Austria's fourth-seeded Thiem struggled badly on serve throughout, managing to land just 39 percent of first serves in the second set as his opponent and regular practice partner took full advantage. A code of conduct point deduction for Sock for belting a ball up into the crowd and it looked as though the young American had lost his head.
That has already earned him £578,220 - with a semi-final and potentially a final still to come.
'That was a roller-coaster match for sure, ' said Sock.
The sixth seed stormed to a 6-0, 6-2 win against World No.7 Goffin in only 74 minutes, joining six-time victor Roger Federer as the only two singles players who secured semifinal places on Wednesday, reports Xinhua news agency.
A double fault from Thiem gifted Goffin a break back to love, though, and the Belgian was soon level at 3-3 after winning 11 consecutive points.
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Federer, the current world No. 2 in tennis, qualified for the semi-finals of the year-end ATP Finals in London on Tuesday night with a 7-6, (8-6), 5-7, 6-1 victory over German world No. 3 Alexander Zverev. Grigor Dimitrov and Jack Sock meet in the other semifinal.
Cilic, eliminated after two three-set losses, was hoping to end his year on a high in the city where his Wimbledon dream was ended in this year's final by Federer - the Croatian sobbing on court after suffering blisters. "I won the most important points, especially in the first set". "But still very far away at this point".
Federer could have been excused for stepping off the gas but the 19-times grand slam champion went up a gear.
A 100mph forehand service return gave Federer an early break in the decider and Cilic's resistance crumbled quickly as Federer turned on the style to race to victory. So I'm just happy I'm playing a great season.
The crowd were behind the Swiss player the whole way; a chorus of "let's go Roger let's go" fired up in the tiebreak when Cilic inched to a 4-1 lead.