Crystal structure of [3,10-bis-(4-fluoro-pheneth-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne]nickel(II) diperchlorate.

Chee-Hun Kwak,Mee Chang

doi:10.1107/s2056989020016795

Abstract

The square-planar nickel(II) title complex, [Ni(C24H36F2N6)](ClO4)2 or [NiL](ClO4)2 (L = 3,10-bis-(4-fluoro-pheneth-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne) was synthesized by a one-pot reaction of template condensation and its X-ray crystal structure was determined. The nickel(II) ion lies close by a twofold axis and the complex displays whole-mol-ecule disorder. Ligand L, a hexa-aza-cyclo-tetra-decane ring having 4-fluoro-phenethyl side chains attached to uncoordinated nitro-gen atoms, adopts a trans III (R,R,S,S) configuration. The average Ni-N bond distance is 1.934 (9) Å, which is quite similar to those of other nickel(II) complexes with similar ligands. The nickel(II) ion is located 0.051 (7) Å above the least-squares plane through the four coordinated N atoms. The average C-N bond distance and C-N-C angle involving uncoordinated nitro-gen atoms are 1.425 (12) Å and 118.0 (9)°, respectively, indicating a significant contribution of sp 2 hybridization for these N atoms. The inter-molecular N-H⋯O, C-H⋯O/F hydrogen bonds of the complex form a network structure, which looks like a seamless floral lace pattern.

Highlights

Ligand L, a hexaazacyclotetradecane ring having 4-fluorophenethyl side chains attached to uncoordinated nitrogen atoms, adopts a trans III (R,R,S,S) configuration
A metal template condensation reaction with formaldehyde and appropriate amines is a useful method for the synthesis of saturated polyazamacrocyclic complexes
The information derived from polyazamacrocyclic complexes containing pendant arms helps in the understanding of apical effects in the biological behavior of tetraazamacrocyclic metalloenzymes having a square-planar geometry (Liang & Sadler, 2004; Costamagna et al, 2000)

Summary

Chemical context

A metal template condensation reaction with formaldehyde and appropriate amines is a useful method for the synthesis of saturated polyazamacrocyclic complexes. The donor atoms in the pendant arms of these macrocyclic complexes can be coordinated to another metal ion or participate in hydrogen bonding. These complexes can be applied in the field of supramolecular chemistry or metal–organic frameworks. Many studies on metal–organic frameworks have been performed using complexes of 3,10bis(alkyl)-1,3,5,8,10,12-hexaazacyclotetradecane-type ligands (Jeoung et al, 2019; Stackhouse & Ma, 2018; Lee & Moon, 2018; Lin et al, 2014) In this communication, we report the preparation of a new nickel(II) complex [NiL](ClO4), where L is a 3,10-bis(alkyl)-1,3,5,8,10,12-hexaazacyclotetradecane ligand having 4-fluorophenethyl pendant arms at positions 3 and 10, and its structural characterization by single-crystal X-ray crystallography.

Supramolecular features

Database survey

Synthesis and crystallization

Refinement