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Constructions of Seven Noncovalent-Bonded 3D Supramolecules from Reactions of Zn(II)/Cd(II) with 4-Dimethylaminopyridine and Carboxylic Acids

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Abstract

Seven novel 4-dimethylaminopyridine(dmap)-based metal complexes of [Zn(dmap)(cna)2]2 (1) (Hcna = cinnamic acid), [Zn(dmap)(dcpa)2]2 (2) (Hdcpa = 2,6-dichlorophenylacetic acid), [Zn(dmap)(mpba)2]2 (3) (Hmpba = 3-phenoxybenzoic acid), [Zn(dmap)(bdmba)2]2 (4) (Hbdmba = 4-bromo-3,5-dimethoxybenzoic acid), [Cd(damp)2(ibfa)2(H2O)2] (5) (Hibfa = ibuprofen), [Cd(dmap)2(H2O)4]·(dnba)2·H2O (6) (Hdnba = 3,5-dinitrobenzoic acid) and [Cd(dmap)2(bdmba)2(H2O)] (7) have been afforded by the introduction of the carboxylates as the auxiliary ligands and are structurally featured by distinct techniques of EA, IR spectra, TG and SCXRD analysis. The X-ray studies told that these complexes display mononuclear, binuclear to polymeric appearances with tetrahedral/square-pyramidal arrangement at the Zn2+, and octahedral/pentagonal-bipyramidal geometry for the Cd2+. The dmap in 1–7 are coordinated only in monodentate fashion with its ring N. The carboxylates coordinated to the metal ions in monodentate, chelating bidentate and bismonodentate bridging modes for 1–5 and 7. The carboxylates at 6 did not coordinated to the Cd and exhibited only as the counter ion to balance the charge. The CH3···O contacts from the N(CH3)2 of the dmap were built in all compounds, apart from 1 and 6. The π-associates originating from the aryl kernel of the anions were existed in 2–3 and 6–7. The intricate intra- and intermolecular classical H-bonds, CH···C, CH···O/CH3···O, CH···CH/CH3···CH/CH3···CH3, CH···Cl, CH3···Br, Br···Br, CH···π/CH2···π/CH3···π and π···π associations are elucidated by the X-ray crystallographic investigations, which push the discrete complexes into high-dimensional ordered supramolecular structures.

Graphical Abstract

In the seven prepared coordination complexes there are plenty of weak nonbonding interactions such as directional hydrogen bonds of O–H···O, intra- and interchain CH–C, CH–O/CH3–O, CH–CH/CH3–CH/CH3–CH3, CH–Cl, CH3–Br, Br–Br, CH–π/CH2–π/CH3–π and π–π interactions, on account of these collective weak interactions, these compounds displayed the 3D framework structures.

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Funding

The work was supported by the Open Foundation of Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province, Zhejiang A & F University and Jiyang 533 for Shouwen Jin.

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Authors and Affiliations

  1. Jiyang college, Zhejiang A & F University, Zhu’ji, 311800, Zhejiang Province, China

    Chengzhe Shi, Shouwen Jin, Yaoqi Zhen & Weiqiang Xu

  2. Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province, Zhejiang A & F University, Hangzhou, 311300, Zhejiang, China

    Chengzhe Shi, Shouwen Jin, Yaoqi Zhen & Weiqiang Xu

  3. Department of Chemical Engineering, Liaocheng University, Liaocheng, 252059, China

    Daqi Wang

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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by DW, CS, YZ. The first draft of the manuscript was written by SJ and BL. All authors read and approved the final manuscript. Please check and confirm the processing of Supplementary Material is correct. The processing of the supplemetary materials were right.

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Shi, C., Jin, S., Zhen, Y. et al. Constructions of Seven Noncovalent-Bonded 3D Supramolecules from Reactions of Zn(II)/Cd(II) with 4-Dimethylaminopyridine and Carboxylic Acids. J Inorg Organomet Polym 34, 235–250 (2024). https://doi.org/10.1007/s10904-023-02796-5

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