Synthesis and Crystal Structures of Tetraazamacrocycle Nickel^II Complexes Containing O-Phenylenedioxydithiophosphate Anion

Abstract

A tetraazamacrocycle nickel^II complex of O,O′-diaryldithiophosphate, [Ni(hmtade)] [S₂P(O₂C₆H₄-o)]₂ (1), and its unexpected complex methanolysis product, [Ni(hmtade)] [S₂P(OMe)(OC₆H₄(OH-o)]₂ (2) (the ligand hmtade is 5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-1,11-diene), have been synthesized and characterized by elemental analysis, IR, ¹H(¹³C, ³¹P) NMR spectroscopies, thermogravimetric analysis, and single-crystal X-ray diffraction methods. The results show that the difference in O,O′-diaryldithiophosphate anions hardly brings about any influence on the structure of complex cation [Ni(hmtade)]²⁺. In the packing of 1, the molecules self-assemble into a folded two-dimensional (2D) network and which further links into a complicated 3D supramolecular framework. Two different kinds of 2D networks form independently via intermolecular hydrogen bonds and alternatively arrange into a novel 3D lamellar sandwich-layer structure in the packing of 2.

GRAPHICAL ABSTRACT

Keywords:

• Synthesis
• complex
• tetraazamacrocycle
• O,O′-Dialkyldithiophosphate
• crystal structure