THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION .27. THE EFFECT OF CHARGE COMPENSATING ANION ON THE CRYSTALLIZATION BEHAVIOR OF [CO(EN)2OX]CL.4H2O, [CO(EN)2OX]BR.H2O, [CO(EN)2OX]PF6 AND [CO(EN)2OX]I
I. Bernal et al., THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION .27. THE EFFECT OF CHARGE COMPENSATING ANION ON THE CRYSTALLIZATION BEHAVIOR OF [CO(EN)2OX]CL.4H2O, [CO(EN)2OX]BR.H2O, [CO(EN)2OX]PF6 AND [CO(EN)2OX]I, Journal of coordination chemistry, 30(1), 1993, pp. 29-51
[Co(en)2ox]Cl.4H2O (I) and [Co(en)2ox]Br.H2O (II), crustallize from wa
ter at 21-degrees-C as conglomerates, space group P2(1)2(1)2(1). Their
structures and absolute configurations were determined by refinement
of data using both enantiomeric configurations. [Co(en)2ox]PF6 (III) c
rystallizes as a racemate, space group P2(1)/c. [Co(en)2ox]I (IV) crys
tallizes in both of the monoclinic space groups C2 and C2/c, in agreem
ent with the phase diagram studies of Yamanari, et al. (see ref. 4). H
owever, we have not been successful in crystallographic studies of thi
s substance since in neither case was it possible to obtain ordered cr
ystals. The conglomerate crystallization pathway selected by (I) and (
II), and probably (IV), is shown to be the result of inter-cationic, t
hree-point attachments reminiscent of that postulated as the origin of
enzymatic chiral recognition. In this-process, spiral strings are for
med which resemble polypeptide helices, and which are stitched togethe
r by the counternions (and/or waters of crystallization, where relevan
t) such that each crystal contains, exclusively, homochiral strings of
one helicity.