Carboxylate Groups in a 90° Arrangement: 1,3-Allenedicarboxylic Acid and Its Alkali Metal and Thallium(I) Coordination Compounds
Carboxylate Groups in a 90° Arrangement: 1,3-Allenedicarboxylic Acid and Its Alkali Metal and Thallium(I) Coordination Compounds
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DOI：
10.1002/ejic.201900520
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发表时间：
2019-06-16
影响因子：
2.3
通讯作者：
Christoffers, Jens
中科院分区：
文献类型：
--
作者：
Kahrs, Christoph;Schmidtmann, Marc;Christoffers, Jens
由于其两个羧酸酯官能团以90度角排列，1，3-丙二烯二羧酸（点群C-1）具有与通常用作配位聚合物或MOF中的连接体化合物的所有其它二羧酸不同的对称性。本文首次报道了1，3-丙二烯二羧酸根配合物的晶体结构。用金属碳酸盐M2 CO 3转化二酸以提供结晶锂、钠、铷、铯和铊（I）化合物。在固态下，它们的结构有很大的不同。常见的基序是二价阴离子，其通过阳离子连接到柱、层或链。钠化合物显示出一种不寻常的结构功能：三种晶体学上不同的钠离子之一与四个而不是六个氧原子配位，具有跷跷板几何形状，即八面体配位的两个赤道位置未被占据。因此，几乎线性（179度）的O-Na-O单元保持两个具有垂直几何形状（角度94度和95度）的辅助氧原子。
With its two carboxylate functions arranged in an 90 degrees angle, 1,3-allenedicarboxylic acid (point group C-1) possesses a symmetry distinguished from all other dicarboxylic acids which are generally utilized as linker compounds in coordination polymers or MOFs. Crystal structures of coordination compounds with the 1,3-allenedicarboxylate dianion are reported herein for the first time. The diacid was converted with metal carbonates M2CO3 to furnish the crystalline lithium, sodium, rubidium, cesium and thallium(I) compounds. In the solid state, their structures differ significantly. Common motif is the dianion, which is linked by the cations to columns, layers or strands. The sodium compound exhibits an unusual structural feature: One of the three crystallographically different sodium ions coordinates to four instead of six oxygen atoms with seesaw geometry, i.e. two equatorial positions of an octahedral coordination are unoccupied. Thus, an almost linear (179 degrees) O-Na-O unit holds two ancillary oxygen atoms with perpendicular geometry (angles 94 degrees and 95 degrees).