Crystal packing in planar platinum(II) and palladium(II) complexes. Hydrogen-bond-mediated supramolecular assembly of ten wedge-shaped molecules into a cyclic array

Emily M. Gussenhoven, Martyn Jevric, Marilyn M. Olmstead, James C. Fettinger, Mark Mascal, Alan L. Balch

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The molecular packing arrangements for the unsolvated compounds, PtCl 2(ATQ-CH 2NH 2) (la) and PdCl 2(ATQ- CH 2NH 2) (2) (ATQ = azatriquinane), and two solvates of the platinum complex, 6{PtCl 2(ATQ-CH 2NH 2)} •2(CH 3CN) (lb) and 3{PtCl 2(ATQ-CH 2NH 2)) •2(CH 2C1 2) (lc), are reported. These planar, d 8 complexes have a wedgelike shape due to the presence of the bulky azatriquinane unit coordinated directly to the metal. All of the crystals exhibit hydrogen bonding between the N-H groups of one molecule and the chloride ligands on another. Despite the similar sizes and shapes of the complexes, the unsolvated compounds, PtCl 2(ATQ-CH 2NH 2) (la) and PdCl 2(ATQ-CH 2NH 2) (2), pack in entirely different fashions, with metallophilie interactions between pairs of cofacial complexes in the palladium complex. The platinum complex lacks the metallophillic interactions. The structure of 6{PtCl 2(ATQ- CH 2NH 2)} •2(CH 3CN) (lb) is noteworthy for two features. First, these crystals contain an ordered cyclic assembly of 10 molecules of the complex with all the Pt-CI groups directed toward the inside of the ring. The formation of this supramolecular maerocyclic array is facilitated by extensive hydrogen bonding between the NH groups of one molecule and the chloride ligands of another. Second, these crystals also contain a poorly organized region where one PtCl 2(ATQ-CH 2NH 2) molecule is disordered over several orientations. 3{PtCl 2(ATQ-CH 2NH 2)) •2(CH 2C1 2) (lc) crystallizes with three molecules of the platinum complex in a crescent-shaped array that shows some similarity with the cyclic structure found in 6{PtCl 2(ATQ-CH 2NH 2)) •2(CH 3CN) (lb).

Original languageEnglish (US)
Pages (from-to)1786-1792
Number of pages7
JournalCrystal Growth and Design
Volume9
Issue number4
DOIs
StatePublished - Apr 1 2009

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Palladium
Platinum
wedges
palladium
Hydrogen bonds
platinum
assembly
methylidyne
hydrogen bonds
Crystals
Molecules
crystals
molecules
Chlorides
Ligands
Metals
chlorides
ligands
hydrogen

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Crystal packing in planar platinum(II) and palladium(II) complexes. Hydrogen-bond-mediated supramolecular assembly of ten wedge-shaped molecules into a cyclic array. / Gussenhoven, Emily M.; Jevric, Martyn; Olmstead, Marilyn M.; Fettinger, James C.; Mascal, Mark; Balch, Alan L.

In: Crystal Growth and Design, Vol. 9, No. 4, 01.04.2009, p. 1786-1792.

Research output: Contribution to journalArticle

Gussenhoven, Emily M. ; Jevric, Martyn ; Olmstead, Marilyn M. ; Fettinger, James C. ; Mascal, Mark ; Balch, Alan L. / Crystal packing in planar platinum(II) and palladium(II) complexes. Hydrogen-bond-mediated supramolecular assembly of ten wedge-shaped molecules into a cyclic array. In: Crystal Growth and Design. 2009 ; Vol. 9, No. 4. pp. 1786-1792.
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abstract = "The molecular packing arrangements for the unsolvated compounds, PtCl 2(ATQ-CH 2NH 2) (la) and PdCl 2(ATQ- CH 2NH 2) (2) (ATQ = azatriquinane), and two solvates of the platinum complex, 6{PtCl 2(ATQ-CH 2NH 2)} •2(CH 3CN) (lb) and 3{PtCl 2(ATQ-CH 2NH 2)) •2(CH 2C1 2) (lc), are reported. These planar, d 8 complexes have a wedgelike shape due to the presence of the bulky azatriquinane unit coordinated directly to the metal. All of the crystals exhibit hydrogen bonding between the N-H groups of one molecule and the chloride ligands on another. Despite the similar sizes and shapes of the complexes, the unsolvated compounds, PtCl 2(ATQ-CH 2NH 2) (la) and PdCl 2(ATQ-CH 2NH 2) (2), pack in entirely different fashions, with metallophilie interactions between pairs of cofacial complexes in the palladium complex. The platinum complex lacks the metallophillic interactions. The structure of 6{PtCl 2(ATQ- CH 2NH 2)} •2(CH 3CN) (lb) is noteworthy for two features. First, these crystals contain an ordered cyclic assembly of 10 molecules of the complex with all the Pt-CI groups directed toward the inside of the ring. The formation of this supramolecular maerocyclic array is facilitated by extensive hydrogen bonding between the NH groups of one molecule and the chloride ligands of another. Second, these crystals also contain a poorly organized region where one PtCl 2(ATQ-CH 2NH 2) molecule is disordered over several orientations. 3{PtCl 2(ATQ-CH 2NH 2)) •2(CH 2C1 2) (lc) crystallizes with three molecules of the platinum complex in a crescent-shaped array that shows some similarity with the cyclic structure found in 6{PtCl 2(ATQ-CH 2NH 2)) •2(CH 3CN) (lb).",
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AU - Gussenhoven, Emily M.

AU - Jevric, Martyn

AU - Olmstead, Marilyn M.

AU - Fettinger, James C.

AU - Mascal, Mark

AU - Balch, Alan L.

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AB - The molecular packing arrangements for the unsolvated compounds, PtCl 2(ATQ-CH 2NH 2) (la) and PdCl 2(ATQ- CH 2NH 2) (2) (ATQ = azatriquinane), and two solvates of the platinum complex, 6{PtCl 2(ATQ-CH 2NH 2)} •2(CH 3CN) (lb) and 3{PtCl 2(ATQ-CH 2NH 2)) •2(CH 2C1 2) (lc), are reported. These planar, d 8 complexes have a wedgelike shape due to the presence of the bulky azatriquinane unit coordinated directly to the metal. All of the crystals exhibit hydrogen bonding between the N-H groups of one molecule and the chloride ligands on another. Despite the similar sizes and shapes of the complexes, the unsolvated compounds, PtCl 2(ATQ-CH 2NH 2) (la) and PdCl 2(ATQ-CH 2NH 2) (2), pack in entirely different fashions, with metallophilie interactions between pairs of cofacial complexes in the palladium complex. The platinum complex lacks the metallophillic interactions. The structure of 6{PtCl 2(ATQ- CH 2NH 2)} •2(CH 3CN) (lb) is noteworthy for two features. First, these crystals contain an ordered cyclic assembly of 10 molecules of the complex with all the Pt-CI groups directed toward the inside of the ring. The formation of this supramolecular maerocyclic array is facilitated by extensive hydrogen bonding between the NH groups of one molecule and the chloride ligands of another. Second, these crystals also contain a poorly organized region where one PtCl 2(ATQ-CH 2NH 2) molecule is disordered over several orientations. 3{PtCl 2(ATQ-CH 2NH 2)) •2(CH 2C1 2) (lc) crystallizes with three molecules of the platinum complex in a crescent-shaped array that shows some similarity with the cyclic structure found in 6{PtCl 2(ATQ-CH 2NH 2)) •2(CH 3CN) (lb).

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