Evaluation of the Role of Isostructurality in Fluorinated Phenyl Benzoates

Abstract

In this report, the occurrence of three-, two-, and one-dimensional (3D, 2D, and 1D) isostructurality in phenyl benzoate (D00) and their fluorinated analogues was investigated in terms of their molecular assembly in solid state structures. A one-dimensional C–H···OC chain is observed as a robust motif (∼ −21 kJ/mol) in the formation of the supramolecular architectures in these isostructural compounds. The isomorphous crystal structures exhibit 3D isostructurality or vice versa. The crystal packing shows that weak intermolecular C–H···F, C–H···O, C–H···π interactions, and π···π stacking are the main contributors providing stability toward the crystal lattice. The nature and energetics of all the geometrically or energetically equivalent building blocks associated with similar or different intermolecular interactions delineate the role of different molecular pairs in the crystal structures. The fingerprint plots of the isostructural set of crystal structures help to understand the similarities and the differences in the various interatomic contacts. A comparison of these crystal structures with fluorinated N-phenyl benzamides shows the change in supramolecular assembly in terms of intermolecular interactions as well as the lattice energy due to the participation of a strong donor (N–H).

Role of halogen-involved intermolecular interactions and existence of isostructurality in the crystal packing of —CF3 and halogen (Cl or Br or I) substituted benzamides

“…The importance of interactions involving halogens in the absence of strong hydrogen bonds has been well established in the crystal engineering community (O'Hagan, 2008;Mondal et al, 2018). The evaluation of weak interactions involving halogens in the presence of strong hydrogen bonds has generated extensive interest in recent literature, particularly in the areas of isostructurality (Dey & Chopra, 2017), polymorphism (Prohens et al, 2012;Cruz Cabeza & Bernstein, 2014), cocrystals (Chattoraj et al, 2014;Mondal, Rao et al, 2017;Eccles et al, 2012), crystal structure prediction (Hulme et al, 2005), host-guest chemistry (Noa et al, 2016), nanoindentation (Mondal, Kiran et al, 2017;Rupasinghe et al, 2015) and supramolecular chemistry (Mondal, Yadav et al, 2017;Nagarajan et al, 2014).…”

Molecular and crystal structure, lattice energy and DFT calculations of two 2′-(nitrobenzoyloxy)acetophenone isomers

“…The corresponding bond lengths and bond angles in isomers I and II are very similar in the two molecules and are close to the standard values. The only unexpected value is angle O1-C14-C7, which is 111.42 (10) (I) and 111.15 (9) (II) for steric reasons, which is quite common for a bridging geometry in molecules with the same molecular core, such as phenyl benzoate and fluorinated phenyl benzoates (Dey & Chopra, 2017).…”

“…Three entries were found for the same core structure as in the title molecules. (Adams & Morsi, 1976;Dey & Chopra, 2017;Shibakami & Sekiya, 1995). One is an inclusion compound of phenylbenzoate with Ni complexes with isonicotinic acid and thiocyanato coordination bridges (Sekiya et al, 2004).…”

“…The dihedral angles between the two aromatic rings vary. The methyl-substituted compounds tend to have a near-perpendicular geometry with dihedral angles ranging from 73.04 (8) to 87.43 (5) (Gowda, Tokarcík et al, 2008;Gowda et al, 2009), while pure phenylbenzoate and many of its fluorinated derivatives have angles in the range 52.66 7to 62.76 (4) (Adams & Morsi, 1976;Dey & Chopra, 2017). The number of entries in the database for nitro-substituted phenylbenzoates is limited and is not sufficient for drawing final conclusions on the role of the nitrogroup position on the molecular geometry (Saha & Desiraju, 2017).…”

Isomorphous Crystals Formed by the Similar Supramolecular Motifs in Sorafenib Hydrochloride and Regorafenib Hydrochloride Salts

“…Isomorphism is when the crystal structures of two or more related compounds have the same space group, similar unit-cell parameters as well as conformation of molecules, and, thus, the identical position of atoms (molecules) in the crystal structures [27]. Several organic compounds were reported to be isomorphous crystals [28][29][30], for example, desmethylselegiline hydrochloride and p-fluorodesmethylselegiline hydrochloride have similar crystal structures [28], or phenyl benzoate and phenyl ortho-fluoro-benzoate are isomorphous [31]. In addition, the isomorphous phenomenon is often observed in similar types of compounds with comparable functionalities, such as -H, −CH 3 , -F, -Cl, -Br, and -I [32,33].…”