This doesn't help you, because the contents of the padding bytes is not guaranteed to be anything in particular. Two structs containing identical field values can have different padding bytes. Reading the padding bytes is UB.
Just pack the struct and be done with it.
We can argue whether that's a smart thing to do or not, but I wasn't in charge of implementing it - it's a relic from a codebase that's more than a decade old at this point. It's a simple hashing method that works with most types, but obviously dies horrendously in a case like this.