* Messi moves up to third on La Liga scoring list
* Nets double in Barca's 6-0 drubbing of Rayo
* Atletico 3-0 winners at home to Valladolid
* Villarreal match disrupted by teargas attack (Adds quotes, Villarreal match)
By Iain Rogers
MADRID, Feb 15 (Reuters) - Lionel Messi overhauled Alfredo Di Stefano's La Liga goals tally as Barcelona and Atletico Madrid warmed up for midweek Champions League action with wins on Saturday that put them three points clear of Real Madrid at the top.
Back to his best after returning from a two-month injury layoff in early January, Messi struck twice in Barca's 6-0 thrashing of Rayo Vallecano at the Nou Camp to take his total in Spain's top flight to 228 goals from 263 matches, one more than Real Madrid great Di Stefano managed in 329 games.
Still only 26, Messi climbed above his Argentine compatriot to joint third on the all-time list behind record marksman Telmo Zarra (251) and Hugo Sanchez (234) and level with Raul.
"I would like to think that Messi has still not completely recovered (from his injury)," Barca coach Gerardo Martino told a news conference.
"If he wants to, he will break all the records that he likes," added the Argentine, who hails from Messi's home town of Rosario.
Barcelona, who play their Champions League last 16, first leg match at Manchester City on Tuesday, and Atletico, who visit AC Milan in the competition on Wednesday, have 60 points from 24 matches, ahead of Real who play at Getafe on Sunday.
Atletico's Raul Garcia and Diego Costa struck early to set up a 3-0 win over visitors Real Valladolid, while Villarreal's match at home to Celta Vigo was suspended for about half an hour when what appeared to be a teargas canister was thrown on to the pitch with about three minutes remaining.
Celta were leading 1-0 and after play restarted Nolito made it 2-0 with a free kick in the 90th minute meaning Villarreal missed a chance to close to within a point of fourth-placed Athletic Bilbao.
Barca, chasing a fifth La Liga title in six years, totally outclassed Madrid-based Rayo and took the lead in the second minute when fullback Adriano cut inside from the left and his low effort scooted inside the far post.
Messi and Pedro then cracked shots off the frame of the goal before a pinpoint Cesc Fabregas pass sent Messi clear in the 36th minute and he produced a trademark chip over onrushing goalkeeper Ruben.
The four-times World Player of the Year released Alexis on the right to make it 3-0 eight minutes after the break before a moment of inspiration from Andres Iniesta helped create Barca's fourth in the 56th.
The Spain playmaker's backheel put Fabregas through and he squared for Pedro to tap into an empty net as a dominant Barca turned the screw on their hapless visitors.
Messi scored his second with a precise shot from the edge of the area in the 68th and Neymar crowned a near-perfect night for the home side when he came off the bench and netted a fierce long-range drive in the 89th minute.
The Brazil forward has been out injured for a month and his reappearance suggested he could play a role at Manchester City on Tuesday.
"When the team is having fun we play better and today a lot of people had fun," Martino said. "If I had to choose I would prefer to go into the match against City playing like this."
Atletico came into the game against Valladolid at their Calderon stadium after resounding losses in both legs of their King's Cup semi-final against city rivals Real either side of a surprise 2-0 La Liga reverse at promoted Almeria.
Diego Simeone's side needed a convincing performance to lift morale before Wednesday's game at the San Siro and Garcia gave them the perfect start.
He picked up Gabi's clever free kick in the third minute and netted with a first-time strike from the edge of the area.
A minute later Garcia conjured a fine assist for Costa and the Brazil-born forward lifted the ball over Valladolid keeper Diego Marino for his 21st league goal of the campaign, one behind top scorer Cristiano Ronaldo of Real.
With a two-goal cushion, Atletico played well within themselves for the rest of the match and centre back Diego Godin added a third in the 74th with a header from a Diego corner.
"The 2-0 did not give me peace of mind, the 3-0 a little more," Simeone told a news conference. "From that point, we made some changes so I could rest some players and above all to give the others a chance," added the Argentine.
"We need everyone who is not playing regularly because when we need them to come on they have to play as well as possible."
Valladolid, who have won only four games this term, are down in 18th on 21 points, one ahead of second-bottom Rayo. (Editing by Ken Ferris)