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首页> 外文期刊>Chemistry: A European journal >Structural Motifs in Secondary Ammonium Halides:Ring-Stacking and Ring-Laddering in the Organic Solid State
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Structural Motifs in Secondary Ammonium Halides:Ring-Stacking and Ring-Laddering in the Organic Solid State

机译：二级卤化铵中的结构基序：有机固态的环堆积和环跃作用

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The ring-stacking and ring-laddering concepts of structural inorganic chemistry may be applied to rationalize motifs observed for secondary ammonium halides R_2NH_2X(X= Cl,Br)in the organic solid state.General examination of the directional preferences of N~+...X~- contacts in 166 crystal structures confirms that the shortest contacts(3.0-3.2 and 3.2-3.4 A,X=Cl,Br)are N~+-H...X~- hydrogen bonds lying approximately along the directions of the N~+-H bond vectors.The next shortest N~+...X~- contacts display two preferred directions of approach:i)contacts in the distance range 3.2-3.5(X=Cl)and 3.2-3.9 A(X=Br)lie close to the H-N~+-H plane,along the direction of the bisector of the H-N~+ -H angle;ii)contacts in the distance range 4.0-4.2(X=Cl)and 4.0-4.4 A(X=Br)lie close to the H-N~+-H plane,along the direction of an axis extending to the rear of one of the N~+-H bonds.Both directions of approach lead frequently to association of R_2NH_2 ~+X~- ion pairs into laddered motifs.Stacking association is also observed,giving rise in one case to discrete cubanes and in several other cases to extended stacked-cube arrangements.In each case,the distribution of N~+...X~-contacts reflects a balance between the directional properties of the N~+-H...X~-1 hydrogen bonds and(primarily steric)interactions between the R groups of the organic moieties.The ladder and stack motifs of the organic ammonium halides are in many cases directly comparable to those in alkali metal amides,[R_2NM]_n,and information derived from the extensive organic sample provides insight into the motifs adopted by the inorganic complexes.
机译：结构无机化学的环堆叠和梯化概念可用于合理化有机固态中卤化仲铵R_2NH_2X（X = Cl，Br）的基序。 166个晶体结构中的X〜-接触证实最短的接触（3.0-3.2和3.2-3.4 A，X = Cl，Br）为N〜+ -H ... X〜-氢键，大致沿着下一个最短的N〜+ ... X〜-触点显示两个首选的接近方向：i）距离范围3.2-3.5（X = Cl）和3.2-3.9 A（ X = Br）靠近HN〜+ -H平面，沿着HN〜+ -H角的等分线方向; ii）接触的距离范围为4.0-4.2（X = Cl）和4.0-4.4 A （X = Br）靠近HN〜+ -H平面，沿着延伸到N〜+ -H键之一后部的轴的方向。接近的两个方向经常导致R_2NH_2〜+ X的缔合离子对成梯形图案。还观察到这种情况，一种情况下是离散的库纳，另一种情况下是扩展的堆叠立方体排列。在每种情况下，N〜+ ... X〜接触的分布反映了方向性之间的平衡。有机部分R基团之间的N〜+ -H ... X〜-1氢键和（主要是空间）相互作用。在许多情况下，有机卤化铵的梯形和堆叠图案可直接与碱性盐相比金属酰胺，[R_2NM] _n，以及来自大量有机样品的信息提供了对无机配合物所采用基序的了解。

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