Benzimidazolene-2-thiones:  A New Class of Molecules for the Engineering of Molecular Tapes in the Organic Solid State

Abstract

Derivatives of benzimidazolene-2-thione differing in substitution at the 4 and 5 positions have been synthesized and studied by single-crystal X-ray diffraction and/or X-ray powder diffraction. These derivatives include five monosubstituted compounds (1-SX; X = Me, F, Cl, Br, I), four disubstituted compounds (1-SX 2 ; X = Me, F, Cl, Br), the parent dihydro compound (1-SH 2 ), and the naphthyl compound (2-SH 2 ). Five of these molecules gave crystals suitable for single-crystal X-ray diffraction. In all of these crystals, the molecules pack as parallel, hydrogen-bonded tapes. Alternate molecules of a tape occupy two different planes that are separated by approximately 1 Å. The resulting structure is named a stepped tape. These stepped tapes are divided into two classes based on packing: tapes of 1-SH 2 , 1-SMe 2 , and 1-SF pack in flat, parallel planes. Tapes of 2-SH 2 , 1-SF 2 , and 1-SCl 2 pack at an angle; of these, two (2-SH 2 and 1-SF 2 ) incorporate molecules of solvent. None of the structures is isomorphic.

Design of Layered Crystalline Materials Using Coordination Chemistry and Hydrogen Bonds

“…This paper describes our efforts to design coordination complexes that self-assemble into two-dimensional supramolecular networks, or layers. We and others have used hydrogen bonds successfully in purely organic crystals to restrict molecular packing to specific one-dimensional motifs (e.g., chains or tapes) − and two-dimensional motifs (e.g., sheets or layers), − as shown schematically in Figure . Constraining molecules to assemble into layers has several advantages from the standpoint of design and control over bulk crystalline structure: it significantly reduces the degrees of translational freedom available to individual molecules while packing; it limits molecular packing to just a few possible packing arrangements by defining the relative position and orientation of molecules within layers; and it reduces the problem of predicting crystal packing in three dimensions from that of individual molecules to that of well-ordered layers of molecules.…”

Exploring the Strength of the H‐Bond in Synthetic Models for Heme Proteins: The Importance of the N−H Acidity of the Distal Base

“…Finally, 5‐iodo‐2‐bromo‐1 H ‐benzimidazole ( 16 ) was synthesized by treatment of 5‐iodo‐1,3‐dihydro‐2 H ‐benzimidazole‐2‐thione ( 21 ) with HBr/Br 2 in MeOH . Compound 21 was synthesized by the thiocarbonylation of 4‐iodobenzene‐1,2‐diamine ( 20 ) using 1,1′‐thiocarbonyldiimidazole …”

Crystal structure of 1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazole- 2(3H)-thione, C9H7F3N2S

“…X-ray structure analysis reveals that the title compound in the solid state prefers the thio form with N2 protonted rather than the alternative tautomeric ene-thiol form [4][5][6]. The bond length of C7-S1 is with a value of 1.673(3) Å slightly shorter than that in the nucleoside containing a benzimidazole (1.693(4) Å) [7] and 1-methyl-1H-benzimidazole-2(3H)-thione (1.684(2) Å) [8].…”