Ten-men Chile secured a berth of the World Cup top 16, although sunk by Spain 1-2 in their last match of Group H here on Friday in Loftus Versfeld Stadium.
With the victory and a scoreless draw between Switzerland and Honduras, Spain gained the top place of the group and Chile the second due to goal differences.
Prior to the duel, Chile had took the leading position in Group H by accumulating six points in previous two matches. A loss in this match might send European champions Spain back home.
Spain became the third team in World Cup history to finish top in their group after losing their opener.
Chilean coach Marcelo Bielsa told reporters after the game, "I don' t think we used force excessively. We didn't have intention to do so. We managed to keep even after the sending off (of Marco Eatrada)."
"We knew before the game that not making big mistakes in the game is paramount," added Bielsa.
As for the gloomy mood of the Chilean players after the game, he said, "It's ambivalent. We qualified but lost the game. We can't celebrate."
Spanish coach Vicente Del Bosque termed the match as "intense" . "Our rivals are praiseful. They worked very hard to make our life difficult with 10 men. After Chile scored, we became more conservative."
As both sides sought chances before the goal, the men of coach Vicente Del Bosque organized attacks in a more systematic way.
The ball fell to Spanish talented forward David Villa in the 24th minute when Chilean goalkeeper rushed out, eager to clear the threat posed by Fernando Torres. Villa curled the ball into the empty net.
That enabled Villa to become the first Spaniard to score 10 goals in major championships. His 41 goals for Spain have made him coming closer to equal the record set by Raul who brought 44 goals for the national team.
The side of Del Bosque extended their lead 13 minutes later when Andres Iniesta shot the ball from the edge of box into the corner of the net.
When Spaniards enjoyed a comfortable lead with the second goal, Chile was mirred into a worse nightmare in the 37th minute. Midfielder Marco Estrada received his second yellow card for a tackle on Fernando Torres.
Chilean coach Marcelo Bielsa replaced forward Mark Gonzalez by Rodrigo Millar after the interval. After just one minute Millar's shot deflected off the knee of Gerard Pique in the 49th minute and flew into the back of the net.
Spain had been unbeaten in their seven previous World Cup meetings with Chile, with six wins and one draw.
Spain will face Portugal in their first knockout match next week while Chile will try to challenge five-time World Cup winners Brazil.
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