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WIMBLEDON, England — Five-time champion Venus Williams was ousted in the quarterfinals at Wimbledon on Tuesday, losing 6-2, 6-3 to 82nd-ranked Tsvetana Pironkova of Bulgaria.

The second-seeded Williams, who had reached the Wimbledon final in eight of the past 10 years, was undone by a slew of unforced errors and double faults in the biggest upset of the women’s tournament.

In another surprise, 21st-seeded Vera Zvonareva of Russia rallied to beat two-time U.S. Open winner Kim Clijsters 3-6, 6-4, 6-2 to reach her first Wimbledon semifinal.

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Venus Williams never got untracked against the 22-year-old Pironkova, who was the lowest-ranked player left in the women’s draw and had never previously passed the second round of a Grand Slam.

The result rules out another all-sister final between Venus and Serena Williams, the defending champion who faced China’s Li Na in a later quarterfinal.

Pironkova beat Williams in the first round of the Australian Open in 2006, but few gave her a chance of replicating the feat on the grass of Wimbledon, where Williams has been so dominant for the past decade.

But Williams was clearly off her game and Pironkova took advantage.

Williams committed 29 unforced errors, compared to just six for Pironkova. Willians served five double-faults, including back-to-back doubles in two games.

Pironkova denied Williams her 200th career match win on grass and spoiled the prospect of a fifth Wimbledon final against Serena, who beat her older sister last year for her third title at the All England Club.

Pironkova becomes the first woman representing Bulgaria to reach a Grand Slam semifinal in the Open era. Bulgarian-born Manuela Maleeva-Fragniere was representing Switzerland when she got to the U.S. Open semis in 1992 and 1993.

Pironkova broke Williams twice in the first set and won four straight games from 2-all, finishing the set with a backhand passing shot down the line.

After Williams broke to go up 2-1 in the second set, it looked like she might be able to take command. But Pironkova broke right back in the next game that included the shot of the match: After Williams hit a forehand drop volley, the Bulgarian raced forward and flipped a backhand lob winner over Williams’ head. Pironkova swung her arm in an uppercut celebration.

Williams saved two match points while serving at 5-2 down, but Pironkova served out the match in the next game. After Williams missed a forehand volley, Pironkova squealed and fell on her back on the turf.

Pironkova earned a semifinal berth against Zvonareva, who came back from a set down to beat Clijsters on Centre Court. It was the Russian’s first win over Clijsters in six matches.

Clijsters, returning to Wimbledon for the first time since 2006 after coming out of retirement, beat fellow Belgian Justine Henin on Monday and was viewed as a potential title threat.

The eighth-seeded Clijsters looked in command after sailing through the first set, but the match turned in the Russian’s favor after she broke to go up 3-1 in the second.

Clijsters finished with 36 unforced errors, compared to 19 for Zvonareva.

In another quarterfinal, unseeded Petra Kvitova of the Czech Republic played qualifier Kaia Kanepi of Estonia.

The men had the day off ahead of Wednesday’s quarterfinals.

Roger Federer and Rafael Nadal are there. So are Novak Djokovic, Andy Murray and Robin Soderling.

But there’s one name among the list that may not be quite so familiar — Yen-hsun Lu.

He’s the 82nd-ranked player from Taiwan who shocked three-time runner-up Andy Roddick to become the first Asian player to reach the men’s quarters of a Grand Slam tournament in 15 years.

The 26-year-old from Taipei outlasted fifth-seeded Roddick 4-6, 7-6 (3), 7-6 (4), 6-7 (5), 9-7 in a match that stretched over 4½ hours.

Lu will face third-seeded Djokovic.

Federer, chasing a record-tying seventh Wimbledon title, will meet Tomas Berdych.

Nadal renews his rivalry with sixth-seeded Robin Soderling, the Swede who beat him in the fourth round at the French Open last year and lost to him in last month’s final in Paris.

Murray, the only player in the men’s draw who hasn’t lost a set, will next meet 10th-seeded Frenchman Jo-Wilfried Tsonga. Murray is seeking to become the first British player to win the men’s singles title since Fred Perry in 1936.

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