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Tetrakis(tetrasulphur tetranitrogen dioxide)silver hexafluoroarsenate(V) |
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Dalton Transactions,
Volume 1,
Issue 2,
1983,
Page 405-407
Herbert W. Roesky,
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摘要:
J. CHEM. SOC. DALTON TRANS. 1983 405Tetra kis( tet rasu I phu r tetran itrogen d ioxide)si lver Hexaf I uoroarsenate( v) tHerbert W. Roesky," Manfred Thomas, Hans G. Schmidt, William Clegg,Mathias Noltemeyer, and George M . Sheldrick *lnstitut fur Anorganische Chemie der Universitat, Tammannstrasse 4, D -3400 Gottingen,Federal Republic of GermanyA complex of silver(!) containing tetrasulphur tetranitrogen dioide ligands has been prepared. Thecrystals of [Ag(S4N402)4] +[AsF,] - are triclinic, space group PI, with unit-cell dimensionsa = 1 142.6(6), b = 1 194.9(5), c = 1 254.8(6) pm, a = 66.44(4), fl = 96.71(4), y = 91.30(4)",and Z = 2, final R = 0.039 for 4 968 unique diffractometer data with F > 30(F). The Ag atom lies 53 pmbelow a square of four nitrogen atoms (mean Ag-N 256 pm).Bisdisphenoidal (triangulateddodecahedral) co-ordination of Ag is completed by two intramolecular Ag-0 contacts (mean 307pm), and intermolecular Ag-N and Ag-0 interactions (both 273 pm). These intermolecular interactionsgive rise to a centrosymmetric cationic dimer. The S4N402 ligands are approximately planar except for theSO2 units; only nitrogen and oxygen atoms attached to Sv' interact with Ag, thereby causing the leastdisruption of delocalised bonding in the rest of the ring.A few years ago we reported the synthesis of tetrasulphurtetranitrogen dioxide, S4N402, from sulphamide and S3N2C12.1Several papers 2-5 have been published describing the productsof reactions of S4N402. The X-ray crystal structure of S4N402was of low while an isomer of S4N402 containedthe S5N5+ cation and the s&O4- anion.Recently we wereable to show * that S3Nz0, a five-membered sulphur-nitrogenring, forms a crystalline product [Ag(S3N20)4] + [AsF6]- withsilver(1). We have now studied the reaction of S4N402 withsilver hexafluoroarsenate(v) to determine the nature of theco-ordination and its effect on the sulphur-nitrogen x-system.Co-ordination by sulphur, nitrogen, or oxygen is in principlepossible.Experiment a1The general preparative and spectroscopic techniques were asdescribed in other recent papers from this laboratory.Tetrakis(tetrasulphur tetranitrogen dioxide)siluer Hexa-f?uoroarsenate(v).-Silver hexafluoroarsenate(v) (1 -44 g,0.0048 mol) and S4N402 (2.1 g, 0.0097 mol) 1-2 were cooled to-78 "C in a pressure flask and SO2 (20 cm3) added.Theflask was allowed to warm to room temperature, stirred for20 h, and the solid removed by filtration. Orange crystals wereobtained by slowly removing SO2 from the filtrate (yield98%, freezing point 152-153 "C) (Found: F, 9.5; N, 20.2.piped crystal with approximate dimensions 0.4 x 0.4 x 0.6mm was sealed in a Lindemann glass capillary for the X-raydata collection.Cak. for AgASF6N1608S16: F, 9.8; N, 19.3%). A parakl0-X-Ray Structural Analysis.