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Issue 11, 2011
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Co-crystallization of coordination compounds through second-coordination sphere interactions

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Abstract

The mononuclear complexes belonging to the [M(valXn)]0/+ family [H2valXn are bicompartmental ligands derived from o-vanillin and 1,2- or 1,3-diamines; M = Ni(II), Cu(II), Au(III)] can efficiently act as receptors towards various hydrogen bond donors. The co-crystallization processes between [Ni(valXn)] complexes and ammonium salts (NH4Z, Z = ClO4; PF6; C6H5NH3ClO4) led to different supramolecular arrangements in the crystals depending on the host : guest molar ratio used in reactions. For a 2 : 1 stoichiometry, supramolecular dimers were obtained in the crystals: 2[Ni(valen)]·NH4Z (Z = ClO4, 1a; Z = PF6, 1b), 2[Ni(valphen)]·NH4ClO4·CH3OH 1c, 2[Ni(valmen)]·C6H5NH3ClO43, while for a 1 : 1 stoichiometry a supercomplex with a quadruple deck architecture resulted: 4[Ni(valen)]·3NH4ClO42. The co-crystallization of the Reinecke salt with mononuclear complexes from the [M(valXn)] family affords the following crystals: [Ni(valen)]2·NH4[Cr(NCS)4(NH3)2]·CH3OH 4, [Ni(valdmpn)]2·NH4[Cr(NCS)4(NH3)2]·2H2O 5, and [Cu(valpn)]·NH4[Cr(NCS)4(NH3)2]·CH3CN 6, in which the [M(valXn)] complexes interact with the ammonium ions and ammonia ligands, resulting in supramolecular chains. The composition and the topology of the supramolecular chain can be changed by replacing the ammonium ion from the Reinecke salt with a cationic receptor, [Au(valpn)]+ : [Au(valpn)][Cr(NCS)4(NH3)2] 7.

Graphical abstract: Co-crystallization of coordination compounds through second-coordination sphere interactions

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Publication details

The article was received on 21 Jan 2011, accepted on 09 Mar 2011 and first published on 08 Apr 2011


Article type: Paper
DOI: 10.1039/C1CE05112A
Citation: CrystEngComm, 2011,13, 3756-3766
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    Co-crystallization of coordination compounds through second-coordination sphere interactions

    A. Cucos, A. Ursu, A. M. Madalan, C. Duhayon, J. Sutter and M. Andruh, CrystEngComm, 2011, 13, 3756
    DOI: 10.1039/C1CE05112A

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