BINUCLEAR PHTHALATO MANGANESE(II) COMPLEX WITH 2,2’-DIPYRIDYLAMINE, [Mn2(C8H4O4)2(C10H9N3)2(H2O)2]n

Abstract

Ternary manganese(II) complexes containing aromatic dicarboxylato and diamine ligands have fascinating crystal structures [1]. As a continuation of our research on design and synthesis of transition metal complexes [2], a novel titled Mn(II) complex has been prepared. The starting mixture of Mn(CH3COO)2•4H2O, 2,2’-dipyridylamine (dipya), phthalic acid (H2pht) and NaOH (molar ratio of 1:2:1:2, respectively) and H2O was treated in a Teflon-lined steel autoclave at t = 140 °C for 5 days, yielding the title complex. To the best of our knowledge, the obtained complex is the first example among aromatic dicarboxylato Mn(II) complexes with seven-coordinated Mn(II) ions. Mn(II) ions in the centrosymmetric binuclear unit (Fig. 1) have pentagonal-bipyramidal geometry. There are also two intramolecular hydrogen bonds making a deformed Mn2O6 cubane-like core. The aromatic rings of two pht2– ions are almost parallel with dihedral angle of only 1.81 º, while pht2– rings and dipya are nearly perpendicular with dihedral angles of 84.24 and 83.36 º. By intermolecular hydrogen bonds the binuclear units are packed in layers parallel to the ac-plane (Fig. 2). The layers are stacked by - interactions between dipya ligands belonging to adjacent layers (Cg•••Cg distance about 3.7 Å) resulting in formation of 3D framework. Crystal data: C36H30Mn2N6O10, Mr = 816.54, triclinic, space group , a = 8.3607(5), b = 9.1259(7), c = 11.8551(10) Å,  = 69.307(8),  = 77.471(6), γ = 79.893(6) o, V = 821.18(11) Å3, Z = 1, F(000) = 418, x = 1.651g cm–3,  (Mo K) = 0.842 mm–1. The refinement on F 2 (253 parameters) yielded R1 = 0.062, wR2 = 0.082, S = 1.08 for all data, and R1 = 0.044 for 2509 observed reflections with I  2σ(I).

Kompleksi mangana(II) koji sadrže aromatične dikarboksilato i diaminske ligande imaju fascinantne kristalne strukture [1]. Novi Mn(II)-kompleks rezultat je nastavka naših istraživanja na dizajnu i sintezi kompleksa prelaznih metala [2]. Početna smeša Mn(CH3COO)2•4H2O, 2,2’-dipiridilamina (dipya), ftalne kiseline (H2pht) i NaOH (u molskom odnosu 1:2:1:2) i H2O zagrevana je 5 dana na t = 140 °C u čeličnom autoklavu obloženom teflonom, pri čemu je dobijen navedeni kompleks. Prema našim saznanjima, nastali kompleks predstavlja prvi primer među aromatičnim dikarboksilato Mn(II)-kompleksima u kojem postoje sedmokoordinirani Mn(II)-joni. U centrosimetričnoj binuklearnoj jedinki (slika 1), Mn(II)-joni imaju pentagonalno- -bipiramidalnu geometriju. Postoje i dve intramolekulske vodonične veze koje grade deformisano Mn2O6 jezgro nalik kocki. Aromatični prstenovi iz dva pht2– su gotovo paralelni sa uglom od samo 1,81 º, dok su prstenovi pht2– i dipya skoro normalni sa uglovima od 84,24 i 83,36 º. Preko intermolekulskih vodoničnih veza, binuklearne jedinke se pakuju u slojeve paralelne ac-ravni (slika 2). Slojevi su povezani - interakcijama između dipya liganada iz susednih slojeva (Cg•••Cg rastojanje iznosi oko 3,7 Å) gradeći tako 3D mrežu. Kristalografski podaci: C36H30Mn2N6O10, Mr = 816,54, triklinični sistem, prostorna grupa , a = 8,3607(5), b = 9,1259(7), c = 11,8551(10) Å,  = 69,307(8),  = 77,471(6), γ = 79,893(6) º, V = 821,18(11) Å3, Z = 1, F(000) = 418, x = 1,651g cm–3,  (Mo K) = = 0,842 mm–1. Utačnjavanje sa F 2 (253 parametra) dalo je R1 = 0,062, wR2 = 0,082, S = 1,08 za sve podatke, i R1 = 0,044 za 2509 refleksija sa I 2σ(I).