Since both members of the union are effectively the exact same type, there is no issue. C99: "If the member used to access the contents of a union is not the same as the member last used to store a value, the object representation of the value that was stored is reinterpreted as an object representation of the new type". Meaning, you can initialise keyvalue and that will initialise both key and value, so writing "union slot s{0}" initialises everything to 0. One issue is that the exact layout for bit fields is implementation defined, so if you absolutely need to know where key and value are in memory, you will have to read GCC's manual (or just experiment). Another is that you cannot take the address of key or value individually, but if your code was already using uint64_t, you probably don't need to.
Edit: Note also that you can cast a pointer to slot to a pointer to uint64_t and that does not break strict aliasing rules.
Maybe trying to avoid struct padding? Although having done a quick test on {arm64, amd64} {gcc, clang}, they all give the same `sizeof` for a struct with 2x`uint32_t`, a struct with a single `uint64_t`, or a bare `uint64_t`.
In any struct where all fields have the same size (and no field type requires higher alignment than its size), it is guaranteed on every (relevant) ABI that there is no padding bytes.
You could work around that with a union or casts with explicit alignment constraints, but this is the shortest way to express that.