Role of supramolecular interactions in crystal packing of Strandberg-type cluster-based hybrid solids
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J. Chem. Sci. (2020)132:137 https://doi.org/10.1007/s12039-020-01826-w
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Role of supramolecular interactions in crystal packing of Strandberg-type cluster-based hybrid solids JISHA JOSEPHa, CINU WINSONa, BHARTI SINGHb, JEMINI JOSEc and JENCY THOMASa,* a Centre
for Sustainability Science, Research & PG Department of Chemistry, St. Thomas College (Autonomous), Thrissur, Kerala 680 001, India b Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110 016, India c Department of Chemistry, CHRIST (Deemed to be University), Bengaluru 560 029, India E-mail: [email protected] MS received 5 May 2020; revised 2 July 2020; accepted 9 July 2020
Abstract. Two new Strandberg-type cluster-based phosphomolybdates {H-2a3mp}5[{PO3(OH)}{PO4}Mo5O15], 1 and {H-2a4mp}5[{PO3(OH)}{PO4}Mo5O15]6H2O, 2 have been crystallized via solvent evaporation technique using 2-amino-3-methylpyridine (2a3mp) and 2-amino-4-methylpyridine (2a4mp) respectively. The solids were characterized using single-crystal X-ray diffraction, powder X-ray diffraction, fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and cyclic voltammetry. The solid 1 crystallized in monoclinic system with space group P21/c, a = 8.394(1), ˚ , b = 97.68(3), Z = 4. The solid 2 crystallized in triclinic system with space b = 27.398(6), c = 21.521(4) A ˚ , a = 68.906(3), b = 89.454(3), c = 66.559(3), group P-1, a = 11.728(1), b = 14.234(1), c = 19.589(1) A Z = 2. The solids 1 and 2 formed a supramolecular framework stabilized by hydrogen bonding interaction between cluster anions and organic moieties. CH…p interactions between the organic moieties reinforced the crystal packing in 1 and 2. While crystal packing effects resulted in the formation of solvent-accessible voids in 1; aggregation of lattice water molecules in 2 facilitated the formation of pentameric water cluster. In addition, electrochemical behavior of 1 and 2 has also been investigated. Keywords. Phosphomolybdate; Strandberg-type; supramolecular interactions; electrochemical behavior.
1. Introduction Supramolecular assemblies based on phosphomolybdate (PMO) cluster anions are captivating organicinorganic hybrid solids on account of their diverse topologies, tunable size and structural versatility.1,2 Owing to their unique structural features, they exhibit a wide range of applications in multiple areas such as catalysis,3,4 magnetism,5 ion-exchange6,7 and electrochemistry.8–10 Among the PMO cluster anions, Strandberg-type {P2Mo5O23}6- (abbreviated as {P2Mo5} henceforth) is the most stable cluster anion that can be crystallized under ambient conditions.11–13 It was first reported by Strandberg in 197314 and so far several hybrid solids have been reported based on {P2Mo5} cluster anion with promising properties.15–18
Majority of these solids have been crystallized along with protonated organic ligands having nitrogen donor atoms.19–21 Since {P2Mo5} cluster anion i
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