Compounds of 5-Hydroxymethyl-5-nitro(and 5-amino)hexahydropyrimidine-1,3-bisethanol With Nickel(II). The Structure of mer-Bis(5-amino-5-hydroxymethylhexahydropyrimidine-1,3-bisethanol-N¹,N⁵,O¹)nickel(II) Acetate Perchlorate

Abstract

Reaction of a nickel(II) salt, 2-aminoethanol, formaldehyde and nitromethane yields a nickel(II) complex of 5-hydroxymethyl-5-nitrohexahydropyrimidine-1,3-bisethanol, hnpdH₂, isolated as sparingly soluble blue salts of the cation [Ni( hnpdH )]⁺, and as insoluble green [Ni( hnpd )]. The nitro group of the ligand was reduced by catalytic hydrogenation to form 5-amino-5-hydroxymethylhexahydropyrimidine-1,3-bisethanol, ahpdH, isolated as salts of cations [Ni( ahpdH )₂]²⁺ and [Ni( ahpdH )( ahpd )]⁺. The structure of [Ni( ahpdH )₂] (CH₃COO) (ClO₄), determined by X-ray diffractometry, showed a cis NiN₄O₂ octahedral arrangement, with two ahpdH ligands in meridional coordination by the primary amino and one tertiary amino nitrogens, and the linked hydroxyethyl oxygen atom of each ligand. [ mer-Bis (5-amino-5- hydroxymethylhexahydropyrimidine-1,3-bisethanol-N¹,N⁵,O¹)nickel(II) acetate perchlorate, triclinic, space group Pī, a 9.233(2), b 9.567(3), c 16.775(3) Ǻ, α 81.87(2), β 76.08(2), γ 84.15(2)°p;, R 0.0325, Rw 0.0334 for 3859 reflections.]