Poly[[μ-(3-amino­pyridine)-κ2 N:N′-μ-chlorido-chlorido(N,N′-dimethyl­formamide-κO)nickel(II)] N,N′-dimethyl­formamide monosolvate]

Chun-Wei Yeh; Chi-Hsiung Jou; Chi-Hui Tsou; Maw-Cherng Suen

doi:10.1107/S1600536812036215

. 2012 Aug 25;68(Pt 9):m1204–m1205. doi: 10.1107/S1600536812036215

Poly[[μ-(3-aminopyridine)-κ² N:N′-μ-chlorido-chlorido(N,N′-dimethylformamide-κO)nickel(II)] N,N′-dimethylformamide monosolvate]

Chun-Wei Yeh ^a, Chi-Hsiung Jou ^b, Chi-Hui Tsou ^c, Maw-Cherng Suen ^d,^*

PMCID: PMC3435618 PMID: 22969491

Abstract

The title compound, {[NiCl₂(C₅H₆N₂)(C₃H₇NO)]·C₃H₇NO}_n, is a two-dimensional polymer in which the Ni^II atom is coordinated by two N atoms from two 3-aminopyridine ligands, one O atom from a dimethylformamide (DMF) group, one terminal Cl and two bridging Cl atoms in a distorted octahedral geometry. The Ni^II atoms are bridged by the 3-aminopyridine ligands [Ni⋯N = 6.7048 (3) Å] and Cl⁻ atoms [Ni⋯N = 3.5698 (3) Å], forming (4,4) two-dimensional nets. The DMF solvent molecule and the non-bridged Cl⁻ ions participate in N—H⋯O and N—H⋯Cl hydrogen bonds with the amino groups.

Related literature

For background to coordination polymers, see: Kitagawa et al. (2004 ▶); Chiang et al. (2008 ▶); Yeh et al. (2008 ▶, 2009 ▶); Hsu et al. (2009 ▶). For related 3-aminopyridine complexes, see: Zhu & Kitagawa (2002 ▶); Lah & Leban (2005 ▶, 2006 ▶); Kochel (2006 ▶); Wu et al. (2005 ▶); Qian & Huang (2006 ▶).

Experimental

Crystal data

[NiCl₂(C₅H₆N₂)(C₃H₇NO)]·C₃H₇NO
M _r = 369.92
Monoclinic,
a = 10.3684 (2) Å
b = 15.0571 (3) Å
c = 10.0976 (2) Å
β = 103.832 (2)°
V = 1530.70 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.62 mm⁻¹
T = 293 K
0.38 × 0.30 × 0.18 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.628, T _max = 1.000
6140 measured reflections
2748 independent reflections
2333 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.058
S = 1.04
2748 reflections
193 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812036215/xu5609sup1.cif

e-68-m1204-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036215/xu5609Isup2.hkl

e-68-m1204-Isup2.hkl^{(134.9KB, 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
N2—H2NA⋯Cl2ⁱ	0.89 (2)	2.60 (2)	3.4869 (16)	176.4 (1)
N2—H2NB⋯O2ⁱⁱ	0.84 (2)	2.11 (2)	2.925 (2)	173.3 (1)

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

Acknowledgments

We are grateful to the Taoyuan Innovation Institute of Technology for supporting this work.

supplementary crystallographic information

Comment

The synthesis of metal coordination polymers has been a subject of intense research due to their interesting structural chemistry and potential applications in gas storage, separation, catalysis, magnetism, luminescence, and drug delivery (Kitagawa et al., 2004). Roles of anion, solvent and ligand comformations in self-assembly of coordination complexes containing polydentate nitrogen ligands are very intersting (Chiang et al., 2008; Yeh et al., 2008; Hsu et al., 2009; Yeh et al., 2009). In the past, the 3-aminopyridine ligands have been subjected to many studies of its coordination ability to structure chemistry (Zhu et al., 2002; Lah & Leban, 2005; Lah & Leban, 2006; Kochel, 2006; Wu et al., 2005; Qian et al., 2006). The Ni²⁺ cations are coordinated with two N atoms from two 3-aminopyridine (L) ligands, one O atom from dimethylformamide group, one terminal Cl and two bridging Cl atoms (Fig. 1). The Ni···Ni distances separated by the bridging Cl^- anions and L groups are 3.5698 (3) and 6.7048 (3) Å, while the unit of dinuclear [Ni₂Cl₂] cores are forming (4,4) polymeric nets (Fig. 2). The co-crystallized DMF molecules and terminal Cl^- ions are interacted with the amino hydrogen atoms forming N—H···O and N—H···Cl inter– and intra–molecular hydrogen bonds (Tab. 1).

Experimental

An aquous solution (5.0 ml) of nickel chloride (1.0 mmol) was layered carefully over a mixed CH₃OH/DMF solution (5.0 ml, 1:1) of 3-aminopyridine (1.0 mmol) in a tube. Green crystals were obtained after several weeks. These were washed with methanol and collected in 72.8% yield.