EC 4211 then FR 2507 at Barcelona
Napoli → Barcelona → Cologne
Timetable, Barcelona time
17:00EC 4211 from Napoli at the gate
06:20FR 2507 to Cologne leaves the gate
13 h 20 apart on the timetable, overnight
FR 2507 leaves 13 h 20 after EC 4211 arrives on the timetable: more than half a day, so not a connection we count.