The former world No.1, who is now ranked 60 in the world lost 6-3 7-5 to qualifier Petra Krejsova, who recorded her maiden WTA Tour main draw win.
Sixth seed Timea Babos was also dumped out as home favourite Arantxa Rus won 5-7 7-2 6-3.
Seventh seed Lesia Tsurenko made light work of Elise Mertens 6-4 6-1, while Camila Giorgi beat Varvara Lepchenko 6-2 6-7 (8-6) 6-2.
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