The Crystal Structures of (+)589- and (−)589-trans(O)-Ethylenediaminebis(glycinato)cobalt(III) Hydrogen-d-tartrates and Their Thermal Behavior
- 1 December 1979
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 52 (12) , 3702-3712
- https://doi.org/10.1246/bcsj.52.3702
Abstract
The crystal structures of two diastereoisomeric salts, (+)589-trans(O)-[Co(gly)2en]H-d-tart·3H2O (1) and (−)589-trans(O)-[Co(gly)2en]H-d-tart·H2O (2), have been determined by three-dimensional X-ray analysis. The less-soluble salt (1) is monoclinic; space group, P21; Z=2, a=12.351(5), b=7.671(3), c=10.189(5) Å, and β=110.71(4)° (R=0.043, 2241 reflections). The more-soluble salt (2) is monoclinic; space group, P21; Z=2, a=11.135(4), b=10.037(3), c=7.716(3) Å, and β=98.61(3)° (R=0.064, 2076 reflections). A comparison of the (unit cell volume)/Z values of the two crystals shows that the crystal 1 is more tightly packed than the crystal 2. In both salts, adjacent complex cations form quite similar chain structures linked by (N–H…O) hydrogen bonds. The H-d-tart anions in 1 take a characteristic “head-to-tail” arrangement of an infinite chain of {H-d-tart}∞ along the b-axis. In contrast, this arrangement is not found in the more-soluble salt (2). From these findings, it can be considered that the discrimination of optical isomers in the H-d-tart system originates from the spiral chain structure of {H-d-tart}∞. The absolute configurations of (+)589- and (−)589-trans(O)-[Co(gly)2en]+ are determined to be Λ-δ and Λ-λ respectively. TG and DSC measurements were carried out for both salts, and the ΔH values of the dehydration step were estimated to be 64.4 kJ mol−1 for 1 and 73.0 kJ mol−1 for 2.This publication has 12 references indexed in Scilit:
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