The sixth seed got off to the ideal start, winning his opening round-robin match in the Pete Sampras Group as he was able to keep his nerves in check to beat the Austrian 6-3 5-7 7-5.
Goffin claimed an ugly opening set via a tiebreak and was on the verge of victory in the second, but Nadal's fighting spirit saved four match points to force another tiebreaker and draw level. He lost in three sets to Grigor Dimitrov.
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"You fail and then you get back up and go again", Dimitrov said. I mean, I think there's a lot of components that are kind of coming together at some point.
Back came Dimitrov, though, with a break to love and he made no mistake in the final game of the match, converting his third match point as Thiem fired long from the baseline.
"There's always a little bit of tension before every match, and especially here, of course, a little bit because of all the atmosphere, arena".
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The 26-year-old earned a break point on Thiem's first service game but let the Austrian off the hook with a backhand into the net.
Dimitrov broke in the seventh game of the decider to take control once more.
"It, for me, was just one of those new experiences that I think I'm going to remember for the rest of my life, I think appreciate for the rest of my life", Dimitrov said.
Dimitrov overcame the disappointment of failing to serve out the rollercoaster encounter from 5-4 up in the deciding set before breaking Thiem for a third time to prevail after nearly two and a half hours.
Thiem, ranked fourth in the world, won the Rio Open and was a finalist in Barcelona and Madrid. I was like, Not again, definitely not again.