Solid-state chemistry of organic polyvalent iodine compounds. VII. The relationships between crystal packing modes, solid-state intermolecular interactions, and infrared spectra of benzoxiodole compounds☆
Solid-state chemistry of organic polyvalent iodine compounds. VII. The relationships between crystal packing modes, solid-state intermolecular interactions, and infrared spectra of benzoxiodole compounds☆
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有机多价碘化合物的固态化学 VII. 苯并碘酮化合物的晶体堆积模式、固态分子间相互作用与红外光谱的关系☆
DOI：
10.1016/0022-4596(76)90057-8
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发表时间：
1976
影响因子：
3.3
通讯作者：
M. C. Etter
中科院分区：
文献类型：
--
作者：
M. C. Etter
本文研究了一系列3-氧代-3H，2，1-苯并氧碘-1-取代化合物的分子间相互作用在确定晶体结构中的重要性。这些化合物都含有三价碘原子，其参与与相邻分子的电负性原子（氧或卤素）的立体特异性配位相互作用。已经发现，对于这些化合物，仅发生四种基本堆积模式，其形式特征在于与碘配位的官能团的性质。这些化合物的溶液和固态样品的红外分析表明，I（III）和羰基之间发生的结构可识别的分子间配位模式实际上涉及化学稳定的相互作用。与溶液样品中的频率相比，固态样品中未配位羰基的羰基伸缩带的波数降低了约10 cm− 1。配位羰基的羰基伸缩频率从20-80 cm−1降低（这些谱带在固态时出现在1614-1678 cm− 1）。一些化合物存在于固态的分子构象中，其中I（III）和羰基之间的可能的分子内相互作用也可能有助于观察到的频率偏移。
The importance of intermolecular interactions in determining crystal structures has been investigated for a series of 3-oxo-3H,2,1-benzoxiodol-1-substituted compounds. These compounds all contain a trivalent iodine atom which is involved in a stereospecific coordination interaction with an electronegative atom (oxygen or halogen) of a neighboring molecule. It has been found that only four basic packing modes occur for these compounds, formally characterized by the nature of the functional group which is coordinated to iodine. Infrared analysis of solution and solid-state samples of these compounds shows that the structurally identifiable intermolecular coordination modes which occur between I(III)and carbonyl groups do in fact involve chemically stabilizing interactions. Shifts of about 10 cm−1to lower wavenumber are observed for the carbonyl stretching band of anuncoordinatedcarbonyl group in solid-state samples, as compared to its frequency in solution samples. The carbonyl stretching frequency of acoordinatedcarbonyl group is lowered from 20–80 cm−1(these bands occur at 1614–1678 cm−1in the solid state). Some of the compounds exist in molecular conformations in the solid state in which a possibleintramolecular interaction between I(III)and a carbonyl also may be contributing to the observed frequency shifts.