CHCl3 molecules were found to form two types of dimers via C-H ... Cl and C-Cl ... Cl-C interactions in the cavities of a coordination polymer. The Cambridge Structural Database studies indicated that the Cl ... Cl dimer is the first example of CHCl3 with Cl to Cl distance (3.478(4), 3.501(3) Angstrom) below the sum of the van der Waals radii of two Cl-atoms.