Betrayed by a bitfield

Again, this is implementation-defined behavior. The standard you're looking for is the ABI for your target. That's where all the memory layout, access size, calling convention and other low-level stuff is specified.

Volatile is perfectly fine for I/O as long as you know the address being accessed is suitably aligned to avoid problems, as the ABI should indicate.

This is why volatile is non-portable. Unfortunately, C99 has no standard way to force alignment of any object.