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The accident took place around 4 am when the luxury bus was going towards Surat from Rajasthan, they said.
It hit the trailer from behind while trying to overtake it on a bridge on the highway, an official from Panigate police station said.
As many as six passengers were killed and around 15 others injured in the accident, Deputy Commissioner of Police (Zone-3) Yashpal Jaganiya said.
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The deceased included a child, a woman and four men, the police said.