
%0 Journal Article
%A Kepert, DL 
%A Waters, AF 
%A White, AH 
%T Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. VIII. Some Mixed-Ligand Complexes of Group 2 Metal Halides With Aromatic N,N'-Bidentate and Oxygen Donors
%J Australian Journal of Chemistry
%D 1996/01/01
%V 49
%N 1
%P 117-135
%K 
%R https://doi.org/10.1071/CH9960117
%U https://www.publish.csiro.au/paper/CH9960117 
%X Room-temperature single-crystal X-ray structural characterizations have defined an interesting array of species obtained by variously crystallizing Group 2 halides with 2,2'-bipyridine ( bpy ) and 1,10-phenanthroline ( phen ) from hydroxylic solvents. [( phen )2Ca(OH2)3]Br2 (1) is monoclinic, P21/c, a 16.896(5), b 8.620(2), c 17.814(5) &#506;, &#946; 97.05(2)&#176;, Z = 4 f.u .; conventional R on &#1472; F &#1472; was 0.057 for 1707   independent 'observed' (I > 3&#963;(I)) reflections No, the complex   containing seven-coordinate Ca(N2)2O3 calcium. [( bpy )2CaBr(OH2)( HOPri )]   Br (2) is monoclinic, P21/c, a 9.674(4), b 18.236(8), c 14.716(8) &#506;, &#946; 90.83(4)&#176;, Z = 4 f.u ., R 0.044 for No 2349, with seven-coordinate [CaBr (N2)2O2] calcium. [( bpy )2CaBr2( HOPr )] (3), [( bpy )2CaBr2( HOBu )] (4) and [( bpy )2SrBr2( HOPr )] (5) are all isomorphous, triclinic, P&#299;, a &#8776; 17,   b &#8776; 9.6, c &#8776; 7.7 &#506;, &#945; &#8776; 105, &#946; &#8776; 94, &#947; &#8776; 95&#176;, Z = 2 f.u .; R 0.055, 0.037, 0.061 for No 3111, 3102, 2424 respectively; all have a seven-coordinate [MX2(N2)2O] metal environment. A similar array is found in [(phen)2CaBr(OH2)( HOMe )] Br (6), triclinic, P&#299; , a 16.761(8), b  10.647(6), c 7.376(6) &#506;, &#945; 75.78(6), &#946; 82.47(5), &#947; 75.86(5)&#176;, Z = 2 f.u ., R 0.057 for No 3216. With bpy , from aqueous methanol, however, [(bpy)2Ca(OH2)2( HOMe )2] Br2 (7) was obtained, monoclinic, C2/c, a   17.645(7), b 10.899(4), c 16.071(5) &#506;, &#946; 118.88(2)&#176;, Z = 4 f.u ., R 0.044 for No 1448, containing eight-coordinate Ca(N2)2O4 calcium; the calcium is disposed on a twofold axis. [( bpy )2SrBr2( HOMe )2] (8) is triclinic, P&#299; , a 13.784(5), b 10.605(4), c 9.653(1) &#506;, &#945; 115.78(2), &#946; 96.87(3), &#947; 96.67(3)&#176;, Z = 2 f.u ., R 0.045 for No 2754; the  strontium is eight-coordinate [SrBr2(N2)2O2]. [( phen )2Sr(OH2)4] I2.2phen (9), triclinic, P&#299; , a 13.314(4), b 12.311(3), c 7.066(2) &#506;, &#945; 99.77(2), &#946; 92.43(2), &#947; 77.27(2)&#176;, Z = 1 f.u ., R 0.049 for No 2703, is isomorphous with the previously studied perchlorate analogue, the strontium being disposed on a centre of symmetry. Species (1)-(9) are all mononuclear; the barium adducts (10) and (11) are binuclear: [( phen )2Ba(OH2)2Cl(&#956;-OH2)2Cl(H2O)2Ba( phen )2] Cl2.2phen.4H2O (10) is triclinic, P&#299; , a 14.590(3), b 14.109(4), c 10-862(2) &#506;, &#945; 74.56(2), &#946; 65.87(2)&#176;, &#947; 63.59(2)&#176;, Z = 1 centrosymmetric dimer, R 0.027 for No 5249, with nine-coordinate Ba (N2)2ClO2(&#956;-O)2 barium. [( bpy )2Ba(I/OH2)(&#956;- I)3(I/OH2) Ba ( bpy )2] (11) is monoclinic, P 2/c, a 13.988(2), b 11.00(2), c 20.900(7) &#506;, &#946; 127.59(2)&#176;, Z = 2 dimers , R 0.069 for No 3353, with eight-coordinate Ba (N2)2(I/OH)(&#956;-I)3 barium. All of (1)-(11) contain M(N2)2 arrays with diverse associations of solvent oxygen atoms, and in some cases halogens. Species (12), [( bpy )BaBr2( HOMe )2] (&#8734; &#1472; &#8734;), is polymeric, monoclinic, C 2/c, a 17.119(2), b 13.844(1), c 7.489(1) &#506;, &#946; 111.21(1)&#176;, Z = 4 f.u ., R 0.057 for No 2326; the barium lies on a twofold axis in an eight-coordinate [ Ba (N2)(O)2(&#956;-Br)4] environment. An adduct (13) of barium iodide with 4,4'-bipyridine, BaI2/(4,4'-bpy)/ PrOH (1:2&#189;:2), monoclinic, P 21/c, a l5.467(5), b 12.639(7), c 21.004(5) &#506;, &#946; 118.99(3)&#176;, Z = 4, R 0.059 for No 2.003, is a one-dimensional polymer, linked by two of the 4,4'-bpy ligands , one of these being centrosymmetric; the third ligand occupies a lattice site, so that the complex is [(4,4&#8242;-bpy)(4,4&#8242;-bpy)&#189;Ba( HOPr )2](&#8734; &#1472; &#8734;).(4,4'-bpy). The barium environment is seven-coordinate pentagonal bipyramidal, the two iodines occupying the axial/trans sites and the two oxygens non-adjacent in the pentagonal plane. 
