Steric effects in chemistry are a consequence of the space required to accommodate the atoms and groups within a molecule, and are often thought to be dominated by repulsive forces arising from overlapping electron densities (Pauli repulsion). An appreciation of attractive interactions such as van der Waals forces (which include London dispersion forces) is necessary to understand chemical bonding and reactivity fully. This is evident from, for example, the strongly debated origin of the higher stability of branched alkanes relative to linear alkanes(1,2) and the possibility of constructing hydrocarbons with extraordinarily long C-C single bonds through steric crowding(3). Although empirical bond distance/bond strength relationships have been established for C-C bonds(4) (longer C-C bonds have smaller bond dissociation energies), these have no present theoretical basis(5). Nevertheless, these empirical considerations are fundamental to structural and energetic evaluations in chemistry(6,7), as summarized by Pauling(8) as early as 1960 and confirmed more recently(4). Here we report the preparation of hydrocarbons with extremely long C-C bonds (up to 1.704 angstrom), the longest such bonds observed so far in alkanes. The prepared compounds are unexpectedly stable-noticeable decomposition occurs only above 200 degrees C. We prepared the alkanes by coupling nanometre-sized, diamond-like, highly rigid structures known as diamondoids(9). The extraordinary stability of the coupling products is due to overall attractive dispersion interactions between the intramolecular H center dot center dot center dot H contact surfaces, as is evident from density functional theory computations with(10) and without inclusion of dispersion corrections.