FR 6814 then FR 572 at Madrid
Manchester → Madrid → Porto
Timetable, Madrid time
23:55FR 6814 from Manchester at the gate
22:40FR 572 to Porto leaves the gate
22 h 45 apart on the timetable, overnight
FR 572 leaves 22 h 45 after FR 6814 arrives on the timetable: more than half a day, so not a connection we count.