N,N-Dimethylbiguanidinium bis(hydrogensquarate) features an impressive range of hydrogen bonds within the same crystal structure: neighbouring anions aggregate to a dianionic pair through two strong O-H···O interactions; one of these can be classified among the shortest hydrogen bonds ever studied. Cations and anions in this organic salt further interact via conventional N-H···O and nonclassical C-H···O contacts to an extended structure. As all these interactions occur in the same sample, the title compound is particularly suitable to monitor even subtle trends in hydrogen bonds. Neutron and high-resolution X-ray diffraction experiments have enabled us to determine the electron density precisely and to address its properties with an emphasis on the nature of the X-H···O interactions. Sensitive criteria such as the Laplacian of the electron density and energy densities in the bond-critical points reveal the incipient covalent character of the shortest O-H···O bond. These findings are in agreement with the precise geometry from neutron diffraction: the shortest hydrogen bond is also significantly more symmetric than the longer interactions.

Silver meso-and rac-tartrate and silver squarate have been synthesized, and the crystal structure of a new polymorph of the latter is reported. Three reaction products of these silver salts with pyrazine have been obtained and structurally characterized: From silver squarate, a chain polymer with linear coordination of Ag(I) by two pyrazine ligands is formed, whereas the silver tartrates yield solids in which the inner coordination sites around the metal are only partially occupied by N donors; in contrast to expectation, oxygen coordination prevails. All the four new Ag(I) coordination compounds reported show high packing coefficients in the range between 0.789 and 0.885. In order to put these results into a meaningful context, packing coefficients for the crystal structures of almost 30,000 compounds retrieved from the Cambridge Structural Database have been determined. Tartrates pack significantly closer than pyrazine complexes or metalcontaining compounds in general. The exceptionally high packing coefficient of the new polymorph of silver squarate is due to stacking of anions and concomitant AgÁÁÁAg contacts, both along the shortest lattice parameter which amounts to only 3.3990(9) Å .