Number of the records: 1
When does a supramolecular synthon fail? Comparison of bridgehead-functionalized adamantanes: the tri- and tetra- amides and amine hydrochlorides
- 1.
SYSNO ASEP 0506307 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title When does a supramolecular synthon fail? Comparison of bridgehead-functionalized adamantanes: the tri- and tetra- amides and amine hydrochlorides Author(s) Boldog, I. (DE)
Reiss, G. (DE)
Domasevitch, K.V. (UA)
Baše, Tomáš (UACH-T) RID, SAI, ORCID
Bräse, S. (DE)Source Title Crystal Growth & Design. - : American Chemical Society - ISSN 1528-7483
Roč. 19, č. 9 (2019), s. 5218-5227Number of pages 10 s. Language eng - English Country US - United States Keywords adamantane ; crystal structure ; H-bond, prediction ; supramolecular synthon ; violation Subject RIV CA - Inorganic Chemistry OECD category Inorganic and nuclear chemistry Method of publishing Limited access Institutional support UACH-T - RVO:61388980 UT WOS 000484830800035 EID SCOPUS 85071246389 DOI 10.1021/acs.cgd.9b00594 Annotation 1,3,5-trisubstituted adamantane carboxamide and amine hydrochloride, Ad(CONH2)3 · 2.5H2O and [Ad(NH3)3]Cl3 · H2O (Ad = adamant-n-yl) respectively, crystallized from aqueous solutions, possess crystal structures with predictable H-bonded assembly, consistent with the C3v symmetry of the building blocks. The triamide structure consists of interpenetrated hexagonal networks, sustained by the well-known cyclic H-bonded bis-amide synthon, R22(8), which ensures linear connectivity. The structure of the triamine hydrochloride, assembled through the tetrahedral {RN+H3---(Cl-)3} synthon, features a remarkably symmetric assembly with narrow trigonal pore-channels, hosting water molecules. The structures of the tetrahedral 1,3,5,7-tetrasubstituted Ad(CONH2)4 and [Ad(NH3)4]Cl4, obtained similarly, demonstrate a formal prediction failure of synthon based approach. Instead of the anticipated bis-amide synthon based diamond network (1.485 g cm-3) analogous to the 5-fold interpenetrated paradigmatic structure of Ad(COOH)4, a non-interpenetrated assembly, sustained by a dense network of H-bonds, is realized (1.433 g cm-3). Lessened geometric regularity was also found in the tetrahydrochloride salt assembled via 5-connected nodes, {RN+H3---(Cl-)4}, which involve a bifurcated H-bond. The failures of the supramolecular synthons in these simple cases could be interpreted either in terms of symmetry and/or limitations associated with the ‘synthon-density’. A potential machine learning approach oriented on heuristic retrosupramolecular synthesis relies on such selected high-weight conceptual cases. Workplace Institute of Inorganic Chemistry Contact Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Year of Publishing 2020 Electronic address https://pubs.acs.org/doi/10.1021/acs.cgd.9b00594
Number of the records: 1