Molecular complexes. Part XI. Crystal and molecular structure of the 1 : 1 complexes of 1,3,5-trinitrobenzene and bis-(N-t-butylsalicylideneiminato)-cobalt(II), -nickel(II), and -copper(II)

Abstract

The three-dimensional crystal structures of the 1 : 1 complexes of 1.3.5-trinitrobenzene and bis-(N-t-butylsalicylideneiminato) -cobalt( 11). -nickel(ll), and -copper(ll) have been determined. They are essentially isomorphous and have a structure formed from pairs of donor [bis-(N-t-butylsalicylideneiminato) metal(i I)] and acceptor (1.3.5-trinitrobenzene) molecules. The 1.3.5-trinitrobenzene interacts with only one of the salicylideneiminato ligands of a given chelate. The co-ordination around the metal atom is a flattened M02N2 tetrahedron with angles between the M , N ( l ) , 0(1) and M, N(2). O(2) planes of 81' 34'. 78" 51'. and 61" 36'for the cobalt, nickel, and copper structures respectively. Inter-ligand steric strains increase with flattening but prevent the metal adopting square planar or octahedral co-ordinations. South Parks Road, Oxford OX1 30s RECENTLY the effects of ligand structure on the stereochemical and electronic properties of Schiff -base metal complexes (I) have been extensively studied in solution R (1) and in the solid by different physical methods.lS2 In connection with a part of this work a crystallographic investigation of the donor-acceptor interactions of these complexes (in which X = H, R = But) has been carried out. EXPERIMENTAL Bis-(N-t-butylsalicylidenei~zinato)cobalt (11)-1,3,5-trinitrobenzene

Spin-state isomerism of tris(2-picolylamine)iron(II). The diiodide and the hydrated dichloride

“…C(l) 0.6170 (9) 0.6783 (7) 0.6542 ( 6) 126 ( 13) 82 ( 8) 59 ( 6) 73 ( 9) 35 ( 7) (6) C( 2) 0.6545 (11) 0.6110 (9) 0.6443 ( 6) 193 ( 16) 101 ( 10) 57 ( 6) 103 ( 11) 44 (8) ( 7) C( 3) 0.5509 ( 14) 0.5054 ( 9) 0.6153 ( 7) 260 ( 21) 127 ( 12) 62( 7)…”

Synthesis and crystal and molecular structure of the 2:1 molecular adduct between N,N'-(1,2-phenylene)bis(salicylaldiminato)copper(II) and 7,7,8,8-tetracyanoquinodimethane

“…7V,Ar,-(l,2-Phenylene)bis(salicylaldiminato)copper(II) [Cu(salphen)] was prepared (i) as prescribed by Pfeiffer et al,21 by reaction of 1,2-phenylenediamine with bis(salicylaldehyde)copper(II), or (ii) by direct action of copper acetate on the tetradentate Schiff base N,N'-(l,2-phenylene)salicylaldimine (salphen) in ethanol and recrystallized from chloroform. 7,7,8, (TCNQ) was purchased from Aldrich-Europe.…”

“…N (1) T 0.3045(4) 0,1617(4) 0.3305 (7) 82,( 4) 6660(4) 0,1647(3) 0.2772(7) 88,(4) CO) 0.2754(3) 0.1479(4) -0.1706(6) 60,(3) C (2) -0.0368(3) 0.3903(3) 0.1445(6) 34,4(28) C(1)T 0.3956(3) 0.4424(4) 0.4806(6) 38,(3) C (2) T 0.5997(3) 0,4487(4) 0.4552(6) 41. (3) C(3)T 0.4954(3) 0.3846(3) 0.4322(6) 52.…”

“…(3) C(3)T 0.4954(3) 0.3846(3) 0.4322(6) 52. (3) C(4)T 0.4917(3) 0.2736(4) 0.3649(6) 49,(3) C(S)T 0.3876(4) 0.2091(4) 0.3432 (7) 73,( 4)…”

Structure, electronic, and CV properties of hydroxy-naphthaldehyde Schiff-base copper(II) complexes derived from alkyl amines: X-ray structure of bis(n-i-propyl-3-hydroxy-2-naphthaldiminato)copper(II)

“…The UV-Vis spectrum is consistent with this flat tetrahedral arrangement. The coordination sphere is less distorted than in bis(N-t-butyl-salicylaldiminate)copper(II) [33] as seen from the dihedral angles between the planes, including Cu-N1-O2 and Cu-N2-O2 (Dih) of 51.4 and 61.6 , respectively, as expected for the larger t-Bu group. Comparison with bis(N-tbutyl-2-hydroxy-1-naphthaldiminato)copper(II) (4) shows, in contrast, a smaller dihedral angle, 45.4 .…”