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What Triggers Supramolecular Isomerism in Nonmolecular Solids? A case study of Copper Pyridazine Halides

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Abstract

Molecular recognition and aggregation occurring in solution are critical events towards the nucleation and growth of a crystal. However, controlling aggregation towards a particular supramolecular assembly is difficult due to lack of information on its thermodynamics and kinetics. Hence, the occurrence of supramolecular isomers is hardly recognized. In this paper, therefore, we demonstrate a retrosynthetic analysis to interpret the occurrence of isostructures and supramolecular isomers and predict the possibility of new phases in copper halide-pyridazine-H 2O system. A significant feature of this paper is the use of crystal engineering tools, namely, synthons and tectons to interpret the phase diagram of a system. The structure-synthesis correlation discussed here provides chemical insight to evolve a synthetic protocol to interpret and predict the possibility of supramolecular isomers in metal organic solids.

[CuII(pdz)X2], 1–2; [Cu2 I(pdz)X2], 3-5; [CuI(pdz)X], 6–8 and [Cu2 I(pdz)3Cl2].3H2O, 9 where pdz = pyridazine, were crystallized from aqueous solution for the first time and their structure elucidation was carried out using X-ray crystallographic techniques. Growth of isostructures and supramolecular isomers in 1–9 has been interpreted in terms of tectons (I–III).

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Acknowledgements

The work is a part of Ph.D. dissertation of Jency Thomas submitted at Indian Institute of Technology, Delhi, India. A R acknowledges DST, Government of India, for financial support as well as powder and single crystal X-ray diffraction facility to the Department of Chemistry, IIT Delhi, India.

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Authors and Affiliations

  1. Research and P G Department of Chemistry, St. Thomas’ College (Autonomous), Thrissur, Kerala, 680 001, India

    JENCY THOMAS

  2. Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110 016, India

    ARUNACHALAM RAMANAN

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  1. JENCY THOMAS
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  2. ARUNACHALAM RAMANAN
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Correspondence to JENCY THOMAS or ARUNACHALAM RAMANAN.

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Supplementary Information (SI)

Crystallographic information files (CIF) for 1–9; crystal structure description of 1–9; figures showing weak interactions in 1–9; simulated and experimental powder XRD (Figures S8–S15); á posteriori analysis of solids reported in literature with pyridazine, pyrimidine and pyrazine (Figures S16–S23); results of rietveld refinement for phase quantification of orthorhombic and triclinic phases in 6 and 7 (Figure S24); results of vibrational and thermal analysis (Figures S25–S28); crystallographic details for solids 1–9 (Table S5) are given in the Supplementary Information available at www.ias.ac.in/chemsci.

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THOMAS, J., RAMANAN, A. What Triggers Supramolecular Isomerism in Nonmolecular Solids? A case study of Copper Pyridazine Halides. J Chem Sci 128, 1687–1694 (2016). https://doi.org/10.1007/s12039-016-1179-9

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  • DOI: https://doi.org/10.1007/s12039-016-1179-9

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