How to calculate 2^n-1 efficiently without overflow?

Use a lookup table. (Generated by your present code.) This is ideal, since the number of values is small, and you know the results already.

/* lookup table: n -> 2^n-1 -- do not touch */
const static uint64_t N2MINUSONE_LUT[] = {
0x0,
0x1,
0x3,
0x7,
0xf,
0x1f,
0x3f,
0x7f,
0xff,
0x1ff,
0x3ff,
0x7ff,
0xfff,
0x1fff,
0x3fff,
0x7fff,
0xffff,
0x1ffff,
0x3ffff,
0x7ffff,
0xfffff,
0x1fffff,
0x3fffff,
0x7fffff,
0xffffff,
0x1ffffff,
0x3ffffff,
0x7ffffff,
0xfffffff,
0x1fffffff,
0x3fffffff,
0x7fffffff,
0xffffffff,
0x1ffffffff,
0x3ffffffff,
0x7ffffffff,
0xfffffffff,
0x1fffffffff,
0x3fffffffff,
0x7fffffffff,
0xffffffffff,
0x1ffffffffff,
0x3ffffffffff,
0x7ffffffffff,
0xfffffffffff,
0x1fffffffffff,
0x3fffffffffff,
0x7fffffffffff,
0xffffffffffff,
0x1ffffffffffff,
0x3ffffffffffff,
0x7ffffffffffff,
0xfffffffffffff,
0x1fffffffffffff,
0x3fffffffffffff,
0x7fffffffffffff,
0xffffffffffffff,
0x1ffffffffffffff,
0x3ffffffffffffff,
0x7ffffffffffffff,
0xfffffffffffffff,
0x1fffffffffffffff,
0x3fffffffffffffff,
0x7fffffffffffffff,
0xffffffffffffffff,
};

How about a simple r = (n == 64) ? -1 : (1ULL<<n)-1;?

If you want to get the max value just before overflow with a given number of bits, try

r=(1ULL << n-1)+((1ULL<<n-1)-1);

By splitting the shift into two parts (in this case, two 63 bit shifts, since 2^64=2*2^63), subtracting 1 and then adding the two results together, you should be able to do the calculation without overflowing the 64 bit data type.