The local structures of the new phosphorus chalcogenide-copper iodide coordination compounds (CuI)P4Se4, (CuI)(2)P8Se3, (CuI)(3)P4Se4, and (CuI)(3)P4S4 are investigated using comprehensive Cu-63, Cu-65, and P-31 magic angle spinning NMR techniques. Peak assignments are proposed on the basis of homo- and heteronuclear indirect spin-spin interactions, available from lineshape analysis and/or two-dimensional correlation spectroscopy. In particular, the P-31-Cu-63,Cu-65 scalar coupling constants have been extracted from detailed lineshape simulations of the P-31 resonances associated with the Cu-bonded P atoms. In addition, the RNnnu pulse symmetry concept of Levitt and coworkers has been utilized for total through-bond correlation spectroscopy (TOBSY) of directly-bonded phosphorus species. The resonance assignments obtained facilitate a discussion of the P-31 and Cu-63,Cu-65 NMR Hamiltonian parameters in terms of the detailed local atomic environments. Analysis of the limited data set available for this group of closely related compounds offers the following conclusions: (1) bonding of a special phosphorus site in a given P4Xn (X = S, Se) molecule to Cu+ ions shifts the corresponding P-31 NMR signal upfield by about 50 ppm relative to the uncomplexed molecule, (2) the magnitude of the corresponding scalar P-31-Cu-63,Cu-65 spin-spin coupling constant tends to decrease with increasing Cu-P distance, and (3) the Cu-63,Cu-65 nuclear electric quadrupolar coupling constants appear to be weakly correlated with the shear strain parameter specifying the degree of local distortion present in the four-coordinated [CuI2P2] and [CuI3P] environments. Overall, the results illustrate the power and potential of advanced solid state NMR methodology to provide useful structural information in this class of materials.

Bright orange (CuBr)(3)P4Se4 is obtained from the reaction of CuBr, P, and Se in stoichiometric amounts (CuBr : P : Se = 3 4 : 4). The composition and the crystal structure of the compound were determined from single crystal X-ray diffraction data. Lattice constants are a = 33.627(2) Angstrom, b = 6.402(1) Angstrom, c = 19.059(1) Angstrom, beta = 90.19(3)degrees, V = 4103.2(3) Angstrom(3), and Z = 12. The compound crystallizes in a structure that is related to (CUI)3P4Se4. Cages of beta-P4Se4 are stacked along the b-axis and are separated by columns of copper(I) bromide. However, the coordination of the beta-P4Se4 cage molecules to the copper atoms in the CuBr columns in (CuBr)(3)P4Se4 is quite different from (CuI)(3)P4Se4. The monoclinic compound (space group: P2(1), no. 4) has an almost orthorhombic metric in combination with a threefold superstructure in [100]. Structural aspects of (CuBr)(3)P4Se4 are discussed with respect to the heavier homologue (CuI)(3)P4Se4.

Pale yellow (AgI)(2)Ag3SbS3 was synthesized by the reaction of stoichiometric amounts of AgI and Ag3SbS3 (2 : 1) at 683 K. It is air stable for several months. The crystal structure was determined at different temperatures in the range from 173 K to 573 K by single crystal X-ray diffraction. (AgI)(2)Ag3SbS3 crystallizes in the orthorhombic system, space group Pnnm (no. 58) with a = 10.9674(8) Angstrom, b = 13.5200(12) Angstrom, c = 7.7460(5) Angstrom, V = 1156.3(5) Angstrom(3), and Z = 4 (data at 298 K). The title compound is isotypic with (CuI)(2)Cu3SbS3, at least for the positions of I, Sb, and S. The silver atoms are highly disordered and therefore their displacement parameters were re. ned using a Gram - Charlier non- harmonic development. No phase transition is observed between 173 K and the melting point at 720 K (DSC, onset temperature). The distribution of silver changes drastically with temperature and the localization of silver increases at low temperature. A high ionic conductivity is observed in combination with a pronounced disorder of the silver atoms. Impedance spectroscopic measurements reveal specific conductivity data of sigma = 8.15 x 10(-5) Omega(-1) cm(-1) at 332 K and of sigma = 1.52 x 10(-3) Omega(-1) cm(-1) at 478 K. The activation energy is E-A = 0.29 eV. Raman spectra are dominated by the stretching modes of the [SbS3](3-) units at 357, 327 and 316 cm(-1) at room temperature.

(CuI)3P4S4 is obtained by reaction of stoichiometric amounts of CuI, P, and S in evacuated silica ampoules. The yellow compound consists of monomeric -P4S4 cage molecules that are separated by hexagonal columns of CuI. (CuI)3P4S4 crystallizes isotypic to (CuI)3P4Se4 in the hexagonal system, space group P63cm (no. 185) with a 19.082(3), c 6.691(1) ä, V 2109.9(6) ä3, and Z 6. Three of the four phosphorus atoms are bonded to copper, whereas no bonds between copper and sulfur are observed. The two crystallographically distinct copper sites are clearly differentiated by 65Cu magicangle spinning (MAS) NMR spectroscopy. Furthermore, an unequivocal assignment of the 31P MAS-NMR spectra is possible on the basis of homoand heteronuclear dipole ± dipole and scalar interactions. Dipolar coupling to the adjacent quadrupolar spins 63, 65Cu generates a clear multiplet structure of the peaks attributable to P1 and P2, respectively. Furthermore, the utility of a newly developed two-dimensional NMR technique is illustrated to reveal direct connectivity between P atoms based on (31P ± 31P) scalar interactions.

