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Croatia's Prime Minister, Andrej Plenkovic, later confirmed the former general had died and offered his condolences.
"On behalf of the Government of the Republic of Croatia and on my own behalf, I want to express my deepest condolences to the family of General Slobodan Praljak," Plenkovic said, according to a tweet from an official government account.
The nature of the substance ingested by Praljak was not immediately clear.
Praljak, a former assistant defense minister of Croatia and commander of the Croatian Defense Council, was appealing a jail term of 20 years in prison.
He was one of six former Bosnian Croat leaders found guilty of crimes against humanity and war crimes, including the rape and murder of Bosnian Muslims, in 2013.
Praljak played an important role in securing weapons and ammunition for the Croatian Defense Council army, according to the original indictment.
The offenses, which date to between 1992 and 1994, were part of a wider conflict that followed the breakup of the former Yugoslavia in the early 1990s.
The appeal judges upheld the findings of an earlier trial that implicated the Croatian regime under then-President Franjo Tudjman in a criminal conspiracy with the goal of "ethnic cleansing of the Muslim population" of parts of Bosnia to ensure Croatian domination.
The Bosnian Croat leadership, along with Croat leaders, wanted to make this territory part of a "Greater Croatia," the ICTY said when the case first went through the court.
The six received sentences that ranged from 10 to 25 years. No further appeals are possible.
