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Acta Cryst. (2007). E63, m2033    [ doi:10.1107/S1600536807031066 ]

trans-Bis{2-[3-(cyclohexylamino)propyliminomethyl]phenolato-[kappa]2N,O}bis(thiocyanato-[kappa]N)iron(II)

K. Chen, Y.-L. Zhang, M.-Q. Feng and C.-H. Liu

Abstract top

The title complex, [Fe(NCS)2(C32H46N4O2)2], is a mononuclear iron(II) complex with a distorted octahedral coordination geometry and the central Fe2+ ion, located on an inversion centre, is coordinated by four N atoms and two O atoms from two Schiff-base ligands and two thiocyanate anions. The Schiff base was obtained by condensation of equimolar amounts of salicylaldehyde and N-cyclohexyl-1,3-diaminopropane in acetonitrile. The crystal structure involves intermolecular N-H...O and N-H...S hydrogen bonds.

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 & Zhu, 2004, You et al., 2004, 2005; Zhu, Xia et al., 2003). When trying to synthesize iron(II) complexes with a Schiff base, condensed from salicylaldehyde and N-cyclohexyl-1,3-diaminopropane, we isolated the title complex.

The title complex is a discrete iron(II) complex, which isisostructural to those of the nickel (Zhu, Zeng et al., 2003), the cobalt (You et al., 2003; Yue et al., 2005), and the copper complexes (Nie, 2004). The central iron(II) atom is six-coordinated by two oxygen atoms and two nitrogen atoms from two Schiff base ligands, and by two nitrogen atoms from two thiocyanate anions. The Schiff base acts as a bidentate ligand with the amine nitrogen atom uncoordinated. The iron(II) atom is in a distorted octahedral coordination geometry and is located on an inversion centre.

In the crystal structure, the intramolecular (N2—H2B···O1i, symmetry code -x, -y + 1, -z + 2) and intermolecular (N2—H2A···S1ii, symmetry code -x, -y + 2, -z + 2) hydrogen bonds link the molecules to form one-dimensional chains along b axis. As expected, the cyclohexyl groups in the complex are in chair conformations.

Related literature top

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

Experimental top

In a similar procedure to that of Zhu, Zeng et al. (2003) the title complex was prepared. Yield 43%.

Refinement top

C– and N-bound H atoms were included in the riding model approximation with C—H = 0.93–0.97 Å and N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(C,N).

