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Chemical and structural diversity in chiral magnesium tartrates and their racemic and Meso analogues

机译：手性酒石酸镁及其外消旋和内消旋类似物的化学和结构多样性

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摘要

Nine crystalline modifications of magnesium tartrate (tart(2-) = C4H4O6) have been synthesized by hydrothermal reactions between magnesium acetate tetrahydrate and the ,D,L-,D-, and meso-forms of tartaric acid in the temperature range 100-200 degrees C. Two racemic crystals, a dimeric Mg(D,L-tart)(H2O)(2)center dot 3H(2)O in space group Pban, (1), and a two-dimensional coordination polymer Mg(D,L-tart)(H2O)center dot 3H(2)O, P2/c, (2), were obtained from the D,L-acid reactions at 100 degrees C and 125-150 degrees C, respectively. Two chiral structures were obtained from the D-acid reactions at these temperatures: a layered Mg(D-tart)(H2O)center dot 1.5H(2)O, P2(1)2(1)2(1), (3), and a three-dimensional (3-D) network, Mg(D-tart)center dot 1.5H(2)O, C222(1), (4). In addition, an anhydrous 3-D coordination polymer, Mg(D-tart), I222, (5), was obtained by dehydrating 3 under vacuum at 85 degrees C. Finally, four achiral structures were obtained from reactions with the meso-acid at 100 degrees C, 125-150 degrees C, 180 degrees C, and 200 degrees C, respectively: three one-dimensional (1-D) chains, Mg(meso-tart)(H2O)(2)center dot H2O (6, P2(1), and 7, Pbca) and Mg(meso-tart)(H2O)(2), P2(1)/c, (8), and one 3-D framework, Mg(meso-tart), C2/c, (9). Within each family, the structures become less hydrated and more condensed with increasing temperature, indicating that the reactions proceed under thermodynamic control. The chiral D-tartrates, 3 and 4, adopt entirely different architectures compared to the racemic D,L-tartrates, 1 and 2, with the former exhibiting higher dimensionalities and lower levels of hydration than their D,L-analogues formed at the same temperatures.At 180 and 200 degrees C, the D,L-magnesium tartrate undergoes spontaneous resolution to form a conglomerate corresponding to one of the lower temperature D-phases (4). The unexpected complexity of this ostensibly simple system points to the extraordinary richness of the emerging field of chiral inorganic-organic framework structures.
机译：酒石酸镁的九种结晶修饰形式（tart（2-）= C4H4O6）是通过四水醋酸镁与酒石酸的-D，L-，D-和内消旋形式在100-200温度范围内进行水热反应合成的两个外消旋晶体，空间群Pban中的二聚体Mg（D，L-tart）（H2O）（2）中心点3H（2）O，（1）和二维配位聚合物Mg（D， L酸（H2O）中心点3H（2）O，P2 / c，（2）分别从D，L-酸反应在100摄氏度和125-150摄氏度下获得。从D-酸反应在这些温度下获得了两个手性结构：层状Mg（D-）（H2O）中心点1.5H（2）O，P2（1）2（1）2（1），（3 ）和三维（3-D）网络，Mg（D--）中心点1.5H（2）O，C222（1），（4）。另外，通过在真空下于85℃下脱水3，获得无水3-D配位聚合物Mg（D-tart），I222，（5）。最后，由与内消旋酸的反应获得了四个非手性结构。分别在100摄氏度，125-150摄氏度，180摄氏度和200摄氏度下：三个一维（1-D）链，Mg（中o）（H2O）（2）中心点H2O（6 ，P2（1）/ n和7，Pbca）和Mg（meso-tart）（H2O）（2），P2（1）/ c，（8）和一个3-D框架Mg（meso-tart ），C2 / c，（9）。在每个家族中，随着温度的升高，结构变得更不易水合，更易于冷凝，表明反应在热力学控制下进行。与外消旋的D，L-酒石酸酯1和2相比，手性D-酒石酸酯3和4采用完全不同的结构，前者比它们相同形成的D，L-类似物表现出更高的维数和更低的水合度。在180和200摄氏度下，酒石酸D，L-镁镁自发分解，形成对应于较低温度D相之一的团块（4）。这种表面上简单的系统出乎意料的复杂性表明，手性无机-有机骨架结构的新兴领域异常丰富。

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