The triclinic structure of the title compound, cyclo-tetra-kis-(-1,1-dioxo- 1 6,2-benzothia-zole-3-thiol-ato- 2 S:S)tetra-kis- [(triphenyl-phosphane-P)silver(I)], [Ag4(C7H4NO2S2)4(C18H15P)4], is a polymorph of the previously reported monoclinic structure [Dennehy, Mandolesi, Quinzani & Jennings (2007). Z. Anorg. Allg. Chem. 633, 2746-2752]. In both polymorphs, the complex lies on a crystallographic inversion centre and the bond distances are closely comparable. Some differences can be found in the inter-atomic angles and torsion angles involving the inner Ag4S4 skeleton. The polymorphs contain essentially identical two-dimensional layers, but with different layer stacking arrangements. In the triclinic form, all layers are related by lattice translation, while in the monoclinic form they are arranged around glide planes so that adjacent layers are mirrored with respect to each other.Fil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Sur; ArgentinaFil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Unidad de Actividad de Materiales (CAC); Argentin

Baggio, Ricardo Fortunato

Dennehy, Mariana

Freire Espeleta, Eleonora

Acta Crystallographica Section C Crystal Structure Communications

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electronic reprintActa Crystallographica Section CCrystal StructureCommunicationsISSN 0108-2701Editor: Anthony LindenA triclinic polymorph of cyclo-tetra-μ-thiosaccharinato-κ8S :S -tetrakis[(triphenylphosphane-κP)silver(I)]Mariana Dennehy, Eleonora Freire and Ricardo BaggioActa Cryst. (2012). C68, m17–m20Copyright c© International Union of CrystallographyAuthor(s) of this paper may load this reprint on their own web site or institutional repository provided thatthis cover page is retained. Republication of this article or its storage in electronic databases other than asspecified above is not permitted without prior permission in writing from the IUCr.For further information see http://journals.iucr.org/services/authorrights.htmlActa Crystallographica Section C: Crystal Structure Communications specializes in therapid dissemination of high-quality studies of crystal and molecular structures of interestin fields such as chemistry, biochemistry, mineralogy, pharmacology, physics and mate-rials science. The numerical and text descriptions of each structure are submitted to thejournal electronically as a Crystallographic Information File (CIF) and are checked andtypeset automatically prior to peer review. The journal is well known for its high stan-dards of structural reliability and presentation. Section C publishes approximately 1000structures per year; readers have access to an archive that includes high-quality structuraldata for over 10000 compounds.Crystallography Journals Online is available from journals.iucr.orgActa Cryst. (2012). C68, m17–m20 Dennehy et al. · [Ag4(C7H4NO2S2)4(C18H15P)4]A triclinic polymorph of cyclo-tetra-l-thiosaccharinato-j8S:S-tetrakis-[(triphenylphosphane-jP)silver(I)]Mariana Dennehy,a Eleonora Freireb,c*‡ and RicardoBaggiob*aDepartamento de Quı́mica, Universidad Nacional del Sur, Bahı́a Blanca, Argentina,bGerencia de Investigación y Aplicaciones, Centro Atómico Constituyentes,Comisión Nacional de Energı́a Atómica, Buenos Aires, Argentina, and cEscuela deCiencia y Tecnologı́a, Universidad Nacional General San Martı́n, Buenos Aires,ArgentinaCorrespondence e-mail: freire@tandar.cnea.gov.ar, baggio@cnea.gov.arReceived 31 October 2011Accepted 13 December 2011Online 23 December 2011The triclinic structure of the title compound, cyclo-tetrakis(-1,1-dioxo-16,2-benzothiazole-3-thiolato-2S:S)tetrakis[(tri-phenylphosphane-P)silver(I)], [Ag4(C7H4NO2S2)4(C18H15-P)4], is a polymorph of the previously