摘要:

J. Chem. SOC. (A), 1970 Carbon Compounds of the Transition Metals. Part XX.l Crystal and Molecular Structure of p-Cycloundeca-allyl-heptacarbonyldi-iron By P. F. Lindley and 0. S. Mills,' Department of Chemistry, University of Manchester, Manchester M13 9PL The reaction of allenes with enneacarbonyldi-iron results in the formation of binuclear complexes. Details of the crystal and molecular structure of the product of the reaction between a cyclicX.,,-allene and enneacarbonyldi-iron are presented. The complex crystallises in the triclinic system with a unit cell of dimensions, a = 10.39, b = 8-33. c = 14.62 A, Q! = 102" lo', p = 11 0" 25'. and y = 11 4" 58'. It contains an allylic group of carbon atoms with C-C bond lengths of 1-41 and 1.42 A and an internal angle of 11 4.6".One iron atom, which is bonded to three carbonyl groups, is 7-bonded to this group at a distance of 1 -96 A from the central allylic carbon atom and 2-20 and 2.1 7 A from the other two allylic carbon atoms. The second iron atom, which is bonded to the remaining four carbonyl groups, is o-bonded to the central allylic carbon atom at a distance of 2.02 8. The two iron atoms are linked by a metal-metal bond of length 2.65 A. THE reaction of allenes with an excess of enneacarbonyl- di-iron results in the formation of binuclear complexes ,2 the lower members of which are liquid at room tem- perature. We undertook the analysis of the higher melting Cll-allene complex, since this would yield information about the conformation of an eleven- membered ring in addition to the overall structure of an apparently novel organo-octacarbonyldi-iron complex. EXPERIMENTAL 10.39 f 0.02, b = 8.33 f 0.02, c = 14.62 f 0.03 A, a = 102" 10' -J= 15', y = 114' 58' f 15', U = 974AS, D, = 1-56,Z = 2, F(000) = 468.~ ( M o - K , ) = Crystal Data.--ClaHlaFe207, M = 458.1, Triclinic, a = p = llOo 25' f 15', 15.6 cmyl. Space group P1 (Ci, No. 1) or PI (Ci, No. 2). The crystals were reddish-brown and irregularly shaped. Lattice dimensions and intensity data were obtained by the precession method with Zr-filtered Mo-K, radiation and Adox ' Doneo ' X-ray film. A crystal fragment GU. 0-1 mm. cube was used for the intensity measurements. The levels 0-2kl, hk 0-2, and hkl, 12 - l = 0,l and 2h + I = 0,l were estimated visually and used without absorption correction. Approximately 2600 reflexions were measured, corrected for Lorentz and polarisation effects, and scaled by the method of Hamilton, Rollett, and Sparks.* 2172 in- dependent reflexions were obtained, 492 of which were recorded as having zero intensity; only the 1680 reflexions with non-zero intensities were used in the structure analysis.Structure Solution and Refinement.