LG 3591 then LL 5472 at Barcelona
Luxembourg → Barcelona → Valladolid
Timetable, Barcelona time
15:30LG 3591 from Luxembourg at the gate
12:20LL 5472 to Valladolid leaves the gate
20 h 50 apart on the timetable, overnight
LL 5472 leaves 20 h 50 after LG 3591 arrives on the timetable: more than half a day, so not a connection we count.