A new coordination polymer [Hg(LI)I]n (1) and a new discrete coordination complex [Hg(HLII)I2] (2) are synthesized and X-ray characterized. The existence of positive π-holes at the spodium atoms in both compounds is evidenced by DFT calculations. In 1, a Hg–S semicoordination bond and a Hg⋯I spodium bond are formed at opposite sides of the π-hole. In 2, two different Hg⋯I spodium bonds are formed at both sides of the π-hole. This is the first study describing structure-guiding π-hole spodium bonding.