-Intensities were collected at18 "C by a real-time profile-fitting procedure on a Stoe-Siemens four-circle diffractometer with graphite-mono-chromated Mo-K, radiation. 5 735 Reflections were measured7 Tetrakis( 1, l-dioxo-lh6,3,5,7,2,4,6,8-tetrathiatetra-azocine-N2)silver hexafluoroarsenate(v).Supplementary data available (No.SUP 23468, 35 pp.): structurefactors, thermal parameters. See Notices to Authors No. 7, J .Chem. SOC., Dalton Trans., 198 1, Index issue.in the range 7 < 28 < 55". After application of Lorentz,polarisation, and empirical absorption corrections (basedon measurements of equivalent reflections at different azi-muthal angles) the data were merged to yield 5 450 uniquereflections, of which 4 968 with F > 3o(F) were employed forall calculations. The unit cell was determined by a least-squares fit to the optimum angles for 40 strong reflections,28 values being determined from o measurements at &28.Crystal data. AgAsF6Nl6O8Sl6, Triclinic, space group Pi,a = 1 142.6(6), b = 1 194.9(5), c = 1254.8(6) pm, a =66.44(4), p = 96.71(4), y = 91.30(4)", U = 1.559 nm3, 2 =2, D, = 2.475 mg m-3, F(OO0) = 1 132, Mo-K, radiation,h = 71.069 pm, and p = 2.82 mrn-'.The structure was solved by Patterson and Fourier methods.Least-squares refinement with all atoms anisotropic, complexneutral-atom scattering factors, and the weighting schemew = [o*(F) + 0.OOO 53 F2]-' converged to R' = CwilAl/CwilFol = 0.043, R = 0.039.A final difference map showedno peaks higher than 0.0009 e nm-'; the largest differencepeaks were in the hF6- region. Atomic parameters are givenin Table 1 and bond distances and angles in Table 2. Thestructure of the [Ag(S4N402)4]+ cation is shown in the Figure.Calculations were performed using the SHELXTL programsystem (written by G.M. S.).Results and DiscussionThe Ag atom lies 53 pm below the plane of four nitrogen atoms(deviations from coplanarity &6 pm). The cation exhibitsapproximately two-fold symmetry, with two trans Ag-Ndistances [250.8(3), 253.4(3) pm] slightly shorter than theother two [259.7(5), 259.0(5) pm]. The two ligands with thelonger Ag-N distances also exhibit weak intramolecularAg-0 interactions [314.3(4), 300.5(4) pm], involving an 00 distance of 329.7(7) pm. The other two SO2 groups arefurther from each other and from the Ag atom [Ag-O 332.4(5),334.2(5); 0 0 628.3(8) pm], leaving a co-ordination ' hole 'beneath the Ag, which is occupied by two atoms of anothercation [Ag-N(14') 272.7(4), Ag-O(l1') 273.4(4) pm1.S This1 The primed atoms are related to the unprimed ones by thetransformation - - x , 1 - y , 1 - z406 J.CHEM. SOC. DALTON TRANS. 1983Table 1. Atomic parameters ( x 10") with estimated standard deviations in parenthesesX1 752(1)8 054( 1)1 198(1)3 298(1)3 053(1)448(1)3 597(1)1 185(1)4 336(1)2 354(1)1017(1)3 41 l(1)4 194(1)2 093( 1)1935(1)3 750(1)4 290(1)1 674(1)8 OOl(4)9 451(3)8 095(3)6 650(3)8 507(4)7 564(5)Y3 733(1)6 301(1)6 549(1)5 279( 1)7 143(1)6 882(1)1 722(1)1 467(1)1 420(1)6 108(1)5 848(1)6 369(1)8 068( 1)816(1)2 467( 1)485( 1)208(1)4 956(3)6 510(5)7 616(3)6 069( 5)5 547(4)7 064(4)- 326(1)Z6 295(1)8 