The 35-year-old was travelling back to the athletes’ village in a taxi with Cristian Katini, a sports scientist on the team, when they hit a concrete barrier head on.
Henze, a former Olympian who won a silver medal in the canoe slalom C2 at the 2004 Games in Athens, was taken to the nearest hospital for emergency brain surgery and his condition was described as “critical”.
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DOSB announced his death in a statement on its website, saying: “The coach of the German canoe slalom team at the Olympic Games succumbed to his head injuries in the presence of his family.”
DOSB president Alfons Hormann said: “We are very sad today. Words can not describe approximately what we feel in the Olympic team after this terrible loss.”
“Today sports, for which the entire team came to Rio, moves into the background,” said team chief Michael Vesper.
“Our thoughts are with his family who had the chance here to bid farewell.”
The German team said it will hold a ceremony on Tuesday at the Place of Mourning inside the Olympic Village where the athletes live and has asked the International Olympic Committee to fly all German flags in the venues at half staff.