruker APEX area-detector
diffractometer		3106 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2404 reflections with I > 2σ(I)
Tmin = 0.759, Tmax = 0.829Rint = 0.069
11948 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.170Δρmax = 0.45 e Å−3
S = 0.69Δρmin = −0.27 e Å−3
3106 reflectionsAbsolute structure: Flack (1983), 1279 Friedel pairs
226 parametersFlack parameter: −0.09 (4)
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 > 2sigma(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
xyzUiso*/Ueq
C11.1934 (12)0.3423 (4)0.1633 (4)0.0426 (15)
C21.3846 (14)0.3878 (4)0.1349 (4)0.0521 (17)
H21.48750.36730.09690.063*
C31.4207 (15)0.4650 (4)0.1642 (4)0.060 (2)
H31.55080.49580.14620.072*
C41.2652 (16)0.4965 (4)0.2199 (4)0.060 (2)
H41.29170.54810.23900.072*
C51.0714 (14)0.4514 (4)0.2471 (4)0.0541 (18)
H50.96520.47300.28360.065*
C61.0350 (13)0.3734 (4)0.2197 (4)0.0453 (15)
C70.7082 (12)0.3363 (4)0.3033 (4)0.0490 (16)
H70.73740.38460.32890.059*
C80.5157 (12)0.2872 (4)0.3314 (4)0.0488 (16)
C90.3786 (15)0.3146 (5)0.3949 (4)0.0571 (18)
H90.41830.36350.41800.069*
C100.1874 (14)0.2704 (5)0.4231 (4)0.067 (2)
H100.10150.28820.46620.080*
C110.1221 (15)0.1991 (5)0.3876 (5)0.062 (2)
H11−0.01250.17050.40570.075*
C120.2531 (14)0.1696 (5)0.3256 (4)0.0567 (19)
H120.20870.12100.30310.068*
C130.4562 (12)0.2135 (4)0.2962 (3)0.0443 (15)
C141.0161 (12)0.0988 (4)0.0916 (4)0.0430 (14)
C150.9921 (14)0.0188 (4)0.0622 (4)0.0526 (17)
H150.8568−0.01170.07640.063*
C161.1597 (16)−0.0137 (4)0.0145 (4)0.0582 (18)
H161.1385−0.0664−0.00230.070*
C171.3645 (16)0.0293 (4)−0.0106 (4)0.0609 (19)
H171.47650.0065−0.04450.073*
C181.3949 (14)0.1061 (4)0.0164 (4)0.0556 (18)
H181.53150.13530.00100.067*
C191.2225 (12)0.1426 (4)0.0677 (4)0.0479 (16)
C201.2689 (12)0.2227 (5)0.0936 (4)0.0472 (14)
H201.40900.24820.07550.057*
Fe10.85107 (14)0.22313 (5)0.18970 (4)0.0326 (2)
N10.8475 (11)0.3190 (3)0.2446 (3)0.0423 (12)
N21.1281 (10)0.2625 (3)0.1408 (3)0.0402 (11)
O10.5742 (9)0.1826 (3)0.2377 (3)0.0512 (12)
O20.8516 (10)0.1260 (3)0.1390 (3)0.0559 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.050 (4)0.040 (3)0.037 (3)0.000 (3)−0.006 (3)0.005 (3)
C20.059 (4)0.047 (4)0.050 (4)−0.006 (3)0.000 (3)0.000 (3)
C30.075 (5)0.052 (4)0.054 (4)−0.014 (4)0.001 (4)−0.001 (3)
C40.081 (5)0.048 (4)0.051 (4)−0.013 (4)0.002 (4)−0.008 (3)
C50.059 (5)0.049 (4)0.055 (4)0.002 (3)0.006 (3)−0.007 (3)
C60.049 (4)0.041 (3)0.046 (3)−0.003 (3)−0.007 (3)0.002 (3)
