1836 Mar 28 PAYNE John. Syresham N'hants KNIBB Catherine
Wit: David KIRBY Hannah KNIBB

Was Hannah who witnessed the marriage, Hannah Knibbs (nee Bennett) the wife of Kitty's brother Joseph, or was it perhaps Kitty's aunt Hannah, her dad's sister?

I have learned from Joanna Kafarowski that John was the son of Thomas Payne and his wife Martha Randall. He had 7 siblings - Anne (c.1807), Thomas (c.1810), Steven (c.1813), Richard (c.1814), George (c.1816), George (c.1818) and William (c.1820).
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John and Kitty seemed to have moved to live in Whitfield, Northamptonshire soon after they married. They were living there at the time of the 1841 census:

John Paine 30 farmer Y
Catherine 30 N
Elizabeth Knibbs 11 N
George Gackins 14 Y

I'm pretty sure that the Elizabeth Knibbs who was living with them was Elizabeth Ann Knibbs b.1829 at Somerton, Oxfordshire. She was Kitty's niece, a daughter of Kitty's brother Joseph Knibbs and his wife Hannah Bennett. Joseph emigrated to New York in about 1840 and we think that Hannah and the children may have followed soon after. We know that in 1850, Joseph, Hannah and their son Cornelius can all be seen living at Albany, New York, USA. Elizabeth wasn't living with them so presumably she married before 1850.

I'm not sure who George Gackins was, but quite possibly a farm labourer who was lodging with them.
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We can see John and his family in the 1861 census, living at Crowfield, Syresham, Northamptonshire:

John Payne Head 50 Farmer of 25 Acres Northamptonshire Syresham
Catherine Payne wife 52 Oxon Somerton
James Payne son 19 Northamptonshire Whitfield
Sarah Payne dau 17 Northamptonshire Whitfield
George Payne son 16 Northamptonshire Whitfield

We can see James in 1881 living at High Street, Syresham, Northamptonshire, England:
James PAYNE Head 39 Whitfield, Northampton, Ag Lab Occupier Of 7 Acres Land
Elizabeth PAYNE Wife 37 Silverstone, Northampton, England Pillow Lace Maker
John PAYNE Son 13 Silverstone, Northampton, England Ag Lab
Sarah Ann PAYNE Daur 11 Syresham, Northampton, England Scholar
James PAYNE Son 8 Syresham, Northampton, England Scholar
Oliver PAYNE Son 6 Syresham, Northampton, England Scholar
Elizabeth PAYNE Daur 4 Syresham, Northampton, England Scholar
Frank PAYNE Son 2 Syresham, Northampton, England
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I've learned from Joanna Kafarowski who's husband is James' great-great-grandson, that:
10 July 1867 - James and Elizabeth Varney were married at Silverstone, Towcester. Both parties living in Silverstone - laborer at this time.
1891- near King's Head Inn Syresham, Northamptonshire
1891- farm bailiff
1901- listed as laborer on son Frank Payne's marr cert
1901- James and Elizabeth still living next door to Kings Head Inn, Syresham (or border with Brackley district) with James as laborer foreman.

Elizabeth was born 30 March 1844 at Silverstone, Towcester, Northamptonshire, England and baptised 10 September that same year.

James and Elizabeth had 7 children - John (c.1868), Sarah (c.1870), James (c.1873) , Oliver (c.1875), Elizabeth (c.1877), Frank (c.1879) and Harriet (c.1884).

Joanna tells me that Sarah married a man named Arthur Emmanuel Wilkinson in q1/1872 in Brackley District, Northamptonshire, England, and they had two daughters, Catherine (c.1874) and Edith (C.1878).

George married Hannah Letts in q2/1872 in Banbury District, Oxfordshire, England, and they had 4 children - John Edward (c.1874), William (c.1876), George (c.1878) and Elizabeth (c.1881).