reported monoclinicstructure [Dennehy, Mandolesi, Quinzani & Jennings (2007).Z. Anorg. Allg. Chem. 633, 2746–2752]. In both polymorphs,the complex lies on a crystallographic inversion centre and thebond distances are closely comparable. Some differences canbe found in the interatomic angles and torsion anglesinvolving the inner Ag4S4 skeleton. The polymorphs containessentially identical two-dimensional layers, but with differentlayer stacking arrangements. In the triclinic form, all layers arerelated by lattice translation, while in the monoclinic formthey are arranged around glide planes so that adjacent layersare mirrored with respect to each other.CommentHeterocyclic thiones are versatile S,N-chelating ligands and aconsiderable amount of work has centred around their coor-dination chemistry. They are capable of binding to metals in avariety of coordination modes and a large number of mono-nuclear, binuclear and complex polynuclear coordinationcompounds have been reported after the pioneering work byRaper (1996, 1997). We have developed a sustained interest inthe coordination behaviour of heterocyclic thiones in general,and thiosaccharin [the thione form of saccharin, C6H4-SO2NHCS, hereinafter tsac; systematic name: 1,1-dioxo-16,2-benzothiazole-3(2H)-thione] in particular. As is well knownfor other heterocyclic thiones, tsac has a tautomeric equili-brium in solution (see Scheme 1) and in its thiol form it can actas a good coordinating agent for soft metals, building inter-esting mono- and polynuclear structures with or without thepresence of additional ligands. In particular, we have workedon the silver–tsac system, aiming to control its stereochemistryand nuclearity, and we have been able to develop newproducts, for example, by changing the stoichiometry of thesoft bulky triphenylphosphane (PPh3) co-ligand. Surprisingly,the Ag–PPh3 stoichiometries in the resulting complexes do notalways follow the molar ratios in the reaction mixture. Forexample, a stable tetracoordinated complex [Ag(tsac)(PPh3)3]was obtained from reaction mixtures with Ag–PPh3 molarratios greater than 1:2, but a different Ag6(tsac)6 complexresulted for molar ratios of 1:1 or less (Dennehy, Quinzani &Jennings, 2007). In our search for the appropriate conditionsto prepare silver(I) thiosaccharinates with less than threephosphane ligands on the metal nuclei, we recently producedthe monoclinic tetranuclear complex [Ag4(tsac)4(PPh3)4](Dennehy, Mandolesi et al., 2007). Through a slight variationin the synthesis conditions, we have now obtained a triclinicpolymorph of the same compound, which we report herein.The triclinic and monoclinic polymorphs are referred to as (I)and (II), respectively.Some comparative crystal data for polymorphs (I) and (II)are given in Table 1. In order to highlight the similarities anddifferences between the structures, triclinic form (I) isdescribed using a nonconventional nonreduced unit cell. Thecorresponding reduced cell is a = 13.8914 (7), b = 14.0768 (6),c = 14.1309 (7) Å,  = 77.771 (4),  = 73.572 (4) and  =66.603 (4).metal-organic compoundsActa Cryst. (2012). C68, m17–m20 doi:10.1107/S0108270111053674 # 2012 International Union of Crystallography m17Acta Crystallographica Section CCrystal StructureCommunicationsISSN 0108-2701‡ Member of Consejo Nacional de Investigaciones Cientı́ficas y Técnicas,Conicet.electronic reprintThe tetranuclear unit in (I) (Fig. 1) is very similar to itscounterpart in (II). The molecule is composed of four fusedAg(tsac)(PPh3) units, two of them independent and theremaining two generated by an inversion centre. The maincharacteristic is the centrosymmetric eight-memberedskeleton, composed of four thione exocyclic S atoms and fourAg atoms