Tottenham moved up to third place above Arsenal -- who have played two fewer games after coming from behind to draw 1-1 at Aston Villa, who remained in fifth.
The Bianconeri squandered a two-goal lead as Napoli went one better than the come-from-behind midweek draw at AC Milan to climb to fifth in the table on goal difference above Parma.
Madrid twice came from behind to draw level, but goalkeeper Iker Casillas' error in stoppage time gifted Villarreal the victory which leaves Juande Ramos' side eight points behind Barca with just two games left.
The draw leaves Liverpool four points behind fourth-place Manchester City having played a game more than their rivals in the race for the final Champions League slot.
In the Italian capital, Sampdoria protected their unbeaten record as they recovered from going behind to a first half Francesco Totti goal to draw 1-1 at Roma and take third spot, three points behind the leaders.
South Africa was frequently behind in that series, pulling off an unlikely draw in the second Test at Adelaide after being four down and 353 behind going into the final day, then roaring back with a 309-run victory in the final Test at Perth.
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Having clinched a fourth title in five seasons when second-placed Real could only draw with Espanyol on Saturday, Barca went behind five minutes after halftime in the Spanish capital.
In the original tie at United's Old Trafford ground, Chelsea had to come from two goals behind to secure a 2-2 draw.
Morocco will need to defeat South Africa to guarantee its place in the last-eight after it came from behind to secure a 1-1 draw against Cape Verde.
The victory was doubly important for Tottenham after fellow Champions League hopefuls Aston Villa had to come from behind to snatch a 2-2 draw with lowly Wolverhampton in the Midlands derby earlier on Saturday.
Stoke joined Sunderland on 20 points from 14 matches after drawing 0-0 at Blackburn, while Fulham came from behind to earn a 1-1 draw at Bolton, who stayed in the bottom three.
There were four other Champions League matches on Tuesday, with the most exciting encounter coming in Portugal as Italian Serie A side Fiorentina claimed a 2-2 draw at Sporting Lisbon after recovering from two goals behind.
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The draw leaves both teams locked on 32 points, two points behind seventh-placed Dundee United in the Scottish Premier League.
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Woking have a replay after coming from behind to a 3rd minute goal from Brentwood Town to draw 1-1.
The draw was enough to seal Barcelona's 21st Spanish title, 10 behind Real's all-time record, but it means the club cannot reach 100 points this season -- having 92 now.
The 33-year-old was replaced by Ignazio Abate 28 minutes into the 1-1 draw at the San Siro last Wednesday, which left Milan two points behind group leaders Real Madrid ahead of the final match away to Swiss side Zurich on December 8.
Fourth-placed Hamburg remained nine points behind the leaders after also dropping two points in a 3-3 draw at Cologne.
CNN: Bayern join Leverkusen at the top; Juventus falter again
In France , Lyon was held to a 1-1 draw at Brest, while Marseille reclaimed third place in Ligue 1 after coming from behind to defeat Troyes 2-1.
The executive committee will hold an emergency meeting in Cape Town on Wednesday, two days ahead of the draw for the finals, to assess the idea of extra match officials, one behind each goal.
Two-time champions Manchester United , who are a point behind in third spot, can return to the top spot with a draw or win over Fulham at Old Trafford on Sunday, but will have played a game more than Chelsea.
The wily Argentine, who scored twice in the 2-2 draw between the sides at Dens Park earlier this month, had a free role behind strikers Steve Lovell and Mark Burchill and was a constant threat with his sharp twists and turns.
Tottenham's 2-2 draw at Wigan on Saturday left it on the outside looking in, now two points behind Arsenal, albeit with a game in hand over its North London rival.
Unai Emery's side opened their campaign with a draw against Lille but were well worth their win at the Mestalla , although they fell behind to a Sergio Floccari goal.
Elsewhere, Senegal and China played out a goalless draw in an international friendly in Harbin while Junichi Inamoto's late strike helped Japan come from behind to claim a 4-3 victory over Ghana in an entertaining friendly in Utrecht.
The decision follows Saturday's goalless home draw against Hull City that has left the west London club fourth in the table -- seven points behind defending champions and league leaders Manchester United.
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