The crystal structure of synthetic shannonite, Pb2O(CO3), orthorhombic, P212121, a = 5.1465(7), b = 9.014(1), c = 9.315(1)Å, V = 432.12(10)Å3, Z = 4, has been solved by direct methods and refined to R = 0.054. There are two symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The structure can be described as composed of chains of [OPb2] composition running parallel to [100] that are built by corner-sharing of OPb3 oxocentred triangles. The [OPb2] chains are surrounded by CO3 groups to form complex [OPb2](CO3) chains that are linked into a 3-dimensional framework by additional Pb–O bonds. The structure has channels that are parallel to [100] in which the lone-electron pairs of the Pb2+ cations are probably located.

The crystal structures of synthetic Pb3O2(CO3) and NaPb2(OH)(CO3)2, have been solved by direct methods and refined to R = 0.062 and 0.024, respectively. Pb3O2(CO3) is orthorhombic, Pnma, a = 22.194(3), b = 9.108(1), c = 5.7405(8) Å, V = 1160.4(3) Å3, Z = 8. There are four symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone electron pairs. The structure is based upon double [O2Pb3] chains of [O(1)Pb4] and [O(2)Pb4] oxocentred tetrahedra and CO3 groups. The [O2Pb3] chains are parallel to the c axis, whereas the CO3 groups are parallel to the (010) plane. NaPb2(OH)(CO3)2 is hexagonal, P63mc, a = 5.276(1), c = 13.474(4)Å, V = 324.8(1) Å3, Z = 2 and has been solved by direct methods. There are two symmetrically distinct Pb2+ cations in asymmetric coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The single symmetrically unique Na+ cation is in trigonal prismatic coordination. The structure is based on hexagonal sheets of Pb atoms. Within these sheets, Pb atoms are located at vertices of a 36 net, such that each Pb atom has six adjacent Pb atoms that are ~5.3 Å away. Two sheets are stacked in a close-packing arrangement, forming layers that contain the (CO3) groups. The layers are linked by OH groups that are linearly coordinated by two Pb2+ cations. Na+ cations are located between the layers. The structure is closely related to the structures of other lead hydroxide carbonates (leadhillite, macphersonite, susannite, hydrocerussite, ‘plumbonacrite’).