Less electronegative atom is the central atom. $\ce{N}$ is more electronegative than $\ce{Cl}$ as $\ce{Cl}$ has larger atomic radius. So why in $\ce{NCl3}$, $\ce{N}$ is the central atom?
Answer
Cl is slightly more electronegative according to the tables I've seen: http://en.wikipedia.org/wiki/Electronegativity
But I wouldn't say it's an absolute rule that the less electronegative atom is central. For example, $\ce{NH3}$ has the N central and $\ce{Cl_2O}$ has the O central.
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