Ana Ivanovic became the second high-profile player to tumble out of the Kremlin Cup in two days after losing to Dominika Cibulkova on Wednesday.
The Serbian fourth seed followed Wimbledon champion and sixth seed Venus Williams, who was ousted by Italy's Flavia Pennetta in the first round on Tuesday.
World number five Ivanovic had two match points in the 10th game but the unseeded Slovak fought back to force a tiebreak, where she held her nerve to clinch a memorable victory.
Olympic champion Elena Dementieva also showed her fighting qualities to outlast Slovenian qualifier Katarina Srebotnik 6-3, 4-6, 7-6 to reach the quarter-finals.
The Russian third seed hit two successive aces in the tie-break to end a contest that lasted nearly three hours.
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