Bis(2-{5-[(2-carb­oxy­phen­yl)sulfanylmeth­yl]-2,4-dimethyl­benzyl­sulfan­yl}benzoato-κ2 O,O′)bis­(pyridine-κN)iron(II)

Yu-Min Xu; Tuo-Ping Hu

doi:10.1107/S1600536810054619

. 2011 Jan 12;67(Pt 2):m159. doi: 10.1107/S1600536810054619

Bis(2-{5-[(2-carboxyphenyl)sulfanylmethyl]-2,4-dimethylbenzylsulfanyl}benzoato-κ² O,O′)bis(pyridine-κN)iron(II)

Yu-Min Xu ^a,^*, Tuo-Ping Hu ^a

PMCID: PMC3051472 PMID: 21522840

Abstract

The title compound, [Fe(C₂₄H₂₁O₄S₂)₂(C₅H₅N)₂], has 2 symmetry. The Fe^II cation is located on a twofold rotation axis and is O,O′-chelated by two 2-{5-[(2-carboxyphenyl)sulfanylmethyl]-2,4-dimethylbenzylsulfanyl}benzoate anions and further coordinated by two pyridine ligands in a distorted octahedral geometry. In the anion, the terminal benzene rings are oriented at dihedral angles of 63.81 (14) and 84.50 (14)° with respect to the central benzene ring. Intermolecular O—H⋯O and C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For applications of multithioether ligands in inorganic chemistry, see: Li et al. (2002 ▶). For structures of related complexes with multithioether ligands, see: Bu et al. (2002 ▶); Alcock et al. (1978 ▶) and with carboxylate ligands, see: Dai et al. (2008 ▶).

Experimental

Crystal data

[Fe(C₂₄H₂₁O₄S₂)₂(C₅H₅N)₂]
M _r = 1089.10
Orthorhombic,
a = 16.987 (5) Å
b = 9.635 (3) Å
c = 31.982 (10) Å
V = 5234 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.928, T _max = 0.951
29090 measured reflections
5950 independent reflections
3431 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.114
S = 1.00
5950 reflections
336 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810054619/xu5127sup1.cif

e-67-0m159-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054619/xu5127Isup2.hkl

e-67-0m159-Isup2.hkl^{(291.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Fe1—O1	2.412 (2)
Fe1—O2	2.0400 (18)
Fe1—N1	2.100 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O1ⁱ	0.96 (4)	1.77 (4)	2.702 (3)	162 (4)
C16—H16A⋯O3ⁱⁱ	0.93	2.54	3.421 (3)	158

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The author is grateful for funding support from the Natural Science foundation of Shanxi province, China (2007011033).

supplementary crystallographic information

Comment

Multithioether ligands possess unusual potential for structure control in inorganic chemistry (Li et al., 2002). Some crystal structures of complexes with multithioether ligands have been reported previously (Bu et al., 2002; Alcock et al., 1978). The title compound with the flexible multithioether ligand was obtained in preparing of metal-organic framework (MOF) compounds.

In (I), the central Fe²⁺ ion is coordinated by four oxygen atoms from the carboxylate group of the ligand and two nitrogen atoms from the pyridine molecule in a distorted octahedron (Fig. 1).

The asymmetry unit contains one ligand, one pyridine molecule, and half Fe²⁺ ion sitting on the twofold axis, with the other part being generated by the symmetry operation of C<ι>₂.

Strong H-bondings are observed between the O-H group of the carboxylate group and O2 in the crystal structure (Table 2).

Experimental

2,4-Bis(2-(benzylacid)thiophenylmethyl)-1,5-dimethylbenze (2 mg, 4.6 mmol) and FeSO₄ (4 mg, 26.3 mmol) were dissolved in 1 ml mixed solution of H2O, DMF and MeOH (5:3:2), then 1 drop pyridine was added. The mixed solution was sealed into a Pyrex glass tube. The mixed solution was heated at 363 K for 60 h, and then cooled down to room temperature over 17 h. Orange crystals were obtained from the reaction mixture.