in a regular chair conformation. Each Ag atom istriply coordinated by two S atoms and one PPh3 group in aslightly distorted planar arrangement; the deviations of the Agatoms from the ligand coordination plane are 0.0192 (3) Å forAg1 and 0.1392 (3) Å for Ag2, compared with the corre-sponding values of 0.0062 (14) and 0.0650 (16) Å for poly-morph (II). The coordination distances in both complexes areextremely similar (Table 2), and the bond distances and anglesin the bridging tsac ligands are typical of those observed inother related polynuclear silver thiosaccharinates (Dennehy,Mandolesi et al., 2007). A least-squares overlay of thecomplexes in (I) and (II) gives an r.m.s. deviation of 0.4 Å for128 non-H atoms (Macrae et al., 2008). A least-squares overlayof the central core of the complex (Fig. 2) shows that (I)adopts a more regular chair conformation than (II), asreflected by the Ag1—S1—Ag2—S2 torsion angles [89.17 (5)in (I) versus 79.80 (10) in (II)]. These relatively small differ-ences in the skeleton are magnified towards the outermostparts of the bulky PPh3 groups on account of the variation inthe degree of rotation around the P—Ag bonds. However, inboth polymorphs the overall globular shape for the moleculeis conserved. The changes which arise are reflected in thegeometries of the intra- and intermolecular interactions(Tables 3 and 4) to the extent that they cannot readily becorrelated between one structure and the other.The two polymorphs have closely comparable calculateddensities (Table 2) but different distributions of the moleculesin space. The choice of cell axes for (I) is intended to highlightthe similarities in the (001) planes in both structures (see a, band  in Table 1, and the shaded ab faces in Fig. 3). Indeed, thestructures contain essentially identical layers of moleculesparallel to the (001) planes, and they look identical whenprojected along the b axis. Fig. 3, where for simplicity only theinorganic skeletons are drawn, presents for each structure twoconsecutive layers (with and without shading) of these (001)planes, projected onto the layer plane. In (I), the layermetal-organic compoundsm18 Dennehy et al.  [Ag4(C7H4NO2S2)4(C18H15P)4] Acta Cryst. (2012). C68, m17–m20Figure 1The molecular structure of (I), showing the atom-numbering scheme.Displacement ellipsoids are drawn at the 30% probability level. H atomshave been omitted. The eight-membered Ag4S4 skeleton is highlighted.[Symmetry code: (i) x, y, z.]Figure 2A least-squares overlay of the eight-membered rings in (I) (full lines) and(II) (dashed lines). [Symmetry code: (i) x, y, z.]Figure 3Packing diagrams of (I) (top) and (II) (bottom), projected perpendicularto the (001) plane, showing two consecutive layers in different shading.Only the central ring of each molecule has been drawn, for clarity. Notethe very similar a, b and  cell parameters in the shaded cell faces.electronic reprintstacking takes place via a consistent c(I) cell shift, so that alllayers are related by lattice translation. In (II), the n-glidesgenerate alternating mirror images shifted by one half of thec(II) translation. Taking into account the differences in celllengths and cell angles, this corresponds to slightly differentinterplanar spacings: d(001) = 11.159 (2) Å for (I) and d(002) =10.910 (2) Å for (II).The globular shape of the molecules involved and theabsence of strong directional intermolecular interactions leadsto arrangements compatible with the packing of spheres. Anearest-neighbours calculation for the molecular centroidsgives exactly 12 neighbours for each structure, in the narrowrange 14.667 (2)–15.672 (3) Å for (II) and the slightly broaderrange 13.8914 (12)–17.7086 (13) Å for (I), in both