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. [Symmetry code for unlabelled atoms: -x, -y + 1, -z + 2.]
trans-Bis{2-[3-(cyclohexylamino)propyliminomethyl]phenolato- κ2N,O}bis(thiocyanato-κN)iron(II) top
Crystal data top
[Fe(NCS)2(C32H46N4O2)2]F(000) = 736
Mr = 692.75Dx = 1.311 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.912 (7) ÅCell parameters from 1885 reflections
b = 7.797 (5) Åθ = 3.4–27.0°
c = 20.778 (13) ŵ = 0.59 mm−1
β = 96.899 (13)°T = 293 K
V = 1755.1 (19) Å3Prism, red
Z = 20.30 × 0.20 × 0.15 mm
Data collection top
Bruker APEX area-detector
diffractometer		2975 independent reflections
Radiation source: fine-focus sealed tube1337 reflections with I > 2σ(I)
graphiteRint = 0.101
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→12
Tmin = 0.843, Tmax = 0.917k = −9→7
7131 measured reflectionsl = −12→24
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.198H-atom parameters constrained
S = 0.85 w = 1/[σ2(Fo2) + (0.0924P)2]
where P = (Fo2 + 2Fc2)/3
2975 reflections(Δ/σ)max = 0.001
205 parametersΔρmax = 0.51 e Å−3
0 restraintsΔρmin = −0.56 e Å−3
Crystal data top
[Fe(NCS)2(C32H46N4O2)2]V = 1755.1 (19) Å3
Mr = 692.75Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.912 (7) ŵ = 0.59 mm−1
b = 7.797 (5) ÅT = 293 K
c = 20.778 (13) Å0.30 × 0.20 × 0.15 mm
β = 96.899 (13)°
Data collection top
Bruker APEX area-detector
diffractometer		2975 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1337 reflections with I > 2σ(I)
Tmin = 0.843, Tmax = 0.917Rint = 0.101
7131 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.198Δρmax = 0.51 e Å−3
S = 0.85Δρmin = −0.56 e Å−3
2975 reflectionsAbsolute structure: ?
205 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Fe10.00000.50001.00000.0428 (4)
N10.0966 (4)0.6470 (7)1.0731 (3)0.0574 (14)
N20.2901 (4)0.7562 (6)0.9480 (2)0.0560 (14)
H2A0.29190.87020.94150.067*
H2B0.21090.72210.93970.067*
N3−0.1560 (5)0.6574 (7)1.0106 (3)0.0685 (16)
O1−0.0527 (4)0.3417 (5)1.0693 (2)0.0609 (12)
S1−0.32276 (16)0.8260 (2)1.08020 (10)0.0731 (6)
C10.1231 (5)0.5937 (10)1.1321 (4)0.0647 (19)
H10.16270.67191.16140.078*
C20.0982 (5)0.4266 (10)1.1577 (3)0.0590 (18)
C30.0147 (5)0.3076 (9)1.1257 (3)0.0578 (17)
C40.0015 (6)0.1509 (9)1.1568 (3)0.0629 (18)
H4−0.05150.06861.13660.075*
C50.0640 (7)0.1157 (11)1.2159 (4)0.073 (2)
H50.05340.01011.23530.088*
C60.1438 (7)0.2356 (12)1.2477 (4)0.081 (2)
H60.18560.21201.28840.097*
C70.1591 (6)0.3859 (11)1.2186 (3)0.069 (2)
H70.21260.46631.23980.083*
C80.1343 (6)0.8239 (9)1.0603 (3)0.0663 (19)
H8A0.10640.89951.09270.080*
H8B0.09440.85961.01820.080*
C90.2736 (6)0.8421 (9)1.0616 (3)0.073 (2)
H9A0.29160.95891.04970.087*
H9B0.31170.82411.10570.087*
C100.3333 (6)0.7209 (9)1.0174 (3)0.0674 (19)
H10A0.42230.73371.02490.081*
H10B0.31340.60351.02750.081*
C110.3644 (5)0.6695 (8)0.8995 (3)0.0569 (17)
H110.37470.54820.91140.068*
C120.4912 (6)0.7514 (11)0.9035 (4)0.095 (3)
H12A0.53500.73440.94640.114*
H12B0.48280.87380.89580.114*
C130.5644 (7)0.6705 (14)0.8526 (4)0.111 (3)
H13A0.64330.72840.85360.134*
