Abstract:A new superstructure was found in bafertisite [(Ba0.98Na0.02)1.00(Fe1.71Mn0.26Mg0.01)1.98 TiO [(Si1.82Ti0.04Al0.03Cr0.01)1.90O7](OH1.40F0.53Cl0.03)1.96] from Donghai County, Jiangsu Province, China. The occurrence of the superstructure reflections were observed by single crystal diffraction using a SMAR APEX CCD. The a*, b* and c* axis directions revealed extra weak reflection spots of the superstructure. The apparent 2a, 2b and 2c superstructure is monoclinic with unit cell a= 10.6502(15) Å, b= 13.7233(19)Å, c= 21.6897(3)Å, α= 90°, β= 94.698(3)°, γ=90°, space group Cm, Z= 16. If c* extra weak reflections are ignored, the secondary supercell gave a cell a= 10.6548(15)Å, b=13.7284(19)Å, c= 11.6900(17)Å, α= 90°, β= 112.322(28)°, γ= 90°, space group Cm, Z= 8. The basic subcell was obtained by ignoring all extra weak reflection spots and gave: a= 5.3249(17)Å, b=6.8669(22)Å, c= 10.8709(36) Å, α= 90°, β= 94.740(62)°, γ= 90°, space P21/m, Z= 2. The superstructure has been refined to R= 0.063 for 7805 [R(int)= 0.0266] unique reflections I>2δ(I). The structure consists of an octahedra (O) sheet sandwiched between two heteropolyhedral (H) sheets. These sheets consist of Ti‐octahedra and twin tetrahedral disilicate groups [Si2O7]. The O sheet comprises (Fe,Mg)O4 octahedra. The large Ba cation is located in the interlayer area. The refined structure shows Fe, Mg are partly ordered. The shifting of the TiO6 octahedron and SiO4 tetrahedron sites in the sheet may be a consequence of the superstructure.