C70.058 (4)0.050 (3)0.039 (3)0.007 (3)−0.001 (3)−0.004 (3)
C80.049 (4)0.053 (4)0.044 (3)0.006 (3)0.001 (3)0.007 (3)
C90.066 (5)0.054 (4)0.051 (4)0.009 (4)0.010 (4)−0.003 (3)
C100.068 (5)0.081 (6)0.051 (4)0.020 (5)0.016 (4)0.007 (4)
C110.049 (4)0.068 (5)0.069 (5)0.009 (4)0.014 (4)0.015 (4)
C120.048 (4)0.058 (4)0.064 (5)0.006 (3)0.001 (3)0.007 (4)
C130.041 (3)0.045 (3)0.047 (4)0.011 (3)0.002 (3)0.008 (3)
C140.044 (4)0.049 (4)0.036 (3)0.002 (3)0.001 (3)−0.003 (3)
C150.069 (5)0.043 (3)0.046 (4)−0.005 (3)0.004 (4)−0.003 (3)
C160.080 (5)0.044 (3)0.051 (4)0.014 (4)−0.005 (4)−0.005 (3)
C170.069 (5)0.060 (4)0.054 (4)0.018 (4)0.011 (4)−0.009 (3)
C180.056 (5)0.057 (4)0.054 (4)0.002 (3)0.000 (3)−0.012 (3)
C190.046 (4)0.058 (4)0.040 (3)0.002 (3)−0.003 (3)0.001 (3)
C200.042 (3)0.055 (4)0.044 (3)−0.006 (3)−0.001 (3)−0.002 (3)
Fe10.0365 (4)0.0296 (4)0.0318 (4)0.0026 (4)0.0019 (4)0.0010 (3)
N10.047 (3)0.040 (3)0.040 (3)0.010 (3)−0.001 (3)0.001 (2)
N20.042 (3)0.042 (3)0.037 (2)−0.002 (2)0.000 (2)0.003 (2)
O10.050 (3)0.046 (2)0.057 (3)−0.002 (2)0.006 (2)−0.001 (2)
O20.060 (3)0.046 (2)0.061 (3)−0.008 (3)0.013 (3)−0.009 (2)
Geometric parameters (Å, °) top
C1—C21.381 (9)C11—H110.9300
C1—C61.403 (9)C12—C131.423 (10)
C1—N21.427 (8)C12—H120.9300
C2—C31.394 (10)C13—O11.306 (7)
C2—H20.9300C14—O21.299 (7)
C3—C41.388 (11)C14—C191.405 (9)
C3—H30.9300C14—C151.429 (9)
C4—C51.381 (10)C15—C161.346 (10)
C4—H40.9300C15—H150.9300
C5—C61.395 (9)C16—C171.398 (11)
C5—H50.9300C16—H160.9300
C6—N11.433 (8)C17—C181.368 (10)
C7—N11.302 (8)C17—H170.9300
C7—C81.417 (9)C18—C191.429 (9)
C7—H70.9300C18—H180.9300
C8—C131.406 (9)C19—C201.428 (10)
C8—C91.406 (9)C20—N21.303 (8)
C9—C101.368 (11)C20—H200.9300
C9—H90.9300Fe1—O21.838 (4)
C10—C111.382 (12)Fe1—O11.854 (5)
C10—H100.9300Fe1—N21.855 (5)
C11—C121.379 (10)Fe1—N11.856 (5)
C2—C1—C6121.0 (6)O1—C13—C12117.5 (6)
C2—C1—N2126.9 (6)C8—C13—C12118.1 (6)
C6—C1—N2112.1 (6)O2—C14—C19124.2 (6)
C1—C2—C3118.8 (7)O2—C14—C15119.0 (6)
C1—C2—H2120.6C19—C14—C15116.8 (6)
C3—C2—H2120.6C16—C15—C14121.9 (7)
C4—C3—C2120.9 (7)C16—C15—H15119.0
C4—C3—H3119.5C14—C15—H15119.0
C2—C3—H3119.5C15—C16—C17122.0 (7)
C5—C4—C3120.1 (7)C15—C16—H16119.0
C5—C4—H4119.9C17—C16—H16119.0
C3—C4—H4119.9C18—C17—C16117.9 (7)
C4—C5—C6119.9 (7)C18—C17—H17121.0
C4—C5—H5120.1C16—C17—H17121.0
C6—C5—H5120.1C17—C18—C19121.8 (7)
C5—C6—C1119.4 (6)C17—C18—H18119.1
C5—C6—N1125.8 (6)C19—C18—H18119.1
C1—C6—N1114.8 (5)C14—C19—C20122.2 (6)
