Efficient Diffusion-Controlled Ligand Exchange Crystal Growth of Isostructural Inorganic–Organic Halogenidorhodates(III): The Missing Hexaiodidorhodate(III) Anion

Abstract

Crystal system Orthorhombic Orthorhombic Monoclinic Triclinic Space group Pnma Pnma C2/c P1 a/Å 26.3712(9) 27.4238(9) 11.4831(5) 6.5186(3) b/Å 10.1433(5) 10.5512(4) 5.9049(2) 7.4950(3) c/Å 7.9013(3) 8.3875(3) 13.9367(6) 8.1312(4) /º

Formation and distortion of iodidoantimonates(III): the first isolated [SbI6]3−octahedron

“…At 85 K the cations are fully ordered, which indicates the dynamical nature of disorder. The bond lengths and angles of cations are consistent with those found in other crystals containing piperazine-1,4diium cations (Table S1; Bujak, 2015a;Flatken et al, 2014;Ré rat, 1960;Dehghanpour et al, 2001;Parkin et al, 2004;Baisch et al, 2008).…”

“…The Cambridge Structural Database (ConQuest and Mercury programs) was used for searching and analysing the structures containing Sb-I and I-Sb-I fragments (Macrae et al, 2006(Macrae et al, , 2008Allen, 2002;Bruno et al, 2002;Groom et al, 2016). To avoid biases in the structural parameters resulting from comparison of the crystal data obtained for two different crystal samples of PDD at 295 (2) K (Bujak, 2015a) and 100 K (Flatken et al, 2014), and affecting our analysis of the structural evolution with decreasing temperature, the structure of PDD was redetermined, using the same instrument and the same singlecrystal sample, at both 295 (2) and 85.0 (5) K. Computer programs: CrysAlis CCD and CrysAlis Pro (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008(Sheldrick, , 2015, Mercury (Macrae et al, 2006(Macrae et al, , 2008.…”

“…The structure of organic PDD is built up from piperazine-1,4-diium cations and I 2 molecules, both located at inversion centres, and I À ions that occupy general positions ( Fig. 1c; Bujak, 2015a;Flatken et al, 2014). At 295 K, the I 2 molecule shows an I-I distance of 2.7651 (8) Å (Table S1) which is clearly longer than in the solid iodine [2.68 Å , 2.715 (6)/2.722 (2) Å and 2.717 (2) Å determined at room temperature, 110 K and 5 K, respectively; Kitaigorodskii et al, 1953;van Bolhuis et al, 1967;Ibberson et al, (1992)].…”

“…Our recent study on diffusion-controlled ligand exchange crystal growth along with the structure-property determination of inorganic-organic monohydrates of piperazine-1,4diium hexabromidorhodate(III) bromide and hexaiodidorhodate(III) iodide showed that the anionic substructure of the latter hybrid is efficiently thermodynamically stabilized by the second coordination sphere Rh-IÁ Á ÁIÁ Á ÁI-Rh and O/N/C-HÁ Á ÁI interactions (Bujak, 2015a;Dalrymple & Shimizu, 2002;Mercer & Loeb, 2010). Further, because a large number of inorganic-organic hybrids containing piperazine-1,4-diium cations crystallize as hydrates (James et al, 1996), one expects to find the hydrogen bonded water of crystallization molecules embedded in the crystal lattice that could effectively separate inorganic structural components and prevent them from forming complicated inorganic substructures.…”

Isostructural Inorganic–Organic Piperazine-1,4-diium Chlorido- and Bromidoantimonate(III) Monohydrates: Octahedral Distortions and Hydrogen Bonds

“…The introduction into the structure of 2 the heavier, more polarizable and less electronegative Br compared to Cl atoms, opens the possibility of the formation of weaker organic-inorganic N/C-H•••X hydrogen bonds and thus weakens the secondary octahedral distortion factor. Further, the piperazine-1,4-diium cations due to their tendency to formation of hydrogen bonds and the relatively large spatial dimensions that create a pattern with appropriate cavities for inclusion of water of crystallization molecules [32,33] provide an opportunity to explore the occurrence, hierarchy and competition of N/C-H•••X and O-H•••X hydrogen bonds on the distortions of inorganic polyhedra. Moreover, the temperature effect, using the same single crystal samples in order to rationalize the contribution of different factors on the structural changes of crystals of 1 and 2, was studied.…”