To target users, you need to JOINtable userstwice, once for the initiating user, and another for the target user:
SELECT room.room_id
FROM rooms room
INNER JOIN users initiating
ON room.room_initiating_user_id = initiating.user_id
INNER JOIN users target
ON room.room_target_user_id = target.user_id
WHERE initiating.user_connected=0 AND target.user_connected=0
To remove these rooms, you can use this as a subquery:
DELETE FROM rooms
WHERE room_id IN (
SELECT room.room_id
FROM rooms room
INNER JOIN users initiating
ON room.room_initiating_user_id = initiating.user_id
INNER JOIN users target
ON room.room_target_user_id = target.user_id
WHERE initiating.user_connected=0 AND target.user_connected=0
)
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