Crystal structures and Hirshfeld surface analysis of [κ2-P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3 and the product of its reaction with piperidine, [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br]

Franco Palominos, Carolina Muñoz, Poldie Oyarzun, Marianela Saldías, Andrés Vega

Research output: Contribution to journalArticlepeer-review


The coordination of the ligands with respect to the central atom in the complex bromidotricarbonyl[diphenyl(pyridin-2-yl)phosphane-κ2 N,P]rhenium(I) chloroform disolvate, [ReBr(C17H14NP)(CO)3]·2CHCl3 or [κ2-P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3, (I·2CHCl3), is best described as a distorted octahedron with three carbonyls in a facial conformation, a bromide atom, and a biting P,N-diphenylpyridylphosphine ligand. Hirshfeld surface analysis shows that C - Cl⋯H interactions contribute 26%, the distance of these interactions are between 2.895 and 3.213 Å. The reaction between I and piperidine (C5H11N) at 313 K in dichloromethane leads to the partial decoordination of the pyridylphosphine ligand, whose pyridyl group is replaced by a piperidine molecule, and the complex bromidotricarbonyl[diphenyl(pyridin-2-yl)phosphane-κP](piperidine-κN)rhenium(I), [ReBr(C5H11N)(C17H14NP)(CO)3] or [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II). The molecule has an intramolecular N - H⋯N hydrogen bond between the non-coordinated pyridyl nitrogen atom and the amine hydrogen atom from piperidine with D⋯A = 2.992 (9) Å. Thermogravimetry shows that I·2CHCl3 losses 28% of its mass in a narrow range between 318 and 333 K, which is completely consistent with two solvating chloroform molecules very weakly bonded to I. The remaining I is stable at least to 573 K. In contrast, II seems to lose solvent and piperidine (12% of mass) between 427 and 463 K, while the additional 33% loss from this last temperature to 573 K corresponds to the release of 2-pyridylphosphine. The contribution to the scattering from highly disordered solvent molecules in II was removed with the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9-18] in PLATON. The stated crystal data for M r, μ etc. do not take this solvent into account.

Original languageEnglish
Pages (from-to)1005-1010
Number of pages6
JournalActa Crystallographica Section E: Crystallographic Communications
Publication statusPublished - 1 Jan 2019


  • Crystal structure
  • Diphenylpyridylphosphine
  • Hirshfeld surface analysis
  • Rhenium(I) tricarbonyl
  • Thermogravimetric analysis
  • Two-dimensional fingerprint plots

ASJC Scopus subject areas

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


Dive into the research topics of 'Crystal structures and Hirshfeld surface analysis of [κ<sup>2</sup>-P,N-{(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>5</sub>N)P}Re(CO)<sub>3</sub>Br]·2CHCl<sub>3</sub> and the product of its reaction with piperidine, [P-{(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>5</sub>N)P}(C<sub>5</sub>H<sub>11</sub>N)Re(CO)<sub>3</sub>Br]'. Together they form a unique fingerprint.

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