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Paul Lee Stine, 29 was shot and killed on October 11, 1969, in Presidio Heights in San Francisco.
On October 11, 1969, the Zodiac killer hailed Paul Stine's cab at the corner of Mason and Geary Streets in San Francisco, California. he asked Stine to take him to Washington and Maple Streets in Presidio Heights. For some reason, Stine drove another block to Cherry Street. Stine was shot once in the head with a 9mm handgun. The killer left with his wallet and car keys and tore a section from his bloody shirt.
Three teenagers saw the crime from across the street at 9:55 pm, and called the San Francisco Police Department. They reported seeing the killer wiping down the cab. They said he then headed one block north, towards the Presidio. The police arrived on the scene shortly afterward whereupon the teen witnesses told police that the killer was nearby.
Two blocks away, S.F.P.D. Officer Don Fouke observed a white man walking along the sidewalk then stepping onto a stairway leading up to the front yard of one of the homes on the north side of the street. The encounter lasted only seconds. Fouke's partner, Eric Zelms, did not see the man. For some reason, dispatcher described the suspect as a black male instead of white.
There is some disagreement about whether or not the Zodiac himself was actually stopped on that night. Officer Armond Pelissetti insists he was told by officer Fouke that he actually spoke with the suspect. Fouke denies speaking with the man. officer Pelissetti did not believe that the man was really the Zodiac, reasoning that the man would have been covered in blood and Fouke would have noticed. upon reaching Cherry Street, Officer Fouke was given the correct description of a white male suspect. Fouke beleives they had just passed the killer because he did not fit the original description. Fouke believed the Zodiac headed into the Presidio, but he could not be found on the grounds.
The three teen witnesses worked with a police sketch artist to create an initial composite, and then a second one a few days later. The killer was estimated to be 35-45 years of age. Detectives Bill Armstrong and Dave Toschi were assigned to the homicide investigation.

On October 14, 1969, the San Francisco Chronicle received a letter from the Zodiac containing a bloody piece of Paul Stine's shirt. the letter also threatened to shoot school children.
Source: Wikipedia