Synthesis and investigation of Tin(II) pyrophosphate Sn2P2O7

The structural investigation of Sn2P2O7 was carried out for the first time by means of single crystal and powder X-ray diffraction. The crystal structure of beta-Sn2P2O7 pyrophosphate was solved using single-crystal X-ray.data at room temperature and at 93 K. At room temperature the structure (triclinic, P(1) over bar, a = 5.2776(5) Angstrom, b = 11.5413(12) Angstrom, c = 11.6360(12) Angstrom, alpha = 102.911(8)degrees, beta = 99.303(8)degrees, gamma = 98.899(8)degrees, V = 668.2(3) Angstrom(3), Z = 4) contains the [P2O7](4-) pyrophosphate groups oriented in mutually perpendicular directions with tin atoms situated in large structural interstices. This structure remains intact at low temperatures. The Sn2P2O7 undergoes a reversible structural transition at 623 K found by thermal analysis which is accompanied by increase of the unit cell symmetry to monoclinic. The crystal structure of the high temperature alpha-Sn2P2O7 form was solved using high-temperature powder diffraction data collected at 773 K. The structural motif of the high temperature form (monoclinic, P2(1)/n, a = 7.1765(4) Angstrom, b = 9.2874(6) Angstrom, c = 5.2968(4) Angstrom, beta = 106.034(3)degrees, V = 339.30(5) Angstrom(3), Z = 2) is closely related to the room temperature modification. The stereochemically active lone pairs of the tin atoms were localized with the ELF calculations for both polymorph modifications. In addition, the electronic state of tin was characterized using Sn-119 Mossbauer spectroscopy.