Complexes of ligands derived from the condensation of 2-formyl- or 2-acetylpyridine with ethanolamine and the formation of two rearrangement products; X-ray crystal structures of Mn(L1)2(NCS)2, [Mn(L1)(NCS)2]x, [Cu(L1)(H2O)2(ClO4)]2(ClO4)2, [Zn(L1)(H2O)2(ClO4)]2(ClO4)2 and [Mn(L3)(L4)] 2(ClO4)4·2EtOH (L1 = N-(2-hydroxyethyl)-2-pyridinecarboxaldimine, L3 = N-(2-hydroxyethyl)-methyl-2-pyridylketimine, L4 = (Z)-1,3-di(2-pyridyl)but-2-enone)

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Abstract

Four structurally diverse complexes of L1 (N-(2- hydroxyethyl)-2-pyridinecarboxaldimine) have been synthesised and characterised. Mn(L1)2(NCS)2 is a monomer, orthorhombic, unit cell dimensions a= 9.786(4), b=12.748(4), c=17.615(6) Å, U= 2197(1) Å3; [Mn(L1)(NCS)]x is a polymer, monoclinic, a=16.718(8), b=5.788(2), c=28.135(11) Å, β=91.61(3)°, U=2721(2) Å3; [Cu(L1)(H2O)2- (ClO4)]2(ClO4)2 is a dimer, monoclinic, a= 15.132(11), b=9.235(8), c=23.030(17) Å, β= 102.32(5)°, U=3144(4) °3; [Zn(L1)(H2O)2- (ClO4)]2(ClO4)2 is also a dimer, monoclinic, a= 15.114(7), b=9.428(3), c=22.649(9) Å, β= 100.86(3)°, U=3170(2) Å3. The formation of these complexes is discussed in relation to a proposed rearrangement scheme which accounts for the formation of a second, alternative product (L2)+ (2-(2- hydroxyethyl)-3-(2-pyridyl)-imidazo [1,5-a]-pyridinium cation). Use of an equivalent methyl ketone precursor in place of the aldehyde led to formation of L3 (N-(2-hydroxyethyl)-methyl-2-pyridylketimine) in situ. The dimeric manganese complex [Mn(L3)- (L4)]2(ClO4)4·2EtOH (L4=(Z)-1,3-di(2-pyridyl)- but-2-enone) was structurally characterised, orthorhombic, a=23.987(7), b=12.697(3), c=19.355(5) Å, U=5895(3) Å3, and a possible rearrangement scheme to form L4 is proposed.

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