Crystal structures and Hirshfeld surface analysis of [κ-,-{(CH)(CHN)P}Re(CO)Br]·2CHCl and the product of its reaction with piperidine, [-{(CH)(CHN)P}(CHN)Re(CO)Br].

The coordination of the ligands with respect to the central atom in the complex bromido-tricarbon-yl[diphen-yl(pyridin-2-yl)phosphane-κ ,]rhenium(I) chloro-form disolvate, [ReBr(CHNP)(CO)]·2CHCl or [κ-,-{(CH)(CHN)P}Re(CO)Br]·2CHCl, (·2CHCl), is best described as a distorted octa-hedron with three carbonyls in a facial conformation, a bromide atom, and a biting ,-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 and piperidine (CHN) 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-κ](piperidine-κ)rhenium(I), [ReBr(CHN)(CHNP)(CO)] or [-{(CH)(CHN)P}(CHN)Re(CO)Br] (). 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 ⋯ = 2.992 (9) Å. Thermogravimetry shows that ·2CHCl 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 . The remaining is stable at least to 573 K. In contrast, 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 was removed with the SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9-18] in . The stated crystal data for , μ . do not take this solvent into account.