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At one polling station in the capital, Harare, police are reported to have used tear gas and fired guns into the air to disperse people still waiting to vote.
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One observer has told the BBC that the elections were the most shambolic and chaotic he had witnessed.
The opposition Movement for Democratic Change ( MDC) warned of "an expression of anger" in the capital Harare after so many were turned away from polling stations.
An unscheduled third day of voting had been ordered by the Harare High Court after long queues were still waiting outside polling stations in the capital on Sunday night.
But the final day was thrown into chaos when polling stations stayed closed for several hours because of confusion between electoral officials and the government.
The MDC asked for another day's voting but the High Court threw the request out saying such a decision was outside its jurisdiction.
President Robert Mugabe's ruling Zanu-PF party, which is expected to do well in rural areas, has denied the claim.
Earlier on Monday evening, the chairman of the elections directorate, Mariyawanda Nzuwah, told state television that the voting was over despite the pending High Court ruling.
In the Harare suburb of Glen Norah police wielding batons fired tear gas to disperse 600 people waiting to vote.
When ordered to go home, they began chanting "Change, change, we want to vote!" the Associated Press news agency reported.
He said that at one polling station the monitor reported police beating up MDC agents as riot police took ballot boxes away.
He said: "I am sad to report that this has been one of the most shambolic and chaotic elections we have witnessed."
"It has been very disappointing. (There have been) huge administrative problems in particular in the major cities, more so in Harare," said Mr Matchaba-Hove.
But Justice Minister Patrick Chinamasa said that anyone criticising the election was "spreading malicious propaganda".
In other incidents on Monday, two American diplomats accredited as election observers were held by police for several hours, while in Brussels European Union foreign ministers said they had received reports of voting irregularities.
link below for latest news from around the country:
The diplomats, detained along with two colleagues, were held for several hours by Zimbabwean police in the town of Chinhoyi, 120 km (75 miles) north of Harare.
The European Union and US have warned President Mugabe's government to allow free and fair elections or face international sanctions.
Austrian Foreign Minister Benita Ferrero-Waldner said the elections "are not fair".
"The reports we are getting from Harare do not lead to positive conclusions," she said after a meeting of foreign ministers.
"Voters do not have sufficient access to polling stations."
The MDC also said three of its leaders, including secretary general Welshman Ncube, had been arrested by police in the south-western town of Plumtree.