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Crystals 2018, 8(12), 461; https://doi.org/10.3390/cryst8120461

Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2?

Department of Chemistry, University Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland
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Received: 28 November 2018 / Revised: 7 December 2018 / Accepted: 7 December 2018 / Published: 10 December 2018
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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Abstract

In this paper, the bromo- and phosphonate-ester-functionalized complexes [Zn(1)2][CF3SO3]2 and [Zn(2)2][CF3SO3]2 (1 = 4′-(4-bromophenyl)-2,2′:6′,2″-terpyridine, 2 = diethyl (4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl)phosphonate) are reported. The complexes have been characterized by electrospray mass spectrometry, IR and absorption spectroscopies, and multinuclear NMR spectroscopy. The single-crystal structures of [Zn(1)2][CF3SO3]2.MeCN.1/2Et2O and [Zn(2)2][CF3SO3]2 have been determined and they confirm {Zn(tpy)2}2+ cores (tpy = 2,2′:6′,2″-terpyridine). Ongoing from X = Br to P(O)(OEt)2, the {Zn(4′-XC6H4tpy)2}2+ unit exhibits significant “bowing” of the backbone, which is associated with changes in packing interactions. The [Zn(1)2]2+ cations engage in head-to-tail 4′-Phtpy...4′-Phtpy embraces with efficient pyridine...phenylene π-stacking interactions. The [Zn(2)2]2+ cations pack with one of the two ligands involved in pyridine...pyridine π-stacking; steric hindrance between one C6H4PO(OEt)2 group and an adjacent pair of π-stacked pyridine rings results in distortion of backbone of the ligand. This report is the first crystallographic determination of a salt of a homoleptic [M{4′-(RO)2OPC6H4tpy}2]n+ cation. View Full-Text
Keywords: phosphonate ester; zinc(II); 2,2′:6′,2″-terpyridine; crystal structure phosphonate ester; zinc(II); 2,2′:6′,2″-terpyridine; crystal structure
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Zare, D.; Prescimone, A.; Constable, E.C.; Housecroft, C.E. Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2? Crystals 2018, 8, 461.

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