Trichloridotris{N-[phen­yl(pyridin-2-yl)­methyl­idene]hydroxyl­amine-κ2 N,N′}samarium(III)

Tao Lei; Wenqian Chen; Yanmei Chen; Bin Hu; Yahong Li

doi:10.1107/S1600536812008100

. 2012 Feb 29;68(Pt 3):m344–m345. doi: 10.1107/S1600536812008100

Trichloridotris{N-[phenyl(pyridin-2-yl)methylidene]hydroxylamine-κ² N,N′}samarium(III)

Tao Lei ^a, Wenqian Chen ^b, Yanmei Chen ^b, Bin Hu ^a, Yahong Li ^a,^b,^*

PMCID: PMC3297284 PMID: 22412474

Abstract

The Sm^III ion in the title compound, [SmCl₃(C₁₂H₁₀N₂O)₃], shows a coordination number of nine with a slightly distorted tricapped trigonal prismatic geometry based on a Cl₃N₆ donor set. The molecular structure is stabilized by three intramolecular O—H⋯Cl hydrogen bonds.

Related literature

For related literature on the phenyl-2-pyridyl ketone oxime ligand chelating one metal centre, see: Yin & Liu (2009 ▶); Yan & Liu (2009 ▶); Xiang et al. (2006 ▶); Milios et al. (2004 ▶). For the phenyl-2-pyridyl ketone oxime ligand bridging two metals, see: Liu et al.. (2011 ▶); Holynska & Dehnen (2011 ▶); Papatriantafyllopoulou et al. (2007 ▶). For the applications of phenyl-2-pyridyl ketone oxime complexes, see: Korpi et al. (2005 ▶); Stamatatos et al. (2006 ▶).

Experimental

Crystal data

[SmCl₃(C₁₂H₁₀N₂O)₃]
M _r = 851.37
Triclinic,
a = 8.6415 (17) Å
b = 10.422 (2) Å
c = 19.771 (4) Å
α = 92.18 (3)°
β = 94.47 (3)°
γ = 92.62 (3)°
V = 1771.8 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.93 mm⁻¹
T = 293 K
0.30 × 0.17 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.595, T _max = 0.802
32032 measured reflections
8553 independent reflections
7752 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.068
S = 1.04
8553 reflections
445 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812008100/tk5061sup1.cif

e-68-0m344-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008100/tk5061Isup2.hkl

e-68-0m344-Isup2.hkl^{(418.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sm1—N1	2.578 (2)
Sm1—N2	2.634 (2)
Sm1—N6	2.649 (2)
Sm1—N4	2.668 (2)
Sm1—N5	2.673 (2)
Sm1—N3	2.713 (2)
Sm1—Cl3	2.7501 (9)
Sm1—Cl4	2.7658 (9)
Sm1—Cl2	2.8114 (10)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl3	0.82	2.22	2.960 (2)	150
O2—H2⋯Cl4	0.82	2.18	2.920 (2)	150
O3—H3⋯Cl2	0.82	2.18	2.920 (2)	149

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Acknowledgments

The authors appreciate the financial support of the Hundreds of Talents Program (grant No. 2005012) of CAS, the Natural Science Foundation of China (grant No. 20872105), ‘Qinglan Project’ of Jiangsu Province (grant No. Bu109805) and the Open Project of the Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education of Lanzhou University (grant No. LZUMMM2010003).

supplementary crystallographic information

Comment

Phenyl-2-pyridyl ketone oxime is a ligand used in the synthesis of metal-organic complexes. It usually binds to metals in a bidentate fashion, either chelating one metal centre (Yin & Liu, 2009; Yan & Liu, 2009; Xiang et al., 2006; Milios et al., 2004) or bridging two metals (Liu et al., 2011; Holynska & Dehnen, 2011; Papatriantafyllopoulou et al., 2007). Its complexes find applications in diverse areas such as functional supramolecular design, magnetic materials and catalysis (Korpi et al., 2005; Stamatatos et al., 2006). However, these complexes are focused on transition metals. Here we report a new samarium complex, which is formed by the reaction of SmCl₃.6H₂O with phenyl-2-pyridyl ketone oxime. The compound consists of three N,N-chelating ligands and three chloride anions. The central Sm^III ion adopts a distorted tricapped trigonal prism geometry (Fig. 1), which is ligated by six N atoms from three different phenyl-2-pyridyl ketone oxime ligands and three Cl anions. The Sm—N and Sm—Cl bond distances are in the expected ranges of 2.578 (2)–2.713 (2) Å and 2.7501 (9)–2.8114 (10) Å, respectively (Table 1), and the bond angles around the Sm atom are in the range of 59.12 (6)–146.13 (7)°. Three intramolecular O—H···Cl hydrogen bonds are noted (see Fig. 2 and Table 2).

Experimental

A mixture of phenyl-2-pyridyl ketone oxime (0.0200 g, 0.1 mmol), SmCl₃.6H₂O (0.0180 g, 0.05 mmol), and C₂H₅OH (2 ml) was sealed in a 6 ml Pyrex-tube. The tube was heated at 85 °C for 3 days under autogenous pressure. Cooling of the resultant solution to room temperature gave colourless crystals of the product. The crystals were collected by filtration, washed with C₂H₅OH (2 ml) and dried in air. Anal. Calcd for C₃₆H₃₀Cl₃N₆O₃Sm: C, 50.79; H, 3.55; N, 9.87%. Found: C, 50.45; H, 3.25; N, 9.65%.