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Crystal and molecular structure of dichlorotetrakis(dimethyl sulphoxide)ruthenium(II) |
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Dalton Transactions,
Volume 1,
Issue 23,
1975,
Page 2480-2483
Anthony Mercer,
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摘要:
J.C.S. Dalton INFRARED and Crystal and Molecular Structure of Dichlorotetrakis(dimethy1 sulphoxide)-ruthenium( 11) By Anthony Mercer and James Trotter* Department of Chemistry University of British Columbia Vancouver, British Columbia Canada V6T 1 W5 Crystals of the title compound are monoclinic. a = 8.939(3) b = 18.045(7) c = 11.363(3) A p = 91.52(2)", Z = 4 space group P2,/n. The structure was determined by Patterson and Fourier syntheses and refined by full-matrix least-squares procedures to a final R of 0.041 for 2 720 independent reflections measured by diffractometer. The co-ordination geometry about the ruthenium atom is essentially octahedral with cis-chlorine atoms. Of the four dimethyl sulphoxide ligands three are S- and one is O-bonded. the O-bonded ligand being trans to a S-bonded ligand.Important mean bond distances are RU-CI 2.435(1) RU-S 2.277(1) (trans to CI) 2.252(1) (transto 0), 2u-0 2.1 42(3) S-0 1.484(5) (S-bonded) and 1.557(4) A (O-bonded). lH n.m.r. spectral data on dichloro-tetrakis (dimet hyl sulphoxidefiut henium (11) indicated the possibility of a mixture of S- and O-bonded dimethyl sulphoxide 1igands.l The X-ray crystallographic study of [(Me,SO),RuCl,] was undertaken to verify this unusual arrangement and provide additional information for an attempted correlation between structure and the catalytic properties of these molecules. EXPERIMENTAL Crystals of [(Me,SO),RuCl,] trom methanol were yellow and approximately cube-shaped. The crystal chosen was mounted with G* parallel to the goniostat axis and had dimensions ca.0.20 x 0.20 x 0.25 mm. Unit-cell and space-group data were obtained from film and diffracto-meter measurements. The unit-cell parameters were refined by a least-squares treatment of sin20 values for 21 reflections measured on a diffractometer with Mo-K, radiation. Crystal Data.-C,H,,Cl,O,RuS, M = 484.54 Mono-clinic a = 8.939(3) b = 18.045(7) G = 11.363(3) A @ = 91.52(2)" U = 1832(1) Hi3 D = 1.74(1) g ~ m - ~ 2 = 4, D = 1.76(1) g ~ m - ~ F(000) = 984. Mo-K radiation, h = 0.710 69 A p = 15.66 cm-l. Absent reflections: hOZ h + I # 2n OkO k # 2n define uniquely space group P2,ln (Cih No. 14). Intensities were measured on a Datex-automated General Electric XRD 6 diffractometer with a scintillation counter Mo-K (zirconium filter and pulse-height analyser), and a 8-20 scan at 2" min-l over a range of (1.80 + 0.86 tan 8)' in 28 with 20 s background counts being measured a t each end of the scan.Data were measured to 20 45" (minimum interplanar spacing 0.93 A). Lorentz and polar-ization corrections were applied and structure amplitudes derived. No absorption correction was applied owing to the low value of p and the fairly uniform shape of the crys-tal. Of 3 231 independent reflections measured 511 had I < 3 4 1 ) above background where ~ ~ ( 1 ) = S + B + (0.05S)2 with S = scan count and B = time-averaged background count. These reflections were classified as unobserved and given zero weight in the refinement. Structure A naZysis.