The internal syscall numbers are defined in syscall_64.tbl in kernel source and you can parse the (libc-used) syscall numbers from various /usr/include/asm/syscall.h files, but these files don't necessarily contain all the available syscalls in your currently running kernel.

You can read your kernel's/platform's currently available syscalls from the relevant /sys/kernel/debug/tracing tracepoint files (I posted a link to my script in another comment here). That way you'll see all currently available system calls and their arguments, but tracefs doesn't show the syscall internal numbers (syscall table slot numbers), but rather the new syscall ID.

The internal syscall numbering can change when you switch/build a new kernel and syscalls have different numbers across platforms. Syscall 0 is "read" on x86_64, but is "io_setup" on aarch64, for example. The new syscall ID aims to provide stable numbering with no conflicts and overlaps across platforms and kernel versions, as I understand.