Lewis-Base Adducts of Group 11 Metal(I) Compounds. XLVI. Synthesis and Conformational Systematics of Some Novel Polymeric Adducts of Pyridine-4-carbonitrile With Copper(I) Halides

Abstract

The isolation and structural characterization of 1 : 1 adducts of copper(1) chloride (1) and bromide (2) with pyridine-4-carbonitrile (L) is described; crystals of the two complexes are isomorphous (monoclinic, P21/c, a ≈ 3.9, b ≈ 14.7, c ≈ 13.0 � , β ≈ 96°, Z 4; R0.047, 0.063 for No 630, 707 'observed' reflections respectively). Unlike the 1 : 1 adducts with the parent pyridine and benzonitrile ligands which are 'stair' polymers, these complexes comprise 'split-stair' strands woven into a two-dimensional sheet by crosslinking ambidentate ligands. Cu-N ( nitrile ) (1.942(9), 1.96(1) � ) are appreciably shorter than Cu-N (pyridine) (2.066(8), 2.04(1) � ), as in the parent base complexes. The two Cu-X are similar in each case: 2.336(6), 2.366(3) � (CI); 2.460(3), 2.486(3) � (Br). The iodide adduct (3) isolated is of novel stoichiometry (Cul : L, 4 : 5) (monoclinic, P21/c; a 10.140(5), b 12.214(6), c 15.157(8) � , β 99.99(4)° Z 2; R 0.048, No 2416). It is a linear polymer, comprising tetranuclear Cu414L4 'step' units, crosslinked across inversion centres by disordered ambidentate ligands.

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

“…Thus, the ligand acts as a tridentate S , N , N -ligand, and the torsion angles (τ 1 and τ 2 ) are 19.2° and 25.1°, respectively. Only a few examples of stepped-cubane Cu 4 I 4 substructures similar to that in 5 have been reported, such as [(CuI) 4 (2-methylpyridine) 6 ], [(CuI) 4 (4-cyanopyridine)], and [(CuI) 4 (1,1′-di­(pyrazinyl)­ferrocene) 2 ] …”

Controlling copper(I) halide framework formation using N-donor bridging ligand symmetry: use of 1,3,5-triazine to construct architectures with threefold symmetry

“…two-dimensional sheet structures; in [CuCl(pyz)] ∞ the pyrazine molecules link (CuCl) ∞ split stair chains (Scheme 4a), 15 whereas in 17 4-Cyanopyridine (pyridine-4-carbonitrile; pycn), a molecular rod with both pyridinyl and nitrile bases, gives 1 : 1 complexes [CuX(pycn)] ∞ (X = Cl or Br) which adopt a twodimensional sheet structure analogous to that of [CuCl(pyz)] ∞ , with 4-cyanopyridine molecules linking (CuCl) ∞ split-stair chains. 18 The remaining copper() halide frameworks found in coordination polymers containing linear bidentate bridging N-donor ligands are discrete dinuclear or tetranuclear species. In [Cu 2 I 2 (phz)] ∞ , phenazine molecules link Cu 2 I 2 rhomboids to form a one-dimensional chain structure (Scheme 3a).…”

“…17 3b). 18 The extended structure of [CuCl(4,4Ј-bipy)] ∞ , comprises an interpenetrated arrangement of mutually perpendicular sheets based on an hexagonal arrangement of Cu 2 Cl 2 rhomboids linked by alternating single and double 4,4Ј-bipyridine (4,4Ј-bipy) bridges (Scheme 3c). 19 To support our contention that the choice of copper() halide framework is dependent on ligand symmetry, we now report the results of our study of complex formation between the tridentate bridging ligand 1,3,5-triazine (tri) and copper() halides.…”

Impacts of the counter ions on 4,5-dicyano-1-methylimidazole silver coordination

“…10,11 Catena or network complexes with bridging multidentate cyanopyridyls are found e.g. for cadmium 12,13 , ruthenium, 14 rhodium 15 , and more typically for silver and copper 16,17,18 .…”