-The structure was determined by Patterson and Fourier syntheses and was refined by full-matrix least-squares methods with minimization of Cw-(F - FJ2.The scattering factors of ref. 3 were used for non-hydrogen atoms and those of ref. 4 for hydrogen 1 I. P. Evans A. Spencer and G. Wilkinson J.C.S. Dalton, 1973 204. 2 R. S. McMillan A. Mercer B. R. James and J. Trotter, J.C.S. Dalton 1975 1006. 3 D. T. Cromer and J . B. Mann A d a Cryst. 1968 A24 321. atoms. Anomalous scattering corrections (ref. 5) were applied for the non-hydrogen atoms. The anisotropic temperature factors employed in the refinement are U ~ J TABLE 1 Final positional parameters (fractional x lo4), with estimated standard deviations in parentheses Atom RU CW) CW) S(1) S(2) S(3) s (4) O(1) 0 (2) O(3) O(4) C(11) C(1.2) C(21) C(22) C(31) C(32) C(41) H(112) * H(113) * H(121) * H(122) H(123) * H(211) H(212) H(213) * H(221) * H(222) H(223) H(311) H(312) * H(313) * H(321) * H(322) H(323) * H(411) H(412) H(413) * H(421) H(422) * H(423) * g?l) X 2 484.2(4) 1 570(1) 2 361(2) 3 332(1) 3 528(1) 1036(6) 3 041(6) - 343 2 765(4) 2 596(9) 5 292(7) 2 660(7) 5 OOl(1) 63(1) 3 980(8) - 604 -1 191 2 524(8) 5 262(8) 3 600 4 819 3 739 2 055 2 488 3 686 6 027 5 577 5 432 1597 2 950 3 081 - 47 -1 516 - 869 - 754 -1 170 -2 150 2 392 1477 2 915 4 397 5 795 5 867 Y 1217.6(2) 701 (1) 1051(1) 2 403(1) 1 591(1) 766(1) 1302(3) 2 SOO(2) 2 378(2) 1377(2) 1413(4) 2 486(4) 2 982(3) 1365(4) 1047(4) 843(5) 1176(4) 1851 1075 1460 - 219 95 - 39 2 329.3 058 2 480 2 888 3 004 3 456 1638 1654 832 959 490 1307 1321 1197 490 1421 829 1287 - 28 96(4) z 2 654.6(3) 2 652(1) 3 040(1) 690(1) 2 507(1) 2 791(1) 5 290(1) - 16 1379(4) 2 677(4) 4 616(3) 349(6) 2 867(8) 3 649(6) 4 216(6) 1 886(6) 6 619(6) 5 778(7) 10 77 - 887 896 - 500 420 2 347 3 184 3 753 3 775 4 429 3 620 4 969 4 370 4 241 1111 2 150 1770 7 080 6 664 7 211 6 023 6 304 5 100 - 36 * Calculated positions. in the expression f = f0exp[-27r2( Ul,h2a*2 + U2,k2b*2 + U,,Z2c*2 + 2U12hka*b* + 2U,,hla*c* + 2U2,kZb*c*)] where R. F. Stewart E.R. Davidson and W. T. Simpson J. CJum. Phys. 1965 42 3176. 6 D. T. Cromer and D. Liberman J . Chem. Phys. 1970 53, 1891 1975 2481 f0 is the tabulated scattering factor and f is that corrected for thermal motion. The weighting scheme dw = 1F01/12.8 if IFo] < 12.8 2/w = 1 if 22.6 > lFol > 12.8 d w = 22.6/lF01 if lFol 22.6 and dw = 0.0 for un-observed reflections gave constant average values of w(F -F,) over ranges of IF I and was employed in the final stages of refinement. The conventional R using all non-hydrogen atoms was 0.047; a difference-Fourier performed a t this stage indicated the positions of elex-en of the twenty-four hydrogen atoms and the remaining thirteen positions were calculated allowing for minimum intramolecular inter-actions (see Table 1).The final R for the 2 720 observed sulphur- and one is oxygen-bonded the O-bonded ligand being trans to one of the S-bonded ligands [S(l)]. Figure 1 shows the atom labelling scheme and a general view of the molecule. Individual bond lengths and angles with standard deviations are given in Tables 3 and 4. Slight distortion does occur the angles subtended at the central ruthenium atom between the three mutually cis S-bonded ligands being larger than 90" [92.6-94.9", mean 