The clathrate Cd(CN)(2) . CCl4 is theoretically studied by means of extended Huckel tight-binding (EHTB) band calculations and the corresponding crystal orbital difference (COD and ICOD) curves. The small energy required for partial rotation of the CCl4 molecules inside the cavities may explain the rotational disorder of the guest molecules found in the experimental structure. The host and guest sublattices interact through the 2a(1), It(1), and 2t(2) lone-pair orbitals of Cl and the sigma*(Cd-N) and sigma*(Cd-C) orbitals of the Cd(CN)2 framework, with smaller contributions from the pi*(CN) orbitals. Ab initio (HF-MP2) calculations on bimolecular models provide rough estimates of the host guest and guest guest interaction energies in the Cd(CN)(2) . CCl4 and Cd(CN)(2) . CMe(4) clathrates, indicating that all interactions are weakly attractive, with the guest ... guest interactions favoring a structure with all the guest molecules at the same rotation angle relative to the Cd(CN)(2) skeleton.