Aqua­glutarato(2,4,6-tri-2-pyridyl-1,3,5-triazine)nickel(II) trihydrate

Chun-Hua Jin

doi:10.1107/S1600536811006842

. 2011 Mar 2;67(Pt 4):m393. doi: 10.1107/S1600536811006842

Aquaglutarato(2,4,6-tri-2-pyridyl-1,3,5-triazine)nickel(II) trihydrate

Chun-Hua Jin ^a,^*

PMCID: PMC3099847 PMID: 21753929

Abstract

In the title compound, [Ni(C₅H₆O₄)(C₁₈H₁₂N₆)(H₂O)₂]·3H₂O, the Ni^II atom shows a distorted octahedral coordination by three N atoms of the tridentate chelating ligand and three O atoms of two aqua ligands and an O atom of one carboxylate group of the glutarate anion. Molecules are self-assembled via intermolecular O—H⋯O and O—H⋯N hydrogen-bonding interactions and π–π stacking interactions [centroid–centroid distance = 3.836 (3) Å] into a supramolecular network.

Related literature

For general background to 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), see: Glaser et al. (2004 ▶); Zibaseresht & Hartshorn (2005 ▶); Zheng et al. (2006 ▶); Zhou et al. (2007 ▶). For potential applications of tptz-containing complexes, see: Gupta et al. (1993 ▶); Witter & Luther (2002 ▶).

Experimental

Crystal data

[Ni(C₅H₆O₄)(C₁₈H₁₂N₆)(H₂O)₂]·3H₂O
M _r = 591.22
Triclinic,
a = 9.3437 (19) Å
b = 10.486 (2) Å
c = 14.320 (3) Å
α = 83.09 (3)°
β = 87.16 (3)°
γ = 69.02 (3)°
V = 1300.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 295 K
0.30 × 0.23 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.796, T _max = 0.868
12866 measured reflections
5901 independent reflections
4575 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.087
S = 1.14
5901 reflections
382 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006842/pk2302sup1.cif

e-67-0m393-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006842/pk2302Isup2.hkl

e-67-0m393-Isup2.hkl^{(288.8KB, 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
O5—H5B⋯O8	0.77 (3)	1.97 (3)	2.719 (3)	167 (3)
O5—H5C⋯O4ⁱ	0.87 (3)	1.79 (3)	2.651 (2)	176 (4)
O6—H6B⋯O3ⁱ	0.86 (2)	1.80 (3)	2.655 (2)	173 (3)
O6—H6C⋯O3ⁱⁱ	0.82 (3)	1.90 (3)	2.706 (3)	166 (3)
O7—H7B⋯O4ⁱ	0.82 (3)	2.12 (3)	2.940 (3)	172 (3)
O7—H7C⋯O2ⁱ	0.86 (4)	1.91 (4)	2.747 (3)	166 (3)
O8—H8B⋯O9ⁱⁱⁱ	0.82 (4)	1.92 (4)	2.695 (3)	157 (4)
O8—H8C⋯O7	0.84 (4)	1.96 (4)	2.753 (3)	156 (4)
O9—H9B⋯O8	0.86 (4)	2.06 (4)	2.907 (3)	170 (4)
O9—H9C⋯N6^iv	0.75 (4)	2.18 (4)	2.854 (3)	150 (4)

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

Acknowledgments

This project was sponsored by the K. C. Wong Magna Fund in Ningbo University, the Science and Technology Department of Zhejiang Province (2009C03017-4), the 863 National High-Tech Research and Development Plan (2007AA10Z409), the Natural Science Foundation of Zhejiang Province (project No. Y307542) and the Science and Technology Department of Ningbo City (2006C100036).

supplementary crystallographic information

Comment

As an interesting polydentate nitrogen donor ligand, 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) has attracted increasing attention in the synthesis of novel transition metal complexes (Glaser, et al., 2004; Zibaseresht & Hartshorn, 2005; Zheng, et al., 2006; Zhou, et al., 2007). It was applied in the extraction and separation of metal ions, and in the preparation of DNA cleaving agents. It has also been widely empolyed to determine the concentration of mono- and polysaccharides in seawater (Gupta, et al., 1993; Witter & Luther, et al., 2002). Our interest in tptz transition metal complexes prompts us to report a new tptz containing structure, [Ni(C₁₈H₁₂N₆)(C₅H₆O₄)(H₂O)₂].3H₂O, obtained by self-assembly from Ni^II, tptz and glutaric acid in aqueous methanolic solution.

The title compound, consists of [Ni(C₁₈H₁₂N₆)(C₅H₆O₄)(H₂O)₂] complex molecules and three lattice waters, as shown in Fig. 1, in which the Ni atoms are in a distorted octahedral coordination environment defined by three N atoms of one tridentate tptz ligand and three O atoms of two aqua ligands and the glutarate group. Three nitrogen atoms (N1, N2 and N3) from the tptz ligand and one O atom (O6) of water molecule form the equatorial base, while the carboxylate O atom (O1) and the other water ligand O atom (O5) occupy the axial positions. Ni-N distances vary from 1.986 (2) to 2.173 (2) Å, and the Ni-O bond distances fall in the region 2.021 (2) to 2.056 (2) Å. The deviation from the ideal octahedral geometry is indicated by the difference in cisoid [76.38 (7)°-106.06 (7)°] and transoid angles [153.59 (6)°-177.01 (7)°]. In the tptz ligand, the C(sp²)-C(sp²) distances within the ring are normal [1.373 (4)-1.392 (2) Å], and the exterior bond distances, 1.482 (3)-1.491 (3) Å, are also normal. The tptz ligands deviate little from planarity, the three pyridyl rings are twisted with respect to the central triazine ring by angles of 3.4 (2)°, 4.1 (1)° and 8.6 (1)° with the N3 ring displaying the highest degree of twisting. The [Ni(C₁₈H₁₂N₆)(C₅H₆O₄)(H₂O)₂] complex molecules are assembled into a 3D network by hydrogen bonds between the coordinated water and lattice water molecules and the carboxylate group and pyridyl nitrogen atoms with the distances from 2.651 (4) Å to 2.938 (5) Å (Table 1). The crystal structure is also stabilized by intermolecular π-π stacking interactions between tptz ligands [centroid-centroid distance = 3.836 (3) Å].

Experimental

Dropwise addition of 2.0 ml NaOH (1.0 M) to a stirred solution of NiCl₂.6H₂O (0.238 g, 1.00 mmol) in 5.0 ml H₂O produced a green precipitate, which was then centrifuged and washed with double-distilled water until no Cl^- anions were detectable. The collected precipitate and 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tptz) (0.312 g, 1.00 mmol) were added to a stirred solution of glutaric acid (0.132 g, 1.00 mmol) in CH₃OH/H₂O (30.0 ml; 1:1 v/v). The resulting mixture was stirred for a further 30 min. After filtration, the dark green filtrate (pH = 5.12) was evaporated slowly at room temperature and afforded dark green crystals over two weeks (yield 45.4%, based on initial NiCl₂ input).