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The size of the Cl atom is such that formation of molecules of SCl6 does not occur. As SF6 has the smaller F atoms around the central S atom, this molecule is known. Think about the electron configuration and the effect on the sizes of Cl and F - Cl is in Period 3 and thus has electrons in the third energy level, whereas the electrons in F are in the second. This added energy level is such that 6 Cl atoms cannot 'fit' around one S atom.

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