The negotiations will take place after nearly a week of Russian bombardment which, according to the Ukrainian emergency service, killed more than 2,000 civilians
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A Russian delegation is travelling to a meeting point for talks with Ukrainian counterparts, Belarus' Belta news agency reported ahead of negotiations that are expected to resume later on Wednesday.
Ukrainians said they were fighting on in the southern port of Kherson, the first sizeable city Russia claims to have seized, while Russian air strikes and bombardment caused devastation in cities that Moscow's bogged-down forces have failed to capture.
After nearly a week, Russia has yet to achieve its aim of overthrowing Ukraine's government, but has, according to the Ukrainian emergency service, killed more than 2,000 civilians and destroyed hospitals, kindergartens and homes.
Western countries worry that bogged-down Russian forces are now trying to blast their way into the cities.
Bombing of Kharkiv, an eastern city of 1.5 million people, has left its centre a wasteland of ruined buildings and debris.
"The Russian 'liberators' have come," one Ukrainian volunteer lamented sarcastically, as he and three others strained to carry the dead body of a man wrapped in a bedsheet out of the ruins on a main square.
After an air strike on Wednesday morning, the roof of a police building in central Kharkiv collapsed as it was engulfed in flames. Authorities said 21 people were killed by shelling and air strikes in the city in the past 24 hours, and four more on Wednesday morning.
Moscow denies targeting civilians and says it aims to disarm Ukraine, a country of 44 million people, in a "special military operation".
Apple, Exxon, Boeing and other firms joined an exodus of international companies from Russian markets that has left Moscow financially and diplomatically isolated since President Vladimir Putin ordered the Feb. 24 invasion.
"He thought he could roll into Ukraine and the world would roll over. Instead, he met a wall of strength he could never have anticipated or imagined: he met Ukrainian people," US President Joe Biden said on Tuesday in his annual State of the Union address.