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The defeat was another blow to Barca and manager Xavi Hernandez after they were left on the brink of Champions League elimination following a draw with Inter Milan last week.
Liverpool won the match against Rangers on Wednesday, putting themselves on the verge of qualification for the Champions League knockout stages.
Group B looks equally difficult with former champions Netherlands and current world champions France drawn alongside 2004 Euro winners Greece, Ireland and Gibraltar.
European champions Italy, who missed out on a place at the World Cup in Qatar, finished top on 11 points from six games, one point above second-placed Hungary who needed to avoid defeat to secure a place in their first Nations League semifinals.
The match ended goalless with both sides hitting the woodwork.
Newcastle United's record signing Alexander Isak scored on his debut to put his side ahead at Anfield but Liverpool snatched a 2-1 victory deep in stoppage time through Fabio Carvalho.
Incredibly, Mo Salah was not one of the scorers for the title favourites.
Taylor Fritz blasted his way to a 6-3, 6-2 win over Australian Nick Kyrgios while Cameron Norrie fought back to beat former world No. 1 Andy Murray 3-6, 6,-3 6-4 in an all-British clash.
The opening act marked the beginning of 11 days of sporting action in the city. More than 5000 athletes from 72 countries will compete in 280 events across 19 sports in 15 venues.
Police earlier said Robert E Crimo III should be considered armed and dangerous and was pulled over by police on Monday evening after a brief pursuit.