FR 5322 then FR 4066 at Madrid
Milan → Madrid → Catania
Timetable, Madrid time
12:45FR 5322 from Milan at the gate
09:30FR 4066 to Catania leaves the gate
20 h 45 apart on the timetable, overnight
FR 4066 leaves 20 h 45 after FR 5322 arrives on the timetable: more than half a day, so not a connection we count.