Lionel Messi moved into joint third place in the all-time Primera Division scoring charts with a brace as Barcelona warmed up for its UEFA Champions League showdown against Manchester City with a comprehensive 6-0 demolition of Rayo Vallecano.

Messi struck in the 36th and 68th minutes of a completely one-sided match at Camp Nou to move above Alfredo Di Stefano (227) in the record books and level with another Real Madrid legend, Raul, on 228 La Liga goals.

At just 26 years old it now seems only a matter of time before the prolific Messi claims the outright record, which is the 251 goals scored by former Athletic Bilbao star Telmo Zarra.

Hugo Sanchez is second on the list and next in Messi's sights with 234 goals for Atletico Madrid, Real Madrid and Rayo.

Rayo must be wishing it could still call on the Mexico ace as it battles to avoid relegation from the top flight this season, but even he would have been powerless to prevent the Madrid outfit from being swept aside by brilliant Barca.

Adriano opened the floodgates in just the second minute and Alexis Sanchez (53), Pedro Rodriguez (56) and a fantastic Neymar goal (89) added to Messi's double as Barca reclaimed top spot in La Liga from Atletico Madrid, which won earlier in the day.

The performance also fired out an ominous warning to European opponent City, which plays host to Gerardo Martino's men on Wednesday morning (AEDT) in the first leg of its last-16 tie.

Barca came into the match in buoyant mood after reaching the Copa del Rey final in midweek and it never looked like slipping up against second-bottom Rayo after Adriano had drilled in that early opener from the edge of the box.

Messi and Pedro both hit the post while the Argentina ace was also denied by a superb save from Ruben Martinez as Barca cut through Rayo's defence almost at will in the opening half-hour.

The second goal was coming and it was only a surprise that Barca had to wait so long for it to arrive, with Messi finally doubling the lead with a superb chip after Cesc Fabregas had intercepted an Anaitz Arbilla pass.

Messi then turned provider to set up Alexis for Barca's third goal soon after half-time and it was 4-0 two minutes later when Pedro slotted home after a clinical move involving two of his Spain team-mates, Andres Iniesta and Fabregas.

In between those two goals Barca goalkeeper Victor Valdes produced a fine finger-tip save to keep out Joaquin Larrivey's curling shot but that was a rare foray forward for embattled Rayo.

Messi and Dani Alves both missed chances to net before the former got his name on the scoresheet for a second time with another pinpoint finish - leaving the Argentina with 228 goals from only 263 league games. Raul, in contrast, took 550 matches to notch the same amount.

Messi, who has now scored 337 goals in all competitions for Barca, made way soon after for Cristian Tello as Martino opted to give his superstar a break ahead of the trip to Manchester, but for Rayo the misery did not end there.

Neymar, who came on in the second half having recovered from injury, added gloss to the win with the goal of the game late on, the Brazil superstar racing from halfway before smashing home an unstoppable 25-yard strike.

Atletico Madrid reaffirmed its title aspirations with a commanding 3-0 win at home to Real Valladolid, ending a three-game losing streak.

Two goals in the opening four minutes from Raul Garcia and Diego Costa got Atletico off to a flying start and Diego Godin added a third in the second half to seal a morale-boosting victory for Diego Simeone's men.

Atletico's confidence had been rocked by a 5-0 aggregate defeat to Real Madrid in the Copa del Rey semi-finals and a shock 2-0 reverse at Almeria last weekend, which knocked it off the top of the Primera Division standings.

A home fixture with struggling Valladolid was just the tonic Atletico needed, and it took it just three minutes to go ahead.

Gabi stood over a free-kick but instead of whipping the ball into the box, squared to Garcia, and the midfielder sent his first-time shot past Diego Marino.

Valladolid sought a quick response but was caught on the counter, Garcia playing a long ball over the top to Costa, who lifted his shot over Marino to make it 2-0.

The two early goals settled the host's nerves and it was more than content to sit on its lead for the remainder of the first half.

But Valladolid was unable to break its opponent down, which in turn meant Atletico had fewer opportunities to counter.

The best opportunities for the visitor fell to Javi Guerra early in the second period, and Manucho in injury-time, but neither player was able to hit the target.

Mario Suarez came close to grabbing a third for Atletico, his header striking the crossbar, before the host did add another goal when, in the 74th minute, Godin appeared at the back post to head in a corner from Diego Ribas, adding an extra shine to a much-needed win that turns the heat up on title rivals Barcelona and Real Madrid.

At the other end of the standings, Valladolid remains 18th and could be further away from safety by the end of the weekend.

There were ugly scenes at El Madrigal where Celta Vigo's unlikely 2-0 win over Villarreal was marred by a serious incident which almost saw the match abandoned.

Fabian Orellana had just headed Celta into the lead late in the second half when what appeared to be a smoke bomb was thrown on to the pitch, forcing the referee to take the players from the field and leading to most of the supporters leaving the stadium.

It led to a lengthy stoppage - and considerable confusion as at one stage it seemed the match would not continue - but eventually the players re-emerged and the four remaining minutes were played, enough time for Nolito to add a barely deserved second goal for the visitor.

A wonderful strike by David Barral was all Levante needed to see off Almeria and move up to seventh.

The striker hit a sensational volley after 61 minutes, finally converting one of the numerous chances that had fallen at his feet during the game, although once again Joaquin Caparros's side was grateful to its goalkeeper Keylor Navas, who produced an outstanding save to prevent a late equaliser from Oscar Diaz.

Levante has now gone six games without defeat. Almeria is much closer to the danger zone than its victor, 14th in the tablle, but is safe in the knowledge that it will still have a four-point margin over 18th placed Valladolid come next weekend.