The general election follows the ousting of long time Zimbabwean leader, Robert Mugabe in November past year by the military. He said he did not understand why the election commission was taking so long to release results and that it would lose credibility with further delays.
The Southern African Development Community called the elections "a political watershed in Zimbabwe's history", but with some shortcomings, urging anyone with grievances to refrain from violence. "No amount of results manipulation will alter your will", he tweeted before the army was deployed.
A man is bandaged after being wounded by a live round fired by the Zimbabwean Army during a protest against the vote count in Harare.
Soldiers arrived at the scene, jumping out of several armoured personnel carriers.
The commission has said it would announce the results of the presidential race, pitting President Emmerson Mnangagwa against opposition leader Nelson Chamisa, only after all the votes have come in from across the country.
The opposition "are testing our resolve", he said, "and I think they are making a big mistake".
"This is our government".
It alleges that the governing Zanu-PF party has rigged Monday's elections.
"As we speak, it has been discovered that ZEC did not post V11 forms at 21% of the polling stations, and we are gravely concerned by their failure to do so", he said.
The UN and former colonial power the United Kingdom both expressed concern about the violence, in which three people were killed after troops opened fire.
"Now they tell us to leave town. This time we will not allow it, we will fight", said one protester who wore a red MDC beret in central Harare.
Zimbabwe election protesters clash with police
He added: "The presence of the army is not to intimidate people but to ensure that law and order is maintained". I was beaten by soldiers", Norest Kemvo, who had gashes to his face and right hand. "This is our government".
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The violence appeared to dash the hopes of Zimbabweans that the peaceful vote would lift them out of decades of economic and political stagnation under Mr Mugabe.
Live ammunition was sacked as the Zimbabwe military was brought in to contain the situation. Another 58 seats are yet to be declared.
Chamisa has said he is confident of victory, and has threatened in the lead-up to the polls he will not to accept a Zanu-PF victory.
Mnangagwa, a former deputy president who fell out with Mugabe and then took over from him, urged people to wait for official results.
More than five million people were registered to vote, and there was a high turnout of 70 percent. The MDC Alliance claimed it had the "popular vote" and would win the presidential poll.
ZEC Chairwoman Priscilla Chigumba said: "It depends with whether those who disagree with something would like to use legal remedies but sometime tomorrow we should be able to advise you what time we can, if any, start announcing the presidential election results".
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"The results are biased, trying to give the impression that ZANU has won", said Lawrence Maguranyi, 21, an MDC supporter and university student.
Chamisa, a lawyer and pastor, yesterday said results had not been posted outside 21% of the country's almost 11,000 polling stations, raising concerns about possible vote-rigging.
As results have yet to be officially announced by the ZEC sources counting the ballots have said it is "close".
Chamisa's MDC won in most urban centres, where it enjoys majority support. "Let me also warn such individuals and groups that no one is above the law", Home Affairs Minister Obert Mpofu said.