794( 1)3 785( 1)3 914(1)1 425(1)1 445(1)5 782(1)5 114(1)3 852(1)4 408(1)7 218(1)6 992(1)8 950( 1)7 915(1)8 762(1)8 760( 1)11 171(1)11 138(1)9 970(3)9 222( 3)7 581(3)8 353(4)8 018(4)9 519(5)X2 053(3)3 543(3)1661(4)306(3)2 232(3)1441(3)3 560(3)4 149(3)2 094(3)1 224(3)3 340(4)4 063(3)2 487(3)4 395(3)3 015(4)1 206(3)477(3)1 862(3)4 131(3)3 641(3)3 944(3)3 349(3)1078(3)2 856(3)Y5 339(3)6 192(4)7 277(3)6 347(3)2 223(3)378(3)3 13(3)2 203(3)5 322(3)7 291(3)7 476(4)5 497(3)2 175(3)1 587(3)73(3)774(3)6 450(3)7 620(3)2 402(4)419(3)5 094(3)7 143(3)838(3)- 98(3)Z4 325(3)2 684(4)1 046(3)2 777(3)5 376(4)4 797(3)3 985(3)4 548(3)7 216(3)7 430(4)8 594(4)8 302(3)8 321(3)9 937(3)11 535(3)9 808(3)4 673(3)3 296(3)6 403(4)6 335(3)6 530(3)6 351(3)7 834(3)9 195(3)~~~~Table 2.Bond distances (pm) and angles (") with estimated standard deviations in parentheses(a) DistancesAg-N(11) 250.8(3)Ag -N(3 1) 259.0(5)As-F(l) 169.8(3)AS -F( 3) 170.0(3)AS -F( 5) 169.3(5)S(ll)-N(ll) 162.2(3)S( 11)-O(11) 142.8(4)S( 12)-N( 1 1) 158.1(4)S( 13)-N(12) 15734)S( 1 4) -N( 1 3) 1 52.9(4)S(21)-N(21) 163.2(4)S(21)-0(21) 141.8(5)S(22)-N(21) 156.6(4)(b) AnglesN(ll)-Ag-N(21) 84.1(1)N(21)-Ag-N(31) 159.1(1)N(21) -Ag-N(4 1) 90.7( 1)F( 1) -AS -F( 2) 92.3(2)F( 2) -AS -F( 3) 88.8(2)F(2) -As-F(4) 179.0(3)F( 3) -AS -F( 5 ) 87.9(2)F( l)-As-F(6) 91.0(2)F( 3) -AS -F( 6) 90.9(2)F( 5 ) -AS -F(6) 177.8(2)N(l1)-S(ll)-O(ll) 106.0(2)N(ll)-S(11)-0(12) 110.7(2)O(l1)-S(l1)-O(l2) 119.2(2)N( 12) -S( 1 3)-N( 1 3) 1 19.0(2)N(21) -S(2 1) -N(24) 10242)N(24) -S(21) -O(21) 106.3(2)N(24)-S(21)-0(22) 111.2(2)N(21) -S( 22) -N(22) 1 19.6(2)N(22)-S(23)-N(23) 119.1(2)N( 3 1) -S( 3 1) -N( 34) 1 03.0(2)F( 1) -AS-F( 5 ) 90.1(2)Ag -N(2 1 )Ag -N(4 1)As-F(2)As-F(4)AS -F(6)S(l l)-N(14)S(l1)-0(12)S( 12) -N( 12)S( 13)-N(13)S( 14) -N( 14)S(2 1) -N(24)S(21) -0(22)S(22) -N(22)259.7(5)25 3.4(3)1 66.9(4)1 68.9(4)166.8( 7)162.1(4)1 42.4( 3)154.6(4)159.9(4)156.0(4)162.1(4)142.8(3)154.7(5)N( 1 1) -Ag-N(3 1)N(l l)-Ag-N(41)N( 3 1)-Ag -N(41)F( 1) -As -F( 3)F( l)-As-F(4)F( 3) -AS -F(4)F(2)-As-F(5)F(4) -As -F(5)F(2)-As-F(6)F(4)-As-F(6)N( 1 1)-S( 1 1)-N( 14)N( 14) -S( 1 1) -0( 1 1)N( 14)-S( 1 1)-O( 12)N( 1 1)-S( 12) -N( 12)N( 1 3)-S( 14) -N( 14)N(21) -S(21) -0(21)N(21) -S(2 1) -0(22)O(21) -S( 21) -O( 22)N(23)-S(24) -N(24)N(3 1)-S(32) -N( 32)N( 3 1)-S(3 1)-O(3 1)90.3(1)153.0(1)85.2(1)177.7(2)87.4(2)91.4(2)90.7(3)88.3(3)91.1(3)89.9(3)104.1(2)104.7(2)110.9(2)1 18.7(2)119.6(2)106.2(3)110.3(2)119.2(2)1 20.1(2)120.0(2)1 05.3( 2)S(24)-N(23)S(23)-N(22)S(32)-N(31)S(3 1)-N(3 1)S( 3 1) -O(3 1 )S( 34) -N( 3 3)S( 33) -N( 32)S(41) -N(41)S(41) -0(41)S(42)-N(41)S(43) -N(42)S(44) -N(43)N(34) -S(3 1) -O(3 1)N(34)-S( 3 1)-O( 32)N(33) -S( 34) -N(34)N(41) -S(41) -N(44)N(44) -S(41) -O(41)N(44) -S(41)-O(42)N(41)-S(42)-N(42)N(43)-S(44)-N(44)Ag-N(11)-S(12)S( 12) -N( 12)-S( 1 3)S( 1 1) -N( 14) -S( 14)Ag -N(2 1) -S(22)S(22) -N(22) -S(23)S(21)-N(24)-S(24)Ag -N( 3 1) -S( 3 1)S( 32) -N( 32) -S( 3 3)S(31)-N(34)-S(34)Ag -N(4 1) -S(42)S(42)-N(42) -S(43)S(41)-N(M) -S(44)154.0(4)158.8(5)156.5(4)163.0(4)142.9(4)154.4(4)157.7(5)162.9(3)142.3(4)156.6(4)159.7(3)154.7(4)106.7(2)110.7(2)120.9(2)102.9(2)106.1(2)110.8(2)1 