metal-organic papers
m1046
You and Zhu [Fe2(C17H16ClN2O2)2] DOI: 10.1107/S1600536804015727 Acta Cryst.(2004). E60, m1046±m1048 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
A dinuclear Schiff base iron(III) complex with
the ligand
N
,
N
000-bis(2-oxidophenylmethylene-imino)propane-1,2-diamine
Zhong-Lu You and Hai-Liang Zhu*³
Department of Chemistry, Fuyang Normal College, Fuyang, Anhui 236041, People's Republic of China, and Department of Chemistry, Lanzhou University, Lanzhou 730000, People's Republic of China
³ Present address: Department of Chemistry, Wuhan University of Science and Engineering, Wuhan 430073, People's Republic of China.
Correspondence e-mail: hailiang_zhu@163.com
Key indicators
Single-crystal X-ray study T= 298 K
Mean(C±C) = 0.012 AÊ Rfactor = 0.086 wRfactor = 0.224
Data-to-parameter ratio = 13.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The centrosymmetric title compound, bis[-N,N0-bis(
-2-oxidophenylmethyleneimino)propane-1,2-diaminato(3ÿ )]-iron(III), [Fe2(C17H16ClN2O2)2], is a dinuclear iron(III)
complex. Each FeIIIatom is six-coordinated by two N atoms
and three O atoms from two Schiff base ligands, and one Cl atom, giving an approximately octahedral coordination environment.
Comment
Investigations into the magnetic properties of molecular-based materials containing a polynuclear assembly have become a fascinating subject in the ®eld of condensed matter physics and materials chemistry (Dalai et al., 2002; Bhaduri et al., 2003). Much attention has been focused on coordination complexes with novel magnetic properties, which may have potentially useful applications in materials science (Rayet al., 2003). The prime strategy for designing these molecular materials is using a suitable bridging ligand, which determines the nature of the magnetic interactions (Koner et al., 2003). Recently, we have reported a few Schiff base complexes (You, Linet al., 2003; You, Xionget al., 2004; You, Chenet al., 2004). As an extension of our work on the structural characterization of Schiff base complexes, the title dinuclear iron(III) complex, (I), is reported here
.
The asymmetric unit consists of one-half of (I), with the other half generated by a crystallographic inversion centre (Fig. 1). The two FeIII ions of the dinuclear complex are
bridged by two -Oÿ(phenolate O atoms) ions. The
octahe-dral coordination of each FeIIIion is completed by a
tetra-Schiff base ligand and a terminal Clÿion. The two Clÿligands
are exactlytransabout the Fe Fe vector, due to the inversion centre.
The longer Fe1ÐO1(ÿx, 1ÿy, 1ÿz) bond (Table 1), compared with the Fe1ÐO1 bond, is indicative of a greater
transin¯uence of the Clÿcompared to the Schiff base N atom.
The Fe1ÐCl1 bond is a little longer than the corresponding distance of 2.254 (2) AÊ observed in another iron(III) complex (Abrahamset al., 1996). The Fe1ÐO2 bond is a little shorter than the corresponding distance of 1.926 (6) AÊ observed in a similar Schiff base iron(III) complex (You, Zhu & Liu, 2004). The Fe1ÐO1 bond is much longer than Fe1ÐO2, due to coordination of atom O1 to atom Fe1(ÿx, 1ÿy, 1ÿz). The average FeÐN(imine) bond length of 2.100 (6) AÊ is a little less than the corresponding value of 2.138 (7) AÊ observed in the same complex (You, Zhu & Liu, 2004).
The three trans angles at the FeIII atom lie in the range
159.5 (2)±171.27 (13)(Table 1). The other angles subtended
at the FeIIIatom are close to 90, varying from 76.10 (19) to
107.90 (19), indicating a somewhat distorted octahedral
geometry of the FeIIIatom. The FeIIIatom is 0.182 (3) AÊ out of
the plane de®ned by the four chelating atoms, N1/N2/O2/O1. Atoms C8 and C10 deviate from the Fe1/N1/N2 plane by 0.413 (12) andÿ0.234 (12) AÊ, respectively. The dihedral angle between the two benzene rings is 24.6 (3). As a result of the
centre of symmetry, the Fe2O2core of (I) is perfectly planar.