H13B0.58050.55100.86350.134*
C140.4981 (7)0.6816 (11)0.7869 (4)0.092 (3)
H14A0.54510.62310.75680.110*
H14B0.49020.80100.77400.110*
C150.3731 (7)0.6032 (12)0.7838 (4)0.098 (3)
H15A0.38150.48070.79120.118*
H15B0.32950.62040.74080.118*
C160.2983 (6)0.6799 (11)0.8336 (3)0.083 (2)
H16A0.28040.79900.82280.099*
H16B0.22040.61930.83220.099*
C17−0.2235 (6)0.7290 (8)1.0391 (3)0.0538 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0333 (7)0.0486 (8)0.0487 (7)−0.0031 (5)0.0143 (5)−0.0059 (6)
N10.045 (3)0.065 (4)0.066 (4)−0.003 (3)0.021 (3)−0.013 (3)
N20.046 (3)0.053 (3)0.070 (4)−0.006 (2)0.010 (3)−0.007 (3)
N30.054 (4)0.068 (4)0.084 (4)0.005 (3)0.012 (3)−0.011 (3)
O10.052 (3)0.069 (3)0.063 (3)−0.014 (2)0.009 (2)−0.002 (2)
S10.0683 (12)0.0581 (12)0.0974 (15)0.0042 (9)0.0287 (10)−0.0034 (11)
C10.050 (4)0.084 (6)0.061 (5)−0.001 (4)0.010 (4)−0.027 (4)
C20.044 (4)0.070 (5)0.065 (5)−0.006 (3)0.017 (4)−0.015 (4)
C30.037 (4)0.075 (5)0.065 (5)0.008 (3)0.021 (3)−0.008 (4)
C40.050 (4)0.063 (5)0.079 (5)0.005 (3)0.019 (4)0.004 (4)
C50.062 (5)0.086 (6)0.076 (5)0.015 (4)0.022 (4)0.019 (5)
C60.070 (5)0.100 (7)0.073 (5)0.016 (5)0.014 (4)0.004 (5)
C70.052 (4)0.094 (6)0.061 (5)0.005 (4)0.005 (4)−0.011 (4)
C80.074 (5)0.055 (5)0.073 (5)−0.004 (3)0.026 (4)−0.015 (4)
C90.077 (5)0.067 (5)0.077 (5)−0.023 (4)0.021 (4)−0.009 (4)
C100.053 (4)0.084 (6)0.065 (5)−0.009 (4)0.006 (3)−0.001 (4)
C110.050 (4)0.049 (4)0.075 (5)0.004 (3)0.022 (3)−0.002 (3)
C120.045 (4)0.140 (8)0.101 (6)−0.007 (4)0.020 (4)−0.031 (6)
C130.055 (5)0.165 (10)0.119 (8)−0.012 (5)0.032 (5)−0.043 (7)
C140.082 (6)0.086 (6)0.116 (7)−0.012 (4)0.046 (5)−0.005 (5)
C150.072 (6)0.137 (8)0.089 (6)0.007 (5)0.021 (5)−0.029 (6)
C160.062 (5)0.118 (7)0.072 (5)0.011 (4)0.021 (4)−0.013 (5)
C170.059 (4)0.041 (4)0.061 (4)−0.001 (3)0.006 (3)−0.001 (3)
Geometric parameters (Å, °) top
Fe1—O1i2.031 (4)C7—H70.9300
Fe1—O12.031 (4)C8—C91.524 (9)
Fe1—N1i2.085 (5)C8—H8A0.9700
Fe1—N12.085 (5)C8—H8B0.9700
Fe1—N32.132 (6)C9—C101.519 (9)
Fe1—N3i2.132 (6)C9—H9A0.9700
N1—C11.294 (8)C9—H9B0.9700
N1—C81.472 (8)C10—H10A0.9700
N2—C101.488 (7)C10—H10B0.9700
N2—C111.524 (7)C11—C161.472 (9)
N2—H2A0.9000C11—C121.517 (8)
N2—H2B0.9000C11—H110.9800
N3—C171.143 (7)C12—C131.535 (10)
O1—C31.333 (7)C12—H12A0.9700
S1—C171.643 (8)C12—H12B0.9700
C1—C21.445 (10)C13—C141.468 (11)
C1—H10.9300C13—H13A0.9700
C2—C71.393 (9)C13—H13B0.9700
C2—C31.410 (9)C14—C151.488 (9)
C3—C41.398 (9)C14—H14A0.9700
C4—C51.359 (9)C14—H14B0.9700
C4—H40.9300C15—C161.516 (9)
C5—C61.389 (10)C15—H15A0.9700
C5—H50.9300C15—H15B0.9700
C6—C71.339 (9)C16—H16A0.9700
C6—H60.9300C16—H16B0.9700
O1i—Fe1—O1180.000 (1)C9—C8—H8B109.1
O1i—Fe1—N1i88.8 (2)H8A—C8—H8B107.8
O1—Fe1—N1i91.2 (2)C10—C9—C8115.5 (5)
O1i—Fe1—N191.2 (2)C10—C9—H9A108.4
O1—Fe1—N188.8 (2)C8—C9—H9A108.4
N1i—Fe1—N1180.000 (1)C10—C9—H9B108.4
O1i—Fe1—N391.2 (2)C8—C9—H9B108.4
O1—Fe1—N388.8 (2)H9A—C9—H9B107.5
N1i—Fe1—N393.0 (2)N2—C10—C9111.2 (6)
N1—Fe1—N387.0 (2)N2—C10—H10A109.4
O1i—Fe1—N3i88.8 (2)C9—C10—H10A109.4
O1—Fe1—N3i91.2 (2)N2—C10—H10B109.4
N1i—Fe1—N3i87.0 (2)C9—C10—H10B109.4