cases fol-lowed by a 3 Å gap to the second nearest-neighbour shell. Thedistribution of the centroids in both structures can be envi-saged as a hexagonal arrangement, parallel to (100) in (I) or(101) in (II), bicapped by two parallel inverted triangles,resembling a 3 distribution (Fig. 4). The distribution in (II) israther regular, with the line through the triangular centresbeing almost perpendicular to the equatorial plane [angle =179.91 (14)] and the interplanar distances [corresponding tod(101)] being 11.838 (2) Å. The distribution in (I) is moredeformed, with corresponding values of 171.78 (16) for theline-to-plane angle and 12.432 (2)Å for d(100).ExperimentalThiosaccharin (Htsac) was prepared by the reaction of saccharin(3.00 g; Mallindkrodt) with Lawesson’s reagent (3.64 g; Fluka) intoluene (25 ml). Ag6(tsac)6 was obtained as a yellow solid by reactionof AgNO3 and thiosaccharin in acetonitrile in a 1:1 molar ratio(Dennehy, Tellerı́a et al., 2007). The title [Ag4(tsac)4(PPh3)4] complexwas prepared by slow addition of an acetonitrile solution containing2,5-dimethylpyrazine (10 mg) to another yellow solution of Ag6-(tsac)6 (0.0120 g, 0.04 mmol of Ag) and PPh3 (0.0100 g, 0.04 mmol) inacetonitrile (10 ml). The resulting clear yellow solution was kept atroom temperature and crystals of (I) had formed after one month.Crystal data[Ag4(C7H4NO2S2)4(C18H15P)4]Mr = 2273.49Triclinic, P1a = 15.3566 (10) Åb = 14.1309 (7) Åc = 14.0768 (6) Å = 77.771 (4) = 123.880 (3) = 86.465 (1)V = 2416.9 (2) Å3Z = 1Mo K radiation = 1.10 mm1T = 291 K0.20  0.16  0.12 mmData collectionOxford Gemini CCD S UltradiffractometerAbsorption correction: multi-scan(CrysAlis PRO; OxfordDiffraction, 2009)Tmin = 0.98, Tmax = 0.9920631 measured reflections11017 independent reflections5568 reflections with I > 2(I)Rint = 0.060RefinementR[F 2 > 2(F 2)] = 0.055wR(F 2) = 0.112S = 0.9411017 reflections577 parametersH-atom parameters constrained	max = 0.72 e Å3	min = 0.70 e Å3All H atoms were visible in a difference Fourier map, but theywere placed in idealized positions and allowed to ride for subsequentrefinement, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).Attention is drawn to a refinement paradox. When checking thefinal results with PLATON checkCIF (Spek, 2009), the Hirshfeldtests implemented therein generated a significant number of alertsregarding suspiciously large ‘Hirshfeld test dfferences’ (HTD) formany of the Ag—S bonds, thus advising careful review of the cation-type assignment. To our surprise, lower R indices and better Hirshfeldindicators were obtained when the structure was refined with Pdatoms in place of Ag; the R, wR and HTD values are 0.0553, 0.0882metal-organic compoundsActa Cryst. (2012). C68, m17–m20 Dennehy et al.  [Ag4(C7H4NO2S2)4(C18H15P)4] m19Figure 4Schematic nearest-neighbours representations of the structures of (I)(left) and (II) (right) (see Comment for details).Table 1Comparison of the crystal data for (I) (this work) and (II) (Dennehy,Mandolesi et al., 2007).(I) (II) (I) (II)Crystal system Triclinic Monoclinic Space group P1 P21/na (Å) 15.3566 (10) 15.024 (3)  () 77.771 (4) 90b (Å) 14.1309 (7) 14.681 (3)  () 123.880 (3) 95.31 (3)c (Å) 14.0768 (6) 21.914 (4)  () 86.465 (1) 90V (Å3) 2416.9 (2) 4812.77 Z 1 2Dx (Mg m3) 1.562 1.569Table 2Comparison of selected bond lengths and angles (Å,) in (I) (this work)and (II) (Dennehy, Mandolesi et al., 2007).