Abstract

The crystal structures of polymorphs II of acetophenone azines YpPhRCNNCRPhYp with R = CH3 and Y = Cl (1M), Br (2M), and CH3 (8M) are discussed. The azine molecules in polymorphs II are Ci-symmetric with trans-azine moieties and conrotatory phenyl twists. Polymorphs 1M-I and 2M-I contain C2-symmetric enantiomers with pronounced azine twists and disrotatory phenyl twists and allow for strong lateral double T-contacts. The three polymorphs II exemplify the new Paradigm IV for the supramolecular architectures of "laterally offset diarenes" and result in "shiplap/flat" idioteloamphiphile monolayers. Intralayer lateral attraction is provided by edge-to-face arene-arene contacts between molecules with substantial longitudinal offset and involves arene edges bridging one azine-N and one phenyl center (EAzArB synthon) or one phenyl center and substituent Y (EYArB synthon) of different neighbors. These bridging synthons are characterized by a survey of pertinent structure parameters and their structural significance is corroborated by analysis of distance mapped Hirshfeld surfaces and the computation of 2D-fingerprint plots. The edge-to-face contacts are the most attractive intermolecular interactions, and these interactions are quantified via the computed pair interaction energies and the results of aromatic analyzer analysis. Synthon binding energies and lattice energies are determined to assess polymorph preference energies.

Department(s)

Chemistry

Publication Status

Full Access

Keywords and Phrases

diphenylazines; hirshfeld surface analysis; pair binding energies and lattice energies; polymorph preference energies; supramolecular chemistry

International Standard Serial Number (ISSN)

1099-0690; 1434-193X

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2025 Wiley, All rights reserved.

Publication Date

01 Jan 2025

Download

Full Text Link

Included in

Chemistry Commons

Share

 
COinS