
%0 Journal Article
%A Skelton, BW 
%A Waters, AF 
%A White, AH 
%T Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. VII. Some Complexes of Group 2 Metal Halides With Aromatic N,N'-Bidentate Ligands
%J Australian Journal of Chemistry
%D 1996/01/01
%V 49
%N 1
%P 99-115
%K 
%R https://doi.org/10.1071/CH9960099
%U https://www.publish.csiro.au/paper/CH9960099 
%X Syntheses and room-temperature single-crystal X-ray structural characterizations are recorded for a number of adducts of Group 2 halides with the aromatic N,N&#8242;- bidentate  ligands L = 2,2'-bipyridine ( bpy ) and 1,10-phenanthroline ( phen ). One adduct of 1 : 1 MX2/L stoichiometry is recorded: [( bpy )Ca(&#956;-Br)(4/2)](&#8734; &#1472; &#8734;) (1) is monoclinic, C 2/c, a l7.102(5), b 9.845(1), c 7.600(2) &#506;, &#946; 107.65(2)&#176;, Z = 4 f.u .; conventional R on #1472; F &#1472; at convergence was 0.057 for No 817 independent 'observed' ( I > 3&#963;(I)) reflections, the compound being a one-dimensional polymer&#8230; CaL (&#956;-Br)2CaL(&#956;-Br)2&#8230;, with six-coordinate calcium, cis-CaN2(&#956;-Br)4, on a twofold axis. 1 : 2 MX2/L systems have been described for two types of array: [( bpy )2CaI2] (2), orthorhombic, Pnca, a 16.914(4), b 13.80(1), c 9.290(4) &#506;, Z = 4 f.u .; R 0.039 for No 1738, is discrete mononuclear, containing cis-CaN4I2 six-coordinate calcium, whereas the barium analogue is an infinite one-dimensional polymer, [( bpy )2Ba(&#956;-I)(4/2)](&#8734;&#1472; &#8734;) (3), triclinic, P&#299;, a 11.318(2), b 11.078(2), c 9.206(4) &#506;, &#945; 80.87(2), &#946; 77.52(2), &#947; 87.53(1)&#176;, Z = 2 f.u .; R 0.032 for No 4154, with eight-coordinate (N2)2Ba(&#956;-I)4. The perchlorate analogue, [( bpy )2Ba(&#956;-OClO2O)(4/2)](&#8734; &#1472; &#8734;) (4), although of similar stoichiometry, has a trans-rather than a cis-linked chain; it is monoclinic, P 21/c, a 6.606(2), b 18.661(7), c 19.440(8) &#506;, &#946; 109.45(4)&#176;, Z = 4 f.u .; R 0.044 for No 4060, with &#956;-I replaced by O,O'-ClO4 bridging units and eight-coordinate barium, (N2)2BaO4. The 1 : 3 MX2/L system is represented (as its hemi( bipyridine ) 'solvate') by mononuclear [( bpy )3SrI2].0.5bpy (5), monoclinic, P 21/c, a 20.834(8), b 9.735(4), c 18.460(7) &#506;, &#946; 114.87(3)&#176;, Z = 4 f.u .; R 0.039 for No 3711, containing eight-coordinate strontium, [(N2)3SrI2]; there is also an isomorphous calcium/ perchlorate analogue [( bpy )3Ca(OClO3)2].0.5bpy (6), a 21.413(6), b 9.813(4), c 18.659(2) &#506;, &#946; 115.67(2)&#176;, R 0.057 for No 3090, in which unidentate O-ClO4 ligands replace the iodine about the metal atom. A 1 : 4 adduct is obtained with CaI2/phen; ionic [Ca( phen )4] I2 (7), triclinic, P&#299; , a 14.703(3), b 13.292(3), c 11.38(1) &#506;, &#945; 92.78(4), &#946; 96.15(4), &#947; 105.22(2)&#176;, Z = 2 f.u ., R 0.053 for No 3658, contains eight-coordinate Ca(N2)4 arrays, while the novel 1 : 5 adduct [ Ba ( phen )4] I2.MeCN (8) is triclinic, P&#299; , a 12.170(6), b 13.760(7), c 18 254(8) &#506;, &#945; 77.05(9), ,&#946; 71.96(4), &#947; 70.83(9)&#176;, Z = 2 f.u ., R 0.040 for No 4447, containing 10-coordinate barium, [ Ba (N2)5]. A 1 : 4 adduct formed with BaBr2 is [ BrBa( phen )4] Br.MeOH (9), triclinic, P&#299; , a 17.748(4), b 17.418(2), c 15.535(7) &#506;, &#945; 91.63(2), &#946; 100.53(3), &#947; 115.39(1)&#176;, Z = 4 f.u ., R 0.062 for No 4092, containing nine-coordinate barium, [ BrBa (N2)4]. 
