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Just for reference, this is the Ann and two boys in 1851:

WILLIAM, John Head Married M 53 1798 Shoe Maker St Buryan Cornwall
WILLIAM, Mary Wife Married F 55 1796 Charwoman Wooden Bath Wiltshire
BOULTON, Ann Daughter Unmarried F 29 1822 Charwoman Burnham Buckinghamshire
BOULTON, William Jas Grand Son Unmarried M 8 1843 Scholar Kensington Middlesex
BOULTON, George F Grand Son M 4 1847 Kensington Middlesex

Registration District: Kensington Sub District: Kensington Town Enumeration District: 3 Ecclesiastical Parish: Saint Mary Abbotts

Civil Parish: Kensington Municipal Borough:
Address: 23, King Street, Kensington County: Middlesex

It does say that Ann's condition to marriage on the original is "un" but there's no guarantee to whether that's correct.

According to Ann's death cert she died in 1908 age 90 so that would make her birth around 1818. On the 1861 census she was born in Slough Buckingham but on the 1851 census she was born Burnham Buckingham.

I don't think that can be a possibility MarieCeleste as she was definately put down as daughter to Mary Williams. Unless her mother was married before.

Thanks everyone for trying to help

My hunch would be that perhaps, as you said, she never actually married Charles (perhaps he was married to someone else) but took his name as she had his children.

That may account for why she is called Boulton in 1851 but status unmarried. (I've found a very similar situation with my own great grandfather).