Bruno Fernandes scored his 13th penalty for Manchester United, though it was not enough to inspire the Red Devils to a comeback in the Champions League.
United slumped to a 3-2 defeat to RB Leipzig on Tuesday, having needed to avoid a loss in order to progress from Group H.
Paris Saint-Germain's match with Istanbul Basaksehir was delayed due to allegations of racism from a UEFA official, but last season's runners up will join Leipzig in the last 16.
Angelino, Amadou Haidara and Justin Kluivert gave Leipzig a 3-0 lead, yet Ibrahima Konate's foul on Mason Greenwood handed United – who have conceded three goals in consecutive Champions League games for the first time since April 2003 – a lifeline.
Fernandes duly sent Peter Gulacsi the wrong way to net his 13th spot-kick in all competitions since making his debut for the club in February, with only former United forward and fellow Portugal star Cristiano Ronaldo – who scored twice from 12 yards in Juventus' 3-0 win at Barcelona, able to match that tally across Europe's top five leagues.
The 26-year-old Fernandes has scored seven Premier League goals in total this season, with three coming from the spot – he has missed one penalty in the English top flight in 2020-21.
Fernandes also struck a penalty in a 2-1 win over PSG in October. Ronaldo, meanwhile, had converted two spot-kicks in Serie A this season prior to his double against Lionel Messi's Barca.
13 - Since his Man Utd debut in February, no player in Europe's top five leagues has scored more penalties in all competitions than Bruno Fernandes (13 - level with C. Ronaldo). Pause. pic.twitter.com/jQy2EBdhfT— OptaJoe (@OptaJoe) December 8, 2020
Paul Pogba, starting on the bench amid speculation over his future following comments from his agent Mino Raiola, came on and made a great impact, with United's second goal arriving just 135 seconds after their first when the France international bundled in at the back post.
Pogba's header appeared to strike Harry Maguire on its way in, but VAR was unable to distinguish whether it had hit the United captain's hand or head, and the goal stood.
United midfielder Pogba almost turned the match completely on its head in the closing moments, when his low cross deflected goalwards off Konate, but Gulacsi reacted to make the save which sent Leipzig through and condemned United to a place in the Europa League.
Fernandes thrived in UEFA's second-tier club competition last term, scoring three penalties and providing one assist as Ole Gunnar Solskjaer's side reached the semi-finals.