Williams put Athletic 2-1 ahead early in the second half and Garcia made it 3-1 after Rayo defender Luis Advincula was sent off.
The Basque side wasted several chances to add to their tally on the break and Raul De Tomas' 14th goal of the season meant they had to hang on for a nervous last five minutes.
Wu Lei played 63 minutes as Espanyol beat Alaves 2-1 thanks to a 19th minute goal from Adria Pedrosa and a Victor Laguardia's own goal which put the home side 2-0 up before Jonathan Calleri gave Alaves hope with a 56th minute strike.
Monday sees Leganes play at home to Real Madrid.
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