94(1)'] while the values for the C1-Ru-Cl and the two C1-Ru-0 angles are slightly less than 90" [87.8-TABLE 2 Final anisotropic thermal parameters ( bTij x lo2 Hi2) with estimated standard deviations in parentheses * u,, 2.08 (2) 2.3 3 (6) 3.72 (6) 3.82(7) 4.00(7) 2.39 (6) 4.00( 7) 5.62 (2 9) 10.47(39) 4.18( 21) 4.09(20) 6.89(42) 3.82(34) 6.14(38) 4.18 (33) 2.44(26) 7.67(46) 9.7 3 (54) 4.35(34) u22 2.5 9 (2) 4.38(7) 2.96(6) 5.23(7) 2.75(6) 3.84 (7) 3.51(6) 12.78(51 4.19(24 4.08(22 3.95(19 5.78(36 6.32(43 5.88(41 3.79(31 7.34(43 7.20( 4C 8.00( 48 6.22(41 u33 3.2 1 (2) 5.74(8) 5.42 (7) 3.34(6) 4.92( 7) 3.76(6) 4.7 3 ( 24) 6.45( 28) 9.27(32) 3.39( 16) 4.93( 32) 1 3.62 (70) 7.86( 41) 6.08 (36) 7.3 l(40) 4.62 (33) 7.42( 42) 5.49(7) 5.34 (3 5) u12 O.OO( 1) 0.62 (5) 0.03(6) 0.3 9 (5) 0.1 9 ( 5) 1.51(26) 0.83(25) 1.78( 18) 0.52(15) 0.76(31) - 0.58 (5) - 0.28 (5) - 1.56(39) - 2.27(31) - 1.15(26) -0.20(26) 0.69( 29) 2.60 ( 38) 0.14( 27) u13 0.09(1) 0.20(5) - 0.0 1 (5) - 0.03 (5) 1.06(5) 0.28(5) - 0.62 (5) - 1.56(21) 2.49 (26) 0.15(20) 2.52 (29) 1.23 (34) 1.04( 38) 1.54(31) 1.93( 27) 0.90( 31) -0.27(14) - 0.81 (24) -2.56(30) u23 0.10( 1) 0.09(5) 0.39(5) 0.16(5) 0.20[5) 0.19(5) 1.86 (26) 1.74( 21) 0.75(21) 1.01 (28) - 0.22(5) -0.11( 14) -2.07(32) - 2.00(43) - 1.85(28) -0.78(32) - 0.10 (30) 0.14(31) 1.65 (32) * All H atoms had isotropic thermal parameters U 6.3 x A2.reflections was 0.041. Final positional and thermal para-meters are given in Tables 1 and 2. Measured and cal-culated structure factors are listed in Supplementary Publication No. SUP 21445 (31 pp. 1 microfiche).* DISCUSSION The co-ordination geometry about the ruthenium atom is essentially octahedral with cis-chlorine atoms.Of the four dimethyl sulphoxide (dmso) ligands three are 88.7" mean SS.2(5)0]. Equations of selected least-squares mean planes with deviations of the atoms from these planes are given in Table 5. This distortion TABLE 3 Bond lengths (A) with standard deviations in parentheses Ru-C1( 1) Ru-C1 (2) Ru-S (1) RU-S (2) RU-S ( 3) RU-0 (4) S(1)-0(1) s (21-0 (2) S(3)-0(3) 2.435( 1) 2.435(1) 2.252( 1) 2.277 ( 1) 2.276( 1) 2.142 (3) 1.483 (5) 1.485 (5) 1.485 (5) S( 1)-C( 11) s ( 1 )-C( 12) s (2)-c (2 1) s (2)-C( 2 2) 0(4)-S(4) S ( 3)-C( 3 1) S( 3)-C( 32) S (4)-C( 41) S (4) -C (4 2) 1.808(6) 1.7 79 (8) 1.7 95 ( 7) 1.783 (6) 1.787(6) 1.7 94 (6) 1.557 (4) 1.783 (6) 1.793 (6) appears to be governed primarily by steric factors associated with the S-bonded dmso groups.The Ru-C1 bond lengths [2.435(1) A] are significantly greater than would be expected for a purely G donor ligand. Typical values of mean Ru-C1 bond lengths in octahedral complexes with trans chlorine atoms are 2.390(7) in [RuCl,(N,C,H,Me) (PPh,),]-Me,O (ref. 6) and 2.398(7) A in [RuCl,(NO) (PMePh,),].7 This lengthening * For details of Supplementary Publications see Notice to 6 J. V. McArdle A. J. Schultz B. J. Corden and R. Eisenberg, 7 A. J. Schultz R. L. Henry J. Reed and R. Eisenberg, Authors No. 7 in J.C.S. Dalton 1974 Index issue. Inorg. Chem. 1973 12 1676. Inorg. Chem. 1974 13 732. (11) FIGURE 1 General view of the structure showing the crystallographic numbering schem 2482 J.C.S.Dalton Bond angles C1( l)-Ru-Cl( 2) C1( l)-Ru-S( 1) C1( l)-Ru-S (2) C1( l)-Ru-S( 3) C1( l)-Ru-0(4) C1( 2)-Ru-S( 1) C1( 2)-Ru-S (2) C1(2)-Ru-S ( 3) C1( 