Simple design for metal-based halogen-bonded cocrystals utilizing the M–Cl⋯I motif. Issue 39 (12th June 2018)

• Record Type: Journal Article
• Authors: Lisac, Katarina; Cinčić, Dominik
• Is Part Of: CrystEngComm. Volume 20:Issue 39(2018)
• Page Start: 5955
• Page End: 5963
• Publication Date: 2018-06-12
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c8ce00754c
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : The halogen bonding proclivity of the chlorine atom coordinated to the Co(ii ) metal centre has been explored by synthesis and crystal structure analysis of a family of 12 novel metal-based halogen-bonded cocrystals with iodine-based donors. Abstract : We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing metal complexes whose pendant chloride group enables halogen bonding. A series of 12 cocrystals involving octahedral CoCl2 L2 complexes (L = 2, 2′-bipyridine or 1, 10 phenantroline) as halogen bond acceptors were prepared by both liquid-assisted grinding and conventional solution-based methods. The efficacy of this strategy is evident by the assembly of a large family of cocrystals involving six perfluorinated halogen bond donors: 1, 4-diiodotetrafluorobenzene, 1, 3-diiodotetrafluorobenzene, 1, 2-diiodotetrafluorobenzene, 1, 3, 5-triiodotrifluorobenzene, iodopentafluorobenzene and octafluoro-1, 4-diiodobutane. Single crystal X-ray diffraction experiments have shown that cocrystals display different crystal packing governed by Cl⋯I halogen bonds between halogen bond donor iodine atoms and metal complex chlorine atoms (varying from 3.061 to 3.471 Å) based on zero-, one-, two- and three- dimensional halogen-bonded architectures.