Abstract The crystal structures of yellow Cu3PS4 and of black Cu3SbS4 were refined from single crystal X-ray diffraction data. Cu3PS4 crystallizes orthorhombic in an ordered wurtzite superstructure type with the space group Pmn21 (no. 31), a = 7.282(1) Å, b = 6.339(1) Å, c = 6.075(1) Å, V = 280.38(8) Å3, and Z = 2. The refinement converged to R = 0.0276, and wR2 = 0.0710 for 737 unique reflections and 44 parameters. Cu3SbS4 crystallizes tetragonal in an ordered sphalerite superstructure type with the space group I4̅2m (no. 121), a = 5.391(1) Å, c = 10.764(1) Å, V = 312.83(9) Å3, and Z = 2. The refinement converged to R = 0.0213, and wR2 = 0.0532 for 492 unique reflections and 14 parameters. The crystal structures of the title compounds and related normal tetrahedral structures are discussed with respect to the preference of either hexagonal or cubic packing of the anions.

(CuI)(3)P4S4 is obtained by reaction of stoichiometric amounts of CuI, P, and S in evacuated silica ampoules. The yellow compound consists of monomeric beta-P4S4 cage molecules that are separated by hexagonal columns of CuI. (CuI)(3)P4S4 crystallizes isotypic to (CuI)(3)P4Se4 in the hexagonal system, space group P6(3)cm (no. 185) with a = 19.082(3), c = 6.691 (1) Angstrom, V = 2109.9(6) Angstrom(3), and Z=6. Three of the four phosphorus atoms are bonded to copper, whereas no bonds between copper and sulfur are observed. The two crystallographically distinct copper sites are clearly differentiated by Cu-65 magic-angle spinning (MAS) NMR spectroscopy. Furthermore, an unequivocal assignment of the P-31 MAS-NMR spectra is possible on the basis of homo- and heteronuclear dipole-dipole and scalar interactions. Dipolar coupling to the adjacent quadrupolar spins Cu-63 65 generates a clear multiplet structure of the peaks attributable to P1 and P2, respectively. Furthermore, the utility of a newly developed two-dimensional NMR technique is illustrated to reveal direct connectivity between P atoms based on (P-31-P-31) scalar interactions.

Angewandte Chemie International EditionVolume 39, Issue 22 p. 4160-4162 Communication (CuI)2P8Se3: An Adduct of D3-Symmetrical P8Se3 Cage Molecules with Cu2I2 Rhomboids Arno Pfitzner Priv.-Doz. Dr., Arno Pfitzner Priv.-Doz. Dr. [email protected] Universität Siegen, Anorganische Chemie 57068 Siegen (Germany) Fax: (+49) 271-740-2555Search for more papers by this authorSara Reiser Dipl.-Chem., Sara Reiser Dipl.-Chem. Universität Siegen, Anorganische Chemie 57068 Siegen (Germany) Fax: (+49) 271-740-2555Search for more papers by this authorTom Nilges Dipl.-Chem., Tom Nilges Dipl.-Chem. Universität Siegen, Anorganische Chemie 57068 Siegen (Germany) Fax: (+49) 271-740-2555Search for more papers by this author Arno Pfitzner Priv.-Doz. Dr., Arno Pfitzner Priv.-Doz. Dr. [email protected] Universität Siegen, Anorganische Chemie 57068 Siegen (Germany) Fax: (+49) 271-740-2555Search for more papers by this authorSara Reiser Dipl.-Chem., Sara Reiser Dipl.-Chem. Universität Siegen, Anorganische Chemie 57068 Siegen (Germany) Fax: (+49) 271-740-2555Search for more papers by this authorTom Nilges Dipl.-Chem., Tom Nilges Dipl.-Chem. Universität Siegen, Anorganische Chemie 57068 Siegen (Germany) Fax: (+49) 271-740-2555Search for more papers by this author First published: 14 November 2000 https://doi.org/10.1002/1521-3773(20001117)39:22<4160::AID-ANIE4160>3.0.CO;2-8Citations: 29 The authors gratefully acknowledge the continuous support from Prof. Dr. H. J. Deiseroth. This work has been financially supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. S.R. thanks the Landesgraduiertenförderung Nordrhein-Westfalen for a stipendium. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Abstract One of the few examples of molecules with D3 symmetry is the novel P8Se3 cage molecule (see structure). This species was obtained as an adduct to copper iodide. This phosphoselenide cage can be formally derived from the polyphosphide “ufosane” P113− through the substitution of P− by Se. Citing Literature Volume39, Issue22November 17, 2000Pages 4160-4162 RelatedInformation

The crystal structure of CuClCu2TeS3 was refined from TOF neutron powder diffraction data in order to verify the distribution of chlorine and sulfur. It is a novel derivative of the zincblende type with an ordered distribution both of the cations Cu+ and Te4+ and of the anions Cl− and S2−. The compound crystallizes in the rhombohedral system, space group R3m (No. 160) with a=7.3502(1) Å, c=10.3873(2) Å, V=485.99 Å3, and Z=3. The structure refinement converged to Rwp=0.039 and RBragg=0.032. From the neutron data it can be derived that there is no significant disorder of Cl and S atoms. Impedance spectroscopic measurements in the temperature range 140–280°C reveal that CuClCu2TeS3 is a semiconductor with an activation energy of 0.75 eV (T<200°C) and 1.25 eV (T>200°C), respectively. On the other hand (CuI)3Cu2TeS3 and (CuI)2Cu3SbS3 exhibit high copper ion conductivity with activation energies of 0.2 and 0.35 eV, respectively, but a negligible electronic conduction.