
%0 Journal Article
%A Harrowfield, Jack M. 
%A Sharma, Raj Pal 
%A Skelton, Brian W. 
%A White, Allan H. 
%T Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. III 2/4-Nitrophenoxides of Univalent Heavy Metals
%J Australian Journal of Chemistry
%D 1998/08/18
%V 51
%N 8
%P 735-746
%K 
%R https://doi.org/10.1071/C97100
%U https://www.publish.csiro.au/paper/C97100 
%X Room-temperature single-crystal X-ray studies are recorded for 2- and 4-nitrophenoxide salts of silver(I) and thallium(I), M(2-np) and Tl(4-np) (anhydrous), and Ag(4-np).H2O. Ag(2-np) is monoclinic, P21/c, a 9&#183;012(4), b 5&#183;743(5), c 12&#183;594(5) &#197;, &#946; 104&#183;34(4)&#176;, Z = 4; conventional R on &#124;F&#124; was 0&#183;042 for No 1378 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) reflections. Tl(2-np) is monoclinic, C2/c, a 27&#183;250(3), b 3&#183;712(1), c 15&#183;147(3) &#197;, &#946; 114&#183;41(1)&#176;, Z = 8, R 0&#183;025 for No 1346. Ag(4-np).H2O is monoclinic, P21/a, a 5&#183;613(6), b 13&#183;191(7), c 9&#183;844(5) &#197;, &#946; 92&#183;50(6)&#176;, Z = 4, R 0 &#183;033 for No 622. Tl(4-np) is tetragonal, I 41/a, a 18&#183;037(8), c 8&#183;979(8) &#197;, Z = 16, R 0&#183;043 for No 924. An acid salt of the latter, Tl(4-np).(4-npH)3, triclinic, P-1, a 11&#183;861(8), b 11&#183;45(1), c 11&#183; 423(1) &#197;, &#945; 114&#183;00(6), &#946; 109&#183;78(5), &#947; 96&#183;87(7)&#176;, Z = 2, R 0&#183;042 for No 3814, is isomorphous with its rubidium analogue. These comprise a novel array of structures: although the structures of the silver(I) complexes are two-dimensional sheets with familiar head-tail connecting ligands, a strong silver-aromatic carbon interaction is found in Ag(2-np) (Ag&#8211;C 2&#183;496(5) &#197;). Tl(2-np) and Tl(4-np) both present unusual forms related to the stair-polymer and cubane adducts found in 1 : 1 coinage metal(I)/halide-unidentate nitrogen base adducts; Tl(2-np) is a double-stranded stair-polymer array, with the phenoxide oxygen atoms incorporated in the stair and the nitro oxygen atoms linking successive thallium atoms. The structure of Tl(4-np) is based on a tetranuclear cubane motif of -4 symmetry, &#91;Tl(O-phenoxide)&#93;4, these being linked into a three-dimensional network by further Tl &#183; &#183; &#183; O-nitro interactions from adjacent units. The structure of silver(I) picrate monohydrate, isomorphous with its sodium counterpart, is also recorded: monoclinic, C 2/m, a 12&#183;818(7), b 20&#183;208(8), c 3&#183; 741(1) &#197;, &#946; 88&#183;25(3)&#176;, Z = 4, R 0&#183;047 for No 1042, void of any significant Ag &#183; &#183; &#183; C contacts. 