-The structure was solved by the heavy-atom method. A set of iron atom co- ordinates, consistent with the space group PI, was obtained from a three-dimensional Patterson synthesis. Repeated application of the Fourier and difference Fourier techniques finally showed the stoicheiometry to be ClaH,,Fe,O7, indicating a bi-nuclear complex containing only seven carbonyl groups. This approximate structure, arbitrarily assigned isotropic temperature factors of 3, 4, and 5 pi2 to the iron, carbon and oxygen atoms respectively, gave an R value of 18%.The intensity data were then scaled, level by level, directly against this model and the unique set of reflexions thereby deduced was used in the least-squares refinement. With unit weights and isotropic temperature factors R was reduced to 10.5% in two cycles of full-matrix refinement. Part XIX, P. F. Lindley and 0. S. Mills, J. Chem. SOC. ( A ) , 1969, 1286. 3 R. Ben-Shoshan and R. Pettit, Chem. Comm., 1968, 247. 3 W. C. Hamilton, J. S. Rollett, and R. A. Sparks, Acta Cryst., 1965, 18, 129. The positions of the hydrogen atoms in the molecule were calculated assuming a C-H bond length of 1-09A and subsequently these atoms were incorporated in the model although their positional and thermal parameters were not refined.Two further cycles of full-matrix refinement with variable weights assigned to the observed structure factors according to the function, 10 = (3.0 + 0.0O5Fo2), gave R 8.0%. A difference Fourier synthesis showed no evidence of misplaced atoms and gave indications of anisotropic thermal motion of the metal atoms. The data for the levels were rescaled to the current model and a further cycle of full-matrix refinement, in which the metal atoms were permitted to vibrate anisotropically, yielded a final R of 7.8%. The positional shifts after the final cycle were all less than the corresponding standard deviations and an analysis of the weighting scheme both in terms of batches of increasing sin2 0/A2 and of IFo[ showed a constancy in the values of Cw.A2/ur (Table 1).Throughout the structure TABLE 1 Analysis of weighting scheme Xw. Aa/n 2w.A2 12 sin2 9lha 0.52 45.94 88 0*00-0*04 0.58 98.72 171 0-04--0*08 0.78 138.42 178 0.08-0.12 0.61 122.98 200 0.12-0.16 0.76 141.48 187 0*16-0.20 0.78 136.27 175 0.20-4.24 0.69 124.61 181 0.24-0-28 0.54 84-17 157 0.28-0.32 0.57 89-69 158 0.32-0.36 0.43 49.42 116 0.36-0.40 0.35 23.87 69 0.40-0.44 Zw.A2/n Zw.A2 n IF01 0.48 35.80 75 24--4.0 0.50 180.48 360 4.0-8.0 0.6 1 344.90 569 8.0-1 6.0 0.79 335.43 422 16*0-32*0 0-62 135.00 216 32.0-64-0 0.60 22.62 38 