If this is an existing installation in which you are going to split off /usr, then do make sure you read my HowTo below.
If on the other hand it’s a new installation, then make sure you modify /etc/mkinitcpio.conf and rebuild the initcpios for all of your kernels before rebooting, because Calamares does not set up the required hooks for a separate /usr partition or an @usrbtrfs subvolume. I discovered that the hard way.