Crystal structure of poly[{μ-N,N′-bis[(pyridin-4-yl)meth­yl]oxalamide}-μ-oxalato-cobalt(II)]

Hengye Zou; Yanjuan Qi

doi:10.1107/S1600536814015608

. 2014 Aug 1;70(Pt 9):m307–m308. doi: 10.1107/S1600536814015608

Crystal structure of poly[{μ-N,N′-bis[(pyridin-4-yl)methyl]oxalamide}-μ-oxalato-cobalt(II)]

Hengye Zou ^a, Yanjuan Qi ^a,^*

PMCID: PMC4186178 PMID: 25309173

Abstract

In the polymeric title compound, [Co(C₂O₄)(C₁₄H₁₄N₄O₂)]_n, the Co^II atom is six-coordinated by two N atoms from symmetry-related bis[(pyridin-4-yl)methyl]oxalamide (BPMO) ligands and four O atoms from two centrosymmetric oxalate anions in a distorted octahedral coordination geometry. The Co^II atoms are linked by the oxalate anions into a chain running parallel to [100]. The chains are linked by the BPMO ligands into a three-dimensional architecture. In addition, N—H⋯O hydrogen bonds stabilize the crystal packing.

Keywords: crystal structure, metal-organic framework, cobalt(II), oxalate anion, hydrogen bonds

Related literature

For information on compounds with metal-organic framework structures, see: Kitagawa et al. (2004 ▶); Ma et al. (2009 ▶); Li et al. (2005 ▶); Wang et al. (2007 ▶). For related Co^II complexes, see: Ma et al. (2005 ▶).

Experimental

Crystal data

[Co(C₂O₄)(C₁₄H₁₄N₄O₂)]
M _r = 417.24
Monoclinic,
a = 8.4143 (12) Å
b = 24.421 (4) Å
c = 9.2884 (14) Å
β = 113.322 (2)°
V = 1752.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 293 K
0.43 × 0.25 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.740, T _max = 0.785
11121 measured reflections
4254 independent reflections
2027 reflections with I > 2σ(I)
R _int = 0.085

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.149
S = 0.98
4254 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814015608/bt6986sup1.cif

e-70-0m307-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015608/bt6986Isup2.hkl

e-70-0m307-Isup2.hkl^{(204.2KB, hkl)}

Click here for additional data file.^{(1.1MB, tif)}

x y z x y z x y z x y z . DOI: 10.1107/S1600536814015608/bt6986fig1.tif

A view of the molecule of (I). Displacement ellipsoids are drawn at the 30% probability level. (i) − x + 1, −y, − z + 1; (ii) −x, −y, − z + 1; (iii) x, − y + Inline graphic , z + ; (iv) x + 1, − y + , z − .

Click here for additional data file.^{(2.1MB, tif)}

. DOI: 10.1107/S1600536814015608/bt6986fig2.tif

View of the three-dimensional structure of (I).

CCDC reference: 1012047

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O6ⁱ	0.86	2.14	2.863 (5)	142

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the Science Foundation of Jilin Province (No. 20140101121JC).

supplementary crystallographic information

S1. Comment

Design of effective ligands and the proper choice of metal centers are the keys to design and construct novel metal-organic frameworks (Kitagawa et al., 2004; Ma et al., 2009). These complexes can be specially designed by the careful selection of metal cations with preferred coordination geometries, the nature of the anions, the structure of the connecting ligands, and the reaction conditions (Li et al., 2005; Wang et al., 2007). We selected oxalic acid as an organic carboxylate anion and N,N'-Bis-pyridin-4-ylmethyl-oxalamide (BPMO) as a N-donor neutral ligand, generating a coordination compound, [Co(C₂O₄)(BPMO)]_n, which is reported here.

In the asymmetric unit of the title compound, [Co(C₂O₄)(BPMO)]_n, the central Co^II is six-coordinated by two nitrogen atoms from different BPMO ligands and four oxygen atoms from two oxalate anions in a distorted octahedral coordination geometry. The Co—N and Co—O distances are comparable to those found in other crystallographically characterized Co^II complexes (Ma et al., 2005). The Co^II atoms are linked by the oxalate anions to give a one-dimensional chain. The chains are linked by BPMO ligands and extend the chains into a three-dimensional supramolecular architecture. Moreover, the hydrogen bonds between the N-donor neutral ligand and oxalate, are crucial for stabilizing the three-dimensional framework.

S2. Experimental

The synthesis was performed under hydrothermal conditions. A mixture of Co(CH₃COO)₂^.4(H₂O),(0.2 mmol, 0.05 g), N,N'-Bis-pyridin-4-ylmethyl-oxalamide (0.2 mmol, 0.054 g), sodium oxalate (0.2 mmol,0.026 g) and H₂O(15 ml) in a 25 ml stainless steel reactor with a Teflon liner was heated from 293 to 443 K in 2 h and a constant temperature was maintained at 443 K for 72 h, after which the mixture was cooled to 298 K. Pink crystals of (I) were recovered from the reaction.