Summary: | The coordination of the ligands with respect to the central atom in the complex bromidotricarbonyl[diphenyl(pyridin-2-yl)phosphane-κ2N,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 Mr, μ etc. do not take this solvent into account.
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