
%0 Journal Article
%A Semenova, Lioubov I. 
%A Skelton, Brian W. 
%A White, Allan H. 
%T Structural Systematics of Rare Earth Complexes. XVIII (Hydrated) Mononuclear 1 : 1 Adducts of Lanthanoid(<emph type="6">III</emph>) Chlorides with 2,2&#x2032;-Bipyridine
%J Australian Journal of Chemistry
%D 1999/08/05
%V 52
%N 6
%P 551-570
%K 
%R https://doi.org/10.1071/CH98049
%U https://www.publish.csiro.au/paper/CH98049 
%X Room-temperature single-crystal X-ray structure determinations are recorded for a number of adducts of hydrated lanthanoid(III) chlorides with 2,2&#8242;-bipyridine, &#8216;bpy&#8217;, crystallized from water/ethanol solutions, which contain mononuclear arrays with 1 : 1 Ln/bpy stoichiometry. Extended isomorphous series have been defined pertinent to the heavy end of the Ln series: crystals of LnCl3/bpy/H2O (1 : 1 : 6) (&#91;(bpy)Ln(OH2)6&#93;Cl3), seemingly inclusive of (at least) the range Ln = Ho(-)Lu and Y, are monoclinic, P 21/n, a &#x2248; 14&#183;2, b &#x2248; 7&#183;7, c &#x2248; 17&#183;4 &#197;, &#946; &#x2248; 91&#176;, Z = 4, with an eight-coordinate LnN2O6 array; conventional R values on &#124;F&#124; were 0&#183;043, 0&#183;029, 0&#183;057 for No 2435, 3120, 1846 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) diffractometer reflections (Ln = Ho, Lu, Y). Crystals of LnCl3/bpy/H2O (1 : 1&#183;5 : 8) (&#91;(bpy)Ln(OH2)6&#93;Cl3.&half;bpy.2H2O), seemingly encompassing (at least) the range Ln = Er(-)Lu and Y, are triclinic, P 1, a &#x2248; 11&#183;7, b &#x2248; 11&#183;0, c &#x2248; 10&#183;1 &#197;, &#945; &#x2248; 85&#183;8, &#946; &#x2248; 74&#183;7, &#947; &#x2248; 79&#183;5&#176;, Z = 2, R 0&#183;038, 0&#183;033, 0&#183;048 for No 3897, 4377, 3130, and contain similar &#91;(bpy)Ln(OH2)6&#93;3+ cations as does HoCl3/bpy/H2O (1 : 2 : 7), &#91;(bpy)Ho(OH2)6&#93;Cl3.bpy.H2O, orthorhombic, Pbca, a 18&#183;02(2), b 20&#183;06(2), c 15&#183;051(9) &#197;, Z = 8, R 0&#183;057 for No 3009. By contrast, only sporadic, diverse and unrelated forms are thus far defined among the lighter Ln: EuCl3/bpy/H2O(1 : 1 : 5) (&#91;(bpy)Eu(OH2)4Cl2&#93;Cl.H2O), triclinic, P 1, a 11&#183;506(7), b 11&#183;098(5), c 6&#183;974(8) &#197;, &#945; 77&#183;35(7), b 85&#183;1(1), &#947; 89&#183;54(4)&#176;, Z = 2, R 0&#183;063 for No 4633, also contains a mononuclear &#91;(N,N&#8242;-bidentate)Ln(unidentate)6&#93; array. PrCl3/bpy/H2O(1 : 1 : 3)(&#215; 4) is a remarkable compound, being 2&#91;(bpy)Pr(OH2)3Cl3&#93; &#91;(bpy)(H2O)2Cl2Pr(&#181;-Cl)2PrCl2(OH2)2(bpy)&#93;.2H2O, triclinic, P 1, a 13&#183;490(4), b 11&#183;121(2), c 10&#183;162(1) &#197;, &#945; 96&#183;06(1), &#946; 90&#183;08(2), &#947; 96&#183;43(2)&#176;, Z = 2 f.u., R 0&#183;045 for No 4127, with a mononuclear species of PrCl3/bpy/H2O (1 : 1 : 3) stoichiometry and a binuclear species of 1 : 1 : 2 stoichiometry. A binuclear ethanol solvated array has been characterized for LaCl3/bpy/EtOH (1 : 1 : 2) &#91;(bpy)(EtOH)2Cl2La(&#181;-Cl)2LaCl2(HOEt)2(bpy)&#93;, with eight-coordinate lanthanum; this complex is triclinic, P 1, a 11&#183;426(8), b 10&#183;673(7), c 10&#183;453(7) &#197;, &#945; 109&#183;60(5), &#946; 113&#183;10(5), &#947; 105&#183;80(5)&#176;, Z = 1 dimer, R 0&#183;046 for No 2786. 
