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I am pretty sure you are out of date, the parking companies now usually win these cases:
https://www.moneysavingexpert.com/reclaim/private-parking-tickets/I recently successfully appealed one with ParkingEye. But I did it within the deadline, and I was fortunate that somebody else who got a fine at the exact same premises had it featured in the Guardian
https://www.theguardian.com/money/2023/oct/03/i-was-fined-100-for-queuing-up-at-a-carwash-queue -
Update on this - went to pay it for the easy life then felt the righteous anger flow through me as I know the car wasn't there.
I believe I was out of time for the POPLA stuff having missed all the original correspondence from the parking company (or at least, it would make my case worse - there is something to do with you having to act reasonably, and ignoring all the correspondence [or in my case, not keeping my VC5 up to date] is seen as unreasonable).
Spent some time on the MSE forum and then sent a polite rocket to the Co-op CEO email address with some evidence backing up that the car hadn't been there, and low and behold, just received an email saying they have instructed the parking company to cancel the charge and they are satisfied that I had left the car park.
A win!
I would contact the Coop and explain, ask them to have a word first. I worked briefly at a sainsburys store that had a private ANPR operated carpark and if staff received tickets, the store was able to contact the company and get rid of the tickets retrospectively.
You should tell the debt collection agency that you do not owe what they say you do. They shouldn't be able to chase you for payment until it is confirmed.
They won't come knocking to take away property or anything, debt collectors don't have any power to, only bailifs and only after a court has ruled you have to pay and the court is unlikely to rule in their favour if it ever went that far. The burden of proof is on the claimant (the parking company) and ANPR is unlikely to be strong enough
similar case here
If the parking company is a member of the British Parking Association, have a look at https://www.popla.co.uk/index.htm they can help with appeals
If you have any evidence that the car can't have been parked there like any messages from your partner saying that they're going here or there within those hours, submit those to the debt collection agency and/or coop and/or the parking co