The coordination of the ligands with respect to the central atom in the complex bromido-tricarbon-yl[diphen-yl(pyridin-2-yl)phosphane-κ2 N,P]rhenium(I) chloro-form 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 octa-hedron with three carbonyls in a facial conformation, a bromide atom, and a biting P,N-di-phenyl-pyridyl-phosphine ligand. Hirshfeld surface analysis shows that C-Cl⋯H inter-actions contribute 26%, the distance of these inter-actions are between 2.895 and 3.213 Å. The reaction between I and piperidine (C5H11N) at 313 K in di-chloro-methane leads to the partial decoord-ination of the pyridyl-phosphine ligand, whose pyridyl group is replaced by a piperidine mol-ecule, and the complex bromido-tricarbon-yl[diphen-yl(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 mol-ecule has an intra-molecular N-H⋯N hydrogen bond between the non-coordinated pyridyl nitro-gen 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 chloro-form mol-ecules 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-pyridyl-phosphine. The contribution to the scattering from highly disordered solvent mol-ecules 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.
Keywords: Hirshfeld surface analysis; crystal structure; diphenylpyridylphosphine; rhenium(I) tricarbonyl; thermogravimetric analysis; two-dimensional fingerprint plots.