64.0-128.0 factor calculations the atomic scattering factors listed by Hanson et were used; the scattering factors for the iron atoms were corrected for anomalous dispersion according to the equation f = [(f + Af' + iAf")(f + Af' - iAf'')]4.6 A final difference Fourier synthesis revealed no electron density maxima greater than 0.6ek-3.A set of structure factors was computed for the 492 reflexions whose inten- 4 H. P. Hanson, F. Herman, J. D. Lea, and S. Skillman, Acta Cryst., 1964, 17, 1040. 6 C. H. Dauben and D. H. Templeton, Acta Cryst., 1955, 8, 841.Inorg. Phys. Theor. sities were too weak to be measured; in no case was lFol greater than 1.51F0 (min.) I where IF,, (min.) I represents the local minimum for the non-zero reflexions. All calculations were carried out on the University of Manchester Atlas computer with programmes developed in this laboratory. RESULTS The final atomic co-ordinates and thermal parameters are given in Table 2.The measured and calculated structure factors are listed in Table 3. Details of the TABLE 2 Atomic parameters xla 0*2232(2) 0.0771 (2) 0-0015( 14) -0*1432(17) -0*0516( 12) -0.1963(19) -0.3811(23) - 0.4378(15) - 0.3769( 17) -0.3958(15) - 0.2892( 13) -0.1038(12) -0*0102(12) 0.3097 (14) 0-3857( 12) 0.2 100( 17) 0.1998 15) 0.1647116) 0.1424( 13) 0.4282(15) 0*5590( 14) -0*0632(14) -0.1530(11) 0.1 920(14) 0-2526( 12) 0- 1897 (1 3) 0.2641 (1 1) - 0.1304 0.0467 0-1057 - 0.2470 - 0.1 146 -0.1610 -0.1257 - 0.4525 - 0.41 13 - 0.4036 - 0.5709 - 0.4393 - 0.2490 - 0.5232 - 0.3737 -0.3179 -0.3186 -0.0415 Y /b 0.1 206 (2) 0.0363 12) 0.2441 [14) 0*2670(16) 0*2589(19) 0.1 137( 24) -0*1157(2) -0*1043( 15) - 0.1823( 17) -0*3764(15) - 0.368 1 (1 2) -0*2314(12) - 0*0265(11) 0.2868( 14) 0*4077( 12) 0*2832( 18) 0*3947(16) -0.0676(16) - 0.1 7 30 ( 1 3) 0-1839(15) 0*2208(14) - 0.3 159 (1 4) - 0.4545(11) 0.0 197 ( 14) 0.1043( 12) - 0.2 17 1 ( 13) - 0.2850(11) - 0.0766 0.2793 0.3495 0.1554 0.4041 0.4049 0.2237 0.1437 0.1418 -0.1292 -0.1935 -0.1981 - 0.0734 - 0.4833 - 0.4365 - 0.3209 - 0.5146 - 0.2982 ZIC 0*3859(1) 0-1806( 1) 0-1828( 7) 0*1966(9) 0.1772 (10) 0-2623( 12) 0.2 1 8 0 ( 1 5) 0*1701(10) 0*2480( 10) 0.1953 (10) 0.1462(8) 0.2306 (7) 0-2646( 7) 0-33 13( 8) 0-3136(7) 0*4770(11) 0-5301 (10) 0*4364( 10) 0*4732(8) 0-4601(9) 0-5040(9) 0.0538(9) - 0.0265(7) 0-1260( 8) 0-0863( 12) 0-2332 8) 0*2630[7) 0~1006 0.1420 0.2764 0.0986 0.1700 0-3103 0-3199 0-1574 0.2815 0.1085 0.1259 0.2951 0.3077 0.1340 0-2543 0-0818 0.1056 0.2661 B (A2) * 3.2(2) 3-9(2) 5-0(2) 7.8(4) 4-6(2) 5.1(3) 4.4(2) 3*3(2) 2-9(2) 2-8(1) 3-8(2) 5.5(2) 5.0(3) 4*6(2) 6.6 2) 4-3[2) 7*0(2) 4*0(2) 5.4(2) 5.812) 3.2(2) 6.3(2) 5-0 5.0 5-0 