Crystal Engineering of N,N′-Diphenylurea Compounds Featuring Phenyl–Perfluorophenyl Interaction

Abstract

Here, aiming to adopt the phenyl–perfluorophenyl interaction to regulate molecular alignment and arrangement for crystal engineering, we examined and compared in detail the crystal structures of N,N′-diphenylurea compounds 1–6. We found that phenyl–perfluorophenyl interaction greatly influenced the intermolecular arrangement in the crystal, and we were able to prepare a cocrystal of 1 and 2, in which the molecules were alternately arranged under the control of the phenyl–perfluorophenyl interaction. This arrangement was driven by the asymmetric geometry of the hydrogen bonds in the cocrystal (1·2), in which 2, bearing two perfluorophenyl groups, worked as a better hydrogen bond donor. In contrast, NH connected to the phenyl group in 3 proved to be a better hydrogen bond donor due to the intramolecular resonance effect. N,N′-Dimethylated derivatives, 4–6, existed in cis-cis form in the crystal. Antiparallel carbonyl–carbonyl arrangements were observed in 4 and 6, while an unexpected carbonyl–perfluorophenyl interaction was observed in the crystal of 5. These findings will be helpful in the design of diphenylurea-based functional molecules, especially for solid-state application.

A pyrazine‐bridged trimer of oxo‐centered triruthenium–carbonyl clusters and the supramolecular assembly built from multiple noncovalent contacts

“…The CO⋯CO contacts are increasingly recognized as an important intermolecular interaction in crystal structures of organic host–guest systems, [ 47–49 ] transition‐metal complexes, [ 50–52 ] and proteins. [ 53–57 ]…”

“…The COÁ Á ÁCO contacts are increasingly recognized as an important intermolecular interaction in crystal structures of organic host-guest systems, [47][48][49] transition-metal complexes, [50][51][52] and proteins. [53][54][55][56][57] Second, intermolecular hydrogen bonding is seen as shown in Figure 4, where CH(pyrazine)Á Á ÁO(carboxylate) and CH(carboxylate)Á Á ÁO(carbonyl) hydrogen bonds are observed. These intermolecular noncovalent contacts are given in Table 3.…”

Exploring the Conversion of Macrocyclic 2,2′-Biaryl Bis(thioureas) into Cyclic Monothioureas: An Experimental and Computational Investigation

“…There are three mechanistic routes (paths A–C) leading to the experimentally isolated thioureas 1 and 2 [from herein we will refer as 1 the bis­(thiourea) whose both thiourea functions feature cis,trans configuration as 1* the bis­(thiourea) with one thiourea function showing trans,trans configuration and the other cis,trans, and as 2 the monothiourea with cis,cis geometry]. To identify the configuration of thiourea functions, we use the most extended nomenclature employed for ureas and thioureas . All paths share the first intermediate, besides others that will be discussed later.…”

“…To identify the configuration of thiourea functions, we use the most extended nomenclature employed for ureas and thioureas. 63 All paths share the first intermediate, besides others that will be discussed later. An overview of each path is described at the bottom of Scheme 7. an attainable energy barrier (see Supporting Information for details).…”

High‐pressure‐induced phase transition in 1,3‐diphenylurea: The approaching of N–H⋯O hydrogen‐bonded chains

“…Therefore, two 1,3‐diphenylurea molecules form a pair of N–H⋯O hydrogen bonds that are spirally arranged and expanded along the direction close to the a ‐axis alternately. According to reported literatures, many supramolecular self‐assembly systems are developed on the basis of the 1,3‐diphenylurea model and exhibit many novel structures and properties . In addition, the variability of 1,3‐diphenylurea molecular conformation also contributes a lot to the study of synthetic new materials …”