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The Thai team, which lost to Azerbaijan last week in the first leg of the tournament in Hong Kong, made a solid start to take the first set 25-21.
However the Azerbaijanis, who finished fourth in the European championships, used their experience to win the next two sets 25-18 25-17.
After some thrilling rallies in the fourth set, Thailand hung on and won a tight set 25-23 before storming on to win the decider 15-10 and the match.
"We have won at last," said Thai coach Suttichai Chanbunchee. "I'm very happy with my girls' form. I did not expect my girls to beat Azerbaijan. They are one of the strongest teams here."
Azerbaijan coach Faig Garayev said: "Thailand played exceptionally well today. We beat them 3-2 in Hong Kong, but not this time. My girls are also tired of playing five sets in every match."
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