Preparation, spectroscopic and magnetic characterization of Cu(cyclam)M(CN)4 complexes exhibiting one-dimensional crystal structures (cyclam = 1,4,8,11-tetraazacyclotetradecane, M = Ni, Pd, Pt)

Abstract

Preparation, spectroscopic and magnetic characterization of Cu(cyclam)M(CN) 4 complexes exhibiting one-dimensional crystal structures (cyclam 5 1,4,8, M 5 Ni, Pd, Pt) Abstract From the systems Cu(II)-cyclam-[M(CN) 4 ] 2-(cyclam = 1,4,8,11-tetraazacyclotetradecane; M = Ni, Pd, Pt), three cyanidocomplexes Cu(cyclam)M(CN) 4 [M = Ni (1), Pd (2), Pt (3)] were isolated and characterized by chemical analysis, IR and UV-VIS spectroscopy. The three compounds are isostructural, and their crystal structures are formed by quasi-linear chains exhibiting [-Cu(cyclam)-l-NC-M(CN) 2 -l-CN-] n composition. The Cu(II) atoms reside on centres of symmetry and are coordinated in the form of an elongated octahedron with mean equatorial Cu-N bonds of 2.015(12), 2.017(13) and 2.011(11) Å in (1), (2) and (3), respectively, and weakly N-bonded bridging cyanido ligands in the axial positions [2.5321(9) Å in (1), 2.518(2) Å in (2) and 2.549(3) Å in (3)]. Hydrogen bonds of the N-HÁÁÁN cyanido ÁÁÁH-N type link neighbouring chains, and a topologically square network of paramagnetic Cu(II) atoms is formed. The magnetic susceptibilities of all three complexes follow the Curie-Weiss law with a weak antiferromagnetic exchange coupling below 5 K.

Crystal structure of (1,4,8,11-tetraazacyclotetradecane-κ4 N,N′,N′′,N′′′)palladium(II) tetracyanonickelate(II), C14H24N8NiPd

“…The highest peak (0.31 e Å −3 ) and the deepest hole (−0.34 e Å −3 ) in the difference Fourier map are located 0.69 Å and 0.74 Å from atoms N1 and Pd1, respectively. [6], respectively. In the title compound, on the contrary, such a cyanido-bridging is not observed: the distance between the Pd1 and N3(cyanido) atoms is relatively long with 3.467(2) Å [4].…”

Syntheses and characterizations of tetracyanoplatinate(II) complexes with 2-pyridineethanol

“…Investigation on cyanide-bridged polymeric metal complexes using tetracyanoplatinate (II) as building blocks are limited [5][6][7][8][9][10]. Because tetracyanoplatinate(II) can use different numbers of cyanide groups to bind to other metal ions, a range of solid-state structures exist.…”

Low-dimensional compounds containing cyanido groups. XXVIII. Crystal structure, spectroscopic and magnetic properties of two copper(II) tetracyanidoplatinate complexes with 1,2-diaminopropane

“…Bis-pn copper(II) arrangement is the most frequently observed (63 structures in the CSD -for example {[Cu(pn) 2 ] 2 (H 2 O)W(CN) 8 } n Á 3nH 2 O [6]) followed with mono-pn copper(II) arrangement (eleven structures -for example [Cu(pn)Ni(CN) 4 ] n Á 0.5nH 2 O [7]). Finally, five structures with both mono-pn and bis-pn arrangements (for example [Cu(pn) 2 ] n {[Cu (pn)] 2 Cu 6 (N 3 ) 18 ]} n Á nH 2 O [8]) and only one compound with tris-pn arrangement ([Cu(pn) 3 ]Br 2 Á 2H 2 O [9]) can be found in the CSD. Moreover, a pair of compounds with discrete protonated Hpn þ [10] or diprotonated H 2 pn 2 þ cations can be found there, too [11].…”

“…In our previous studies on the role of hydrogen bonds as possible exchange path for magnetic interactions in low-dimensional compounds we have prepared and characterized 1D compounds of general formula [CuL x Pt(CN) 4 ] n , where L are bidentate (x¼ 2) [4,[13][14][15], tridentate (x¼1) [16,17] or tetradentate (x¼1) [18] aliphatic N-donor Contents lists available at ScienceDirect journal homepage: www.elsevier.com/locate/jssc ligands. Their structures are formed by chains of all four simple 2,2 types (for more details about chains of 2,2 types and their nomenclature see [2]) and are stabilized by hydrogen bonds of the N-H⋯N type.…”