Experimental
Salicylaldehyde and 1,2-diaminopropane were obtained commer-cially and were used without further puri®cation. Salicylaldehyde (0.2 mmol, 24.2 mg) and 1,2-diaminopropane (0.1 mmol, 7.4 mg) were dissolved in ethanol (10 ml). The mixture was stirred for 1 h to give a clear yellow solution of L(0.1 mmol), whereLis (2-oxido-phenylmethyleneimino)propane-1,2-diamine. To this solution of L
was added an ethanol solution (10 ml) of FeCl3H2O (0.1 mmol,
18.0 mg) with stirring. After keeping the resulting solution in air for 12 d, brown block-shaped crystals of (I) were formed at the bottom of the vessel on slow evaporation of the solvent. The crystals were isolated, washed three times with ethanol and dried in a vacuum desiccator using anhydrous CaCl2 (yield 81.2%). Analysis, found:
C 54.5, H 4.5, N 7.3%; calculated for C34H32Cl2Fe2N4O4: C 54.9, H 4.3,
N 7.5%.
Crystal data
[Fe2(C17H16ClN2O2)2]
Mr= 743.24
Monoclinic, P21=c
a= 10.937 (8) AÊ
b= 20.406 (14) AÊ
c= 7.484 (5) AÊ = 101.864 (11) V= 1635 (2) AÊ3
Z= 2
Dx= 1.510 Mg mÿ3
MoKradiation Cell parameters from 2307
re¯ections = 2.2±22.3
= 1.10 mmÿ1
T= 298 (2) K Block, brown 0.280.220.14 mm
Data collection
Siemens SMART CCD area-detector diffractometer !scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.749,Tmax= 0.862
8018 measured re¯ections
2838 independent re¯ections 1515 re¯ections withI> 2(I)
Rint= 0.176
max= 25.0
h=ÿ13!12
k=ÿ24!23
l=ÿ8!6
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.086
wR(F2) = 0.224
S= 0.94 2838 re¯ections 209 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.1021P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 1.30 e AÊÿ3
min=ÿ0.61 e AÊÿ3
metal-organic papers
Acta Cryst.(2004). E60, m1046±m1048 You and Zhu [Fe2(C17H16ClN2O2)2]
m1047
Figure 2
The crystal packing of (I), viewed along theaaxis. All H atoms have been omitted for clarity.
Figure 1
Table 1
Selected geometric parameters (AÊ,).
Fe1ÐO2 1.886 (5)
Fe1ÐO1 1.977 (4)
Fe1ÐN2 2.089 (6)
Fe1ÐN1 2.111 (6)
Fe1ÐO1i 2.205 (4)
Fe1ÐCl1 2.306 (2)
O1ÐFe1i 2.205 (4)
O2ÐFe1ÐO1 107.90 (19) O2ÐFe1ÐN2 87.7 (2) O1ÐFe1ÐN2 159.5 (2) O2ÐFe1ÐN1 163.3 (2) O1ÐFe1ÐN1 85.0 (2) N2ÐFe1ÐN1 77.4 (3) O2ÐFe1ÐO1i 87.92 (18)
O1ÐFe1ÐO1i 76.10 (19)
N2ÐFe1ÐO1i 91.81 (19)
N1ÐFe1ÐO1i 85.0 (2)
O2ÐFe1ÐCl1 96.35 (15) O1ÐFe1ÐCl1 95.31 (14) N2ÐFe1ÐCl1 95.95 (17) N1ÐFe1ÐCl1 92.83 (18) O1iÐFe1ÐCl1 171.27 (13)
Symmetry code: (i)ÿx;1ÿy;1ÿz.
All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with CÐH distances in the range 0.93±0.97 AÊ, and withUiso(H) = 1.2 or 1.5 timesUeq(C). An
unassigned maximum residual density of 1.30 e AÊÿ3was observed
0.64 AÊ from atom H10A. The minimum residual density was observed 1.10 AÊ from atom Fe1. The value ofRint, 0.176, is probably due to the
poor diffraction quality of the crystal.
Data collection:SMART(Siemens, 1996); cell re®nement:SAINT
(Siemens, 1996); data reduction: SAINT; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:
SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.
The authors thank the Education Of®ce of Anhui Province, People's Republic of China, for research grant No. 2004kj300zd.
References
Abrahams, B. F., Hoskins, B. F. & Robson, R. (1996).Acta Cryst.C52, 2766± 2768.
Bhaduri, S., Tasiopoulos, A. J., Bolcar, M. A., Abboud, K. A., Streib, W. E. & Christou, G. (2003).Inorg. Chem.42, 1483±1492.
Dalai, S., Mukherjee, P. S., Drew, M. G. B., Lu, T.-H. & Chaudhuri, N. R. (2002).Inorg. Chim. Acta,335, 85±90.
