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There is a reason for this and it's due to the fact that pixels are whole integers and can never be fractions, so when converting to cm, it will round off there. I've seen this elsewhere. Go to Image > Image Size and give me pixel dimensions and resolution in pp/cm
Bear in mind Photoshop is pixel based and document size in cm is determined by resolution.
21.00 to 21.01 or .1 mm would not make a visual difference if printed.
Thanks gener7 - very simple! The size of my canvas in pixels did not allow a whole number when divided.
I have adjusted the size to 41.98cm x 41.98cm giving a canvas size of 1190 px X 1190 px at 72 px/inch - I can then split this exactly in half at 595 pixels (21.99cm)
Thank you to JJMack - Your answer really helped me understand - I also didn't know you could set a constraint on the rectangular marquee tool and I've been using Photoshop for years and years... duh!
Very helpful answers - thank you