Crystal structure of 4-chloropyridinium hexachlorostannate(IV)

Abstract

The title compound has been examined by single-crystal X-ray crystallography and crystallizes in the space-group P2,lc with Z = 2 in a unit cell of dimensions a = 8.555, b = 16.962, c = 7.1 22 a and p = 11 3-1 5". The structure was solved by conventional Fourier techniques and was refined anisotropically by full-matrix least-squares methods to R 0-039 using 1600 independent reflections measured by counter methods. The cation is regular and normal.The SnCla2-ion is tetragonally distorted with three crystallographically inequivalent Sn-CI bonds [2.414(4), 2.419(2), and 2.463(3) 81. the source of the distortion being CI . * . H-N hydrogen bonding between the long Sn-CI bonds of SnCIG2-and the cation. These results account very well for the marked splittings in the 35CI n.q.r. signals observed for this anion.RECENT n.q.r. measurements on SnClG2-, PbC1,2-, and Tech2-salts indicate that when the 4-chloropyridinium ion (4-ClpyH) is the counter cation, very large splittings in the chlorine resonance frequencies of the anion appear. N.q.r. spectroscopy can be used to detect chemical and crystallographic inequivalencies of nuclei having quadrupole moments. Crystallographic inequivalence generally leads to small splittings which are rarely >5% of the overall effect. However in [4-ClpyH]2SnC&, for example, resonance multiplets appear that are split by >15% of the overall effect. It is of importance to n.q.r. spectroscopy to know what sorts of interactions can generate such marked splittings in an I'vIC~,~-salt. To the general chemistry of tin it is important to know whether this cation has distorted the SnCh2-ion enough to produce a different anionic arrangement, such as a SnC1,-, C1ion pair. Finally, in the only crystallographic data available on the SnClG2the Sn-Cl bond lengths are either not known or determined approximately to be 2.41 & 0 . 0 5 4 . 1 0 h;.We therefore undertook a crystal structure determination of 4-chloropyridinium hexachlorostannate(Iv) . EXPERIMENTAL u = 8.555(9), b = 16*962(5), c = 7.122(7) A, p = 113.15" Cyystal Data

Utilizing hydrogen bonds and halogen–halogen interactions in the design of uranyl hybrid materials

“…These intermolecular interactions have, in combination with hydrogen bonds, been applied to the rational design of hybrid materials by reacting 4-halopyridines with perhalometallates in acidic, high halide media. 8,[15][16][17][18][19][20][21][22][23][24][25] In this communication we report the synthesis and characterization by single crystal X-ray diffraction of a family of compounds in which the 4-halopyridinium cation displays a variety of intermolecular interactions with the UO 2 X′ 4 2− ion. These compounds were formed by slow evaporation of a highly acidic solution of uranium oxyacetate and 4halopyridinium species which resulted in single crystals suitable for XRD (Table 1); full synthetic and experimental data can be found in the ESI.…”

Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal–Ligand Bonding

“…The supramolecular sheets intersect and interpenetrate at 90° angles to form a pseudo-three-dimensional arrangement. We note this supramolecular bonding motif is common to related transition metal systems such as (4XPyH) 2 [YCl 6 ], where X = Cl, Br and Y = Sn, Pt. − …”