Three Nimesulide Derivatives: Synthesis, Ab Initio Structure Determination from Powder X-ray Diffraction, and Quantitative Analysis of Molecular Surface Electrostatic Potential

Abstract

Three nimesulide derivatives, N-[4-(2,5-dioxo-pyrrolidin-1-yl)-2-phenoxyphenyl] methanesulfonamide (2), N-[4-(4-methanesulfonylamino-3-phenoxy phenylsulfamoyl) phenyl] acetamide (3), and 4-(4-methanesulfonylamino-3-phenoxyphenyl-carbamoyl)-butanoic acid (4), have been synthesized, and their crystal structures have been determined from laboratory powder X-ray diffraction data. The nature of intermolecular interactions in 2–4 has been analyzed through Hirshfeld surfaces and two-dimensional fingerprint plots and compared with that in the nimesulide polymorphs (1a and 1b). The crystal packing in 2–4 exhibits an interplay of N–H···O, O–H···O (in 4), C–H···O, and C–H···π (in 2) hydrogen bonds, which assemble molecules into a supramolecular framework. Hydrogen-bond based interactions in 2–4 have been complemented by calculating molecular electrostatic potential surfaces. In a competitive molecular recognition situation, the effectiveness of the -NH moiety as a hydrogen bond donor is comparable to that of the -COOH moiety in 4. Hirshfeld surface analyses of 2–4 as well as a few related nimesulide derivatives indicate that about 90% of the Hirshfeld surface areas in these compounds are due to H···H, C···H, and O···H contacts.

Crystal structure of 4-[(3,5-dichlorophenyl)carbamoyl]butanoic acid, C11H11Cl2NO3

“…Complementing the twist about the C3-C4 bond, is a second twist in the molecule involving the aryl group as seen in the C5-N1-C6-C7 torsion angle of −133.95(18)°. The highly twisted conformation for (I) matches that seen in (II) [5] and one of two independent molecules of (IV) [7]. Decidedly more planar conformations are noted for the other molecules [6,7].…”

Crystal structure of 4-[(4-methoxy-2-nitrophenyl)carbamoyl]butanoic acid, C12H14N2O6

“…The molecular structure of (I) is shown in the figure (50% probability displacement ellipsoids) and adopts an extended The most closely related compound in the crystallographic literature is the derivative where the Ar group is 4-((methylsulfonyl)amino)-3-phenoxyphenyl. The molecule has a highly twisted conformation in the C 3 chain by contrast to that in (I) [9]. In the molecular packing, an eight-membered { A complementary analysis of the molecular packing of (I) was performed by calculating the Hirshfeld surface and the two-dimensional fingerprint plots employing Crystal Explorer 17 [10] following literature procedures [11]…”

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co2+: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

“…The value of d norm (normalized contact distance) based on d i and d e is given bywhere the van der Waals radii are given by r e vdW and r i vdW of the atoms. Intermolecular contacts may be shorter or longer than van der Waals separations, 40 which can give the d norm value as negative or positive. The color scheme as red-white-blue displays as the d norm parameter, where shorter contacts are indicated by bright red spots, white areas signify van der Waals contacts separation, and blue areas lacking close contacts.…”