2)-Ru-0(4) S ( l)-Ru-S (2) S ( l)-Ru-S (3) S (l)-Ru-0 (4) S (2)-Ru-S (3) S(2)-Ru-0(4) S (3)-Ru-0 (4) Ru-S ( 1)-C ( 1 1) Ru-S ( 1)-C( 12) Ru-S (2)-C( 2 1) Ku-S(2)-C(22) TABLE to) with standard 87.78( 5 ) 88.22 (5) 92.90 (6) 173.49(6) 88.2(1) 92.69 ( 5 ) 173.85 ( 5 ) 86.38 (5) S8.7(1) 93.44 (6) 94.91 (5) 176.1 (1) 92.61 ( 5 ) 85.2(1) 88.8(1) 11 2.6( 2) 112.7( 2) 1 10. O( 2) 112.2(2) 4 deviations in parentheses RU-S (3)-C( 3 1) 109.6 (2) RU-S (3)-C( 32) 11 2.3 (2) Ru-S(1)-O(1) 120.9(2) Ru-S( 2)-0 (2) 11 7.7(2) Ru-S (3)-0(3) 120.1 (2) C( 11)-S( l)-C( 12) 98.6(3) C(31)-S(3)-C(32) 100.1(3) C( 1 1)-S (1)-0 (1) 106.3( 3) C(12)-S(l)-O(l) 106.0(4) C( 2 1)-S (2)-0 (2) 107.7 (4) C( 22)-S (2)-0 (2) 106.9 (3) C( 3 1 )-S (3)-0 (3) 1 06.3 ( 3) C (3 2)-S (3)-0 (3) 106.4 (3) RU-0 (4)-S (4) 120.0(2) 0 (4)-S (4)-C (4 1) 10 1.6 (3) O(4)-S (4)-C(42) 104.2 (3) C (4 1 )-S (4)-C( 42) 99.0 (4) c (2 1)-s (2)< (22) 9 7.5 (3) TABLE 5 Equations of selected weighted least-squares mean planes, with (in square brackets) deviations (A) of the atoms from the planes Plane (1) Ru C1(2) S(l) S(2) and O(4) O.999X + 0.049Y - 0.0132 = 2.249 [Ru -0.042(1) Cl(2) -0.100(1) S(l) -0.079(1) S(2) 0.826(1) O(4) 0.139(4)] Plane (2) Ru C1(1) S(1) S(3) and O(4) 0.335X + 0.933Y - 0.1292 = 2.366 [Ru 0.013(1) Cl(1) -0.102(1) S(l) 0.003(1) S(3) -0.104(1), O(4) 0.076(4)] Plane (3) Ru C1(1) C1(2) S(2) and S(3) -0.043X + 0.024Y - 0.9992 = -3.0537 [Ru 0.0009(3) Cl(1) -0.166(1) Cl(2) -0.027(1) S(2) 0.186(1).S(3) -0.042(1)] is an indication oE the strong trans-effect of S-bonded dmso.8 acceptor as a shortening of the bond between a metal atom and a Q donor ligand should be observed if the 0 donor is trans to a strong x acceptor. For example in [Ru(NO)C1,I2- the mean Ru-Cl(eq) distance is 2.376(2) A, while Ru-C1 for chlorine trans to nitrosyl is significantly shorter at 2.357(1) A.g TABLE 6 Mean bond lengths (A) and angles (") for (I) [RuCI,-(Me,SO),]- (11) [RuC12(Me$O)J (111) [Ru(NH3)5-(Me,S0)I2+ and (IV) free dimethyl sulphoxide (u) Lengths (1) (11) (IW (Iv) RU-S 2.261(8) 2.277(1) 2.188(3) Ru-Cl 2.43(1) 2.435(1) s-0 1.48(2) 1.485(6) 1.527(7) 1.471-1.531 S-C 1.79(3) 1.790(6) 1.840(8) 1.80-1.82(1) (b) Angles RU-S-0 118(1) 119(1) 114.9(3) Ru-S-C 112(2) 112(1) 116(1) 0-S-C 106(2) 106.8(6) 104.2(8) 09.4( 6) 107 98 99(1) c-s-c lOO(2) However evidence supporting some x acceptor nature can be obtained from the Ru-S distances in the S-bonded dmso ligands which are trans to the two chlorine atoms.The mean value [2.277(1) A] indicates the presence of some d,-P, back donation from the central metal to the sulphur atom assuming single-bond covalent radii for ruthenium and sulphur are 1.33 and 1.04 A.lo However, this back donation is considerably less than that found l1 in [Ru(NH,),(Me,SO)12+ where the Ru-S distance is 2.188(3) A.The increased back donation found in the monosulphoxide is due to the lack of competition for the available x donor orbitals from other x acceptor ligands in the co-ordination sphere. A comparison of similar bond lengths and angles for [RuC~,(M~,SO),]-,~ FIGURE 2 Stereodiagram of the unit cell viewed down b In the interaction between the Ru and S atoms the sulphur atom appears to be behaving as a weak x 8 Y. N. Kukushkin M. A. Kuz'mina and A. F. U'yugina, Radiokhimiyu 1968 10 (4) 470. 