Let x be the number of students having both brother and sister.
Brother only is 7-x
Sister only is 6-x
Brother only + sister only + both + neither = 21
(7-x) + (6-x) + x + 4= 21
-4 - x = 21
x = 17
Per definition of conditional probability:
prob( brother | sister) = prob ( brother AND sister) / prob ( sister)
17/6 = 2 5/6
17/6 = 2 5/6 = 25%