crystals Article Synthesis and Structure of Fluorinated (Benzo[d]imidazol-2-yl)methanols: Bench Compounds for Diverse Applications Vasily Romanov 1,2 , Evgeny Tretyakov 1, * , Galina Selivanova 1 , Jiayao Li 1,2 , Irina Bagryanskaya 1 , Alexander Makarov 1 and Dominique Luneau 3, * 1 N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia; romanov@nioch.nsc.ru (V.R.); galseliv@nioch.nsc.ru (G.S.); 1455474790ss@gmail.com (J.L.); bagryan@nioch.nsc.ru (I.B.); makarov@nioch.nsc.ru (A.M.) 2 Department of Natural Sciences, Novosibirsk State University, 2 Pirogova Str., Novosibirsk 630090, Russia 3 Campus de La Doua, Université Claude Bernard Lyon-1, 69622 Villeurbanne CEDEX, France * Correspondence: tretyakov@nioch.nsc.ru (E.T.); dominique.luneau@univ-lyon1.fr (D.L.); Tel.: +7-383-330-9171 (E.T.); +33-472-43-1418 (D.L.) Received: 5 August 2020; Accepted: 3 September 2020; Published: 4 September 2020   Abstract: A simple and general approach to the synthesis (from commercial precursors) of eight out of nine possible (benzo[d]imidazol-2-yl)methanols fluorinated on the benzene ring is reported. Molecular and crystalline structures of most compounds were solved by X-ray diffraction analysis. This made it possible to reveal the influence of the number and arrangement of fluorine atoms in the benzene cycle on the formation of intermolecular hydrogen bonds. It was found that the more fluorine atoms are present in a compound, the higher the dimensionality of the H-bonded structure is. Moreover, the presence of fluorine atoms in the synthesized compounds leads to the emergence of C–F ... π interactions affecting crystal packing. The synthesized fluorinated (benzo[d]imidazol-2-yl)methanols may serve as excellent bench compounds for the synthesis of a systematic series of fluorine-containing derivatives to study structure–property correlations in various fields of research from medicine to materials science. Keywords: polyfluorinated 1,2-diaminobenzenes; heterocyclization; fluorinated benzimidazoles; crystal structure; H-bonding; 1D, 2D, and 3D structures 1. Introduction Benzimidazoles (1H-benzimidazole, 1H-benzo[d]-imidazole, or 1,3-benzodiazole) occupy an important place in the realm of medicinal chemistry and materials science [1–4]. In nature, the most prominent benzimidazole compound is N-ribosyldimethylbenzimidazole, serving as an axial ligand for cobalt in vitamin B 12 [5]. Benzimidazole derivatives are structural isosteres of naturally occurring nucleotides [6], and this property allows them to interact easily with biopolymers of a living system. This motivates medicinal chemists across the world to synthesize a variety of benzimidazole derivatives and to screen them for various biological activities. Thorough optimization of benzimidazole-based structures has resulted in a large series of various marketed drugs. A far-from-complete list of benzimidazole-based drugs includes antitumor agents (bendamustine and pracinostat), proton pump inhibitors (pantoprazole, lansoprazole, and omeprazole), antiparasitic (albendazole and mebendazole) and antibacterial drugs (ridinilazole), and antihistamine (astemizole and bilastine), antiviral (enviradine, dibazol, and maribavir), and antihypertensive drugs (candesartan, telmisartan, azilsartan, and mibefradil) [7–13]. In addition, benzimidazole-containing pesticides and fungicides (carbendazim, Crystals 2020, 10, 786; doi:10.3390/cryst10090786 www.mdpi.com/journal/crystals