5-0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5-0 5.0 5.0 5.0 5-7 (3) 7.7(3) 3.9 2) * An anisotropic temperature factor of the form exp[-(bllh2 + b,,k2 + b3,1a + 2b12hk + 2bl,hZ + 2b2,kZ)] Fe(1) 0.0088(2) 0.0163(3) 0.0040(1) Fe(2) 0.0088(2) 0-0137(3) 0.0040(1) Fe(1) 0.0043(2) 0.0019(1) 0-0020(1) Fe(2) 0.0057(2) 0.0023(1) 0-0023(1) Atom bl, b22 b33 Atom bl, h 3 bas molecular geometry are given in Table 4.Standard deviations, where given, are enclosed in parentheses and are in units of the last place of decimals. R. E. Davies, Chem. Comm., 1968, 248. 7 See, e.g., M.R. Churchill, Inorg. Chem., 1966, 5, 1608. DISCUSSION The molecule of C,,H1,Fe,O, comprises an eleven- membered carbon ring and an heptacarbonyldi-iron fragment. Figure 1 shows the overall configuration of the molecule and indicates the labelling of the atoms. Carbon atoms C(1), C(10), and C(11), presumably co- linear in the uncomplexed allene, are now present in the allylic form with a contained bond angle of 114.6" and mean C-C bond length of 1.42 A. The iron atoms Fe(1) and Fe(2), linked by a metal-metal bond of length 2.65 A, lie on the same side of the plane defined by the allylic carbon atoms and are 0.94 and 1.83 A from it boc1ar FIGURE 1 View of the molecule showing the atom labelling respectively. Fe(l), which is bonded to four carbonyl groups, is 2.02 A from the central allylic carbon atom, C(11) , whereas Fe(2), which carries the remaining three carbonyl groups, is simultaneously 1-96 A from C(l1) and 2.20 and 2*17A from C(l) and C(10) respectively.The arrangement of this portion of the molecule is thus identical, within experimental error, with that found in the complex p-allyl-hexacarbonyl( tripheny1phosphine)di- iron6 It is possible to describe the bonding situation between the allylic groups and the iron atoms in these complexes as involving a o-bond between Fe(1) and the central allylic carbon atom and x-bonds between Fe(2) and the three allylic carbon atoms. The iron atom Fe(2), is significantly closer (approximately 15 o) , to the central allylic carbon atom than to the remainder. It has been noted previously that for several x-ally1 complexes of palladium the metal atom is also slightly closer to the central atom of the allylic group, although the differ- ences in the metal-ally1 bond-lengths are often, at the most, only marginally significant.Determinations of the structure of x-ally1 palladium chloride, at room temperature8 and at -140"~,~ have shown that the differences observed in the metal-ally1 bond-lengths at room temperature are not significant. Variations in the 8 L. F. Dahl and W. E. Oberhansli, J. OrganometaZZic Chem., 0 A. E. Smith, Acta Cryst., 1965, 18, 331. 