Dicopper complexes derived from 4-amino-2,1,3-benzothiadiazole with versatile co-ordination number and geometry

Abstract

Three dicopper complexes of 4-amino-2,1,3-benzothiadiazole (abt) have been isolated and structurally characterized. The reaction of [Cu(CH 3 CN) 4 ][PF 6 ] with abt in THF produced [Cu 2 (abt) 2 (CH 3 CN) 4 ][PF 6 ] 2 ؒC 6 H 12 1ؒC 6 H 12 , while in acetone, Cu I template Schiff-base condensation of the amino group of abt with solvent was found to give [Cu 2In complex 1 there are two crystallographically independent monomeric units in each of which Cu I is co-ordinated by one N atom on the ring of abt and two acetonitrile molecules; two units are linked to each other by weak binding of the amino group of abt with Cu I to give a cyclic dinuclear complex. In complex 2 tetrahedral Cu I centers are bridged by two ibt molecules in a head-to-tail fashion as in 1. Both 1 and 2 have the same metallocyclophane skeletons showing an intramolecular stacking interaction between two parallel aromatic rings and a considerably long Cu ؒ ؒ ؒ Cu separation [7.220(5) Å for 1, 6.542(4) Å for 2]. Following the same synthetic strategy as used for the synthesis of 2 another dicopper complex [Cu 2 (ibt) 2 ][ClO 4 ] 2 3 was obtained, which presents a structural contrast with 2: two Cu I centers are linearly co-ordinated by two ibt molecules in a head-to-head arrangement which leads to a twisted conformation with a shorter Cu ؒ ؒ ؒ Cu distance of 2.699(2) Å. In addition, 1 H NMR measurements reveal that 2 can also be formed directly from 1 in acetone solution.

Role of basic sites of substituted ferrocenes in interaction with the trinuclear 3,5-bis(trifluoromethyl)pyrazolates: thermodynamics and structure of complexes

“…[1]} correspond to the weak coordination found between the two coordinated copper(I) atoms and oxygen containing anions (perchlorate, sulfate, nitrate, triate and others À2.50 to 2.75 Å). [20][21][22][23] The complex {[(AgL) 3 ]$2[1]} occupies a special position in the crystal on the twofold axis passing through the Ag(2) and the middle point of N(3)-N(3A) bond, see Fig. 10.…”

Novel applications of functionalized 2,1,3-benzothiadiazoles for coordination chemistry and crystal engineering

“…2, atoms N 1 and N 4 , respectively). 14,18,25 Both the [Ir(1)Cp*Cl 2 ] 25 and [Cd(1) 2 Br 2 ] 18 complexes contain ligands 1 coordinated by the N 1 atom (Fig. 2, coordination type 1).…”

“…12 As a result, multidimensional networks can be formed, which are believed to cause non-trivial chemical and physical properties of this type of compounds. [13][14][15][16][17] At the same time, the coordination chemistry of compounds under discussion is not well-developed, and only a limited number of structurally characterized transition metal complexes, including those of Ag, Cd, Co, Cu, Pd, Ru and trimeric peruoro-ortho-phenylenemercury (anti-crown compound), are known. [14][15][16][17][18][19][20][21][22][23][24] Recently, we reported the preparation and single-crystal Xray diffraction (XRD) characterization of Ir complexes with the parent 2,1,3-benzothiadiazole, its 4-amino-(1) and 4-hydroxyderivatives, and related acenaphtho [1,2-c] [1,2,5]thiadiazole as ligands.…”

“…[13][14][15][16][17] At the same time, the coordination chemistry of compounds under discussion is not well-developed, and only a limited number of structurally characterized transition metal complexes, including those of Ag, Cd, Co, Cu, Pd, Ru and trimeric peruoro-ortho-phenylenemercury (anti-crown compound), are known. [14][15][16][17][18][19][20][21][22][23][24] Recently, we reported the preparation and single-crystal Xray diffraction (XRD) characterization of Ir complexes with the parent 2,1,3-benzothiadiazole, its 4-amino-(1) and 4-hydroxyderivatives, and related acenaphtho [1,2-c] [1,2,5]thiadiazole as ligands. 25 In continuation of our research, in this paper, we report two novel applications of functionalized 2,1,3-benzothiadiazoles in coordination chemistry and crystal engineering, which covers the synthesis and characterization of a novel 2 : 1 complex between compound 1 and ZnCl 2 (complex 2; previously, Zn complexes with any 2,1,3-benzothiadiazoles were unknown), and unprecedented 1 : 1 co-crystals 26 of compound 1 and its synthetic precursor, 4-nitro-2,1,3-benzothiadiazole (3) (complex 4).…”

A benzothiadiazole-supported N-heterocyclic carbene and its rhodium and iridium complexes

“…For example, they have been used as components of organic-light-emitted diodes and as structural units of low-band gap polymers for photovoltaic applications [24][25][26][27][28][29][30][31][32][33]. They have also found applicability as ligands in transition metal complexes [34][35][36][37][38][39][40]. Annulation of a BTD moiety to an imidazol-2-ylidene provides a promising framework in which the carbene center is a component of an electron-rich, extended aromatic system.…”