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Police were called to the TSG tobacconist on Longueville Road in Lane Cove about 3.50am.
CCTV footage obtained of the incident showed a black Volkswagen Golf reversing through the windows of the shop.
The car stops, with two masked people running behind the store’s counter.
They can be seen taking several packages from behind the counter.
Police said they believed cigarettes had been taken.
A crime scene was established, and a description of the car was shared among police units.
Police said the car was believed to have been stolen from a home in Emu Plains last night.
A police officer in St Marys saw the Volkswagen on Walter Street in St Marys about 5.45am this morning.
Police said they tried to pull the car over, and pursued the car after they allegedly failed to stop.
The car was followed to Werrington, where the car was allegedly driven into a police car.
A 15-year-old boy and a 16-year-old girl were arrested and taken to Penrith Police Station.
No charges have yet been laid.