The crystal structures of two single‐enantiomer amidophosphoesters with an (O)₂P(O)(N) skeleton and one single‐enantiomer phosphoric triamide with an (N)₂P(O)(N) skeleton were studied. The compounds are diphenyl [(R)‐(+)‐α‐4‐dimethylbenzylamido]phosphate, (I), and diphenyl [(S)‐(−)‐α‐4‐dimethylbenzylamido]phosphate, (II), both C₂₁H₂₂NO₃P, and N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis[(R)‐(+)‐α‐ethylbenzyl]phosphoric triamide, C₂₅H₂₈F₂N₃O₂P, (III). The asymmetric units contain two amidophosphoester molecules for (I) and (II), and one phosphoric triamide molecule for (III). In the crystal structures of (I) and (II), molecules are assembled in a similar one‐dimensional chiral ribbon architecture, but with almost a mirror‐image relationship with respect to each other through N—H…O(P) and C—H…O(P) hydrogen bonds along [010]. In the crystal structure of (III), the chiral tape architecture along [100] is mediated by N—H…O(P) and N—H…O(C) hydrogen bonds, and the tapes are connected into slabs by C—H…O interactions (along the ab plane). The differences/similarities of the two diastereotopic phenoxy groups in (I)/(II) and the two chiral amine fragments in (III) were studied on the grounds of geometry, conformation and contribution to the crystal packing, as well as ¹H and ¹³C signals in a solution NMR study.

中文翻译：

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三种新的手性磷酰胺中非对位基团的结构差异/相似性

研究了两种具有（O）₂ P（O）（N）骨架的单对映体酰胺磷酸酯和一种具有（N）₂ P（O）（N）骨架的单对映体磷酸三酰胺的晶体结构。化合物为[ I]和[I]的磷酸二苯基[（R）-（+）-α--4-二甲基苄基酰胺基] [I]和[I]和二苯基[[ S ]-（-）-α-4-4-二甲基苄基酰胺基] [ P ] ₂₁ H ₂₂ NO ₃ P和N-（2,6-二氟苯甲酰基）-N '，N ''-双[（R）-（+）-α-乙基苄基]磷酸三酰胺，C ₂₅ H ₂₈ F ₂ N ₃ Ø ₂P，（III）。对于（I）和（II），不对称单元包含两个酰胺基磷酸酯分子，对于（III），不对称单元包含一个磷酸三酰胺分子。在（I）和（II）的晶体结构中，分子以相似的一维手性带状结构组装，但通过N-H…O（P）和C彼此之间几乎具有镜像关系沿[010]的-H…O（P）氢键。在（III）的晶体结构中，沿着[100]的手性带结构是由NH-O（P）和NH-O（C）氢键介导的，并且这些带通过C-连接成平板。 H…O相互作用（沿ab飞机）。（I）/（II）中的两个非对映异构苯氧基和（III）中的两个手性胺片段的差异/相似性是基于几何学，构象和对晶体堆积的贡献以及¹ H和溶液NMR研究中的¹³ C信号。