Crystal structure of [bis-(2-amino-ethyl-κN)(2-{[4-(tri-fluoro-meth-yl)benzyl-idene]amino}-eth-yl)amine-κN]di-chlorido-copper(II).

The Cu(II) atom in the title compound, [CuCl2(C14H21F3N4)], adopts a coordination geometry that is between distorted square-based pyramidal and very Jahn-Teller-elongated octa-hedral. It is coordinated by three N atoms from the bis-(2-amino-eth-yl)(2-{[4-(tri-fluoro-meth-yl)benzyl-idene]amino}-eth-yl)amine and two chloride ligands. The two crystallographically unique copper complexes present in the asymmetric unit exhibit noticeable differences in the coordination bond lengths. Considering the Cu(II) atoms as having square-pyramidal geometry, the basal Cu-Cl bond lengths are typical [2.2701 (12) and 2.2777 (12) Å], while the apical distances are considerably elongated [2.8505 (12) and 2.9415 (12) Å]. For each mol-ecule, a Cu(II) atom from inversion-related mol-ecules are in nearby proximity to the remaining axial Cu(II) sites, but the Cu⋯Cl distances are very long [3.4056 (12) and 3.1645 (12) Å], attributable to van der Waals contacts. Nonetheless, these contacts appear to have some structure-directing properties, leading to association into dimers. These dimers associate via stacking of the aromatic rings to form extended zigzag chains.

Crystal structure of [tris-(pyridin-2-ylmeth-yl)amine-κ(4) N]copper(II) bromide.

In the asymmetric unit of the title compound, [CuBr(C18H18N4)]Br, there are three crystallographically independent cations. One of the cations exhibits positional disorder of the pyridin-2-yl-methyl groups over two sets of sites with refined occupancies of 0.672 (8) and 0.328 (8). The outer-sphere bromine counter-ion is severely disordered over multiple sites. In each cation, the Cu(II) ion is coordinated by the four N atoms of the tris-(pyridin-2-ylmeth-yl)amine ligand and one bromine and adopts a slightly distorted trigonal-bipyramidal geometry.

Crystal structure of {(but-3-en-1-yl)bis-[(pyridin-2-yl)meth-yl]amine-κ(3) N,N',N''}di-chlorido-copper(II) diethyl ether hemisolvate.

The five-coordinate Cu(II) atom in the title complex [CuCl2(C16H19N3)]·0.5C4H10O, adopts a near-ideal square-pyramidal geometry (τ-5 = 0.01). The apical Cu-Cl distance is 0.2626 (6) Šlonger than the basal Cu-Cl distance. Weak C-H⋯Cl interactions between pyridine rings and the Cl atoms of adjacent complex molecules are present. The solvent molecule, located on a twofold rotation axis, is situated in the voids of this arrangement. Copper atoms coordinated by tridentate nitro-gen-containing ligands have been found to be excellent promoters of Atom Transfer Radical Addition (ATRA) reactions.

Structural studies of (prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine hetero-scorpionate copper complexes.

The structures of five compounds consisting of (prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine complexed with copper in both the Cu(I) and Cu(II) oxidation states are presented, namely chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(I) 0.18-hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena-poly[[copper(I)-µ2-(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(5)N,N',N'':C(2),C(3)] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di-µ-chlorido-bis({(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two Cu(I) complexes results in either a discrete molecular species, as in (1), or a one-dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the Cu(I) atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one-dimensional chain parallel to the crystallographic b axis. Three complexes with Cu(II) show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis-µ-chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core-bridged Cu2Cl2 moiety.

Crystal structure of ortho-rhom-bic {bis-[(pyridin-2-yl)meth-yl](3,5,5,5-tetra-chloro-pent-yl)amine-κ(3) N,N',N''}chlorido-copper(II) perchlorate.

In the title compound, [CuCl(C17H19Cl4N3)]ClO4, the Cu(II) ion adopts a distorted square-planar geometry defined by one chloride ligand and the three nitro-gen atoms from the bis-[(pyridin-2-yl)meth-yl](3,5,5,5-tetra-chloro-pent-yl)amine ligand. The perchlorate counter-ion is disordered over three sets of sites with refined occupancies 0.0634 (17), 0.221 (16) and 0.145 (7). In addition, the hetero-scorpionate arm of the bis-[(pyridin-2-yl)meth-yl](3,5,5,5-tetra-chloro-pent-yl)amine ligand is disordered over two sets of sites with refined occupancies 0.839 (2) and 0.161 (2). In the crystal, weak Cu⋯Cl inter-actions between symmetry-related mol-ecules create a dimerization with a chloride occupying the apical position of the square-pyramidal geometry typical of many copper(II) chloride hetero-scorpionate complexes.