The crystal structure of a Mn-bearing kilchoanite, Ca2.33Mn0.67Si2O7, orthorhombic, I2cm, a = 11.356(2), b = 5.007(1), c = 21.817(1)Å, Z = 8, was refined using single-crystal X-ray data to an R value of 3.1% for 1725 unique reflections. It is isostructural with kilchoanite, Ca3Si2O7, and shows a partial disorder of Mn and Ca over the four octahedral sites. On a basis of occupancy refinement, the M3 site (〈M3-O〉 = 2.307 Å) contains 0.508Ca and 0.492Mn, and the M4 site (〈M4-O〉 = 2.346 Å) contains 0.822Ca and 0.178Mn, whereas the M1 and M2 sites (〈M1-O〉 = 2.538 Å, (〈M2-O〉 = 2.380 Å) are occupied only by Ca. Substitution of Mn cations for Ca can be interpreted as taking place on the following sites in preferential order: (1) the smaller Ca site; (2) the less distorted Ca site; (3) the Ca site showing a loss in neutrality of formal electrostatic valence. A statistical survey of Si-O-Si angles observed in silicates containing [Si2O7] groups confirms that these angles become smaller with an increase in the coordination number of the bridging oxygen. Oversaturation of electrostatic bond-strength to the bridging oxygen in some groups of the crystal structures with two tetrahedra sharing a vertex (pyro-anion, ), which is caused by increase in the coordination number of the bridging oxygen and/or by T cations with larger charge than 4+, results in longer T-Obr bonds length and in smaller T-Obr-T angles.

Two compounds with the chemical composition Ca2.32Mn0.68Si2.00O7 were synthesized from a molten carbonating silicate with the melilite composition. The synthetic samples were subsequently characterized by X-ray powder diffraction, IR absorption and EPMA, and they proved to be the anhydrous phases isomorphous with kilchoanite Ca3Si2O7 and åkermanite Ca2MgSi2O7 respectively, and to be polymorphous with each other. Their crystallochemical properties suggest that Mn-åkermanite is a high-temperature structure type of Mn-kilchoanite. Substitution of Mn2+ with an intermediate ionic radius between those of Mg2+ and Ca2+ cations establishes the polymorphic relationship between åkermanite Ca2MgSi2O7 and kilchoanite Ca3Si2O7.