Rational Syntheses and Structural Characterization of Sulfur-Rich Phosphorus Polysulfides: α-P2S7 and β-P2S7†
Thomas Rödl
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorDr. Richard Weihrich
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorJulia Wack
Department for Inorganic Chemistry III, University of Bayreuth, 95440 Bayreuth (Germany)
Search for more papers by this authorProf. Dr. Jürgen Senker
Department for Inorganic Chemistry III, University of Bayreuth, 95440 Bayreuth (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Arno Pfitzner
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)Search for more papers by this authorThomas Rödl
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorDr. Richard Weihrich
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)
Search for more papers by this authorJulia Wack
Department for Inorganic Chemistry III, University of Bayreuth, 95440 Bayreuth (Germany)
Search for more papers by this authorProf. Dr. Jürgen Senker
Department for Inorganic Chemistry III, University of Bayreuth, 95440 Bayreuth (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Arno Pfitzner
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)
Institute for Inorganic Chemistry, University of Regensburg, Universitätstrasse 31, 93040 Regensburg (Germany)Search for more papers by this authorThis work was financially supported by the DFG within the priority program SPP 1415 (project WE 4284/3-1).
Graphical Abstract
Sulfur, so good: Crystallization of phosphorus polysulfides catena-P2S7 is enhanced by catalytic amounts of anhydrous FeCl3 (see scheme, P blue, S yellow). The formation of polysulfide bridges is observed which is typical for vulcanization reactions.
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- 20X-ray structure analysis and crystallographic data for α-P2S7: Mr=286.36 g mol−1, STOE IPDS, T=296(2) K, MoKα (λ=0.71073 Å), 2θmax=50.30°, crystal size 0.15×0.03×0.02 mm3, monoclinic, space group P21/c (No.14), a=6.526(2), b=10.817(4), c=12.580(3) Å, β=93.24(2)°, V=886.6(4) Å3 (lattice constants refined from powder data (WinXPOW, Stoe & Cie GmbH, Darmstadt, 2000), transmission geometry, STOE STADI P, CuKα1 (λ=1.540598 Å)), Z=4, ρcalcd=2.145 g cm−3, μ(MoKα)=2.050 mm−1, 8088 measured reflections, 1544 independent reflections, Rint=0.0643, numerical absorption correction (X-RED32, Stoe & Cie GmbH, Darmstadt, 2004) after optimizing the shape of the crystal (X-SHAPE, Stoe & Cie GmbH, Darmstadt, 1999), structure solution by direct methods (SIR2004, M. C. Burla, C. Rocco, M. Camalli, B. Benedetta, G. L. Cascarano, L. De Caro, C. Giacovazzo, G. Polidori, R. Spagna, J. Appl. Crystallogr. 2005, 38, 381), structure refinement on F2 (SHELXL, G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112), 82 parameters, R1 (I≥2σ(I))=0.0303, wR2 (I≥2σ(I))=0.0470, R1 (all data)=0.0693, wR2 (all data)=0.0529, GooF=0.836, residual electron density=0.280/−0.278 e Å−3. X-ray structure analysis and crystallographic data for β-P2S7: Mr=286.36 g mol−1, STOE IPDS, T=296(2) K, MoKα (λ=0.71073 Å), 2θmax=51.58°, crystal size 0.24×0.05×0.04 mm3, triclinic, space group
(No.2), a=6.032(3), b=6.512(2), c=11.095(5) Å, α=82.62(4), β=89.20(5), γ=85.28(4)°, V=430.7(3) Å3 (lattice constants refined from powder data (WinXPOW), transmission geometry, STOE STADI P), Z=2, ρcalcd=2.208 g cm−3, μ(MoKα)=2.110 mm−1, 6122 measured reflections, 1557 independent reflections, Rint=0.0240, numerical absorption correction (X-RED) after optimizing the shape of the crystal (X-SHAPE), structure solution by direct methods (SIR2004), refinement on F2 (SHELXL), 82 parameters, R1 (I≥2σ(I))=0.0223, wR2 (I≥2σ(I))=0.0477, R1 (all data)=0.0294, wR2 (all data)=0.0490, GooF=0.974, residual electron density=0.445/−0.192 e Å−3.
Further details on the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany (fax: (+49) 7247-808-666; e-mail: [email protected]), on quoting the depository numbers CSD-423061 (α-P2S7), and CSD-423062 (β-P2S7).
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