9 J. T. Veal and D. J. Hodgson Inovg. Chem. 1972 11 1420. l o L. Pauling ' The Nature of the Chemical Bond,' 3rd edn., Cornell University Press Ithaca New York 1960 pp. 224 249. [RU(NH,),(M~,SO)]~+,~~ and free dmso12 with those of [RuC~,(M~,SO)~] can be found in Table 6.Examples of the change in co-ordinating atom with the l1 F. C. March and G. Ferguson Canad. J. Chem. 1971 49, l2 W. L. Reynolds Progr. Inovg. Chenz. 1970 12 1. 3590 1975 2483 variation of the number of dmso ligands attached are somewhat limited. In four-co-ordinate palladium com-plexes steric influences appear to be of most imp0rtan~e.l~ [Pd(Me,SO),Cld has exclusively sulphur bonding [Pd-( Me2S0),J2+ has both sulphur- and oxygen-bonded ligands in a cis-configuration. As the size of the ligand increases mixed trans-structures are produced i.e. in the propyl and butyl cationic species while only oxygen-bonded ligands occur in the 2-methylbutyl sulphoxide complex [Pd(L2SO)J2+.This change in co-ordination is paralleled in these octahedral systems. [RuCl,(Me,-S0)J- has an all S-bonded cis-structure while the inclusion of another dmso ligand approaches the [Pd-(Me2SO)J2+ situation such that steric influences pro-hibit the formation of an all sulphur-bonded complex, but electronic effects keep the S-bonded ligands in a cis-configuration. The decrease in central-metal size from ruthenium to iron increases the steric interactions considerably i.e. [FeCl,( Me,SO)J + has a trans-con-figuration in which all the dmso ligands are oxygen-bonded.14 The Ru-S bond length for the S-bonded dimethyl sulphoxide ligand trans to the O-bonded sulphoxide is 3.252(1) hi. This slight yet significant shortening [vs. 2.277(1) A] is due to the different atoms in the trans-positions.Ru-O is 2.142(3) A similar to the value l3 J. H. Price R. F. Schramm and B. B. Wayland Chern. Comm. 1970 1377. [2.007(6) hi] found 14 for Fe-0 considering the difference in covalent radii of the two metals to be ca. 0.12 There is considerable variation in the sulphur-oxygen distances for the two types of differently co-ordinated dmso ligands. In the S-bonded ligands the mean is 1.484(5) A while in the O-bonded ligand the distance is 1.557(4) hi. This represents a considerable decrease in the multiple-bond character of the sulphur-oxygen linkage caused by the differences in co-ordination though this is still somewhat short of the estimated S-0 single-bond length (1.70 8) .14 The molecular geometry of the S-bonded dmso ligands is very similar to that in free dimethyl sulph-oxide.12 The 0-S-C angles [mean 106.6(6)'J C-S-C angles [mean 99(1)'] and the S-C bond lengths [mean 1.79(1) A] compare with 107O 98" and 1.80-1.82(1) respectively. The corresponding mean values for the O-bonded ligand are also similar [103( l)' 99.0(4)" and 1.788(5) A]. The other angles in the distorted tetra-hedron have means of 112(2)' for Ru-S-C 120(2)" for Ru-S-0 and 120.0(2)O for Ru-O-S. We thank the National Research Council of Canada fof financial support the University of British Columbia Computing Centre for assistance and Roderick S. McMillan for the crystals. [5/123 Received 20th January 19751 l4 M. J. Bennett F. A. Cotton and D. L. Weaver Natuve, 1966. 212. 287
ISSN:1477-9226
DOI:10.1039/DT9750002480
出版商:RSC
年代:1975
数据来源: RSC
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