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After Rodrigo Moreno put Spain ahead after just six minutes, Germany went into the break level as Mueller hit his 38th goal for the national team on his 90th international appearance.
“I had tried it two or three times in the warm-up and it’s nice when you can pull it off in the game,” Mueller told broadcaster ARD.
“Both teams had their chances and it could have just as easily finished 2-2 or 3-3 — it was a good test for both of us.”
The draw in front of a sold-out 50,653 crowd preserves both sides’ respective unbeaten runs dating back to Euro 2016.
Spain, who host Argentina on Tuesday in Madrid, are now 17 games unbeaten while Germany’s run is 22 without defeat as they prepare to play Brazil in Berlin, also on Tuesday.
Spain coach Julen Lopetegui included three veterans who won the 2010 World Cup in Gerard Pique, Sergio Ramos and Andres Iniesta.
At 33, Iniesta gave the Germany midfield a masterclass during the first 45 minutes, moving the ball at ease with silky passes at the heart of Spain’s attack.
Germany boss Joachim Loew started with six World Cup winners from 2014 in Mats Hummels, Jerome Boateng, Sami Khedira, Toni Kroos, Mueller and Mesut Ozil.
Germany were punished for living dangerously as Spain dominated the early exchanges.
Hummels was at fault for the opening goal, leaving too much space for Iniesta to tuck the ball behind the German defence.
Moreno snapped up his chance to beat Germany goalkeeper Marc-Andre Ter Stegen on six minutes.
It should have been 2-0 to Spain on 18 minutes when Isco’s pass to David Silva was just a fraction too heavy and Ter Stegen had enough time to smoother the attack.
It took a superb piece of skill for Germany to draw level on 35 minutes.
Mueller spotted Spain goalkeeper David de Gea off his line and unleashed a superb strike which hit the top left-hand corner from 20 yards out.
At half-time, Atletico Madrid’s Saul Niguez came on for Iniesta in the Spanish midfield.
Right at the start of the second half, Germany winger Julian Draxler came within a whisker of putting the hosts ahead.
His fierce shot from outside the area was pushed around the post by De Gea’s fantastic save.
Ozil then failed to connect after being put in a great position by Timo Werner.
A knock to Khedira saw Manchester City’s Ilkay Gundogan come on into Germany’s midfield and the game opened up approaching the hour mark.
Only a great Ter Stegen save denied Isco, but the Germans counter-attacked immediately and De Gea had to palm away a shot by Gundogan.
Hummels hit the crossbar on 65 minutes with a header after Toni Kroos floated a free-kick over Spain’s wall.
Both sides had late chances to steal the win, but a flurry of changes by both coaches meant the game’s tempo dropped for the final quarter of an hour.
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