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Barcelona failed to reach the Copa del Rey semi-finals for the third time in five seasons on Wednesday night, falling to a 4-2 extra-time defeat to Athletic Club in the last eight.

The home side’s winner in the second minute of stoppage time at the end of the first half of extra-time, scored by substitute Inaki Williams, proved decisive after a four-goal thriller had been played out over the original 90 minutes.

As Barca pushed for a last-ditch equaliser to force a penalty shootout, Nico Williams – a player heavily linked with a move to Catalonia, sealed it in Athletic’s favour.

The result will serve to put more pressure on Xavi amid recent rumours or unrest, taking one more opportunity for silverware this season off the table after losing the Supercopa de Espana final and falling way behind Real Madrid and surprise contenders Girona in La Liga’s table race.

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Athletic raced into the lead in this quarter-final tie at San Mames courtesy of striker Gorka Guzureta with mere seconds on the clock after a flurry of early attempts.

Robert Lewandowski equalised with Barcelona’s first shot of the game midway through the first half. Bizarrely, they then went ahead with their second a few minutes later as Lamine Yamal struck from the edge of the penalty area.

Athletic continued to pepper the Barcelona goal with shots and got back on level terms shortly after the restart Oihan Sancet’s header. Shots continued to rain down, but none hit the target as the buoyant home side tried to win inside 90 minutes. For all that Barca were dominating possession, a persistent lack of creativity must be worrying for Xavi and his staff.

Williams actually hit the post when he put Athletic into the lead they would never relinquish, with the ball rebounding kindly back off the woodwork and into his path. Inaki Pena somehow kept Barca in the tie when he denied the elder Williams a killer goal in the 113th minute, but younger brother Nico soon took full advantage of the Catalans piling players forward, finishing a swift counter.

Athletic Club player ratings (4-2-3-1)

GK: Agirrezabala (6); RB: Lekue (6), CB: Vivian (7), CB: Paredes (6), LB: Berchiche (7); CM: Pradros (7), CM: Vesga (6); RM: Ares (7), AM: Sancet (8), LM: N. Williams (9); ST: Guruzeta (7)

Subs: Gomez (7), I. Williams (9), Villalibre (5), Herrera (7), De Marcos (6), Jauregizar (6)

Barcelona player ratings (4-3-3)

GK: Pena (5); RB: Kounde (6), CB: Araujo (5), CB: Christensen (5), LB: Balde (6); CM: Gundogan (7), CM: De Jong (7), CM: Pedri (6); RW: Yamal (7), ST: Lewandowski (6), LW: Torres (5)

Subs: Fort (6), Cubarsi (6), Felix (6), Roberto (4), Guiu (5)