The crystal structure of bismuth thiophosphate BiPS₄

Crystal and Electronic Structure of Bismuth Thiophosphate, BiPS4: An Earth-Abundant Solar Absorber

“…The significant distortion from the regular polyhedral angles, by up to ~40 o , is indicative of a stereochemically active 6s 2 lone-pair on Bi sites, which have also been observed in Bi compounds such as Bi2S3 and K2Bi8Se13. 41 As shown in Table 1, our XRD structural analysis is highly consistent with previous structural analysis on single crystals reported by Zimmermann et al, 45 with differences in lattice parameters well below 0.1%. The crystallographic information file of refined structure can also be obtained from the CCDC/FIZ Karlsruhe repository (deposition number: 1961688).…”

“…BiPS4 is prepared by solid-state reaction inspired by procedures reported elsewhere, 45,46 in which stoichiometric amounts of elemental bismuth, red phosphorus and sulphur are sealed in quartz ampoule evacuated to a pressure < 1 x 10 -6 mbar under Ar atmosphere. The reaction was first heated to 860 o C (i.e.…”

New Light on an Old Story: The Crystal Structure of Boron Tetrathiophosphate Revisited

“…The highest coordination number of the trivalent cation is 8 in YPS 4 as well as further lanthanide compounds . The coordination number decreases to 7 in ScPS 4 , and continues decreasing to a mixed sevenfold and sixfold coordination in BiPS 4 , to an octahedrally surrounded Cr in layered CrPS 4 , a fivefold coordination of Sb in SbPS 4 , and finally, a fourfold coordination is found in AuPS 4 ,, AlPS 4 , BPS 4 , GaPS 4 , and InPS 4 . In AuPS 4 , whose structure was finally solved by single‐crystal X‐ray diffraction in 2003, the PS 4 tetrahedra are connected via square‐planar coordinated Au 3+ forming one‐dimensional chains.…”

Synthesis, infrared, and X-ray study of di-µ-thiocyanato-1χN,S′:2χN′,S-bis-[bis(2,2′-bipyridine)di-isothiocyanatobismuth(III)]: a case of eight-co-ordinated bismuth

“…In the present compound the two bipyridyl molecules show different behaviour: the ligand with N(3) and N( 4) is more strongly bonded with similar distances 2.542 (8) and 2.553(7) A, the two rings are slightly tilted forming a dihedral angle of 5.3(3)0, and bismuth deviates from the N(3), C (15), C(16), N(4) chelate-ring plane by 0.447(1) A. The second molecule is more loosely co-ordinated with Bi-N 2.620 (7) and 2.624(5) A; the two rings are mutually bent with a dihedral angle of 12.5(2)' and the chelate ring is coplanar with bismuth.…”

“…in (8), ( 9), (ll), and (12); the unusually short distance of 2.25(2) 8, in (12) concerns one azide group in the axial site of a pentagonal pyramid. The 3.016(3) A interaction of the metal with atom S(l) can be considered as a 'long bond' and is comparable with those found with more loosely bonded or bridging ligands: [Bi2(O2CMe),(tu),]*H20 (tu = thiourea)," 3.132(5) and 3.152(6); [Bi(0,CMe),(t~),],'~ 3.020(2), 3.038(2), and 3.124(2); [Bi,(pcdt),]*EtOH (pcdt = l-pyrrolidinecarbodithioate),' ' 3.017 (8); [{ Bi(t~)(pcdt),Cl,),],~ ' 3.01 7(4) A. The thiocyanate groups are close to linearity.…”