In other ties, Serie A champions Juventus face Europa League winners Atletico Madrid and Barcelona take on Olympique Lyonnais.
Factbox on the 20 Premier League clubs after the transfer window closed.
Real Madrid suffered a humiliating 2-1 home defeat by Leganes on Wednesday to exit the King's Cup at the quarter-final stage on away goals.
Liverpool will feel the weight of increased expectation to deliver silverware this season after making encouraging forays into the transfer market, manager Juergen Klopp said.
Besiktas's Europa League game at home to Tottenham Hotspur was suspended twice on Thursday after the floodlights failed in each half before the Turkish side won 1-0.
France coach Didier Deschamps confirmed his final Euro 2016 squad on Tuesday, including defenders Adil Rami and Samuel Umtiti in place of the injured Raphael Varane and Jeremy Mathieu. Liverpool centre back Mamadou Sakho was not included even though his 30-day provisional suspension for failing a drugs test expired last weekend. Hosts France geared up for the finals with a 3-2 victory over Cameroon in Nantes on Monday. They take on Scotland in Metz on Saturday.
Poland midfielder Grzegorz Krychowiak has signed a five-year contract with Paris St Germain, the French champions said in a statement on Sunday.
Former Sevilla coach Joaquin Caparros and current Granada manager Paco Jemez both said earlier on Thursday that they were interested in the position if Del Bosque was to leave.
Barcelona kept Real Madrid's La Liga title celebrations on hold for a few days at least with a crushing 7-0 victory at Rayo Vallecano on Sunday after Real had cruised to a 3-0 home win over Sevilla.
Barcelona still have very little chance of catching leaders Real Madrid and securing a fourth successive La Liga title despite closing the gap to eight points, coach Pep Guardiola said on Monday.
Real Madrid have started the season flying with three wins from three games.
Midfielder Santi Cazorla gave the home side the lead in the fourth minute of the game, which was rescheduled due to Real's participation in last month's Club World Cup, by bending a wonderful shot into the bottom corner.
Brazilian defender Filipe Luis scored for the second game running as Atletico Madrid beat Real Sociedad 1-0 on Tuesday to rack up a fifth straight win in La Liga and provisionally consolidate third place in the standings.
Barcelona forward Lionel Messi set a La Liga record of 253 goals when he grabbed a hat-trick in Saturday's 5-1 win at home to Sevilla, the latest milestone for the four-times World Player of the Year.
Real Madrid kept alive their hopes of overhauling La Liga leaders Barcelona when a James Rodriguez stunner set them on their way to a serene 3-0 home victory over struggling Almeria on Wednesday.
Real coach Julen Lopetegui has come in for fierce criticism this season, having presided over a run of five games without a win -- the team going eight hours and one minute without scoring -- before Tuesday's unconvincing 2-1 triumph over Viktoria Plzen that saw the team whistled off the pitch by their own fans.
Levante's extraordinary season continued when they thrashed second-division Alcorcon 4-0 on Wednesday to secure a 5-2 aggregate victory and advance to the King's Cup quarter-finals for the first time in more than 70 years.
A late header by Imanol Agirretxe gave Real Sociedad, who are without a coach, a 2-1 victory over 10-man Atletico Madrid in La Liga on Sunday.
West Bromwich Albion have bolstered their defensive ranks by signing centre half Jonny Evans from Manchester United on a four-year deal.
Craig Shakespeare has been appointed as Leicester City's manager for the rest of the season, the Premier League champions announced on Sunday.
Real Madrid's Jose Callejon scored twice and Nuri Sahin bagged his first goal for the club as the holders crushed third-tier Ponferradina 5-1 in a King's Cup last 32 second leg on Tuesday.
Cristiano Ronaldo netted his fifth La Liga hat-trick of the campaign as Real Madrid brushed off Pepe's 44th-minute dismissal to secure a crushing 6-2 victory at Sevilla and move back above Barcelona to the top of the standings on Saturday.
Ten-man Real Madrid slumped to a surprise 1-0 defeat at Levante on Sunday as the tiny Valencia-based club ended the nine-times European champions' perfect start to the season.
Everton have signed winger Gerard Deulofeu from Barcelona on a three-year contract for six million euros ($6.7 million), the Premier League club said on Thursday.
Champions Barcelona lost 2-0 at Celta Vigo while Getafe earned an important 2-0 win over Girona in their bid to secure Champions League qualification.
Photos from the Champions League matches played across Europe on Tuesday
Athletic Bilbao's bid for a berth in next season's Europa League stuttered when they lost 2-1 at Espanyol on Monday.
Madrid recovered from an early goal by Anthony Lozano to take a 2-1 halftime lead thanks to a Lucas Vazquez strike and a cheeky 'Panenka' penalty from captain Ramos but were pegged back by Alex Granell's penalty midway through the second half.
Manchester City humbled their neighbours United by beating them 6-1 and Levante still lead in Spain where European champions Barcelona were held to a 0-0 draw by Sevilla.
Thirteen teams have now qualified for the last 32 including Bayer Leverkusen, FC Zurich and Lazio who had already secured places in the next stage of the competition.
Lionel Messi scored a penalty for the third Champions League game in a row with the Spaniards maintaining their winning start to the group stage.
Centre forward Eder, who scored the winning goal in the Euro 2016 final against France, was among 10 players from that squad omitted from Santos's list. Other unlucky players included midfielders Andre Gomes and Renato Sanches, forward Nani and defender Eliseu.
Underlying tensions mean Luis Enrique will not be remembered with the same reverence as Pep Guardiola, even though he has delivered a similar trophy haul.
Frenchman Lenglet's first league start since his 36 million-euro move from Sevilla turned sour when he was shown a straight red card in the 35th minute at the Nou Camp following a coming together with Pons, after referee Jesus Gil Manzano consulted the video assistant referee (VAR).
Marco Ruben's header put Villarreal up to third in La Liga with a 1-0 win at Athletic Bilbao on Sunday, after Valencia fell to a solitary Ivan Rakitic strike in a pulsating encounter with Sevilla.
The result also means second-placed Real Sociedad can reclaim top spot if they beat Eibar on Sunday.
Spanish media paid tribute to Barcelona captain Andres Iniesta after he starred in his side's 5-0 thrashing of Sevilla in the King's Cup final on Saturday.
Paris St Germain will play Borussia Dortmund and Barcelona were pitted against an unpredictable Napoli, while Chelsea were drawn against Bayern Munich. City, who will be at home in the second leg, have yet to beat the Spanish side with two draws and two defeats in their previous four meetings.
With a comfortable first-leg advantage, Zinedine Zidane rested much of his first team, making 10 changes from the line-up that struggled to a disappointing draw at Celta Vigo on Sunday to fall 16 points behind league leaders Barcelona.
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