Conglomerate crystallization behavior of racemic [Co(N4)(aminoacidato)]2+ complexes

Crystal Engineering Pub Date : 2001-06-09 DOI:10.1016/S1463-0184(01)00004-1

Xiaopeng Hu , Jiwen Cai , Caihong Chen , Xiao-Ming Chen , Liang-Nian Ji

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引用次数: 4

Abstract

Crystal structures, absolute configurations, and crystalline packing features of nine complexes, namely, cis-α-Λ-(RR)(δλδ)-[Co(trien)(D-histidinato)](ClO₄)₂·2H₂O 1, cis-β₁-Δ-(RR)(λδδ)- [Co(trien)(L-asparaginato)](ClO₄)₂ 2, cis-β₂-Λ(SS)(λλδ)-[Co(trien)(L-valinato)](ClO₄)₂·H₂O 3, cis-β₂-Δ-(RR)(δδλ)[Co(trien)(D-methioninato)](ClO₄)₂ and its enantiomer 4, trans(N,t-N)-[Co(tren)(DL-leucinato)]X₂, (X=ClO₄⁻ 5, BF₄⁻ 6, PF₆⁻ 7), and trans(N,t-N)-[Co(tren)(DL- methioninato)]X₂ (X=Br⁻ 8, Cl⁻(BF₄⁻) 9) (trien=triethylenetetramine, tren=tris(2-aminoethyl)amine), have been determined. All compounds were prepared from racemic DL-amino acid. 1–3 crystallize as conglomerates. 5–7 are isomorphous and crystallize as the so-called conglomeratic solids. While 4, 8 and 9 undergo racemic crystallization. In 1–7, the carboxylic oxygen of the amino acid forms double hydrogen bonds with the amino hydrogen atoms of N4 and/or amino acidato of an adjacent cation. By these hydrogen bonds, cations having the same chirality are linked together into helical string. In the isomorphous 8 and 9, the cation containing L-methionine interacts with a cation containing D-methioninine, through hydrogen bonds, to form a racemic pair, and no spiral string arrangements are observed.

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外消旋[Co(N4)(氨基酸)]2+配合物的砾岩结晶行为

晶体结构、绝对构型和水晶包装9复合物的特性,即cis -α-Λ(RR)(δλδ)-[有限公司(trien) (D-histidinato)] (ClO4) 2·2水1、cis -β1 -Δ(RR)(λδδ)-[有限公司(trien) (L-asparaginato)] (ClO4) 2 2, cis -β2 -Λ(SS)(λλδ)-[有限公司(trien) (L-valinato)] (ClO4) 2·H2O 3、cis -β2 -Δ(RR)(δδλ)[有限公司(trien) (D-methioninato)] (ClO4) 2及其对映体4,反式(N, sn) -[有限公司(tren) (DL-leucinato)] X2 (X = ClO4−5 BF4−6 PF6−7),和反式(N, sn) -[有限公司(tren) (DL - methioninato)] X2 (X = Br−8,测定了Cl−(BF4−)9)(trien=三乙基四胺，tren=三(2-氨基乙基)胺)。所有化合物均由外消旋dl -氨基酸制备。1-3结晶成聚集体。5-7是同构的，结晶为所谓的团块状固体。而4、8和9则是外消旋结晶。在1-7中，氨基酸的羧基氧与N4的氨基氢原子和/或相邻阳离子的氨基酸形成双氢键。通过这些氢键，具有相同手性的阳离子被连接成螺旋状的弦。在同构的8和9中，含有l -蛋氨酸的阳离子与含有d -蛋氨酸的阳离子通过氢键相互作用，形成外消旋对，没有观察到螺旋弦排列。

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Crystal Engineering

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