Greece and Macedonia signed an historic agreement to change the name of the Macedonian state, which should stop the 27-year-old dispute for this reason. Several hundred marched to a nearby police blockade and began throwing rocks.
"Traitors, traitors", up to 5,000 protesters gathered in the central Syntagma square chanted.
Tsipras and Macedonia's Zoran Zaev settled on a deal Tuesday that would rename Greece's northern neighbour North Macedonia, while Athens would drop its objections to the country joining NATO and the European Union.
Greek objections delayed United Nations recognition of Macedonia until April 1993 and then only as The Former Yugoslav Republic of Macedonia.
"Skopje and Athens, after 25 years of negotiations, succeeded in reaching a historical agreement. although there are big challenges on the way to its implementation considering the resistance in both states towards this agreement", reports euronews' Borjan Jovanovski.
But the Government suffered a loss in its parliamentary majority after MP Dimitris Kammenos of the nationalist Independent Greeks, the Government's junior coalition partner, voted in favour.
A vote on the motion is expected later on Saturday.
The Greek province of Macedonia spans most of the territories of the ancient kingdom of Macedon, and for more than five centuries it was part of the region known as Macedonia within the Ottoman Empire. (You'll see the acronym FYROM on Google Maps.) In addition to causing confusion, the similar names have been a stumbling block for the nation of Macedonia to join the European Union and North Atlantic Treaty Organisation because of Greece's objections.
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It was supposed to be put before the Cabinet last week, but Merkel refused to approve the point about turning back people at the borders.
But hardliners in both countries are furious at the deal, which they consider concedes too much to the other side. Police used stun grenades and tear gas to prevent them from entering the building.
Conservative New Democracy party leader Kyriakos Mitsotakis, who had brought the no-confidence motion, argued that a vote in favour of the government was a vote in favour of the name deal.
The two premiers will attend on Sunday the signing of the deal by the two countries' foreign ministers, Nikos Kotzias and Nicola Dimitrov.
Ordinary Macedonians now have more information on the deal as on June 15, the government made a decision to declassify it and make it available for public.
However, the deal still has to be approved also by citizens in a "yes" or "no" referendum that will be called in autumn.
"Ultimately they are for sale", the 2016 Olympics 25-metre pistol gold victor said in an Instagram posting with the hashtag "betrayal", apparently referring to the name and identity of Macedonia.
It will require ratification by both national parliaments and approval in a Macedonian referendum, which is not assured.
The deal will finally have to be ratified by the Greek parliament, a process which may also not be straightforward. Today we are writing a new song, a song of joy, of prosperity.