Poly[[chlorido(1,10-phenanthroline-κ²N,N′)copper(II)]-μ₃-1,1,3,3-tetracyano-2-ethoxypropenido-κ³N:N′:N′′]: coordination polymer sheets linked into bilayers by hydrogen bonds

Abstract

In the title compound, [Cu(C9H5N4O)Cl(C12H8N2)]n or [Cu(tcnoet)Cl(phen)]n, where phen is 1,10-phenanthroline and tcnoet is 1,1,3,3-tetracyano-2-ethoxypropenide, the axially elongated (4 + 2) coordination polyhedron around the Cu(II) centre contains N atoms from three different tcnoet ligands. The resulting coordination polymer takes the form of sheets which are linked in pairs by a single C-H...N hydrogen bond to form bilayers. The bond lengths provide evidence for significant bond fixation in the phen ligand and extensive electronic delocalization in the tcnoet ligand, where the two -C(CN)2 units are rotated, in conrotatory fashion, out of the plane of the central C3O fragment.

1,1′-Diethyl-4,4′-bipyridine-1,1′-diium bis(1,1,3,3-tetracyano-2-ethoxypropenide): multiple C—H...N hydrogen bonds form a complex sheet structure

“…Within the anion, the two central C-C distances ( Table 2) are very similar, while the four independent C-N distances are all the same within experimental uncertainty, and they are long for their type [mean value (Allen et al, 1987) = 1.136 Å , upper quartile value = 1.142 Å ]. The peripheral C-CN distances span a very narrow range, ca 0.01 Å , and all are short for their type [mean value (Allen et al, 1987) = 1.427 Å , lower quartile value = 1.420 Å ], consistent with extensive delocalization of the negative charge, as discussed recently (Setifi et al, 2014).…”

“…The dihedral angles between the central C 3 unit and the -C(CN) 2 units containing atoms C11 and C13 are 16.0 (2) and 23.0 (2) , respectively; these values, and the sense of the rotations, are typical of those observed in other systems containing this anion (Setifi et al, 2013(Setifi et al, , 2014. Within the anion, the two central C-C distances ( Table 2) are very similar, while the four independent C-N distances are all the same within experimental uncertainty, and they are long for their type [mean value (Allen et al, 1987) = 1.136 Å , upper quartile value = 1.142 Å ].…”

Coordination polymer chains built from CuIIand adipate ions linked by hydrogen bonds to form a three-dimensional framework structure

“…In the tcnoet unit of (I), the two independent -C(CN) 2 units are twisted, in conrotatory fashion, out of the plane of the central propenide unit. The dihedral angles between the central C 3 fragment and the two -C(CN) 2 units containing atoms C31 and C33 are 23.0 (2) and 23.8 (2) , entirely typical of the behaviour of this anion and its simple analogues (Setifi et al, 2010;Setifi, Domasevitch et al, 2013;Setifi, Setifi, El Ammari et al, 2014;Setifi, Lehchili et al, 2014). On the other hand, the bond distances (Table 2) provide evidence for some localization of the negative charge, in contrast with the strong delocalization often observed for this anion and its analogues.…”

“…In addition to a variety of coordination polymer types, finite complexes have also been observed, ranging from dinuclear (Setifi, Setifi, Ghazzali et al, 2014) to octanuclear (Ghosh et al, 2007). In this context, the aim of some of our recent work has been to extend the potential versatility of such complexes to include four-component systems which also incorporate polynitrile anions as ligands and/or counter-ions, as such anions are of interest in exhibiting both a high degree of electronic delocalization and a variety of coordination modes (Atmani et al, 2008;Setifi, Domasevitch et al, 2013;Setifi, Setifi, El Ammari et al, 2014). Accordingly, we report here the synthesis, molecular structure and supramolecular assembly of the title compound, [Cu 2 (tcnoet) 2 (adipate)(bipy) 2 ] n , (I), where adipate represents hexane-1,6-dionate, bipy represents 2,2 0 -bipyridine and tcnoet represents 1,1,3,3-tetracyano-2-ethoxypropenide.…”

catena-Poly[[[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole-κ2N1,N5](dicyanamido-κN)copper(II)]-μ2-dicyanamido-κ2N:N′]: coordination polymer chains linked into a bilayer by hydrogen bonds and π–π stacking interactions

“…Polynitrile ligands are of great interest as they can lead to a rich variety of supramolecular architectures (Setifi et al, 2009(Setifi et al, , 2014Benmansour et al, 2010Benmansour et al, , 2012. One such ligand is the dicyanamide (dca) anion, [N(CN) 2 ] À , which can coordinate to metal centres in a wide variety of ways, using either the central N atom as a ligating atom or one or both of the terminal N atoms, or various combinations of these three N atoms.…”