Structural systematics of 2/4-nitrophenoxide complexes of closed shell metal ions. III 2/4-Nitrophenoxides of univalent heavy metals

J.M. Harrowfield, R.P. Sharma, Brian Skelton, A.H. White, Allan White

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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, P2(1)/c, a 9.012(4), b 5.743(5), c 12.594(5) Angstrom, beta 104.34(4)degrees, Z = 4; conventional R on \F\ was 0.042 for N-o 1378 independent 'observed' (I > 3 sigma(1)) reflections. Tl(2-np) is monoclinic, C2/c, a 27.250(3), b 3.712(1), c 15.147(3) Angstrom, beta 114.41(1)degrees, Z = 8, R 0.025 for N-o 1346. Ag(4-np).H2O is monoclinic, P2(1)/a, a 5.613(6), b 13.191(7), c 9.844(5) Angstrom, beta 92.50(6)degrees, Z = 4, R 0.033 for N-o 622. Tl(4-np) is tetragonal, I4(1)/a, a 18.037(8), c 8.979(8) Angstrom, Z = 16, R 0.043 for N-o 924. An acid salt of the latter, Tl(4-np).(4-npH)(3), triclinic, , a 11.861(8), b 11.45(1), c 11.423(1) Angstrom, alpha 114.00(6), beta 109.78(5), gamma 96.87(7)degrees, Z = 2, R 0.042 for N-o 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-C 2.496(5) Angstrom). 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) over bar symmetry, [Tl(O-phenoxide)](4), these being linked into a three-dimensional network by further Tl ... O-nitro interactions from adjacent units. The structure of silver(I) picrate monohydrate, isomorphous with its sodium counterpart, is also recorded: monoclinic, C2/m, a. 12.818(7), b 20.208(8), c 3.741(1) Angstrom, beta 88.25(3)degrees, Z = 4, R 0.047 for N-o 1042, void of any significant Ag ... C contacts.
Original languageEnglish
Pages (from-to)735-745
JournalAustralian Journal of Chemistry: an international journal for chemical science
Issue numberN/A
Publication statusPublished - 1998


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