(I) (II)Ag1—P1 2.3904 (13) 2.398 (3)Ag2—P2 2.3952 (15) 2.396 (2)Ag1—S2i 2.5440 (13) 2.551 (2)Ag2—S2 2.5008 (14) 2.505 (2)Ag1—S1 2.5484 (13) 2.549 (3)Ag2—S1 2.5852 (13) 2.582 (3)P1—Ag1—S2i 126.76 (5) 122.81 (9)P2—Ag2—S2 135.38 (4) 135.79 (9)P1—Ag1—S1 133.92 (5) 132.07 (9)P2—Ag2—S1 126.12 (4) 131.66 (8)S2i—Ag1—S1 99.30 (4) 105.13 (8)S2—Ag2—S1 97.49 (4) 92.33 (8)S2i—Ag1—S1—Ag2 164.95 (5) 163.22 (8)S1—Ag2—S2—Ag1i 1.93 (4) 11.17 (10)Ag1—S1—Ag2—S2 89.17 (5) 79.80 (10)Ag2—S2—Ag1i—S1i 88.11 (6) 95.45 (9)Symmetry code: (i) x, y, z.electronic reprintand 17.3, respectively, for Ag, and 0.0543, 0.0830 and 13.2, respec-tively, for Pd. This contradicts clear synthetic and analytical evidencefor the composition of the complex; an EDAX analysis on a Philips515 microscope (Philips Export BV, Eindhoven, The Netherlands)equipped with an EDAX PV9100 probe (EDAX International Inc.,Prairie View, Illinois, USA) showed that Ag was the only metallicelement present. Even if surprising, this is not a novel paradox; wehave previously found similar refinement ‘misbehaviour’ withdifferent cation pairs (e.g. CuII versus NiII; Perec & Baggio, 2010).Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cellrefinement: CrysAlis PRO; data reduction: CrysAlis PRO;program(s) used to solve structure: SHELXS97 (Sheldrick, 2008);program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);molecular graphics: SHELXTL (Sheldrick, 2008); software used toprepare material for publication: SHELXL97 and PLATON (Spek,2009).The authors acknowledge the Spanish Research Council(CSIC) for providing a free-of-charge licence for theCambridge Structural Database (Allen, 2002).Supplementary data for this paper are available from the IUCr electronicarchives (Reference: BI3030). Services for accessing these data aredescribed at the back of the journal.ReferencesAllen, F. H. (2002). Acta Cryst. B58, 380–388.Dennehy, M., Mandolesi, S., Quinzani, O. V. & Jennings, M. (2007). Z. Anorg.Allg. Chem. 633, 2746–2752.Dennehy, M., Quinzani, O. V. & Jennings, M. (2007). J. Mol. Struct. 841, 110–117.Dennehy, M., Tellerı́a, G. P., Tarulli, S. H., Quinzani, O. V., Mandolesi, S. D.,Güida, J. A., Echeverrı́, G. A., Piro, O. E. & Castellano, E. E. (2007). Inorg.Chim. Acta, 360, 3169–3181.Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3898.Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,P. A. (2008). J. Appl. Cryst. 41, 466–470.Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton,Oxfordshire, England.Perec, M. & Baggio, R. (2010). Acta Cryst. C66, m339–m342.Raper, E. S. (1996). Coord. Chem. Rev. 153, 199–255.Raper, E. S. (1997). Coord. Chem. Rev. 165, 475–567.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Spek, A. L. (2009). Acta Cryst. D65, 148–155.metal-organic compoundsm20 Dennehy et al.  [Ag4(C7H4NO2S2)4(C18H15P)4] Acta Cryst. (2012). C68, m17–m20Table 3Hydrogen-bond geometry for (I) (Å, ).Cg1 and Cg2 are the centroids of the S18/N18/C18/C28/C78 and C13/C23/C33/C43/C53/C63 rings, respectively.D—H  A D—H H  A D  A D—H  AC46—H46  O27i 0.93 2.44 3.350 (10) 165C52—H52  O17i 0.93 2.56 3.196 (10) 126C23—H23  Cg1ii 0.93 2.99 3.865 (6) 158C37—H37  Cg2ii 0.93 2.93 3.734 (9) 146Symmetry codes: (i) x  1;y;z; (ii) x;y;z.Table 4– interactions (Å, ) for (I).Cg3 is the centroid of the C27/C37/C47/C57/C67/C77 ring, ccd is the centre-to-centre distance (distance between ring centroids), ipd is the interplanardistance (distance from one plane to the neighbouring centroid) and sa is theslippage angle (angle subtended by the intercentroid vector to the planenormal). For details, see Janiak (2000).Group 1/group 2 ccd (Å) ipd (Å) sa ()Cg3  Cg3ii 3.735 (4) 3.441 (2) 22.8 (2)Symmetry code: (ii) 1  x, y, 1  z.electronic reprint

A triclinic polymorph of cyclo-tetra - Thio-saccharinato- 8 S:S-tetra-kis[(triphenyl-phosphane-P)silver(I)]

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A triclinic polymorph of cyclo-tetra - Thio-saccharinato- 8 S:S-tetra-kis[(triphenyl-phosphane-P)silver(I)]

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