Stone-throwing protesters attacked police officers deployed outside the building where the gunmen — supporters of jailed opposition leader Zhirair Sefilyan — have been holding four police officers hostage since Sunday morning, an AFP reporter said.
Police hit back firing tear gas and stun grenades into the crowd.
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Protesters have called on the government to allow an opposition MP to deliver food to the gunmen.
However the gunmen have refused to accept provisions from the government.
The gunmen, who captured a large arsenal of police weapons, freed four hostages on Sunday and Monday, but were still holding four hostages as of yesterday night.
The hostages include Armenia's deputy police chief General Major Vardan Egiazaryan and Yerevan deputy police chief Colonel Valeri Osipyan.
The attackers have demanded the resignation of President Serzh Sarkisian and the release of Sefilyan.
More than 1,500 anti-government protesters rallied in Yerevan on Monday, calling for a bloodless resolution to the crisis.
Sefilyan — the leader of small opposition group named the New Armenia Public Salvation Front — and six of his supporters were arrested in June after authorities said they were preparing to seize government buildings and telecoms facilities in Yerevan.
A fierce critic of the government, he was arrested in 2006 over calls for "a violent overthrow of the government" and jailed for 18 months. He was released in 2008.
Last year, Sefilyan and several of his supporters were arrested again on suspicion of preparing a coup, but released shortly afterwards.
Sarkisian, a former military officer, has been president of the tiny country of 2.9 million people since winning a vote in 2008 that saw bloody clashes between police and supporters of the defeated opposition candidate in which 10 people died.
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