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1,2-trans-diiodo-ethene (C 2 H 2 I 2 ) – is an overlooked halogen bond donor, which demonstrate the distinct similarity of the geometry and directionality of I···I halogen bonds around the iodine atoms in its native and CpMn(CO) 2 (C 2 H 2 I 2 )  π -complex crystals. Distortion of the planar geometry of C 2 H 2 I 2  upon the  π -coordination result the distortion of the native planar layered geometry of C 2 H 2 I 2 , so that [CpMn(CO) 2 ]( π -C 2 H 2 I 2 ) features more complex I···I XB assisted 3D network. Unusual structural parallels between the native C 2 H 2 I 2  crystals and solid iodine are discussed.

Halogen bonding in crystals of free 1,2-diiodo-ethene (C 2 H 2 I 2 ) and its π -complex [CpMn(CO) 2 ]( π -C 2 H 2 I 2 )