Asymmetric hydrogen bonds in centrosymmetric environment: neutron study of very short hydrogen bonds in potassium...

The structure of the title compound has been studied by neutron diffraction at 30 and 295 K, with the emphasis on the location of the protons. There are two crystallographically independent H atoms in two very short hydrogen bonds, 2.437 (2) and 2.442 (2) A at 30 K. The structure could be refined successfully in the centrosymmetric space group P1;, with the H atoms located at the centres of symmetry. However, the form of the thermal ellipsoids of hydrogen indicated either asymmetric hydrogen bonds or overlap of two closely spaced, partially occupied positions around the centres of symmetry. Several different types of refinements have then been applied, including unconventional models; with all atoms except hydrogen constrained in P1;, but with hydrogen allowed to refine without any constraints in P1, anisotropic refinement of all atoms resulted in clearly off-centred hydrogen positions. Significance tests clearly showed that the results from this constrained refinement give the most satisfactory description of the structure. This structure may be described as 'pseudo-centrosymmetric with non-centred protons'. The results demonstrate that it is very important to also include refinement models with non-centrosymmetric hydrogen in a centrosymmetric environment when studying very short hydrogen bonds. The shifts of the two H atoms from the centres of symmetry are 0.15 (1) and 0.12 (1) A, respectively, at 30 K, and 0.15 (1) A for both H atoms at room temperature. At 30 K: R(F) = 0.036 for 1485 reflections; at 295 K: R(F) = 0.035 for 1349 reflections.