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The Highlanders, who were last in the table in 2022-23, finished seventh with 26 points from 22 matches.
Pep Guardiola's men have 73 points with six games remaining in a rip-roaring three-way title race, two points ahead of both Arsenal and Liverpool, who can climb over City with victories in their respective games on Sunday.
The winners of the single-league knockout tie will qualify for the double-legged semifinals.
Noufal P N scored a brace as the Malabarians crushed TRAU FC 6-1.
Bundesliga leaders Bayer Leverkusen secured a last-gasp 2-0 home win over West Ham United.
With 45 points from 21 games, the Mariners are trailing top-placed Mumbai City FC by two points.
Simpson earned fame, fortune and adulation through football and show business, but his legacy was forever changed by the June, 1994, knife slayings of his ex-wife, Nicole Brown Simpson, and her friend Ronald Goldman in Los Angeles.
Mumbai City FC, Mohun Bagan Super Giant, FC Goa, Odisha FC, Kerala Blasters FC and Chennaiyin FC have qualified for the playoffs.
PSG came into the match unbeaten in their last 27 games in all competitions but were undone by a fired-up Barcelona side looking to return the club to the summit of European football.
Chenniayin, who have 27 points and have a game remaining, joined Mumbai City FC, Mohun Bagan Super Giant, FC Goa, Odisha FC and Kerlaa Blasters in the playoffs.