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Ukraine's acting president has warned Crimea's Kremlin-backed leaders they have only three hours to release the captured head of the splintered ex-Soviet country's navy or face 'an adequate response'.

Kiev also announced on Wednesday a raft of urgent measures aimed at severing its ties with Moscow that included the withdrawal from a Kremlin-led alliance of 11 nations and the introduction of travel visas for Russians seeking entry into Ukraine.

The escalating crisis promoted the White House to warn Russia it was 'creating a dangerous situation' and the NATO commander to call the Kremlin's seizure of Crimea 'the gravest threat to European security and stability since the end of the Cold War'.

For its part, Germany said it was suspending a major arms with Moscow -- a signal that Washington's EU allies were willing to take more serious punitive steps against the Kremlin despite their heavy dependence on Russian energy supplies.

Pro-Russian forces had earlier seized two Crimean navy bases and detained Ukraine's naval chief as Moscow tightened its grip on the flashpoint peninsula despite Western warnings that its 'annexation' would not go unpunished.

Dozens of despondent Ukrainian soldiers - one of them in tears - filed out of the Ukraine's main navy headquarters in the historic Black Sea port city of Sevastopol after it was stormed by hundreds of pro-Kremlin protesters and masked Russian troops.

The local prosecutor's office said Ukraine's navy commander Sergiy Gayduk - appointed after his predecessor switched allegiance in favour of Crimea's pro-Kremlin authorities at the start of the month - had been detained on suspicion of 'ordering Ukrainian military units... to open fire on peaceful civilians'.

Gayduk's capture delivered a huge blow to efforts by the new team of untested pro-Western leaders in Kiev to impose some authority in their crisis-hit country in the face of an increasingly assertive Kremlin.

Ukraine's acting president Oleksandr Turchynov scheduled an urgent security meeting and issued a statement around 6.00pm local time, giving the Crimean authorities until 9.00pm to release the commander and other 'hostages'.

'Unless Admiral Gayduk and all the other hostages - both military and civilian ones - are released, the authorities will carry out an adequate response... of a technical and technological nature.'

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Ukraine demands naval head's release