Syntheses, crystal structures, and solid state NMR investigations of K4M2P6S25 and K3M2P5S18 (M=Ti, Sn)

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Although terminal chalcogeno ligands are well known for the group 5 and 6 transition metals, they are highly unusual for the oxophilic group 4 metals and unknown so far for the lanthanides or actinides. Cs3UP2S8, is the first actinide compound containing a terminal M=S group. It was synthesized by reacting uranium metal, Cs2S, S, and P2S5 in a 4:1:8:3 ratio at 700 °C in an eutectic LiCl/CsCl mixture. The crystal structure was determined by single‐crystal X‐ray diffraction techniques. Cs3UP2S8 crystallizes in the rhombohedral space group R$\bar{3}$ [a = 15.5217(8) Å; c = 35.132(2) Å, V = 8305.0(8) Å3, Z = 18]. The crystal structure is based on a tetrahedral network type, wherein the uranium atoms are coordinated by a unusual sulfido moiety and thiophosphate groups in a pseudo‐tetrahedral fashion. The U=S distance of 2.635(3) Å observed in the sulfide moiety is approx. 0.2 Å shorter than the average U–S single bond length, indicating a double‐bond type character.

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cs₃UP₂S₈, a Coordination Polymer Containing the Unprecedented [U=S]²⁺ Sulfidouranium(2+) Moiety

Neuhausen

Panthöfer

Tremel

2013

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“…Bonding mode I has not been observed for chalcogenophosphates so far, but thiophosphates such as AgZnPS 4 [56] contain entities with fragment II. Bonding mode III is typically encountered in early transition metal compounds such as AgTi 2 (PS 4 ) 3 , [57] ATi 2 (PS 4 ) 3 , [58] and K 3 Ti 2 P 5 S 18 [59] 3-anion chains, whereas mode IV is found in K 3 Bi(PS 4 ) 2 .…”

Section: Bonding Of the Thiophosphate Connecting Groupsmentioning

confidence: 99%

“…In the structure of KCrP 2 S 7 [68] the PS 3 termini are symmetrically bonded in mode XVII, the chain compound K 3 Ti 2 P 5 S 18 [59] contains a pyrothiophosphate in the type XVI arrangement. Except for uranium, metals with high coordination numbers (e.g.…”

Section: Bonding Of the Thiophosphate Connecting Groupsmentioning

confidence: 99%

Comprehensive Uranium Thiophosphate Chemistry: Framework Compounds Based on Pseudotetrahedrally Coordinated Central Metal Atoms

Neuhausen

Hatscher

Panthöfer

et al. 2013

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Abstract. The new ternary compounds UP 2 S 6 , UP 2 S 7 , U(P 2 S 6 ) 2 , and U 3 (PS 4 ) 4 were prepared from uranium metal, phosphorus pentasulfide, and sulfur at 700°C. The crystal structures were determined by singlecrystal X-ray diffraction methods. UP 2 S 6 (I) crystallizes in the ZrP 2 S 6 structure type [tetragonal, P4 2 /m, a = 6.8058(7) Å, c = 9.7597(14) Å, Z = 2], which consists of central uranium(IV) atoms coordinated by P 2 S 6 4-anions (staggered conformation). The anions are two-dimensional connectors for four uranium cations arranged in one plane. The structure of UP 2 S 7 (II) [orthorhombic, Fddd, a = 8.9966 (15) ligands, the resulting 3D network contains large pores (diameter approx. 3.5 ϫ 16.7 Å). In the previously reported compound U(P 2 S 6 ) 2 (III) [I4 1 /a, a = 12.8776(9) Å, c = 9.8367(10) Å, Z = 2], the

“…Integration gives an intensity ratio of 1:1, matching the crystallographic site multiplicities. From similar compounds like LiTi 2 P 3 S 12 or K 3 Ti 2 P 5 S 18 for Ti‐coordinating PS 4 tetrahedra a 31 P NMR shift of about 60 ppm is known , . Therefore, the signal at δ = 61.56 ppm is assigned to P2, while that at δ = 31.87 ppm should represent P1 as part of the P 2 S 6 2– anion.…”

Section: Crystallographic Data and Details Of The Structure Determinamentioning

confidence: 99%

Synthesis and Characterization of the New Ternary Titanium Thiophosphate TiP₂S₇ and Comparison to Ti₄P₈S₂₉

Dressel

Klein

Fässler

2018

The synthesis of the new thiophosphate TiP2S7 succeeded from TiS2, P4S10, and elemental S in presence of Li2S or elemental Cu and additional S. The crystal structure [orthorhombic, Pbcn, a = 23.9895(13), b = 6.8308(4), c = 19.6295(6) Å, V = 1905.0(2) Å3, Z = 8, R1 = 2.78 %, wR2 = 6.35 % (all reflections)] consists of edge‐connected TiS6 octahedra and PS4 tetrahedra, which form corrugated layers. Each of these layers interpenetrates a second one to form double layers parallel to the bc plane. The highly anisotropic characteristics are macroscopically observed by the easy cleavage property. One S atom coordinating the Ti atom is partially replaced by a S2 dumbbell leading to a TiS5(S2) coordination. Including the dumbbell atoms the exact composition of the new compound is refined to TiP2S7.05. According to the crystal structure TiP2S7 shows two signals in 31P NMR spectra. Another known ternary thiophosphate with a very similar composition, Ti4P8S29, was reinvestigated with special consideration of the S/S2 occupational disorder, the composition was determined exactly to Ti4P8S28.68 and found to be different from the previously reported.