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Barcelona suffered their first Champions League defeat in 10 matches on Tuesday when goals from Aleksandr Ryazantsev and Gokdeniz Karadeniz gave Rubin Kazan a shock 2-1 win in their Group F clash.
The holders were rocked back by the Russian champions in the second minute at the Nou Camp when midfielder Ryazantsev let fly from distance and the ball arrowed past Victor Valdes into the top right corner.
Pep Guardiola's side had plenty of possession after falling behind but found it tough to break down Rubin's well-organised defence until Xavi picked out striker Zlatan Ibrahimovic with a lofted pass in the 48th minute.
The Sweden striker controlled with his chest and crashed a low shot past Sergei Ryzhikov from the right of the area but Barca fell behind again after a swift Rubin break engineered by Alejandro Dominguez.
The Argentine striker released the pacy Karadeniz and the Turkish international finished with ease past Valdes with 17 minutes of normal time left.
Ibrahimovic sent an acrobatic volley against the crossbar, Xavi stung Ryzhikov's hands with a fierce drive and Yaya Toure headed against a post in the fourth minute of added time but Barca were unable to find a second equaliser.
The final whistle prompted wild celebrations among the small knot of Rubin fans in the vast Nou Camp arena and Inter's 2-2 home draw with Dynamo Kiev means Rubin are in with a real chance of advancing to the knockout phase.
"These things happen. It's not the first time and I doubt it will be the last," Barcelona coach Pep Guardiola told a news conference. "I didn't feel like we played a bad match."
Barca, Rubin and Dynamo all have four points after three games in Group F.
Liverpool's hopes of progressing to the knockout stages of the Champions League suffered a serious blow after Cesar Delgado hit a stoppage-time winner to hand Olympique Lyon a 2-1 victory on Tuesday.
The five-times European champions had overcome the loss of captain Steven Gerrard, who lasted 24 minutes in his comeback game before limping off injured, to take a 41st minute lead through Yossi Benayoun.
But Lyon substitute Maxime Gonalons headed a 72nd minute equaliser before Delgado's late winner stunned Rafa Benitez's side.
"It was a deserved victory, we deserved what we got," Lyon coach Claude Puel told reporters.
"There's still lots of work to do though. Obviously Liverpool are going to come to our place to win because they have got to win.
"But we're going to savour the moment.
"Liverpool were strong to start with and put us under a lot of pressure, but we managed to remain calm and strong at the back."
Liverpool are in danger of dropping into the Europa League after falling three-points behind second-placed Fiorentina in Group E.
Lyon have a maximum nine points with Fiorentina on six, Liverpool three and Debrecen yet to register a point after three games.
Liverpool were without influential striker Fernando Torres for the second successive game due to injury and Benitez rued the absence of the Spaniard.
"We had too many problems before the game with injuries," he said.
"But we still managed to take the lead and we still managed to create chances."
David Mendes da Silva fired home an equaliser in added time to earn AZ Alkmaar a 1-1 draw against Arsenal in Champions League Group H on Tuesday.
The visitors took the lead through midfielder Cesc Fabregas in the 36th minute after he was found by Dutch international Robin van Persie and then comfortably soacked up the pressure.
But Alkmaar went on the offensive in the last 20 minutes and were finally rewarded when Mendes da Silva salvaged a point after Graziano Pelle set him up following a Stijn Schaars pass.
Arsenal remain top of the group with seven points, while Alkmaar have moved into third with two points.
Inter Milan failed to win in the Champions League for the eighth straight game when they were forced to come from behind twice in a 2-2 home draw with Dynamo Kiev on Tuesday.
Dynamo are joint top of Group F following Barcelona's shock 2-1 defeat by Rubin Kazan while Italian champions Inter, who have flattered to deceive in the Champions League for years, are bottom after three draws in their first three matches.
Enterprising Dynamo took the lead after five minutes when Taras Mikhalik was given time to turn and rifle in off the post following poor Inter defending.
The Ukrainians had already given the hosts a scare in the opening moments when Andriy Yarmolenko somehow missed at the far post after a corner was flicked on.
With Inter struggling to mount an attack, former AC Milan striker Andriy Shevchenko almost grabbed the headlines on his return to a half-empty San Siro when his header whistled just wide.
Dejan Stankovic brought Jose Mourinho's side level on 35 minutes when he was played through by Lucio and knocked the ball past the onrushing goalkeeper from the edge of the area.
Parity did not last long, however, with Lucio heading a corner into his own net under pressure.
Central defensive partner Walter Samuel spared some of his blushes by looping in a header from another corner just after the break before both sides had chances to win.
Shevchenko blasted the best opportunity wide while Inter substitute David Suazo had a goal ruled out for offside in stoppage time.
Serie A leaders Inter thumped Genoa 5-0 away on Saturday with just one upfront and Mourinho opted for the same formation with Diego Milito injured and Mario Balotelli suspended.
Samuel Eto'o, back after a foot problem, took Balotelli's place as the lone striker but apart from a penalty appeal and one good chance he barely troubled the visiting defence.
