Sassuolo went on a counter from a Fiorentina corner, goalkeeper Alban Lafont palmed the cross to the edge of the box, where Duncan controlled to fire home.
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Alfred Duncan scores season's first league goal for Sassuolo
The Ghana international opened the scoring in the 62nd minute after smashing in a a left-foot scorcher.
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Duncan turned provider when he burst down the left and rolled across for Khouma Babacar, who was left criminally unmarked to tap in from eight yards to make it 2-0 in the 67th minute.
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Two minutes later, Edimilson Fernandes' daisy-cutter from outside the penalty area bounced off the upright and into the path of Simeone to tap in.
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Stefano Sensi restored Sassuolo's two-goal lead with a thunderbolt which swerved goalkeeper Lafont.
But the visited did not give up and Marco Benassi reduced the deficit with a tap-in from close range after an Edimilson Fernandes glancing header was parried from point-blank range.
In stoppage time, Kevin Mirallas snatched a dramatic equalizer with an angled drive which squirms under the arms of goalkeeper Consigli for his first Serie A goal.
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