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Neymar moved to within three goals of Pele's all-time national scoring record.
Messi earned $130 million, a figure which includes $55 million of endorsements, during the 12-month period ended May 1, 2022, to sit atop the list of the 10 highest-paid athletes a year after finishing second to Irish MMA fighter Conor McGregor.
Peru (21 points), Colombia (20) and Chile (19) will now vie for fifth place and a play-off spot against a team from the Asian Football Confederation.
PSG also advanced to the last 16 thanks to Leipzig's win over Club Brugge but the loss highlighted their continued problems in finding an effective way to harness their star-studded attack.
Argentina drew goalless with Brazil, while Bolivia boosted their chances with a 3-0 win over Uruguay.
The win extended Brazil’s home run in the qualifiers to 11 consecutive victories, a record in the South American region.
The Dutchman, who had struggled this season after joining from Liverpool, struck in the 21st minute and headed in another goal six minutes before halftime.
It was the 34th time that Messi scored at least two goals in a Champions League game, bringing the Argentina captain's total to 123 goals in the tournament.
Peru missed a second-half penalty in a 1-0 loss to Argentina in Buenos Aires.
The results leave Brazil in top spot with 28 points, six ahead of Argentina.