Pyridinium [2,6-bis­(5-phenyl-1H-pyrazol-3-yl-κN 2)pyridine-κN]tetra­nitrato-κ6 O,O′;κO-samarium(III) pyridine monosolvate

Shui Hu; Yongfeng Zhao; Huai-Ming Hu; Li Liu

doi:10.1107/S1600536811022653

. 2011 Jun 18;67(Pt 7):m945–m946. doi: 10.1107/S1600536811022653

Pyridinium [2,6-bis(5-phenyl-1H-pyrazol-3-yl-κN ²)pyridine-κN]tetranitrato-κ⁶ O,O′;κO-samarium(III) pyridine monosolvate

Shui Hu ^a, Yongfeng Zhao ^a, Huai-Ming Hu ^b,^*, Li Liu ^a,^*

PMCID: PMC3152084 PMID: 21836928

Abstract

In the title compound, (C₅H₆N)[Sm(NO₃)₄(C₂₃H₁₇N₅)]·C₅H₅N, the Sm^III atom is ten-coordinated by the N,N′,N′′-tridentate bis(pyrazole) ligand and seven O atoms from four nitrate anions (three bidentate and one monodentate). The dihedral angles between the central pyridine ring and adjacent pyrazole rings in the ligand are 1.3 (2) and 3.2 (2)°; the dihedral angles between the pyrazole rings and their pendant phenyl rings are 42.0 (3) and 16.1 (2)°. The conformation of the anionic complex ion is supported by an intramolecular N—H⋯O hydrogen bond. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur. The pyridinium cation forms an N—H⋯N hydrogen bond.

Related literature

For the synthesis of the ligand, see: Zhao et al. (2009 ▶). For related transition metal and lanthanide complexes, see: Argent et al. (2005 ▶); Bardwell et al. (1997 ▶); Barrios et al. (2008 ▶); Coronado et al. (2003 ▶); Dong et al. (1999 ▶); Dutta et al. (1996 ▶); Gamez et al. (2002 ▶); Gimenez-Lopez et al. (2005 ▶); Scudder et al. (2005 ▶); Wei et al. (2008 ▶).

Experimental

Crystal data

(C₅H₆N)[Sm(NO₃)₄(C₂₃H₁₇N₅)]·C₅H₅N
M _r = 921.01
Triclinic,
a = 10.5234 (19) Å
b = 12.826 (2) Å
c = 14.190 (3) Å
α = 75.970 (2)°
β = 86.453 (2)°
γ = 84.108 (2)°
V = 1847.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.67 mm⁻¹
T = 296 K
0.18 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.753, T _max = 0.851
9121 measured reflections
6391 independent reflections
5442 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.086
S = 1.09
6391 reflections
517 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536811022653/hb5891sup1.cif

e-67-0m945-sup1.cif^{(34.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022653/hb5891Isup2.hkl

e-67-0m945-Isup2.hkl^{(312.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811022653/hb5891Isup3.cdx

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

Table 1. Selected bond lengths (Å).

Sm1—O10	2.435 (3)
Sm1—O5	2.485 (3)
Sm1—O7	2.490 (3)
Sm1—O1	2.495 (3)
Sm1—N2	2.513 (3)
Sm1—O2	2.520 (3)
Sm1—O4	2.528 (3)
Sm1—N4	2.544 (3)
Sm1—O8	2.628 (3)
Sm1—N3	2.661 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O12	0.86	1.99	2.807 (5)	159
N5—H5⋯O9ⁱ	0.86	2.10	2.947 (4)	169
N10—H10A⋯N11ⁱⁱ	0.85 (2)	1.90 (3)	2.727 (6)	166 (6)

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

supplementary crystallographic information

Comment

Pyrazole derivatives are an important class of organic photochromic compounds. 2,6-Bis-(pyrazolyl)pyridine ligands can be coordinated with transitional metal ions and lanthanide metal ions. Herein we reported the crystal structure of a samarium(III) complex with a bis-(pyrazole) ligand, 2,6-bis-(5-phenyl)-1H-pyrazol-3-yl)pyridine (H₂BPPP).

The atom-numbering scheme of (I) is shown in Fig. 1. The Sm^III atom is ten-coordinated by three N atoms from the bis-(pyrazole) ligand and seven O atoms from four nitrate anions. A dimer structure is formed through hydrogen interactions between the oxygen atoms of nitrate anions and the nitrogen atoms of pyrazolyl –NH groups [N5—H5···O9ⁱ, 2.947 (4) Å, 168.8°, symmetric code i: (-x + 1,-y,-z + 2)].

Experimental

The bis-(pyrazole) ligand, H₂BPPP, was prepared according to the literature method (Zhao et al., 2009). H₂BPPP (0.2 mmol) and Sm(NO₃)₃.6H₂O (0.2 mmol) were dissolved in a DMF (5 ml) and MeOH (5 ml) mixed solvent. Then difuse the solution with ethyl ether. After one week, colourless blocks were obtained. Elmental analysis for C₃₃H₂₈N₁₁O₁₂Sm calculated: C 43.03, H 3.06, N 16.73%; found: C 42.81, H 3.08, N1 16.89%.