Romania striker Adrian Mutu scored twice and created another as Fiorentina won 4-3 away at Debrecen in a frenetic and highly entertaining Champions League Group E match on Tuesday.
Hungarian champions Debrecen took an early lead through Peter Czvitkovics's tap in from close range but Mutu volleyed in Dario Dainelli's cross and then set up Alberto Gilardino to fire the Italian side ahead after just 10 minutes.
In a first-half goal blitz, Mutu blasted in his second after Gilardino returned the favour to his strike partner after escaping his marker at Ferenc Puskas stadium.
Gergely Rudolf pulled one back for the hosts with a superb strike, curling a shot into the top left corner after teasing two defenders with his trickery.
Mario Santana then restored Fiorentina's two-goal cushion eight minutes before halftime.
A quieter second-half produced just one goal with French striker Adamo Coulibaly heading a third goal for Debrecen two minutes from time but the Hungarian side are still waiting for their first Champions League point.
Olympique Lyon have a maximum nine points with Fiorentina on six, Liverpool three and Debrecen yet to register a point after three games.
Sevilla crushed hosts VfB Stuttgart 3-1 with a double strike from defender Sebastien Squillaci on Tuesday to make it three wins out of three in the Champions League and top Group G with nine points.
Squillaci rose high to connect with a deep Adriano cross for the lead against the run of play in the 23rd minute, with Jesus Navas adding a second when keeper Jens Lehmann failed to clear, sending the ball into his path 10 minutes after the restart.
Squillaci headed home his second goal after 72 minutes, after again being left unmarked at the far post, before substitute Elson grabbed a consolation goal for the hosts with a beautiful curled freekick two minutes later.
Stuttgart, who had their chances early in the first half, remain on two points from three matches.
An injury time strike from substitute Ieroklis Stoltidis handed Olympiakos a 2-1 win over Standard Liege 2-1 in their Champions League Group H match on Tuesday.
Midfielder Stoltidis, on as a second half substitute, rose unchallenged following a corner in the third minute of injury time to nod in the winning goal following a breathless finish.
The visitors took the lead in the 37th minute when Igor De Camargo slotted past Antonis Nikopolidis from inside the area.
Olympiakos struck back just six minutes later through Kostas Mitroglou which helped them to maintain second place in Group H with six points, one behind leaders Arsenal who drew 1-1 at AZ Alkmaar.
The Dutch side leapfrogged Standard Liege into third spot.
Olympiakos's Jaouad Zairi and Standard midfielder Wilfried Dalmat both squandered chances in the first half.
Olympiakos enjoyed most of the possession but Standard opened the scoring through De Camargo.
The Liege skipper, who passed a late fitness test after recovering from a broken toe, ran on to Milan Jovanovic's clever through ball and slotted past Nikopolidis in the 37th minute.
Olympiakos reacted immediately through Mitroglou, who scored his first group stage goal with a looping header over Sinan Bolat after connecting with a Luciano Galletti freekick.
Both teams continued to chase victory in an absorbing affair as Mitroglou tried his luck with an over-head kick before Jovanovic cracked a stunning long range effort off the crossbar.
Olympiakos poured forward in the later stages with Mellberg shooting straight at Bolat in the 75th minute.
Dudu had the ball in the Liege net after 84 minutes but his effort was ruled out for handball but Stoltidis pounced in the dying seconds.
Romanian champions Unirea Urziceni crushed Rangers 4-1 helped by two own goals in Champions League Group G on Tuesday.
Unirea, the team from rural Romania whose stadium holds just 7,000 fans, recorded their first win in European competition having scored their first away goals to demolish a hapless Rangers side who led through a Ricardo Vilana own goal.
Second-half own goals by Kyle Lafferty and Lee McCulloch put the visitors 3-1 ahead after Marius Bilasco had equalised and Rangers' Steven Davis missed a penalty before the break.
Pablo Brandan drove home a low shot to make it 4-1 and wrap up the points for Unirea who now have four from three games. Rangers have one point and are bottom of the group.
"I believe in the second half we had a bit of luck," Unirea manager Dan Petrescu told reporters.
"We scored the second goal from a deflection and that made it easy for us, but my players also made it look easy. Before that we didn't play well."
The early Rangers goal, which came after a fierce Pedro Mendes shot hit Vilana and deflected over keeper Daniel Tudor, stunned the Romanians and Petrescu said: "I never expected a goal in the second minute (from them) and I had to take action immediately. I could not afford to lose and we took a risk and we won."
Unirea pulled level with a simple equaliser as Brandan charged into the area on the left before driving a low ball across the face of goal for the unmarked Bilasco to score.
Rangers then wasted a great chance to score when Tudor saved Davis's spot kick on 38 minutes and their anguish was compounded just four minutes into the second period when a shot from Bruno Fernandes clipped substitute Lafferty and flew beyond keeper Allan McGregor.
Unirea made it 3-1 just before the hour as Tiberiu Balan's deep free-kick from the left was headed into his own net at the near post by McCulloch. Six minutes later Brandan drove a low shot into the bottom left for their fourth goal.
"That type of defending at any level is not good enough," said disappointed Rangers manager Walter Smith.