Koner, S., Saha, S., Okamoto, K.-I. & Tuchagues, J.-P. (2003).Inorg. Chem.42, 4668±4672.
Ray, M. S., Mukhopadhyay, G., Drew, M. G. B., Lu, T.-H., Chaudhuri, S. & Ghosh, A. (2003).Inorg. Chem. Commun.6, 961±965.
Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of
GoÈttingen, Germany.
Sheldrick, G. M. (1997b).SHELXTL.Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Systems Inc., Madison, Wisconsin, USA.
You, Z.-L., Chen, B., Zhu, H.-L. & Liu, W.-S. (2004).Acta Cryst.E60, m884± m886.
You, Z.-L., Lin, Y.-S., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L. (2003).Acta Cryst.
E59, m1025±m1027.
You, Z.-L., Xiong, Z.-D., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L. (2004).Acta Cryst.E60, m79±m81.
You, Z.-L., Zhu, H.-L. & Liu, W.-S. (2004). Acta Cryst. E60, m794± m796.
metal-organic papers
supporting information
sup-1 Acta Cryst. (2004). E60, m1046–m1048
supporting information
Acta Cryst. (2004). E60, m1046–m1048 [https://doi.org/10.1107/S1600536804015727]
A dinuclear Schiff base iron(III) complex with the ligand
N
,
N
′
-bis(2-oxido-phenylmethyleneimino)propane-1,2-diamine
Zhong-Lu You and Hai-Liang Zhu
bis[µ-N,N′-bis(µ-2-oxidophenylmethyleneamino)propane-1,2- diaminato(3-)]iron(III)
Crystal data
[Fe2(C17H16ClN2O2)2] Mr = 743.24
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 10.937 (8) Å
b = 20.406 (14) Å
c = 7.484 (5) Å
β = 101.864 (11)°
V = 1635 (2) Å3 Z = 2
F(000) = 764
Dx = 1.510 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2307 reflections
θ = 2.2–22.3°
µ = 1.10 mm−1 T = 298 K Block, brown
0.28 × 0.22 × 0.14 mm
Data collection
Siemens SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.749, Tmax = 0.862
8018 measured reflections 2838 independent reflections 1515 reflections with I > 2σ(I)
Rint = 0.176
θmax = 25.0°, θmin = 2.2° h = −13→12
k = −24→23
l = −8→6
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.086 wR(F2) = 0.224 S = 0.94 2838 reflections 209 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.1021P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 1.30 e Å−3
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sup-2 Acta Cryst. (2004). E60, m1046–m1048
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)
x y z Uiso*/Ueq
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sup-3 Acta Cryst. (2004). E60, m1046–m1048
C16 −0.4374 (11) 0.2875 (5) 0.5535 (14) 0.093 (3) H16 −0.4974 0.2604 0.5869 0.111* C17 −0.3146 (11) 0.2839 (4) 0.6412 (13) 0.086 (3) H17 −0.2919 0.2544 0.7370 0.103*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Fe1 0.0553 (7) 0.0381 (6) 0.0474 (7) 0.0048 (5) 0.0107 (5) 0.0065 (4) Cl1 0.0952 (17) 0.0569 (12) 0.0636 (13) 0.0098 (11) 0.0222 (11) −0.0064 (9) O1 0.045 (3) 0.035 (2) 0.049 (3) 0.006 (2) 0.012 (2) 0.0064 (19) O2 0.043 (3) 0.046 (3) 0.056 (3) −0.004 (2) 