Synthesis and Crystal Structures of Tetraazamacrocycle Nickel^II Complexes Containing <i>O</i>-Phenylenedioxydithiophosphate Anion

<div><p></p><p>A tetraazamacrocycle nickel^II complex of <i>O</i>,<i>O</i>′-diaryldithiophosphate, [Ni(hmtade)] [S₂P(O₂C₆H₄-<i>o</i>)]₂ (<b>1</b>), and its unexpected complex methanolysis product, [Ni(hmtade)] [S₂P(OMe)(OC₆H₄(OH-<i>o</i>)]₂ (<b>2</b>) (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 <i>O,O</i>′-diaryldithiophosphate anions hardly brings about any influence on the structure of complex cation [Ni(hmtade)]²⁺. In the packing of <b>1</b>, 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 <b>2</b>.</p>