Crystal structures and Hirshfeld surface analysis of [κ(2)-P,N-{(C(6)H(5))(2)(C(5)H(5)N)P}Re(CO)(3)Br]·2CHCl(3) and the product of its reaction with piperidine, [P-{(C(6)H(5))(2)(C(5)H(5)N)P}(C(5)H(11)N)Re(CO)(3)Br]

The coordination of the ligands with respect to the central atom in the complex bromido­tricarbon­yl[diphen­yl(pyridin-2-yl)phosphane-κ(2) N,P]rhenium(I) chloro­form disolvate, [ReBr(C(17)H(14)NP)(CO)(3)]·2CHCl(3) or [κ(2)-P,N-{(C(6)H(5))(2)(C(5)H(5)N)P}Re(CO)(3)Br]·2CHCl(3), (I·2CHCl(3)), 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 (C(5)H(11)N) 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(C(5)H(11)N)(C(17)H(14)NP)(CO)(3)] or [P-{(C(6)H(5))(2)(C(5)H(5)N)P}(C(5)H(11)N)Re(CO)(3)Br] (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·2CHCl(3) 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.