Interestingly I have done many simulations of DNA and RNA and thought the question warrants more than the generic answer. In general, like CharonY points out, the actual space filled by all the atoms leaves very little room, however there are ions that fill in the grooves some times transiently, mostly K, Ca2+, Na and Mg2+ is like a magnet. High concentrations of Mg2+, non-natural actually cause DNA cleavage with nothing other than water. Overall the structure is very fluid, think of it as having small ripples that move down either strand constantly. Aside from this, there are several natural nucleotide analogous, uricil for instance in RNA can also be incorporated but rarely, usually only from a diseased state. But there are a wide range of synthetic DNA like molecules, where the sugars or backbone phosphates have been replaced, such as PNA (protein nucleic acids), or modified sugars, but these are all synthetic as mentioned. There are some pathogens that work by modifying DNA into Urcil, or derivative nucleic acids through cytosine mostly, or thymadine. There are also many compounds that work by intercalation between nucleotides, most cause cancer. An example most used is ethidium bromide, used in labs to see DNA in agar gels, where the molecule exploits the kinetic movements I mentioned, and works it's way in between base pair stacks.