Rafael Nadal fought like a lion but, for once, the lion was tamed. The Spaniard, many people’s tip for the trophy after his 10th French Open victory last month, saw his hopes of a third Wimbledon title ended in a dramatic, exhilarating 6-3, 6-4, 3-6, 4-6, 15-13 defeat by Gilles Müller, the No16 seed from Luxembourg. Serving and volleying beautifully throughout, the 34-year-old left-hander kept his nerve when a charging Nadal threatened to turn it around and reached the quarter-finals for the first time in his career.

Twelve years after he stunned Nadal when the Spaniard arrived at Wimbledon after his first Roland Garros triumph, this was an even better performance and a bigger shock, such was the manner in which Nadal, 31, had reached the last 16 without dropping a set. The No4 seed had five break points in the decider but Müller, whose expression barely changed throughout despite the most intense pressure, held firm, clinching a famous victory after four hours and 47 minutes when Nadal sent a forehand just over the baseline.

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“I haven’t really realised what just happened,” Müller said. “It’s a great feeling. I was thinking about if I had to come back next day to finish the match. I am just pleased to get it finished and be in the quarter-finals. I was two sets up, played really well and then Rafa stepped it up. At the end it was just a big battle. I believe I had four match points and didn’t make them, then it was really tough. When I had these last two [match points] I said to myself go for it 100%.”

The late finish to the marathon led to Novak Djokovic’s fourth-round match being held over until Tuesday. The match against Adrian Mannarino is now scheduled for Centre Court at noon on Tuesday, with the winner to face the Czech Tomas Berdych in the quarter-finals on Wednesday.

The All England Club said in a statement: “The safety and security of all visitors to the championships is of paramount importance. The preference was to play the Djokovic v Mannarino match as scheduled on No1 Court. When that was no longer an option, it was determined the match could not be moved to Centre Court due to the number of spectators remaining in the grounds. As late as 8.30pm, 30,000 people still remained in the grounds, and therefore moving the match would have created a significant safety issue. Both players were explained the rationale of postponing the match until tomorrow, which is now scheduled for a 12pm start on Centre Court.”

Müller dominated the first two sets, consistently keeping Nadal off balance with the quality of his serving, backed up by superb volleying. Having won the warm-up event in the Netherlands and reached the Aegon Championships semi-finals at Queen’s Club, he was full of confidence and Nadal, who had hit his head on a door frame when doing warm-up jumps in the corridor in a bizarre incident before the match, took time to find his way.

It was not that the fourth seed was playing badly; it was more that Müller was doing everything right. The Spaniard missed three chances to break, one in the first set and two in the second; Müller took both his two to seize a two-sets-to-love lead. Müller’s short inside-out forehand was especially effective and he mixed up his serve well, volleying beautifully and always keeping Nadal guessing.

A change in his return position to deep behind the baseline helped Nadal get back into the match, allowing himself more time and giving Müller something different to think about. A good return on the baseline was followed by a massive forehand winner and Nadal broke for 3-1 in the third set, prompting an enormous double fist-pump that must have sent shivers through Müller, not that he showed it. Nadal took the set and levelled the match thanks to one break in the fifth game of the fourth.

Facebook Twitter Pinterest Gilles Müller in front of the scoreboard after finally beating Rafael Nadal in five sets. Photograph: Tom Jenkins for the Guardian

The fifth set was an epic. Serving first, Müller had the advantage and Nadal was constantly playing catch-up, having to call on all his mental strength to stay on level terms. If anything, the Luxembourger began to serve better as the set went on and it was he who was forcing the issue. At 5-4, he had two match points on the Nadal serve only for the two-times champion to close the door with good serving, including two aces as he held for 5-5. Nadal missed a break point at 6-6 but his big chances came at 8-8 when he had four more only for Müller to calmly, smoothly, save them.

At 9-10, it looked like Müller might have missed his last chance when he failed to convert two more match points on the Nadal serve but eventually, the pressure told. After holding for 14-13, as the clock ticked past 8.30pm, Müller forced two more match points and on what was his fifth match point overall, he grabbed victory as Nadal sent his forehand long.

For the Spaniard, it was a disappointing end to a tournament that had begun so well, only the second time he had made the last 16 since 2011. “He played well,” Nadal said of Müller. “I think I didn’t play my best the first two sets. I was all the time against the score and that’s so difficult against a player like him. He played great, especially in the fifth set. It probably was not my best match but at the same time I played against a very uncomfortable opponent.

“I lost in the fourth round, not a result I was expecting. It’s tough to analyse that in a positive way right now. I won matches, I played better than other years, that’s true but at the same time I was ready for other things. I missed an opportunity.”

Müller said he was proud of how he had stayed calm when Nadal started to come back, especially in the final set. “I didn’t feel like I was playing bad in the third and fourth sets,” he said. “I just told myself to keep it up.

“I started serving a bit better maybe and at the end it’s just a matter of a few points here and there. It’s tough to say what made the difference.”