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The central atom in a Lewis structure is usually the least electronegative atom.

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If an atom occurs only once, this atom is most likely to be the central atom (exception is hydrogen, as it can make only 1 bond [1 electron necessary to reach a noble gas electron configuration]). The atom that can form the greatest number of bonds (has the least number of valence electrons) or is the least electronegative (least likely to attract atoms).

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