Penarol and Nacional has both moved to the top of their second-round groups, while Tijuana picked up its first ever Copa Libertadores win.

Penarol went three points clear at the top of Group 4 with a 1-0 win over Ecuador's Emelec, while Nacional had to come from behind twice to claim a 3-2 victory away to Toluca, leap-frogging the Mexican club in the process to lead Group 1.

Club Tijuana won its first ever Copa Libertadores match, 1-0 , over Millonarios, with Richard Ruiz scoring the game's only goal.

American international Edgar Castillo crossed from the left flank and the ball eluded both Xolos strikers to fall to Ruiz on the far side. Ruiz drilled a low volley back across the goalkeeper and into the net to open the scoring just after the hour mark.

Roman Torres earned a second yellow card deep in stoppage time to reduce the home side to 10 men.

Penarol overcame Emelec thanks to Juan Manuel Olivera's 68th-minute goal in Montevideo.

After a powerful run into the box from one of his team-mates, Penarol's Fabian Estoyanoff collected the loose ball, before smashing it across the face of goal.

Olivera was the fastest to react, poking the ball past Emelec's goalkeeper Esteban Dreer and extending Penarol's winning streak to six games across all competitions.

Veteran forward Vicente Sanchez was the match-winner for Nacional, scoring both equalising goals as the Uruguayan club recovered two deficits before Ivan Alonso scored the winner in the 57th minute.

Toluca took the lead in the 22nd minute thanks to a crisp Luis Tejada header, with the Panamanian striker finishing from Marvin Cabrera's cross.

Nacional equalised two minutes after half-time when a left-wing cross was parried to the feet of Sanchez and the 33-year-old striker smashed the ball into the roof of the net.

In a frantic start to the second half, Toluca were in front again in the 52nd minute when Brazilian winger Lucas Silva slipped the ball to Edgar Benitez in behind Nacional's defence and the Paraguayan substitute finished calmly under on-rushing goalkeeper Jorge Bava.

Benitez's goal was followed three minutes later by Sanchez's second as he reacted quickest to Juan Albin's partially blocked free-kick to score.

Just two minutes later and Nacional scored the decisive goal with Albin teeing up Alonso, who slotted the ball across Toluca goalkeeper Alfredo Talavera and into the far corner from just inside the penalty area.

The win takes Nacional to four points in Group 1, one ahead of Toluca, who slip to second position.

In the only other result, Paraguayan club Olimpia smashed Universidad de Chile 3-0 to move to second in Group 7.