Cocrystallized Dinuclear−Mononuclear Cu^II₃Na^I and Double-Decker−Triple-Decker Cu^II₅K^I₃ Complexes Derived from N,N′-Ethylenebis(3-ethoxysalicylaldimine)

Abstract

The syntheses and structures of a [2×1+1×2] cocrystal [{Cu II L 1 Na I (H 2 O) 2 }{Cu II L 1 } 2 ](NO 3 ) (1) and [3×1+5×1] cocrystal [{(Cu II L 1 ) 2 K I }(NO 3 )] • [{(Cu II L 1 ) 3 K I 2 (µ-NO 3 )}(NO 3 )] • 0.2H 2 O (2) derived from the hexadentate Schiff base compartmental ligand N,N′-ethylenebis(3-ethoxysalicylaldimine) (H 2 L 1 ) are described. Compounds 1 and 2 crystallize in triclinic P1 j and monoclinic P2 1 /c systems, respectively. The structure of 1 consists of the [Cu II L 1 Νa I (H 2 O) 3 ] + cation and two mononuclear [Cu II L 1 ] moieties. In the dinuclear [Cu II L 1 Νa I (H 2 O) 3 ] + cation, the metal centers are doubly bridged by the two phenolate oxygen atoms. Each of the two coordinated water molecules of the dinuclear unit is encapsulated in the O 4 cavities of the two mononuclear [Cu II L 1 ] moieties resulting in the formation of a [2×1+1×2] cocrystal. In compound 2, one trinuclear double-decker system [{(Cu II L 1 ) 2 K I }(NO 3 )] and one pentanuclear triple-decker system [{(Cu II L 1 ) 3 K I 2 (µ-NO 3 )}(NO 3 )] are cocrystallized. Evidently, compound 2 is a [3×1+5×1] cocrystal. Structural resemblance of 3d metal ions with Na(I) and a rare example of double-decker-triple-decker cocrystal are the major outcomes of the present investigation.

Spacer-Controlled Supramolecular Assemblies of Cu(II) with Bis(2-Hydroxyphenylimine) Ligands. from Monoligand Complexes to Double-Stranded Helicates and Metallomacrocycles

“…The first of these shows interesting molecular recognition behavior towards a water molecule in the outer O4 coordination sphere forming the second complex site. This O4 pocket has also been used for the additional binding of s-or f-block metal ions leading to heterodinuclear Cu(II) complexes [17][18][19]. During our studies, we found that the reaction of the (±)-trans-1,2-cyclohexylidene bridged H2L 1 with Cu(NO3)2·3H2O (molar ratio 1:1) in methanol/tetrahydrofuran (v:v = 1:1) leads to a dinuclear Cu(II) complex.…”

Syntheses, structures and catecholase activity of two cobalt(III) complexes derived from N,N′-ethylenebis(3-ethoxysalicylaldiimine): A special host–guest system from a special ligand

“…Many mono/di/oligonuclear metal complexes have been reported from the following types of acyclic Schiff base ligands: (i) Single-compartment ligands (H 2 L Single ), obtained on [2+1] condensation of salicylaldehyde/2-hydroxyacetophenone/2-hydroxypropiophenone and a diamine [1][2][3][4][5][6][7][8][9][10][11]; Double-compartment ligands H 2 L OMe [1,[12][13][14][15][16][17][18] and H 2 L OEt [1,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] ligands, obtained on [2+1] condensation of 3-methoxysalicylaldehyde and 3-ethoxysalicylaldehyde, respectively, and a diamine. It has been established that H 2 L OEt ligands are something special because its O(phenoxo) 2 O(ethoxy) 2 compartment is strongly potential to act as a hydrogen bond acceptor with hydrogen bond donors such as water [1,[19][20][21][22][23][24][25]…”

“…It has been established that H 2 L OEt ligands are something special because its O(phenoxo) 2 O(ethoxy) 2 compartment is strongly potential to act as a hydrogen bond acceptor with hydrogen bond donors such as water [1,[19][20][21][22][23][24][25][26][27][28][29][30][31], aquated proton [32,33], ammonium ion [22] and diprotonated diamine [34,35]. The metal complexes derived from H 2 L OEt ligands include mononuclear host-guest systems, dinuclear systems, double/triple/quadruple-decker compounds, supramolecular dimers and finite/infinite cocrystals [1,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]. It is worth mentioning that a number of the metal compounds derived from H 2 L OEt ligands are weak interaction directed selfassemblies [1,[19][20][21][22][23][24][25]...…”

“…It is worth mentioning that a number of the metal compounds derived from H 2 L OEt ligands are weak interaction directed selfassemblies [1,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] and thus lie in the domain of general perspectives of crystal engineering [36][37][38][39]. In spite of our extensive works on H 2 L OEt ligands [1,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] and in spite of our observation of a number of interesting self-assemblies over a decade, we have been hopeful that some more new types of weak interaction directed systems can be stabilized with this family of special ligands and therefore we are yet in the process of continuous development.…”

Syntheses, Structures and Magnetic Properties of Trinuclear CuIIMIICuII (M = Cu, Ni, Co and Fe) and Tetranuclear [2×1+1×2] CuIIMnII–2CuII Complexes Derived from a Compartmental Ligand: The Schiff Base 3‐Methoxysalicylaldehyde Diamine Can also Stabilize a Cocrystal

“…[13- 15,20] The significant difference between the two closely related ligand environments is surprising, and we would like to explore this area further. We were particularly interested in the 3d-3d complexes derived from new or unexplored H 2 Crystal structures of 2 and 5 are shown in Figures 1 and 2, respectively, while selected bond lengths and angles of these two compounds are listed in Tables 1 and 2, (2).…”