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Second-placed Venezuela will face the second team in Group B on Friday at the Maracana Stadium in Rio de Janeiro, while Peru must wait to see if their four points are enough to earn them a place as one of the two best third-placed sides.
Brazil had three goals ruled out and missed a series of chances as they were held 0-0 by Group A rivals Venezuela on Tuesday.
Messi wasted the best chance of the game before Martinez's piledriver broke the deadlock when he skewed a rebound wide from close range, and the Barcelona forward also went on a thrilling solo run into the area but could not get a shot away.
Philippe Coutinho scored a second half double and Everton added a cracking third as Brazil recovered from a sleepy start to beat Bolivia 3-0 in their Copa America opener.
Juventus forward Cristiano Ronaldo ($109 million), Paris Saint-Germain forward Neymar ($105 million), Mexican boxer Canelo Alvarez ($94 million) and Swiss tennis great Roger Federer ($93.4 million) rounded out the top five.
Brazil's preparations for the Copa have been overshadowed by Neymar -- firstly the rape allegations against the striker, which he has denied, and then the ankle injury that ruled him out of the tournament last week.
The actress and UN special envoy urged the international community to provide more support to three South American countries with the most migrants from crisis-hit Venezuela.
Venezuela's imploding economy has brought a widespread shortage of basic necessities, while political hostilities have led to waves of fatal violence. Four million Venezuelans have fled the economic and humanitarian crisis unfolding here.
The detained citizens can spend months or even years in such facilities because prisons are too overcrowded to receive them and because of chronic delays in basic criminal justice proceedings required to indict them.
With its state powers locked in conflict and humanitarian agents kept at bay, the lives of Venezuelans are stifled by growing dissent, frequent blackouts and fast depleting rations.