A police officer and an emergency rescue official were killed by that second strike in the village of Budy in Ukraine's northeastern Kharkiv region.
"This is not the first time that Russia has attacked emergency services while they are rescuing civilians," Interior Minister Igor Klymenko said on social media.
"For each such crime, there will be responsibility and accountability -- in the courts and on the battlefield," he wrote.
Regional governor Oleg Synegubov said 22 people were injured, including five railway workers.
"The enemy deliberately struck twice within half an hour of each other, when all relevant services were already in place."
The Ukrainian army said in its daily update that the Kharkiv region, which has been the focus of a new Russian offensive for the past two months, was "under constant bombardment by enemy aircraft".
In the southern Kherson region, governor Oleksandr Prokudin said three people were killed by Russian shelling on Saturday.
The three victims were a 72-year-old woman, a 50-year-old woman, and a 41-year-old man, Prokudin said.
Russian forces have been pressing along the whole front line in recent months and making gradual advances against often outmanned and outgunned Ukrainian troops who are awaiting more Western arms deliveries.
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