Deportivo la Coruna moved off the bottom of the La Liga table after Toche sealed a 3-0 win to dent Valencia's bright start to the season, and Tiago got the opener in Atletico Madrid's 2-0 victory over Espanyol on Sunday.
Deportivo went ahead with a scrappy own-goal from a corner after the ball first came off Valencia's Shkodran Mustafi and then Jose Gaya on the line.
Just before half-time a long punt downfield by Deportivo goalkeeper Fabricio found its way to Lucas Perez who finished clinically with an angled drive for their second.
Toche then ran clear 10 minutes from time and slotted past keeper Yoel Rodriguez to wrap up a victory that moves Deportivo up to 15th in the 20-team standings.
Valencia remain third but are now level on 17 points with Atletico Madrid after eight games. Barcelona are top on 22 points followed by Real Madrid with 18.
Ateltico's Tiago leapt well to steer Gabi's cross into the top corner before the break against Espanyol before substitute Mario Suarez scored from close range in the 71st minute.
Antoine Griezmann could have given them a more resounding win five minutes from the end but his shot came back off the outside of the post with keeper Kiko Casilla beaten.
Diego Simeone's side have been seeking to get back on track and show the consistency that saw them win the championship but they have lacked the solidity in defence of last season.
On Sunday they managed to keep a clean sheet following a 3-1 defeat at Valencia before the international break.
"I think the team did what it had to do and was in control," Simeone told a news conference.
"We were playing in the opposition half with Raul [Garcia] and [Mario] Mandzukic in attack finding space as did Juanfran and Arda [Turan] on the wings.
"We were patient and the goal came. In the second half we were even more dominant."
In Sunday’s two other games, Sevilla beat Elche 2-0 and Villareal had too much for Almeria, being them off 2-0.
Lionel Messi hit the final goal for leaders Barcelona in a 3-0 win over Eibar on Saturday to move one off the league scoring record ahead of next weekend's Clasico with Real Madrid.
Cristiano Ronaldo maintained his blistering scoring form with two goals as Real swept aside Levante 5-0. They are in second place four points off the pace ahead of the showdown.
Barca needed Xavi to come to the rescue on the hour to finally break the resistance of a resolute Eibar side who are enjoying their first season in the top flight.
Neymar quickly added to the lead and then combined with Messi for the Argentine to notch his 250th league goal.
Messi, who this week celebrated 10 years since his Barca debut, has a chance against Real to beat Telmo Zarra's record of 251 goals for Athletic Bilbao in the 1940s and '50s.
Ronaldo slotted home a penalty for Real after 13 minutes following a foul by Juanfran on Javier Hernandez and the Mexican striker headed in from close range before halftime.
After the break Ronaldo completed his brace with a run down the left wing and a clinical finish and he now has 15 goals from the first eight league games.
James Rodriguez volleyed in the fourth after 65 minutes and Isco completed the rout with an 18-metre drive in the 82nd.
Elsewhere on Saturday, Malaga saw off Cordoba 2-1 and Athletic Bilbao and Celta Vigo played out a 1-1 draw.