Preparation and Crystal Structure of a Mixed Metal Assembly [Ni(phen)₃][Cu(H_-1pap)]₂(NO₃) · 8 H₂O Featuring Octahedral Cationic and Square-planar Anionic Modules

Abstract

Oximes, PhenanthrolineThe new mixed metal assembly [Ni (phen)3][Cu(H.ipap)]2(N0 3 ) * 8 H2O (2) (Ehpap = CH 3-C(=N0 H)-C(0 )-NH-(CH2)3-NH-C(0 )-C(=N0 H )-CH 3) was obtained by co-crystallisation of [Li(H20)4][Cu(H.ipap)] • 2 H20 (1) and tris(l,10-phenanthroline)nickel(II) nitrate and studied by means of X-ray crystallography (triclinic, space group P i, a = 13.471(3), b = 13.641(3), c = 15.401(3) A, a = 108.21(3), ß = 97.73(3),7 = 107.74(3)°, V = 2476.6(9) A , Z = 2 ,R \ = 0.0677 for 4672 unique reflections with I > 2a(I)). The assembly indicates a network structure and consists of isolated cationic and anionic modules (octahedral [Ni(phen)3]2+ and square-planar [Cu(H.lPaP)]), non-coordinated nitrate anions and solvating water molecules. The elements of the crystal structure are linked by interactions of different types: by an extended system of H bonds, stacking interactions between aromatic rings, long apical Cu-N contacts and specific 7r-7r interaction between a deprotonated oxime group of the complex anion and a phenanthroline ligand.

Structural Criteria for the Rational Design of Selective Ligands: Convergent Hydrogen Bonding Sites for the Nitrate Anion

“…The CSD yields 184 examples in which at least one hydrogen atom of H 2 O is within 2.0 Å of a NO 3 - oxygen atom. There is only one clear occurrence of asymmetric bidentate hydrogen bonding, as in 1 , where the short hydrogen bond is 1.84 Å and the long hydrogen bond is 2.51 Å . For the rest of these structures there is only a single hydrogen bond between the H 2 O molecule and NO 3 - , as in 2 .…”

Poly[bis[μ4-N-(2-hydroxyiminopropionyl)-N′-(2-oxidoiminopropionyl)propane-1,3-diaminato]dimethanolcalciumdicopper(II)]

“…PPh 4 [Cu(Hpap)].4.5H 2 O (Kanderal et al, 2005) have been reported, as well as a series of modular cationic and anionic complex compounds containing [Cu(Hpap)]anions (Fritsky et al, 2000). The present report describes the crystal structure of the title compound, a three-dimensional coordination polymer of composition [CaCu 2 (Hpap) 2 (CH 3 OH) 2 ], featuring copper(II) complex anions connected by calcium ions.…”

Old Acquaintances and Novel Complex Structures for the Ni(II) and Cu(II) Complexes of bis-Chelate Oxime–Amide Ligands

“…NMR: 1 H, 13 C, 15 N, and 31 P NMR spectra were recorded on a Bruker Avance-III 400 or Bruker Avance-III 500 spectrometer at frequencies of 400/500 MHz ( 1 H) and 100/125 MHz ( 13 C), using either a 5 mm BBOZ-[ 31 P-109 Ag]-{ 1 H} probe or a 5 mm TBIZ-[ 1 H]-{ 31 P}-{ 31 P-109 Ag} probe. All proton and carbon chemical shifts are quoted relative to the relevant solvent signal (e.g., for DMSO-d 6 , 1 H: 2.50 ppm, 13 C: 39.50 ppm).…”

“…Since then, all three ligands considered in this study were prepared and characterised, including their crystal structures, L1 [ 7 , 8 ], L2 [ 1 , 9 , 10 ], and L3 [ 8 , 11 ]. A number of Ni(II) complexes [ 9 , 12 , 13 , 14 ] and Cu(II) complexes [ 9 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ] have also been reported. All of the previously synthesised Ni(II) and Cu(II) complexes with ligands L1–L3 known to the authors are listed in Supplementary Materials Tables S1 and S2 .…”