Aqua­tris[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]-κ6 N,N′,O;κO-dysprosium(III) trihydrate

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

doi:10.1107/S1600536808001943

. 2008 Jan 25;64(Pt 2):m408–m409. doi: 10.1107/S1600536808001943

Aquatris[6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato]-κ⁶ N,N′,O;κO-dysprosium(III) trihydrate

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

PMCID: PMC2960341 PMID: 21201355

Abstract

In the title complex, [Dy(C₁₁H₁₀N₃O₂)₃(H₂O)]·3H₂O, the Dy^III atom is coordinated by four N atoms and four O atoms derived from three tridentate deprotonated 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands and one water molecule. The complex and solvent water molecules are linked together via O—H⋯O, O—H⋯N, C—H⋯O and C—H⋯π hydrogen-bonding interactions, forming a three-dimensional network structure.

Related literature

For related literature, see: Zhao et al. (2008 ▶); Yin et al. (2007 ▶); Baggio et al. (2003 ▶).

Experimental

Crystal data

[Dy(C₁₁H₁₀N₃O₂)₃(H₂O)]·3H₂O
M _r = 883.22
Monoclinic,
a = 15.4709 (18) Å
b = 12.8466 (12) Å
c = 18.543 (2) Å
β = 99.741 (2)°
V = 3632.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 298 (2) K
0.30 × 0.24 × 0.17 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.568, T _max = 0.714
17074 measured reflections
6277 independent reflections
4009 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.118
S = 1.04
6277 reflections
478 parameters
H-atom parameters constrained
Δρ_max = 1.45 e Å⁻³
Δρ_min = −0.93 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 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001943/si2070sup1.cif

e-64-0m408-sup1.cif^{(34.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001943/si2070Isup2.hkl

e-64-0m408-Isup2.hkl^{(307.3KB, 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⋯O8ⁱ	0.85	2.04	2.754 (6)	141
O7—H7E⋯O9ⁱⁱ	0.85	1.90	2.670 (9)	150
O8—H8A⋯O2ⁱⁱⁱ	0.85	1.88	2.728 (8)	172
O8—H8B⋯N9^iv	0.85	2.00	2.847 (10)	173
O9—H9A⋯O6^v	0.85	1.82	2.665 (8)	170
O9—H9B⋯O10^vi	0.85	2.02	2.858 (9)	171
O10—H10A⋯O8^vii	0.85	2.07	2.915 (9)	175
O10—H10B⋯O2ⁱⁱⁱ	0.85	2.14	2.988 (10)	175
C27—H27⋯O8^iv	0.93	2.59	3.406 (11)	147
C29—H29B⋯O4ⁱ	0.96	2.57	3.363 (12)	140
C22—H22A⋯O7	0.96	2.52	3.147 (11)	123
C29—H29C⋯N7	0.96	2.49	2.874 (10)	104
C33—H33B⋯Cg^viii	0.96	2.97	3.893	161

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) . Cg is the centroid of the N2,N3,C8–C10 ring.

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 and 0509ZD047).

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]nickel(II) tetrahydrate (Zhao et al., 2008). The title compound consists of the central asymmetric mononuclear dysprosium(III) complex and three uncoordinated water molecules. The Dy atom is eight-coordinated by four N atoms and four O atoms derived from three tridentate, deprotonated 6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands (DPP) and one water molecule, that define a pseudo-tricapped trigonal environment for the dysprosium atom. The angles around the Dy(III) atom range from 61.39 (18) to 155.29 (19)°, the Dy—O distances range between 2.235 (5) and 2.368 (5) Å, and the Dy—N distances range between 2.511 (6) and 2.598 (6) Å, i.e. normal values. The C1—C2, C12—C13 and C23—C24 bond lengths range between 1.515 (11) and 1.518 (10) Å, being in the normal C—C ranges found in dysprosium carboxylate complexes (Baggio et al. (2003) and literature cited therein).

In the crystal structure, the oxygen atoms contribute to the formation of intermolecular hydrogen bonds involving the solvate water molecules. Four water molecules, two DDP O atoms and one DDP N atom form rings via intermolecular H···O—H···O and H···O—H···N hydrogen bonds (Fig. 2). These interactions and two intermolecular C—H···O hydrogen bonds and a C—H···π contact (Cg^viii is the centroid of ring atoms N2, N3, C8, C9, C10) link the complexes into a three-dimensional network (Table 1). Two weak intramolecular C_methyl—H···O/N hydrogen bonds contribute to the conformational stability of the title complex.

Experimental

6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid, and Dy(NO₃)₃. 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 alcohol (AR,99.9%) (15 ml). The mixture was stirred to give a clear solution. To this solution was added Dy(NO₃)₃. 6H₂O (0.33 mmol,151 mg) in anhydrous alcohol (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 and washed with alcohol three times (Yield75%). Elemental analysis: found: C, 44.63; H, 4.42; N, 14.18; calc. for C₃₃H₃₈DyN₉O₁₀: C, 44.88; H, 4.34; N, 14.27.