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

被引:24
作者
BERNAL, I [1 ]
CETRULLO, J [1 ]
MYRCZEK, J [1 ]
MASSOUD, SS [1 ]
机构
[1] UNIV ALEXANDRIA,FAC SCI,DEPT CHEM,ALEXANDRIA 21321,EGYPT
关键词
CONGLOMERATE CRYSTALLIZATION; RACEMATES; ORDERED CRYSTALS; DISORDERED CRYSTALS; MECHANISMS OF CRYSTALLIZATION; METAL AMINES; METAL OXALATES;
D O I
10.1080/00958979308022745
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
[Co(en)2ox]Cl.4H2O (I) and [Co(en)2ox]Br.H2O (II), crustallize from water 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) crystallizes as a racemate, space group P2(1)/c. [Co(en)2ox]I (IV) crystallizes in both of the monoclinic space groups C2 and C2/c, in agreement with the phase diagram studies of Yamanari, et al. (see ref. 4). However, we have not been successful in crystallographic studies of this substance since in neither case was it possible to obtain ordered crystals. The conglomerate crystallization pathway selected by (I) and (II), and probably (IV), is shown to be the result of inter-cationic, three-point attachments reminiscent of that postulated as the origin of enzymatic chiral recognition. In this-process, spiral strings are formed which resemble polypeptide helices, and which are stitched together by the counternions (and/or waters of crystallization, where relevant) such that each crystal contains, exclusively, homochiral strings of one helicity.
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页码:29 / 51
页数:23
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