Austria's Thiem, the fourth seed in the men's event and the 2018 runner-up, was conducting his post-match press obligations after reaching the last 16 late on Saturday.
Thiem, who reached his first grand slam final here previous year, was discussing his third-round win over Pablo Cuevas with German language journalists when he was told he would need to leave the room.
The 37-year-old Williams, seeded 10th, paid the price for her lack of match practice as she was playing in only her fifth tournament of the year, and her fightback in the middle of the second set was short-lived. But even if a junior is in there, every player has to wait. "I am 100 percent sure Federer or Nadal would never do something like that".
However, Thiem, who will be one of the favourites to take the title due to his clay-court prowess closed out the match, winning the final two sets 6-2 7-5.
"We joked about it, " Federer said. Apparently, Williams asked for Interview Room No. 2 and that room was untaken, but tournament officials wanted her press conference in the same room as Dominic Thiem where his press conference was on-going. What the hell, I don't care. "I would have been jumping off the couch back then".
Roger Federer, meanwhile, leapt to the defence of Thiem, describing him as "a superstar, a male superstar". I said that I am not a junior anymore.
"Now, there must have sure been a misunderstanding or maybe they should have kept Serena still in the locker room, not waiting here in the press centre". "I knew I just had to show the crowd, like, listen, Sonya Kenin is in the house".
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"I wasn't angry or frustrated".
"I didn't really care", Kenin said after her upset win, according to Eurosport's Tumaini Carayol.
"I just think it was an unfortunate situation that I thought was amusing and we joked about it just before".
Barty, 23, has made a career of not thinking too far ahead and won't start now as she hunts Australia's first French Open title since Margaret Court won her fifth in 1973. "I'm still trying to process what just happened", Kenin said, about an hour after the match ended with her covering her face with both hands.
Thiem initially moved to a smaller interview room, before deciding he had officially had enough, leaving without answering any additional questions or doing TV interviews.
"That's really impolite", she was heard to say.
Kenin, who was born in Moscow but raised in Florida and idolizes Serena Williams, took advantage of sloppy play from Serena to break the 23-time grand slam victor twice and close out the first set 6-2.