Powell (70) carried on his good form from the last match and registered his second fifty of the series. Together with Samuels (71), he shared a 117-run second-wicket partnership to lay the foundation for West Indies after the visitors were put into bat by India skipper Mahendra Singh Dhoni.
Towards the end, Darren Bravo (51 not out) and Darren Sammy (37 not out) played aggressively to take West Indies past the 260-run mark.
For the hosts, off-spinner Ravichandran Ashwin was the pick of the bowlers with figures of two for 45 from his quota of 10 overs.
Dhoni's decision to bowl first after winning the toss did not yield the desired result as his bowlers could pick up just one wicket before Powell and Samuels joined hands to take West Indies forward.
Opener Johnson Charles (11) failed yet again when Bhuvneshwar Kumar went through his defence in the fifth over with a perfect inswinger leaving West Indies at 20 for one.
Both Powell and Samuels were cautious in their approach as they brought up the West Indies fifty in 11.3 overs.
Both the batsmen were content to see off the new ball in the morning. The duo kept rotating the strike with ones and twos and punished loose deliveries that came their way.
But once they managed to set in their eyes, both Powell and Samuels played freely and in the process brought up their 50-run stand in 53 balls.
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