Five-time Wimbledon champion Venus Williams became the eighth of the top 10 seeds to be knocked out after a third-round defeat by Kiki Bertens.
Ninth seed Williams, 38, was beaten 6-2 6-7 (5-7) 8-6 by the 26-year-old Dutchwoman on Court One.
Williams’ fellow American Madison Keys lost nine consecutive games in her defeat to qualifier Evgeniya Rodina.
The 10th seed lost 7-5 5-7 6-4 in two hours 10 minutes against the Russian, who is ranked 120th in the world.
However, younger sister Serena went on to reach the last 16.
Meanwhile, Seventh seed Karolina Pliskova was given a scare by Mihaela Buzarnescu of Romania after she lost the first set.
However, the Czech regained her composure to triumph 3-6 7-6 (7-3) 6-1 against the 29th seed.
Ekaterina Makarova, who knocked out second seed Caroline Wozniacki in the third round, also progressed.
The Russian beat Lucie Safarova of the Czech Republic 4-6 6-4 6-1 to seal her place in the last 16.
Germany’s Julia Goerges, the 13th seed, overcame Czech 23rd seed Barbora Strycova 7-6 (7-3) 3-6 10-8.
Georges will face Croatia’s Donna Vekic next after she defeated Yanina Wickmayer 7-6 (7-2) 6-1.