Villarreal CF 0-2 SSC Napoli Goals from Gökhan Inler and Marek Hamšík earned the visitors a place in the last 16 and condemned Villarreal to a sixth Group A defeat.
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Lightning did not strike twice at El Madrigal as SSC Napoli gained a measure of revenge on Villarreal CF, who knocked them out of the UEFA Europa League in February, by winning 2-0 and sealing progress to the UEFA Champions League knockout stage for the first time.
Manchester City FC's Group A elimination was confirmed with 14 minutes left when Marek Hamšík, from close range, added to Gökhan Inler's thundering opener midway through the second half. In a tense, even contest Napoli found extra quality at the crucial moments.
The talk of pride and self-respect in the home camp before kick-off was quickly proved to a bigger jury than expected, the local media having urged Villarreal fans to turn up in numbers and match the enthusiastic Napoli supporters. Despite being on a run of seven defeats in ten games, Juan Carlos Garrido's side looked determined to reward them.
When Napoli broke the offside trap early on, Ezequiel Lavezzi chipping a pass to the onrushing Juan Zúñiga, there was no panic once the Colombian international's effort bounced tamely into the grasp of Diego López. From that moment Villarreal's confidence flourished. Hernán Peréz squared a measured pass for Marco Ruben to strike cleanly at goal and his effort deflected off a post.
Slowly constructed passing moves took Villarreal towards half-time with growing rhythm and assurance. That Napoli are the in-form side with more footballers capable of doing the unexpected was demonstrated − albeit fleetingly. Hamšík and Lavezzi, for example, seemed immune to the lethargy which was gradually diminishing Napoli's efficacy.
The break came and went − news of Manchester City's lead audibly spread nerves among the sizeable visiting support. Evidently the Azzurri thrived on that. Edinson Cavani's surge forward in the 62nd minute was diverted by López sprinting from his goal, but Lavezzi followed up and only a combination of Joan Oriol and the goalkeeper saved the second effort.
Then drama. Inler did not seem pose much menace as he advanced, but he struck a thunderous left-footed drive which left López rooted to the spot. Cue huge celebrations high above that goalmouth from the Napoli fans.
Their joy increased on 76 minutes, when Lavezzi's low corner caused confusion and Hamšík, busy throughout, stabbed in to seal Neapolitan glory. Morgan De Sanctis's fantastic added-time save to turn a stinging Gonzalo Rodríguez drive around the post merely added to the feel-good factor.