0.006 (2) 0.005 (2) N1 0.057 (4) 0.061 (4) 0.049 (4) 0.011 (3) 0.007 (3) 0.006 (3) N2 0.089 (5) 0.035 (3) 0.044 (4) 0.011 (3) 0.012 (3) 0.016 (3) C1 0.046 (5) 0.051 (4) 0.066 (5) 0.005 (4) 0.015 (4) −0.007 (4) C2 0.043 (4) 0.040 (4) 0.052 (4) 0.001 (3) 0.014 (3) −0.007 (3) C3 0.057 (5) 0.052 (5) 0.045 (4) −0.005 (4) 0.008 (3) −0.004 (3) C4 0.072 (6) 0.075 (5) 0.055 (5) −0.015 (5) 0.019 (4) 0.002 (4) C5 0.054 (5) 0.111 (7) 0.065 (6) −0.016 (5) 0.026 (4) −0.014 (5) C6 0.051 (5) 0.072 (6) 0.072 (6) −0.006 (4) 0.008 (4) −0.008 (4) C7 0.051 (5) 0.067 (5) 0.055 (5) 0.016 (4) 0.002 (4) −0.001 (4) C8 0.066 (6) 0.093 (7) 0.059 (5) 0.033 (5) −0.001 (4) 0.017 (5) C9 0.102 (10) 0.180 (14) 0.165 (12) −0.005 (9) 0.005 (8) 0.053 (11) C10 0.114 (8) 0.060 (6) 0.078 (6) 0.009 (6) 0.017 (5) 0.031 (5) C11 0.123 (8) 0.041 (4) 0.058 (5) −0.004 (5) 0.026 (5) 0.012 (4) C12 0.085 (7) 0.046 (4) 0.053 (5) −0.004 (4) 0.008 (4) 0.002 (4) C13 0.059 (5) 0.046 (4) 0.050 (4) −0.006 (4) 0.018 (4) −0.010 (3) C14 0.061 (5) 0.059 (5) 0.070 (5) −0.011 (4) 0.028 (4) −0.011 (4) C15 0.074 (6) 0.067 (6) 0.110 (8) −0.022 (5) 0.032 (5) −0.018 (5) C16 0.105 (9) 0.089 (7) 0.089 (7) −0.043 (7) 0.034 (6) 0.010 (6) C17 0.122 (9) 0.061 (6) 0.081 (7) −0.021 (6) 0.039 (6) 0.019 (5)
Geometric parameters (Å, º)
Fe1—O2 1.886 (5) C6—H6 0.93 Fe1—O1 1.977 (4) C7—H7 0.93 Fe1—N2 2.089 (6) C8—C10 1.489 (12) Fe1—N1 2.111 (6) C8—C9 1.515 (13) Fe1—O1i 2.205 (4) C8—H8 0.98
Fe1—Cl1 2.306 (2) C9—H9A 0.96 O1—C2 1.345 (8) C9—H9B 0.96 O1—Fe1i 2.205 (4) C9—H9C 0.96
supporting information
sup-4 Acta Cryst. (2004). E60, m1046–m1048
C1—C2 1.404 (10) C13—C14 1.391 (10) C1—C7 1.484 (10) C14—C15 1.382 (11) C2—C3 1.390 (9) C14—H14 0.93 C3—C4 1.346 (10) C15—C16 1.342 (13)
C3—H3 0.93 C15—H15 0.93
C4—C5 1.403 (12) C16—C17 1.371 (12)
C4—H4 0.93 C16—H16 0.93
C5—C6 1.362 (11) C17—H17 0.93 C5—H5 0.93
O2—Fe1—O1 107.90 (19) N1—C7—C1 124.7 (7) O2—Fe1—N2 87.7 (2) N1—C7—H7 117.6 O1—Fe1—N2 159.5 (2) C1—C7—H7 117.6 O2—Fe1—N1 163.3 (2) N1—C8—C10 106.5 (7) O1—Fe1—N1 85.0 (2) N1—C8—C9 118.4 (8) N2—Fe1—N1 77.4 (3) C10—C8—C9 102.9 (8) O2—Fe1—O1i 87.92 (18) N1—C8—H8 109.5
O1—Fe1—O1i 76.10 (19) C10—C8—H8 109.5
N2—Fe1—O1i 91.81 (19) C9—C8—H8 109.5
N1—Fe1—O1i 85.0 (2) C8—C9—H9A 109.5
O2—Fe1—Cl1 96.35 (15) C8—C9—H9B 109.5 O1—Fe1—Cl1 95.31 (14) H9A—C9—H9B 109.5 N2—Fe1—Cl1 95.95 (17) C8—C9—H9C 109.5 N1—Fe1—Cl1 92.83 (18) H9A—C9—H9C 109.5 O1i—Fe1—Cl1 171.27 (13) H9B—C9—H9C 109.5
C2—O1—Fe1 121.5 (4) N2—C10—C8 108.0 (6) C2—O1—Fe1i 116.9 (4) N2—C10—H10A 110.1
Fe1—O1—Fe1i 103.90 (18) C8—C10—H10A 110.1
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sup-5 Acta Cryst. (2004). E60, m1046–m1048
C6—C5—H5 120.3 C17—C16—H16 121.1 C4—C5—H5 120.3 C16—C17—C12 122.2 (8) C5—C6—C1 120.8 (7) C16—C17—H17 118.9 C5—C6—H6 119.6 C12—C17—H17 118.9 C1—C6—H6 119.6