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The World Cup runners-up, who will be joined in the June 14-July 14 tournament in Germany by Portugal and Belgium as one of the first three teams to qualify, kept a perfect record in Group B with six wins.
City started their title defence by coming from behind to beat Red Star Belgrade 3-1 at home.
Saudi Professional League (SPL) club Al-Hilal announced that Neymar had signed a deal until 2025.
There was no immediate comment from the Ligue 1 champions, owned by Qatar Sports Investments, but French newspaper L'Equipe said the deal could net 31-year-old Neymar 160 million euros ($175 million).
PSG opened their Ligue 1 title defence with a goalless draw at home against Lorient on Saturday as the team's prize asset watched from the stands.
The practices have allowed PSG, owned by Qatar Sports Investments since 2011, to sign top players and coaches 'well above its potential in a normal market situation', LaLiga alleges in the complaint filed on Saturday.
The 24-year-old French captain, who still has one year remaining on his contract, is unwilling to renew his contract with PSG.
PSG face the dilemma of allowing Mbappe to run down the final year of his contract and being unable to recoup any of the 180 million euros ($195.71 million) they spent in 2017 to sign him from AS Monaco.
France's interior ministry said that 1,311 people had been arrested, compared with 875 the previous night, in violence which it said on Twitter was "lower in intensity".
Buildings and vehicles have been torched and stores looted, and the violence has plunged President Emmanuel Macron into the gravest crisis of his leadership since the Yellow Vest protests that started in 2018.