Tris[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]gadolinium(III) methanol hemisolvate 2.5-hydrate

Zhao Kai; Xian-Hong Yin; Feng Yu; Zhu Jie; Cui-Wu Lin

doi:10.1107/S1600536808001931

. 2008 Jan 25;64(Pt 2):m407. doi: 10.1107/S1600536808001931

Tris[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]gadolinium(III) methanol hemisolvate 2.5-hydrate

Zhao Kai ^a,^b, Xian-Hong Yin ^a,^*, Feng Yu ^a, Zhu Jie ^b, Cui-Wu Lin ^b

PMCID: PMC2960314 PMID: 21201354

Abstract

In the title complex, [Gd(C₁₁H₁₀N₃O₂)₃]·0.5CH₄O·2.5H₂O, the Gd atom is coordinated by six N atoms and three O atoms derived from three tridentate monoanionic 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The molecules are linked together via hydrogen bonds involving the solvent water and methanol molecules.

Related literature

For related literature, see: Zhao et al. (2007 ▶); Yin et al. (2007 ▶).

Experimental

Crystal data

[Gd(C₁₁H₁₀N₃O₂)₃]·0.5CH₄O·2.5H₂O
M _r = 866.97
Monoclinic,
a = 15.5217 (18) Å
b = 16.5515 (19) Å
c = 16.434 (2) Å
β = 107.434 (2)°
V = 4028.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 298 (2) K
0.50 × 0.49 × 0.45 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.483, T _max = 0.514 (expected range = 0.436–0.464)
19991 measured reflections
7101 independent reflections
5129 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.147
S = 1.08
7101 reflections
505 parameters
H-atom parameters constrained
Δρ_max = 1.34 e Å⁻³
Δρ_min = −1.00 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536808001931/om2208sup1.cif

e-64-0m407-sup1.cif^{(37.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001931/om2208Isup2.hkl

e-64-0m407-Isup2.hkl^{(347.5KB, 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
O7—H7D⋯O8	0.85	2.23	3.074 (19)	172
O7—H7E⋯O2ⁱ	0.85	2.07	2.914 (13)	172
O8—H8A⋯O4ⁱⁱ	0.85	1.96	2.740 (11)	153
O8—H8B⋯O11	0.85	2.15	2.93 (2)	153
O9—H9A⋯O8	0.85	1.81	2.633 (18)	162
O9—H9B⋯O6ⁱⁱⁱ	0.85	1.94	2.765 (17)	162
O10—H10A⋯O7	0.85	2.07	2.64 (2)	124
O11—H11⋯O2ⁱ	0.82	2.14	2.664 (17)	122
O12—H12A⋯O6^iv	0.85	2.15	2.89 (3)	146
O12—H12B⋯O9^v	0.84	1.74	2.49 (5)	147
O12—H12B⋯O8^v	0.85	2.47	3.12 (4)	133

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20761002). This research was sponsored by the fund of the Talented Highland Research Programme of Guangxi University (grant No. 205121), the Science Foundation of the State Ethnic Affairs Commission (grant No. 07GX05), the Ministry of Education, Science and Technology Key Projects (grant No. 205121), the Development Foundation of Guangxi Research Institute of Chemical Industry, and the Science Foundation of Guangxi University for Nationalities (grant Nos. 0409032, 0409012, 0509ZD047), People’s Republic of China.

supplementary crystallographic information

Comment

Recently we reported the crystal structures of bis(6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato)zinc(II) trihydrate (Yin et al., 2007) and bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]cobalt(II) 2.5- hydrate (Zhao et al., 2007). As a continuation of these investigations, we report in this paper the crystal structure of tris(6-(3,5-dimethyl-1H-pyrazol-1-yl))picolinato)gadolinium(III) 2.5 hydrate 0.5 methanol solvate.

In the title complex, the gadolinium(III) ion is nine-coordinated by six N atoms and three O atoms derived from the tridentate ligands, 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate (DPP); the angles around Gd(III) atom range from 60.34 (15) to 149.67 (16) °, the Gd—O bond lengths are 2.320 (4), 2.343 (4) and 2.372 (4) Å, The Gd—N distances range from 2.512 (5) to 2.742 (5) Å, i.e. normal values. The C1—C2 bond length is 1.520 (9) Å, being in the normal C—C ranges for gadolinium carboxylate complexes.

In the crystal structure, the oxygen atoms contribute to the formation of intermolecular hydrogen bonds involving the solvate molecules that link the complex into a three-dimensional network. (Fig. 2; for symmetry codes see Table 2).

Experimental

6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid, and GdCl₃. 6H₂O were available commercially and were used without further purification. Equimolar 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid (1 mmol, 217 mg) was dissolved in anhydrous ethyl methanol (AR, 99.9%) (15 ml). The mixture was stirred to give a clear solution, To this solution was added GdCl₃.6H₂O (0.33 mmol, 99 mg) in anhydrous methanol (10 ml). After keeping the resulting solution in air to evaporate about half of the solvents, colorless blocks of the title complex were formed. The crystals were isolated, washed with alcohol three times (yield, 75%). Elemental analysis: found: C, 46.31; H, 4.37; N, 14.46; calc. for C₆₇H₇₄Gd₂N₁₈O₁₈: C, 46.41; H, 4.30; N, 14.54.