Bis(μ-2-{bis­[(2-oxidobenzyl­idene)amino]­meth­yl}phenolato)bis­[(tetra­hydro­furan)­samarium(III)] tetra­hydro­furan disolvate

Li Li; Yuan Zhou; Fugen Yuan

doi:10.1107/S1600536812015759

. 2012 Apr 18;68(Pt 5):m603–m604. doi: 10.1107/S1600536812015759

Bis(μ-2-{bis[(2-oxidobenzylidene)amino]methyl}phenolato)bis[(tetrahydrofuran)samarium(III)] tetrahydrofuran disolvate

Li Li ^a, Yuan Zhou ^a, Fugen Yuan ^a,^*

PMCID: PMC3344343 PMID: 22590109

Abstract

In the centrosymmetric binuclear complex of the title solvate, [Sm₂(C₂₁H₁₅N₂O₃)₂(C₄H₈O)₂]·2C₄H₈O, the Sm^III is coordinated in a distorted monocapped octahedral geometry by four O atoms and two N atoms from two tridentate deprotonated 2-{bis[(2-oxidobenzylidene)amino]methyl}phenolate ligands and an O atom of a tetrahydrofuran (THF) molecule. The Sm⋯Sm distance in the complex is 3.8057 (4) Å. Parts of the coordinating THF molecule are disordered over two sets of sites in a 0.56 (3):0.44 (3) ratio. The complex and solvent molecules are linked into a three-dimensional structure via C—H⋯O hydrogen-bonding interactions.

Related literature

For general reports on the tripodal ligand 2-bis-(salicylidieneamino)methylphenol, see: Nabulsi et al. (1988 ▶); Achim et al. (2001 ▶); Yu et al. (1991 ▶); Snyder et al.(1989 ▶); Chaudhuri et al. (1998 ▶); Illingsworth et al. (2002 ▶). For related structures, see: Howell et al. (1998 ▶); Liu et al. (1998 ▶); Dubé et al. (1998 ▶). For ionic radii, see: Shannon (1976 ▶).

Experimental

Crystal data

[Sm₂(C₂₁H₁₅N₂O₃)₂(C₄H₈O)₂]·2C₄H₈O
M _r = 1275.84
Monoclinic,
a = 11.7184 (11) Å
b = 21.378 (2) Å
c = 11.1464 (11) Å
β = 99.058 (1)°
V = 2757.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.17 mm⁻¹
T = 293 K
0.23 × 0.18 × 0.16 mm

Data collection

Rigaku Rapid I CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.635, T _max = 0.723
23697 measured reflections
6291 independent reflections
5362 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.084
S = 1.01
6291 reflections
353 parameters
42 restraints
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: CrystalClear (Rigaku, 2004 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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: publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015759/wm2610sup1.cif

e-68-0m603-sup1.cif^{(24.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015759/wm2610Isup2.hkl

e-68-0m603-Isup2.hkl^{(307.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O5	0.93	2.56	3.450 (7)	159
C21—H21A⋯O5ⁱ	0.93	2.56	3.424 (6)	155
C22—H22B⋯O3ⁱⁱ	0.97	2.50	3.079 (6)	118

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

Acknowledgments

Financial support from the Jiangsu Key Laboratory for Environment Functional Materials and from a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) is gratefully acknowledged.

supplementary crystallographic information

Comment

Since the tripodal schiff base 2-bis-(salicylidiene-amino)-methyl-phenol (salmp) has been characterized by Nabulsi (1988), it has been used as a chelating ligand for numerous transition metals, including Fe^II, Fe^III, Mn^II, Mn^III, Ti^III, V^III, Cr^III, Co^III and Zr^IV (Achim et al., 2001; Yu et al., 1991; Snyder et al., 1989; Chaudhuri et al.,1998; Illingsworth et al., 2002). However, its coordination behaviour with respect to lanthanide elements has not yet reported to the best of our knowledge. Herein we reported a new dinuclear compound [Sm₂(C₂₁H₁₅N₂O₃)₂(C₄H₈O)₂]^.2(C₄H₈O), (I).

The molecular structure of compound (I) is presented in Fig. 1. The Sm—O bond lengths of 2. 213 (2) Å to the terminal aryloxide and of 2.369 (2) Å to the bridging aryloxide are similar compared to those in the analogous complex [{Sm(api)}₂] (H₃api = 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazoline) (2.282 (4) and 2.388 (3) Å, respectively) (Howell et al., 1998) when the difference of the ionic radii is taken into account. In the title compound, Sm has a coordination number of seven resulting in a distorted mono-capped octahedral coordination geometry for the metal (Fig. 2), whereas in the other structure the coordination number is eight. The radii of seven and eight-coordinate Sm^III are 1.160 and 1.219 Å (Shannon, 1976), respectively. The bond lengths of Sm—N (2.616 (2) to 2.623 (2) Å) are consistent with those in [(η⁵-(C₅H₅)Sm(µ-OC₂₀H₂₀N₂O)]₂.(µ-THF)^.2THF (2.55 (5) to 2.67 (7) Å) (Liu et al., 1998). The Sm···Sm distance in (I) is 3.8057 (4) Å, which is a little shorter than that in [(3,5-Bu^t₄salophen)Sm(OH)]₄^.4toluene (3.9023 (8) Å) (Dubé et al., 1998). Two Sm atoms are bridged by aryloxide groups forming a Sm₂(µ-O)₂ planar rhomb with an acute angles O(1)—Sm(1)—O(1 A) of 73.11 (8)° and an obtuse angle Sm(1)—O(1)—Sm(1 A) of 106.89 (8)°.

The crystal packing is stabilized by C—H···O hydrogen bonds (Table 1, Fig. 3), including an intra-molecular hydrogen bond (C22—H22B···O3 ) and inter-molecular hydrogen bonds (C4—H4A···O5 and C21—H21A···O5).

Experimental

2-bis-(salicylidiene-amino)-methyl-phenol was prepared according to the literature procedure (Illingsworth et al., 2002). To a suspension of SmCl₃ (0.536 g, 2.09 mmol) in 20 ml THF was added a THF solution of Ph₂NK (10.3 ml, 6.27 mmol). The mixture was stirred for 1 d at room temperature. After centrifugation, a clear solution of Sm(NPh₂)₃ was obtained. To this solution was added the tripodal Schiff base (0.724 g, 2.09 mmol) and then stirred for another day. The resulting solution was concentrated and added with a proper volume of 1,2-dimethyloxyethane. Yellow crystals of [Sm₂(C₂₅H₂₃N₂O₄)].2(C₄H₈O) were produced in a yield of ca 50%. m.p. > 250°C, IR(KBr, cm^-1) 3391(w), 3043(w), 2974(w), 2866(w), 1610(s), 1541(s), 1468(s), 1445(s), 1406(s), 1316(s), 1267(m), 1189(w), 1148(m), 1123(w), 1026(w), 1011(m), 968(w), 914(w), 887(m), 852(w), 822(w), 749(s), 691(m), 578(w), 560(w), 452(w).