Local structure of channel ions in carbonate apatite

Refinement of the single-crystal X-ray diffraction structure of a type A carbonate apatite [CAp; Ca10(PO4)6–y(CO3)x+(3/2)y(OH)2−2x  , x=0.75x=0.75, y=0.0y=0.0; space group P3¯] has been continued with independent positional and isotropic displacement parameters for the carbonate oxygen atoms, reducing the residual indices significantly (R=0.024R=0.024, Rw=0.020Rw=0.020) and confirming the earlier structure assignment. The carbonate ion is located in the apatite channel at z≈0.5, and oriented with two oxygen atoms close to the c  -axis. Rigid body refinement, giving a preferred structure, used a novel procedure for defining the ideal equilateral triangular geometry of the channel carbonate ion. Resolution of the channel carbonate ions in type A-B CAp (x=0.69x=0.69, y=0.57y=0.57; P63/m) is also improved. Channel carbonate ions in CAp are canted, rotated and displaced to optimize Ca2–O bond distances. The rotation of the A1 carbonate in type A-B CAp is opposite to that of the channel carbonate in type A CAp, due mainly to the accommodation of a second channel carbonate ion (A2). These structures simulate the local structure of type A carbonate in hydroxyapatite of bone and dental enamel.