What I was trying to do was to define a constant structure containing hard-coded directory and subdirectory names, that would allow me to write nested literal strings. The code would walk this structure forming paths to directories from which it would readdir() the file names. It sounds like Struct doesn't easily support this kind of initialization. Clearly, this can be done by writing a hash-of-hashes-of-hashes as others have suggested, and I eventually used.
This was obviously not a perfect situation in which to use Struct. :-)