20.3(2)120.2(2)114.9(2)149.0(3)1 25.7( 2)116.7(2)147.9(3)1 25.1 (2)107.5(2)147.9( 3)125.1(2)1 1 1.9(2)147.0(3)1 25.3( 2)S(24)-N(24)S(23) -N(23)S( 32) -N( 32)S( 3 1) -N(34)S( 3 1) -0( 32)S(34) -N( 34)S( 33)-N( 33)S(41) -N(44)S(4 1) -0(42)S(42) -N(42)S(43)-N(43)S(W-N(WN(3 1 )-S( 3 1) -0( 32)O( 3 1) -S( 3 1) -0( 32)N( 32) -S(33) -N( 33)N(4 1) -S(41)-O(4 1)N(41) -S(41) -O(42)O(4 1) -S(4 1) -O(42)N(42)-S(43)-N(43)Ag-N(l1)-S(l1)S( 1 1)-N( 1 1)-S( 12)S( 13) -N( 1 3) -S( 14)Ag-N(21) -S(21)S(2 1) -N(21)-S(22)S(24)-N(23) -S(23)Ag -N( 3 1) -S( 3 2)S(32) -N( 3 1) -S(3 1)S(34) -N( 33) -S( 33)Ag-N(4 1) -S(4 1)S(41) -N(41) -S(42)S(43) -N(43) -S(44)154.6(5)1 60.0(4)154.9(5)1 61.6(4)143.0(3)155.3(5)159.3(4)161.8(4)142.9( 3)154.0(3)158.7(4)156.0(4)110.2(2)119.6(2)118.7(2)1 05.8( 2)1 10.4(2)119.4(2)118.5(2)118.5(2)123.6(2)145.6(2)110.8(2)124.6(3)1 #.8(3)118.8(2)123.9(2)145.0(3)118.6(2)12432)146.1(2J. CHEM.SOC. DALTON TRANS. 1983 407Figure. The structure of the [Ag(S4N402)4]+ cation showing 50%thermal ellipsoids and the atomic numbering schemegives rise to dimeric cations in which the two monomer unitsare related by a crystallographic centre of symmetry. Theoverall co-ordination of Ag may be described as bis-disphenoidal (triangulated dodecahedral).The four S4N402 ligands adopt similar conformations; ineach case the ring is within 20 pm coplanar, except for theS atom of the SO2 group, which lies 113(1) pm out of theplane of the other seven ring atoms. The maximum spread ofequivalent S-N bond lengths in the four ligands is only 2 pm,with the longest bonds involving the SO2 sulphurs. Thesimilarity of the S-N bond lengths in the planar SINJ unitsindicates significant electron delocalisation ; all the atomswhich co-ordinate to Ag are attached to the Svl atoms,thereby causing the least disruption of this delocalisation.AcknowledgementsWe are grateful to the Deutsche Forschungsgemeinschaft andto the Fonds der Chemischen Industrie for financial support.References1 H.W. Roesky, W. Schaper, 0. Petersen, and T. Muller, Chem.Ber., 1977, 110, 2695.2 H. W. Roesky, M. Witt, J. W. Bats, H. Fuess, F. J. Bulta Culleja,and F. Ania, 2. Anorg. Allg. Chem., 1979,458, 225.3 H. W. Roesky, M. Witt, B. Krebs, and H. J. Korte, Angew.Chem., 1979, 91, 444; Angew. Chem., Int. Ed. Engl., 1979, 18,415.4 H. W. Roesky, M. Witt, B. Krebs, G. Henkel, and H. J. Korte,Chem. Ber., 1981, 114,201.5 H. W. Roesky, M. Witt, J. Schimkowiak, M. Schmidt, M.Noltemeyer, and G. M..Sheldrick, Angew. Chem., Int. Ed. Engl.,1982, 21, 536.6 H. W. Roesky, W. Grosse-Bowing, I. Rayment, and H. M. M.Shearer, J. Chem. SOC., Chem. Commun., 1975, 735.7 H. W. Roesky, 2. Naturforsch., Teil B, 1976, 31, 680.8 H. W. Roesky, M. Thomas, J. Schimkowiak, M. Schmidt, M.Noltemeyer, and G. M . Sheldrick, J. Chem. SOC., Chem. Commun.,1982, 790.9 W. Clegg, Acta Crystallogr., Sect. A, 1981, 37, 22.Received 22 July 1982; Paper 2112550 Copyright 1983 by The Royal Society of Chemistr
ISSN:1477-9226
DOI:10.1039/DT9830000405
出版商:RSC
年代:1983
数据来源: RSC
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