Spain have suffered the biggest shock of the World Cup so far after the 2010 winners were dumped out by hosts Russia in the last-16.
Fernando Hierro’s side had been taken to spot kicks after Artem Dzyuba’s first half penalty before Koke and Iago Aspas both missed in the shootout.
Hosts Russia reached the quarter-finals of the World Cup on Sunday when they beat Spain 4-3 on penalties after a 1-1 draw.
Koke’s third penalty for Spain was saved by Igor Akinfeev who then saved Aspas’s final shot.
Russia will face either Croatia or Denmark, who were meeting later on Sunday, in Sochi on July 7.
Both the goals came in the first half. Spain took a 12th-minute lead when veteran Russia defender Sergei Ignashevich put into his own net but Dzyuba equalised from a penalty for the hosts in the 42nd minute after Gerard Pique handled in the area.
Alan Shearer said on BBC: "What a magnificent story, from the very first game to now. They have done it the hard way and beat a very good team by defending very well.
"They kept their nerves in an incredible situation, in front of their fans. Well done Russia."
Former Spain international Cesc Fabregas added: "I am speechless because I expected a different game today. I think Spain is a much better side than Russia.
"Russia had a plan which was to go to penalties and pray, and it paid off for them. Andres Iniesta doesn’t deserve to go out like this, in what could be his last game for Spain."
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