The electron-density distribution of the high-pressure polymorph of SiO 2 , stishovite [a = 4.177 (1) , c = 2.6655 (5) A Ê , space group P4 2 amnm, Z = 2], has been redetermined by single-crystal diffractometry using synchrotron radiation of 100.42 and 30.99 keV, respectively, in order to obtain essentially absorptionand extinction-free data. Room-temperature diffraction experiments on two samples of irregular shape were carried out on two different diffractometers installed at HASYLAB/DESY, Hamburg, Germany. The structure re®nement on the high-energy data converged at R(F ) = 0.0047, wR(F ) = 0.0038, GoF = 0.78, for a multipole model with neutral atoms and multipole expansions up to seventh order. For each atom, the radial expansion coef®cients of the multipole orders (l > 0) were constrained to a common value. The absence of extinction was indicated by a re®ned correction parameter equalling zero within error limit. The excellent quality of the data is also illustrated by a high-order (HO) re®nement (s > 0.7 A Ê À1 ) yielding R(F ) = 0.0060, wR(F) = 0.0048, GoF = 0.85. Both static deformation electron-density distribution and structure amplitudes compare well with corresponding results obtained from band-structure calculations using the linearized-augmented-plane-wave (LAPW) method. Ensuing topological analysis of the total model electron density distribution revealed bond critical point properties for the two unique SiÐO bonds, indicating a predominantly closed-shell interaction mixed with a signi®cant shared interaction contribution that decreases with increasing interatomic distance. Calculation of atomic basins yielded charges of +3.39 e and À1.69 e for Si and O, respectively, in good agreement with the theoretically calculated values of +3.30 e and À1.65 e. The volumina of the Si and O basins are 2.32 and 10.48 A Ê 3 , corresponding to spheres with radii of 0.82 and 1.36 A Ê , respectively. The results also conform well with correlations between bond length and bond critical point properties reported in the literature for geometry-optimized hydroxyacid molecules. Estimates of the Si cation electronegativity indicate that the change of Si coordination by oxygen from 4 to 6 is accompanied by an increase of the ionicity of the SiÐO bond of about 7%.