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More than 30 Russian cruise missiles targeted the sprawling facility, which lies not far from the border with NATO member Poland and that has long been used to train Ukrainian military personnel.
The destruction took place despite a Russian pledge to halt firing so at least some trapped civilians could escape the city.
It was unclear if the proposed routes would pass through Russia or Belarus, conditions previously opposed by the Ukrainian government.
Ukrainian President Volodymyr Zelenskiy called on those in areas occupied by Russian troops to fight.
Ukraine's government has said it had no plans to rejoin the nuclear club, having given up its nuclear arms in 1994 following the break-up of the Soviet Union.
Moscow and Kyiv traded blame over a failed ceasefire on Saturday that would have let civilians flee Mariupol and Volnovakha, two southern cities besieged by Russian forces.
Here's a look at key things to know about the conflict Saturday.
Russia and Ukraine traded blame over the failure to provide safe passage to civilians fleeing the two bombarded cities.
Russian defense officials had announced a a temporary cease-fire in two Ukrainian cities to allow civilians to evacuate.
The BBC, Bloomberg News and other foreign media said they would temporarily suspend the work of their journalists in Russia while they assessed the situation.