The 41-year-old woman, identified as Jacqueline Dicks, was approached by three men on Elton Street in East New York just after 11:40 p.m.
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One of the men pulled a gun and shot her at least once in the head.
Dicks, of Brooklyn, was pronounced dead at the scene.
Dicks was an MTA subway conductor who was wearing her uniform. She was off duty at the time of the shooting.
She was the mother of six children. Tuesday night, mourners lit six candles at a vigil, one for each of her children.
Sources tell Eyewitness News that police are looking into the background of one of Dicks's older children as a possible motive for the murder.
Her grandchildren were at the vigil earlier, and like everyone said they are stunned by her loss and the many unanswered questions.
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"Obviously it wasn't no robbery or nothing like that," said the victim's brother Tyrone Hicks. "This wasn't no gang violence, her gang was her kids."
"I wish whoever did this, I wish whoever saw it would just come tell anything, whatever they saw to put this behind my family. We're taking it very hard," said the victim's niece, Michelle Dicks.
The men approached Dicks and shot her point blank in the head.
"He told me to look at the news, my sister had been shot," Tyrone Hicks said. "He said she's dead. That's my baby sister. I will always love her. I looked out for her. I feel let down. I feel I let her down."
Police say she had been dropped off by her boyfriend and was on her way home from work Monday when she was shot.
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"Great sister, great aunt, great mother. She was my everything," said Tyrone Hicks. "We lost our mother when I was 14. She was only 5, 6 years old. I been with her ever since. She looks out for me. I looked out for her. She gave me all the love and the world and I gave it right back."
"She's an awesome person, she's always been a good aunt, she'a always been a good mother, always been a good sister and I don't know why this had to happen to her," said Michelle Dicks.
The victim's six children ranged in age from 4 to 24. She had only worked for the MTA since June of last year, and had just finished her shift on the N line in Queens before she was killed.
The MTA and Dicks' union sent out messages of condolence to her family and supporting the NYPD in its investigation.