
%0 Journal Article
%A Childs, Bradley J. 
%A Cadogan, John M. 
%A Craig, Donald C. 
%A Scudder, Marcia L. 
%A Goodwin, Harold A. 
%T Donor Atom Set and Spin State of Iron(II). Bis(ligand)iron(II) and Bis(ligand)nickel(II) Complexes of 2,2&#8242;-Bipyridine-6-carbothioamide and 2,2&#8242;-Bipyridine-6-carboxamide
%J Australian Journal of Chemistry
%D 1998/04/17
%V 51
%N 4
%P 273-284
%K 
%R https://doi.org/10.1071/C97071
%U https://www.publish.csiro.au/paper/C97071 
%X 2,2&#8242;-Bipyridine-6-carbothioamide (bpytm) and 2,2&#8242;-bipyridine-6-carboxamide (bpyam) are NNS and NNO donors, respectively, in their cationic bis(ligand)iron(II) and bis(ligand)nickel(II) complexes. The former ligand provides the stronger field and salts of &#91;Fe(bpytm)2&#93;2+ have a singlet ground state, while those of &#91;Fe(bpyam)2&#93;2+ have a quintet ground state. The magnetism and the electronic and M&ouml;ssbauer spectra of salts of these cations have been measured. The low-temperature M&ouml;ssbauer spectra of iron(II) complex salts of the carboxamide indicate, for the perchlorate and triflate salts, but not for the fluoroborate salt, a partial transition to singlet-state species. The mode of coordination of the ligands is indicated by infrared spectral data and has been confirmed by determination of the structures of &#91;Ni(bpytm)2&#93; Cl2.4H2O, &#91;Ni(bpyam)2&#93; &#91;BF4&#93;2.H2O and &#91;Fe(bpyam)2&#93; &#91;BF4&#93;2. In addition, the structures of the free ligands have been determined. Hydrogen bonding is present in the free ligands and their complexes. 2,2&#8242;-Bipyridine-6-carbothioamide: monoclinic, space group P21/c, a 8&#183;265(3), b 11&#183;175(2), c 11&#183;114(4) &#197;, &#946; 94&#183;47(2)&#176;, Z 4. 2,2&#8242;-Bipyridine-6-carboxamide: monoclinic, space group P21/c, a 13&#183;581(2), b 9&#183;926(1), c 16&#183;824(3) &#197;, &#946; 116&#183;481(7)&#176;, Z 8. &#91;Ni(bpytm)2&#93; Cl2.4H2O: triclinic, space group P-1, a 9&#183;291(5), b 12&#183;426(7), c 13&#183;425(7) &#197;, &#945; 113&#183;54(3), &#946; 95&#183;63(3), &#947; 94&#183;43(3)&#176;, Z 2. &#91;Ni(bpyam)2&#93;&#91;BF4&#93;2.H2O: triclinic, space group P-1, a 10&#183;663(5), b 10&#183;861(6), c 12&#183;799(6) &#197;, &#945; 68&#183;70(4), &#946; 77&#183;84(4), &#947; 78&#183;47(4)&#176;, Z 2. &#91;Fe(bpyam)2&#93; &#91;BF4&#93;2: orthorhombic, space group P bcn, a 12&iexcl;317(6), B 12&iexcl;609(4), c 16&#183;644(8) &#197;, Z 4. 