N1—C7—C8125.1 (6)C14—C19—C18119.5 (6)
N1—C7—H7117.4C20—C19—C18118.3 (6)
C8—C7—H7117.4N2—C20—C19124.5 (6)
C13—C8—C9119.9 (6)N2—C20—H20117.8
C13—C8—C7121.6 (6)C19—C20—H20117.8
C9—C8—C7118.5 (7)O2—Fe1—O184.0 (2)
C10—C9—C8120.8 (7)O2—Fe1—N295.2 (2)
C10—C9—H9119.6O1—Fe1—N2179.2 (2)
C8—C9—H9119.6O2—Fe1—N1177.7 (2)
C9—C10—C11120.0 (7)O1—Fe1—N194.2 (2)
C9—C10—H10120.0N2—Fe1—N186.5 (2)
C11—C10—H10120.0C7—N1—C6121.0 (5)
C12—C11—C10121.1 (8)C7—N1—Fe1126.5 (5)
C12—C11—H11119.5C6—N1—Fe1112.3 (4)
C10—C11—H11119.5C20—N2—C1119.7 (6)
C11—C12—C13120.1 (7)C20—N2—Fe1126.1 (4)
C11—C12—H12119.9C1—N2—Fe1114.1 (4)
C13—C12—H12119.9C13—O1—Fe1127.4 (4)
O1—C13—C8124.4 (6)C14—O2—Fe1127.5 (4)
C6—C1—C2—C31.1 (10)C18—C19—C20—N2−179.3 (6)
N2—C1—C2—C3−179.8 (6)C8—C7—N1—C6178.8 (6)
C1—C2—C3—C4−1.2 (11)C8—C7—N1—Fe1−6.6 (9)
C2—C3—C4—C50.0 (12)C5—C6—N1—C7−8.0 (10)
C3—C4—C5—C61.4 (12)C1—C6—N1—C7171.2 (6)
C4—C5—C6—C1−1.5 (10)C5—C6—N1—Fe1176.7 (6)
C4—C5—C6—N1177.7 (6)C1—C6—N1—Fe1−4.1 (7)
C2—C1—C6—C50.2 (10)O2—Fe1—N1—C7−33 (6)
N2—C1—C6—C5−179.0 (6)O1—Fe1—N1—C79.0 (5)
C2—C1—C6—N1−179.0 (5)N2—Fe1—N1—C7−171.1 (5)
N2—C1—C6—N11.7 (8)O2—Fe1—N1—C6142 (6)
N1—C7—C8—C13−0.6 (10)O1—Fe1—N1—C6−176.0 (4)
N1—C7—C8—C9−179.1 (6)N2—Fe1—N1—C63.9 (4)
C13—C8—C9—C100.1 (10)C19—C20—N2—C1179.6 (6)
C7—C8—C9—C10178.6 (6)C19—C20—N2—Fe14.2 (9)
C8—C9—C10—C11−2.1 (11)C2—C1—N2—C206.4 (9)
C9—C10—C11—C122.8 (12)C6—C1—N2—C20−174.4 (6)
C10—C11—C12—C13−1.4 (11)C2—C1—N2—Fe1−177.7 (5)
C9—C8—C13—O1−179.1 (6)C6—C1—N2—Fe11.5 (6)
C7—C8—C13—O12.5 (10)O2—Fe1—N2—C20−6.0 (5)
C9—C8—C13—C121.3 (9)O1—Fe1—N2—C20−14 (18)
C7—C8—C13—C12−177.1 (6)N1—Fe1—N2—C20172.5 (5)
C11—C12—C13—O1179.7 (6)O2—Fe1—N2—C1178.5 (4)
C11—C12—C13—C8−0.7 (10)O1—Fe1—N2—C1170 (67)
O2—C14—C15—C16−178.2 (6)N1—Fe1—N2—C1−3.1 (4)
C19—C14—C15—C160.6 (10)C8—C13—O1—Fe13.1 (9)
C14—C15—C16—C17−1.4 (11)C12—C13—O1—Fe1−177.3 (5)
C15—C16—C17—C181.6 (12)O2—Fe1—O1—C13171.0 (5)
C16—C17—C18—C19−1.0 (12)N2—Fe1—O1—C13179 (100)
O2—C14—C19—C20−0.6 (10)N1—Fe1—O1—C13−7.4 (5)
C15—C14—C19—C20−179.3 (6)C19—C14—O2—Fe1−3.3 (9)
O2—C14—C19—C18178.7 (6)C15—C14—O2—Fe1175.5 (5)
C15—C14—C19—C180.0 (9)O1—Fe1—O2—C14−174.6 (6)
C17—C18—C19—C140.3 (11)N2—Fe1—O2—C145.6 (6)
C17—C18—C19—C20179.6 (7)N1—Fe1—O2—C14−132 (6)
C14—C19—C20—N20.0 (10)
Acknowledgements top

This work was supported by the Analytical Test Fund for CHL at Nanjing University.

references
References top

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