Synthesis, crystal structure, magnetic properties and electrochemical behaviour of the mixed valence compound [Cu I(CN) 3Cu II(C 3H 10N 2) 2]

• Published in: Inorganica Chimica Acta Vol. 358; no. 8; pp. 2558 - 2564
• Main Authors: Pretsch, Thorsten, Ostmann, Jan, Donner, Constanze, Nahorska, Monika, Mroziński, Jerzy, Hartl, Hans
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 02.05.2005
• Subjects: Copper; Crystal structure; Hydrogen bonding; Magnetic properties; Mixed valence compounds; N ligands; N ligands; Copper; Hydrogen bonding; Mixed valence compounds; Magnetic properties; Crystal structure
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2005.02.018

Bis(propane-1,3-diamine-κ 2 N, N′)copper(II)tricyanomonocuprate(I) ( 1) and its diacetonitrile solvate ( 2) have been synthesized and structurally characterized. In addition, the magnetic, electrochemical and IR spectroscopic behaviour of 1 is reported. The binuclear mixed valence copper(I/II) compound [Cu I(CN) 3Cu II(tn) 2] ( 1) (tn = propane-1,3-diamine) and its acetonitrile adduct [Cu I(CN) 3Cu II(tn) 2] · 2MeCN ( 2) have been synthesized. Complex 1 crystallizes triclinic, space group P 1 ¯ , a = 8.117(2) Å, b = 8.389(2) Å, c = 11.920(2) Å, α = 108.728(3)°, β = 100.024(3)°, γ = 104.888(4)°, Z = 2, and compound 2 monoclinic, space group P2 1 /m, a = 8.752(2) Å, b = 13.243(3) Å, c = 9.549(2) Å, β = 114.678(4)°, Z = 2. In both crystal structures, the binuclear [Cu I(CN) 3Cu II(tn) 2] complex with slightly different bonding geometries is formed. One of the three nitrogen atoms of a Cu I(CN) 3 moiety is coordinated to Cu(II) at the apex of a square-pyramid with two chelating ligands tn on its base. The shortest intramolecular Cu II⋯Cu II distance in 1 is 5.640(7) Å. The EPR behaviour of 1 has been investigated at room temperature and at 77 K. The magnetic properties were measured in the temperature range 1.8–300 K.