Lithium tetraphenylborate tetrahydrate, [Li(OH2)4]BPh4 (LiTBw; tetragonal, I41/a, a = 27.566(2) Å, c = 12.228(2) Å, Z = 16) is remarkable in that the four H2O molecules coordinating the Li+ ion all form O—H …π hydrogen bonds to the phenyl groups of the anion. LiTBw thus appears to be the first reported example of such an exhaustive O—H …π coordination and can be described as a 3-dimensional, completely H-bonded polymer in which all the H2O hydrogens are bonded to phenyl groups and all the phenyl groups are involved in O—H … phenyl bonds. Six of the O—H … phenyl bonds are essentially normal and two are highly bent, possibly bifurcated. The existence of the H-bonds has been corroborated from variable-temperature FT-ir spectra of weakly deuterated LiTBw. The O—Li—O angles in the LiO4 coordination tetrahedron (of symmetry C1) exhibit large departures from the tetrahedral angle, two of the angles bisected by a quasi-S4 axis being 118.3° and 122.5°, respectively. An ab initio (6-31G*) investigation of the Li(OH2)4+ and Be(OH2)42+ cations has shown that such large O—M—O angles are to be expected even in the free ions and are thus not necessarily the result of packing effects. A detailed comparison with several Li(OH2)4+ and Be(OH2)42+ salts provides a rationale for the observed M(OH2)4n+ (M = Li, Be) geometries.
