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A second, polymorphic, form of the previously reported compound 4,4,6,6-tetra­chloro-2,2-(2,2-dimethyl­propane-1,3-di­oxy)cyclotriphosphazene, C5H10Cl4N3O2P3, is now reported. The mol­ecular structures of these two compounds are similar, aside from minor conformational differences. However, the compounds crystallize in two different space groups and exhibit quite different crystal structure assemblies. Additionally, 6,6-dichloro-2,2:4,4-bis­(2,2-dimethyl­propane-1,3-dioxy)cyclotriphosphazene, C10H20Cl2N3O4P3, is shown to exhibit two different conformational polymorphs when crystallized from different solvent mixtures. The α form crystallizes in the space group Pnma with the mol­ecular structure lying on a mirror plane (symmetry code: x, −y + {1\over 2}, z), whilst the β form is in the space group C2/c with the mol­ecular structure lying on a twofold axis (symmetry code: −x, y, −z + {3\over 2}). The difference between the two mol­ecular structures is in the conformation of the spiro-ring substituents with respect to the phosphazene ring. The resulting crystal structures give rise to differing packing motifs.

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The title ionic solid, [Ti(C2H6N)3(C2H7N)2][Ti(C18BF15N)(C18H2BF15N)Cl(C2H7N)2]·C7H8, (I), comprises a cation with three dimethyl­amide ligands in the equatorial plane and two dimethyl­amine ligands positioned axially in a trigonal–bipyramidal geometry about the central TiIV atom. The anion has a highly distorted octa­hedral structure. The two dimethyl­amine ligands are coordinated mutually trans. The chloride is trans to the tris­(penta­fluoro­phenyl)boron–amide, while the sixth coordination site is occupied by an ortho-F atom of the tris­(penta­fluoro­phenyl)boron–amide group in a trans disposition with respect to the tris­(penta­fluoro­phenyl)boron–nitride ligand. The most significant feature of the anion is the presence of an unprecedented terminal Ti[triple bond]N moiety [1.665 (2) Å], stabilized by coordination to B(C6F5)3, with a Ti[triple bond]N—B angle of 169.50 (19)°.
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