Abstract: | Two novel hypervalent selenium(IV) compounds stabilized by intramolecular interactions, namely 6‐phenyl‐6,7‐dihydro‐5H‐2,3‐dioxa‐2aλ4‐selenacyclopentahi]indene, C14H12O2Se, 14 , and 5‐phenyl‐5,6‐dihydro‐4H‐benzoc]1,2]oxaselenole‐7‐carbaldehyde, C14H12OSe2, 15 , have been synthesized by the reaction of 2‐chloro‐1‐formyl‐3‐(hydroxymethylene)cyclohexene with in‐situ‐generated disodium diselenide (Na2Se2). The title compounds were characterized by FT–IR spectroscopy, ESI–MS, and single‐crystal X‐ray diffraction studies. For 14 , there is whole‐molecule disorder, with occupancies of 0.605 (10) and 0.395 (10), a double bond between C and Se, and the five‐membered selenopentalene rings are coplanar. The packing is stabilized by π–π stacking interactions involving one of the five‐membered Se/C/C/C/O rings centroid–centroid (Cg…Cg) distance = 3.6472 (18) Å and slippage = 1.361 Å], as well as C—H…π interactions involving a C—H group and the phenyl ring. In addition, there are bifurcated C—H…Se,O interactions which link the molecules into ribbons in the c direction. For 15 , the C—Se bond lengths are longer than those of 14 . The two five‐membered rings are coplanar. There are no π–π or C—H…π interactions; however, molecules are linked by C—H…O interactions into centrosymmetric dimers, with graph‐set notation R22(16). |