Gary Neville endured a dispiriting start to life as a head coach when the former England defender's Valencia side lost 2-0 at home to Olympique Lyonnais on to exit the Champions League last night.
Maxwell Cornet put Lyon in front eight minutes before the break and Alexandre Lacazette sealed all three points for the French side in the 76th minute with a solo breakaway effort.
Gent's 2-1 victory over Group H leaders Zenit St Petersburg meant even a win would not have been enough.
Neville and his team now drop into the Europa League.
Meanwhile, a Javier Hernandez strike gave Bayer Leverkusen a 1-1 draw against Group E winners Barcelona but it was not enough for them to reach the last 16.
In-form Hernandez netted his 12th goal in 11 games just three minutes after Lionel Messi had given Barca the lead after 20 minutes.
Leverkusen were guilty of missing several good openings in the second half especially by Hakan Calhanoglu when a win would have seen them qualify for the next round.
However, the draw meant they finished third in Group E level on six points with Roma, who drew 0-0 with BATE Borisov, but eliminated due to a poorer head to head record.
Elsewhere, Bayern Munich eased beyond the group stages after a second-half double by top scorer Robert Lewandowski gave them a 2-0 win at Dinamo Zagreb in their Group F match.