I have a perso on the tree as a sibling of my father, but that sibling married a bloke whose sister was my grandmother. So both are on the tree but are not connected as bother and sister.
For example, my father has a sister named Betty, who married a bloke called Richard who has a sister called June.
My father married the daugher of June, therefore June is my grandmother, but she is also the sister of my father's sister Betty's husband Richard. So Richard and June are both on the tree as separate individuals. There's no option to add brother/sister to someone already on the tree (as their is to add a partner that is already on the tree)
Wait I think I figured it out. If I add Richard as June's brother first, then add him as Betty's partnet I can choose existing person. Very cool.