UX 72 then IB 1401 at Madrid
Caracas → Madrid → Valencia
Timetable, Madrid time
12:35UX 72 from Caracas at the gate
11:30IB 1401 to Valencia leaves the gate
22 h 55 apart on the timetable, overnight
IB 1401 leaves 22 h 55 after UX 72 arrives on the timetable: more than half a day, so not a connection we count.