N1—Fe1—N3i93.0 (2)H10A—C10—H10B108.0
N3—Fe1—N3i180.000 (3)C16—C11—C12111.6 (6)
C1—N1—C8115.9 (6)C16—C11—N2110.5 (5)
C1—N1—Fe1123.3 (5)C12—C11—N2109.4 (5)
C8—N1—Fe1120.8 (4)C16—C11—H11108.4
C10—N2—C11115.2 (5)C12—C11—H11108.4
C10—N2—H2A108.5N2—C11—H11108.4
C11—N2—H2A108.5C11—C12—C13109.7 (6)
C10—N2—H2B108.5C11—C12—H12A109.7
C11—N2—H2B108.5C13—C12—H12A109.7
H2A—N2—H2B107.5C11—C12—H12B109.7
C17—N3—Fe1155.0 (5)C13—C12—H12B109.7
C3—O1—Fe1124.8 (4)H12A—C12—H12B108.2
N1—C1—C2127.4 (6)C14—C13—C12112.1 (7)
N1—C1—H1116.3C14—C13—H13A109.2
C2—C1—H1116.3C12—C13—H13A109.2
C7—C2—C3119.3 (7)C14—C13—H13B109.2
C7—C2—C1116.7 (6)C12—C13—H13B109.2
C3—C2—C1124.0 (7)H13A—C13—H13B107.9
O1—C3—C4120.3 (6)C13—C14—C15111.3 (7)
O1—C3—C2122.7 (7)C13—C14—H14A109.4
C4—C3—C2117.0 (7)C15—C14—H14A109.4
C5—C4—C3121.8 (7)C13—C14—H14B109.4
C5—C4—H4119.1C15—C14—H14B109.4
C3—C4—H4119.1H14A—C14—H14B108.0
C4—C5—C6120.7 (8)C14—C15—C16112.0 (7)
C4—C5—H5119.6C14—C15—H15A109.2
C6—C5—H5119.6C16—C15—H15A109.2
C7—C6—C5118.7 (8)C14—C15—H15B109.2
C7—C6—H6120.7C16—C15—H15B109.2
C5—C6—H6120.7H15A—C15—H15B107.9
C6—C7—C2122.5 (7)C11—C16—C15111.7 (6)
C6—C7—H7118.7C11—C16—H16A109.3
C2—C7—H7118.7C15—C16—H16A109.3
N1—C8—C9112.6 (5)C11—C16—H16B109.3
N1—C8—H8A109.1C15—C16—H16B109.3
C9—C8—H8A109.1H16A—C16—H16B107.9
N1—C8—H8B109.1N3—C17—S1178.1 (6)
O1i—Fe1—N1—C1−164.6 (5)C1—C2—C3—O1−2.5 (9)
O1—Fe1—N1—C115.4 (5)C7—C2—C3—C4−2.1 (9)
N1i—Fe1—N1—C1−126 (94)C1—C2—C3—C4179.7 (5)
N3—Fe1—N1—C1104.3 (5)O1—C3—C4—C5−176.5 (6)
N3i—Fe1—N1—C1−75.7 (5)C2—C3—C4—C51.3 (9)
O1i—Fe1—N1—C818.1 (4)C3—C4—C5—C60.2 (10)
O1—Fe1—N1—C8−161.9 (4)C4—C5—C6—C7−0.9 (11)
N1i—Fe1—N1—C857 (93)C5—C6—C7—C20.1 (11)
N3—Fe1—N1—C8−73.0 (4)C3—C2—C7—C61.5 (10)
N3i—Fe1—N1—C8107.0 (4)C1—C2—C7—C6179.8 (6)
O1i—Fe1—N3—C17−136.2 (13)C1—N1—C8—C971.6 (7)
O1—Fe1—N3—C1743.8 (13)Fe1—N1—C8—C9−110.9 (5)
N1i—Fe1—N3—C17135.0 (13)N1—C8—C9—C1054.0 (8)
N1—Fe1—N3—C17−45.0 (13)C11—N2—C10—C9167.1 (5)
N3i—Fe1—N3—C17−89 (10)C8—C9—C10—N265.0 (8)
O1i—Fe1—O1—C3−77 (100)C10—N2—C11—C16167.1 (6)
N1i—Fe1—O1—C3148.0 (5)C10—N2—C11—C12−69.7 (7)
N1—Fe1—O1—C3−32.0 (5)C16—C11—C12—C13−54.8 (9)
N3—Fe1—O1—C3−119.1 (5)N2—C11—C12—C13−177.4 (6)
N3i—Fe1—O1—C360.9 (5)C11—C12—C13—C1455.3 (10)
C8—N1—C1—C2−179.3 (6)C12—C13—C14—C15−55.6 (11)
Fe1—N1—C1—C23.3 (9)C13—C14—C15—C1654.6 (10)
N1—C1—C2—C7166.0 (6)C12—C11—C16—C1555.0 (9)
N1—C1—C2—C3−15.8 (10)N2—C11—C16—C15176.9 (6)
Fe1—O1—C3—C4−151.8 (4)C14—C15—C16—C11−54.5 (10)
Fe1—O1—C3—C230.4 (8)Fe1—N3—C17—S1−81 (19)
C7—C2—C3—O1175.7 (5)
Symmetry codes: (i) −x, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O1i0.901.792.683 (6)175
N2—H2A···S1ii0.902.443.337 (6)173
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+2, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O1i0.901.792.683 (6)175
N2—H2A···S1ii0.902.443.337 (6)173
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+2, −z+2.
Acknowledgements top

The work was supported by the Analytical Test Fund for Dr Chang-Hong Liu in Nanjing University.

references
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