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Re(CO)5Cl is Cubic alpha N2-derived structured and crystallizes in the orthorhombic Pnma space group. The structure is zero-dimensional and consists of four chlororhenium molecules and twenty formaldehyde molecules.
Re2C3(O2Cl)3 crystallizes in the orthorhombic Pna2_1 space group. The structure is one-dimensional and consists of two Re2C3(O2Cl)3 ribbons oriented in the (-1, 1, 0) direction. there are two inequivalent Re+5.50+ sites. In the first Re+5.50+ site, Re+5.50+ is bonded to three O2- and two Cl1- atoms to form distorted corner-sharing ReCl2O3 square pyramids. There are a spread of Re–O bond distances ranging from 2.09–2.12 Å. There are one shorter (2.27 Å) and one longer (2.69 Å) Re–Cl bond lengths. In the second Re+5.50+ site, Re+5.50+ is bonded to three O2- and two Cl1- atoms to form distorted corner-sharing ReCl2O3 square pyramids. There are a spread of Re–O bond distances ranging from 2.08–2.13 Å. There are one shorter (2.26 Å) and one longer (2.66 Å) Re–Cl bond lengths. There are three inequivalent C+1.33+ sites. In the first C+1.33+ site, C+1.33+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.25 Å) and one longer (1.26 Å) C–O bond length. In the second C+1.33+ site, C+1.33+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both C–O bond lengths are 1.25 Å. In the third C+1.33+ site, C+1.33+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.25 Å) and one longer (1.26 Å) C–O bond length. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Re+5.50+ and one C+1.33+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one Re+5.50+ and one C+1.33+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one Re+5.50+ and one C+1.33+ atom. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Re+5.50+ and one C+1.33+ atom. In the fifth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Re+5.50+ and one C+1.33+ atom. In the sixth O2- site, O2- is bonded in a bent 120 degrees geometry to one Re+5.50+ and one C+1.33+ atom. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted bent 120 degrees geometry to two Re+5.50+ atoms. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Re+5.50+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Re+5.50+ atom.