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

Hua Yang

doi:10.1107/S1600536812014055

. 2012 Apr 13;68(Pt 5):m578–m579. doi: 10.1107/S1600536812014055

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

Hua Yang ^a,^*

PMCID: PMC3344326 PMID: 22590092

Abstract

In the title compound, [NdCl₃(C₁₂H₁₀N₂O)₃], the central Nd^III ion is nine-coordinated by six N atoms from three bidentate chelate N-[phenyl(pyridin-2-yl)methylidene]hydroxylamine ligands and three Cl⁻ ions, and displays a distorted tricapped trigonal prismatic geometry. The complex molecules are stabilized by intramolecular O—H⋯Cl hydrogen bonds.

Related literature

For complexes of oximes, see: Kukushkin & Pombeiro (1999 ▶); Milios et al. (2007 ▶); Fritsky et al. (2004 ▶); Xu et al. (2007 ▶); Papatriantafyllopoulou et al. (2009 ▶). For 3d-metal complexes of N-[phenyl(pyridine-2-yl)methylidene]hydroxylamine, see: Milios et al. (2003 ▶); Milios et al. (2004 ▶). For an Sm complex with this ligand, see: Lei et al. (2012 ▶).

Experimental

Crystal data

[NdCl₃(C₁₂H₁₀N₂O)₃]
M _r = 845.25
Triclinic,
a = 8.6367 (17) Å
b = 10.460 (2) Å
c = 19.847 (4) Å
α = 91.87 (3)°
β = 94.38 (3)°
γ = 92.80 (3)°
V = 1784.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 293 K
0.31 × 0.18 × 0.13 mm

Data collection

Bruker SMART CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.617, T _max = 0.807
30524 measured reflections
7775 independent reflections
7155 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.059
S = 1.04
7775 reflections
445 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.44 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/S1600536812014055/zs2190sup1.cif

e-68-0m578-sup1.cif^{(25.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014055/zs2190Isup2.hkl

e-68-0m578-Isup2.hkl^{(380.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Nd1—N2	2.604 (2)
Nd1—N1	2.661 (2)
Nd1—N5	2.680 (2)
Nd1—N4	2.6953 (19)
Nd1—N6	2.7018 (19)
Nd1—N3	2.742 (2)
Nd1—Cl3	2.7686 (8)
Nd1—Cl2	2.7903 (9)
Nd1—Cl1	2.8296 (10)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl3	0.82	2.22	2.966 (2)	152
O2—H2A⋯Cl1	0.82	2.19	2.9290 (19)	151
O3—H3A⋯Cl2	0.82	2.19	2.930 (2)	150

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Acknowledgments

The author appreciates financial support from Yanan University (grant No. YD2011–20) and the Science and Technology Bureau of Yanan City (grant No. kn2009–16).

supplementary crystallographic information

Comment

The coordination chemistry of oximes (Kukushkin & Pombeiro, 1999; Milios et al., 2007) continues to attract considerable attention, with the efforts of several research groups driven by a number of considerations. These include the use of metal oxime complexes in supramolecular chemistry (Fritsky et al., 2004) and the employment of oximate ligands in the synthesis of complexes with interesting magnetic properties (Xu et al., 2007; Papatriantafyllopoulou et al., 2009; Milios et al., 2007). N-[phenyl(pyridine-2-yl)methylidene]hydroxylamine [(py)C(ph)NOH], is one of the oximes that is currently a popular ligand for synthesis of the 3d-metal complexes (Milios et al., 2003; Milios et al., 2004). However, the structures of rare earth metal complexes with this ligand are uncommon in the crystallographic literature. Here we report the structure of the neodymium complex with [(py)C(ph)NOH], the title compound [NdCl₃(C₁₂H₁₀N₂O)₃], which was synthesized by the reaction of NdCl₃ . 6H₂O with the ligand under autogenous pressure. The title compound is isomorphous with the Sm^III analogue (Lei et al., 2012).

In the title complex, the central Nd^III ion is nine-coordinated by six nitrogen atoms from three bidentate chelate ligands and three Cl^- ions [Nd—N range, 2.604 (2)–2.742 (2) Å; Nd—Cl, 2.7686 (8)–2.8296 (10) Å (Table 1)] and displays a distorted tricapped trigonal prismatic geometry (Fig. 1). The discrete complex molecules are stabilized by intramolecular O—H···Cl hydrogen bonds (Table 2, Fig. 2).

Experimental

A mixture of phenyl-2-pyridyl ketone oxime (0.0198 g, 0.10 mmol), NdCl₃ . 6H₂O (0.0179 g, 0.05 mmol), and ethanol (2 mL) was sealed in a 6 mL Pyrex tube. The tube was heated at 80 °C for 4 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 ethanol (2 mL) and dried in air. Yield: 54%. Anal. Calcd. for C₃₆H₃₀Cl₃N₆NdO₃: C, 51.15; H, 3.58; N, 9.94%. Found: C, 50.93; H, 3.43; N, 9.76%.