1965, 3, 43.40 J. Chem. SOC. (A), 1970 TABLE 3 Observed and calculated structure factors 0 0 3 0 0 4 0 0 7 0 0' sg : : 5 6 0 0 10 0 0 11 o o 13 o i -16 0 1 -q 0 1 -12 0 1 -11 0 1 -10 0 1 -y 0 1 -7 0 1 -5 0 1 -4 0 1 -3 0 1 3 0 1 4 0 1 .5 o 1 6. 0 1 7 0 1 9 0 1 10 0 1 1 2 o i 14 o 2 -17 o 2 -16 o 2 -14 o 2 -13 0" 0" 2 0 1 2 0 2 -12 0 2 -11 0 2 -10 : f 3 0 2 -7 o 2 -6 0 2 -5 0 2 -4 0 2 -3 0 2 - 2 0 2 -1 0 2 0 0 2 1 0 2 2 0 . 2 3 0 2 4 . 0 2 5 0 2 6 : 2 " 5 0 2 9 0 2 10 0 2 11 0 2 1 2 o 2 13 0 2 .o 3 -17 o 3 -16 0 3 -15 0 3 -14 0 3 -13 0 3 -12 0 3 -11 0. 3 -10 0 3 -7 0 3 -6 0 3 -5 0 3 -4 0 3 -3 0 3 0 0 3 1 0 3 2 0 3 3 0 3 4 0 3 5 0 3 6 0 ' 3 0 3 10 0 3 11 0 3 12 o 4 -16 0 4 -14 0 4 :13 0 . 4 -12 0 4 -11 0 .4 -10 0 4 -9 9 4 -8 o 4 -6 0 4 -5 0 3 -3 8 : 3 8 :: 0 3 i IF01 Fc 9.9. -96.6 19.5 19.9 40.2 41.2 26.5 2 .8 12.9 12.4 18.2 18.5 3.5 3.7 25.9 -22.6 10.4 -11. 42-9 40.4 17.7 15.4 36.3 -33.6 17.6 18.1 9.7 -8.7 30.3 29.3 89.8 -8g.S 69.5 -66.5 63.8 63.3 18.8 -14.7 12.8 11.7 28 -24.1 12:g 11.3 11.3 9.3 17.0 -1 .8 9.6 -2.9 21.2 16.7 5 7 8 3.8 2.6 17.0 17.6 46.5 -42.5 19.2 -14.8 22 1;:: 11.0 -8.8 39.5 .-39*1 32.9 -31.2 9.3 -7.9 22:o -1tg 29.3 -27.9 28.27.5 11.9 -13.4 28.9 25.9 23.9 24.4' 2% -g:: 18:8 * -18.3 25.3 24.0 40.4 -41.1 42.5 41.3 57.6 51.7 39.0 -35.4 48.6 -47. 9.2 -10.0 67.2 59.6 6 -6.3 1213 -15.0 8.5 5.5 10.5 -10.2 18.5 15.2 5.2 6.3 5.3 -4*9 7.0 -7.0 4.4 -5.7 5.1 3.5 4.8 6.8 27.5 2 6 19.4 -1319 24.5 -24.0 7.8 7.4 5.2 1.0 33.6 30.8 10.2 -7.1 14.0 -15.9 65.7 66.0 34.7 31.3 59.7 -53.7 13.2 13.1 34.5 -37.2 21.4 21.5 34.5 31.2 30.6 -27.9 40.9 -38.0 6.1 -3.1 17.6 -4.9 16.9 -14.1 20.0 16.6 4.9 3-8 4:; -44.7 1 .2 10.3 -9.0 ;::; -it:: 2:: 3:: 8.3 -9.5 8.0 -5.9 22.3 -20.3 43.8 38.8 3.6 -2.8 17.1 -18.2 45.4 -46.3 14.6 -13.1 0 4 -4 41.7 42.1 0 4 -3 12.3 11.8 0.e 4 -2 3.3 -2.5 6*7 O -: :: : 1 !2:; -3:; 0 4 6 10:3 -10.9 0" 1 E ;;:2 :::: 0 4 2 5.2 4-7 0 4 3 13.4 11.0 0 4 4 39.3 36.0 0 4 5 25 4 .4 0 4 9 19.1 16.1 o 4 10 10.4 -11.1 o 4 ii 10.4 -9.4 o 4 12 5.9 5.2 0 5 -17 4.4 0 5 -14 3.5 5.0 0 5 -13 7.8 7.9 o 5 -12 7.7 8.6 o 5 -11 23.8 -21.6 0 5 -10 17.5 -15.1; 0 5 -9 22.2 22.1 0 5 -8 11.9 14.5 o 5 -7 46.8 47.3 o 5 -6 4 3 - 1 0 5 -4 19.2 20.0 0 5 -3 8.2 -9.0 o 5 -2 39.8 40.9 0 5 -1 4.8 .5 0 5 0 27.6 -23.9 0 5 1 12.4 -11.7: 0 5 2 25.3 -20.5 0 5 3 9.1 8.4 0 5 4 26.3 25.5 0 5 5 14.4 -13.7 o 5 6 4.9 -3.6 0 5 10 -4.7 o 6 -17 3 3.2 o 6 -16 1214 -12.0 o 6 -4 6.4 -4.1 o 6 -13 o 6 -12 12:; 1::: o 6 -if 16.1 -16.5 o 6 -10 16 -16.2 o 6 14:3 -15.1 o 6 -6 16.8 -4.3 o 6 -5 22.9 -21.: 9.2 -9.2 : 5 1: .u.i -1o.G o 6 -2 41 39.0 o 6 o 1418 -14.7 o 6 1 3.8 2.8 o 6 z 16.4 -15.7 o 6 3 18.4 15.1 o 6 4 9.1 8.6 o 6 7 14.8 -4.c o 7 -16 4.8 -5.6 o 7 -14 13.0 -10.9 0 7 -12 13.5 11.7 0 7 -10 3.5 3.7 0 7 -9 19.9 -17.9 0 7 -7 24.5 26.2 0 7 -5 3.4 -3.9 0 7 -4 2 2 -24.5 14.3 19.1 8 2 l1:Z 10.5 0 7 1 0 7 3 0 7 5 6.2 7.2 4.9 4.5 0 8 -11 5.9 5.0 o 8 -g 19.2 -18 o 8 -7 7.5 6:;f o 8 -5 11.7 10.2 17.8 -19.1 o 8 -2 4.0 73.1 o 8 p 16.6 16.3 o 8 i 5.6 -5.4 o 8 2 13.6 -12.5 0 9 -14 7.3 -5.b o g -11 8.5 6.4 0 g -9 10.1 -7.9 0 g -7 9.1 -8.3 o 9 -6 3.4 6.0 0 9 -5 12.3 12.1 o 9 -4 6.0 -5.8 o 9 -2 5.0 -0.3 0 5 -16 15.2 -213 0 5 -5 45:3 -4219 0 5 7 '4:7 -;;:; 0 5 9 1g.O" o 6 3 14.7 13.8 0 6 -7 35.7 35.0 0 7 2 1::3 -3:; 0 7 4 ::36 49:: ; 12 9.2 -7.4 0 8 -10 13.3 11.0 o 8 -6 8.1 7.5 o 8 -1 7.5 6.8 0 5) 0 9.4 10.0 0 10 -7 7.3 -3.7 1-10 6 6.9 -7.8 1 -10 10 7.1 1 -5, -I 6.6 7.0 1 4) o 10.3 10.6 i -9 i 4.6 5.3 1 -9 2 3.9 -5.3 1 -9 3 4.0 -3.8 1 -9 7 4.1 4.5 1 -9 8 5.5 -5.5 1 -9 9 4.0 -3.7 1 -9 10 9.7 9.9 1 -8 o 10.7 10.1 i -8 3 18.1 -19.6 1 -! 4 4.6 -4.6 1 -6 5 10.8 10.7 1 -8 6 4.6 4.0 1 -8 7 7.3 7.7 1 -8 8 13.9 -13.4 1 -8 10 10.7 10.2 1 -8 12 7.2 7.0 1-10 7 2:g -3.1 :: ; 2 't:," t;f:g 1' -8 -2 15.1 -15.7 1 -7 -7 3.8 -4.9 1 -7 -4 10.7 11.1 i -7 -2 16.6 -16.7 1 -7 -1 14.1 14.2 1 -7 o 4.1 2.1 1 -7 1 11.0 11.4 1 -7 .2 7.4 8.3 i -7 3 26.5 -27.0 i -7 7 16.1 16.3 i -7 12 16.3 15.5 1 -7 13 9.2 1 -7 16 G.6 2:;" ~2 3 10.9 11.3 8.7 -9.0 1 -6 -7 -5.3 i -6 -4 it:; i -6 -3 8.0 %: i -6 -2 21.9 -22.3 1 -13 o 14.5 -14.1 i -6 1 31.1 9 . 5 1 -6 2 6.7 6.2 i 4 3 14.1 -1G.5 1 -0 6 24.2 26.4 1 -6 7 29.3 30.0 1 -6 g 16.2 -17.3 1 -6 10 20.4 -19.6 1 -6 12 17.7 15.9 i -6 13 4.6 -4.4 1 -6 15 7.9 -7.2 1 -6 '1'6 5 4 1 -6 17 9:o -4:; 1 -5 -11 9.4 -9.7 7.7 9.1 1 -5 -10 1 -5 -9 15.0 18.2 i -5 -7 6.9 -6.0 1 -5 -6 14.4 -17.0 1 -5 -3 6.6 -5.6 1 -5 -1 20.1 -21.1 1 -5 0 35.1 -36.7 1 -5 1 42.9 45.0 1 -5 2 12.0 11.7 1 -5 3 23.3 25-7 1 -5 1 -7 -6 6.8 7.4 1 -7 6 15.5 15.8 1 -7 8 4 .2 -13.5 1 -7 9 15.4 '-15.7 1 -6 5 33.8 -37.4 :: 1; 1; 2&; 2:; :: 1; < 2:; ;::: 1 -5 9 15.0 17.9 i -5 10 36.7 -37.3 1 -5 12 8.6 9.1 1 -5 13 8.8 9.0 i -5 14 3.2 b.2 1 -5 15 10.8 -11. 1 -5 10 5.5 -5.8 1 -4 -ii 15.9 -18.9 i -4 -10 9.5 10.7 1 -4 -2 1 -4 -7 7.9 5.5 1 -4 -6 26.0 -28-6 1 -4 -4 13.6 iG.0 1 -4 -3 6.4 -7.3 i -4 -2 21.7 23.7 I -4 -1 17.2 -16. 1 -4 1 25.9 26.0 1 -5 17 4.1 3.7 1 -4 -0 2:; 2:: 1 -4 0 5.7 -5.2 h k l 1 -4 2 1 -4 3 1 -4 4 1 -4 7 1 -4 8 1 -4 9 1 -4 10 1 -4 12 1 -4 13 1 -4 14 1 -4 15 i -4 16 1 -4 17 1 -3 -14 i -3 -13 1 -3 -11 1 -3.-9 1 -3 -8 1 -3 -7 i -3 -6 1 -3 -5 1 -3 -3 1 -3 -2 1 -3 -1 1 -3 0 1 -3 1 1 -3 .2 1 -3 3 1 -3 4 1 -3' 7 1 -3 8 1 -3 10 1 -3 11 1 -3 12 1 -3 13 1 -3 14 1 -3 15 1 -3 16 1 -3 17 1 -2 -4 i -2 -13 1 z -12 1 -2 -9 1 -2 -8 3 -2 -7 1 -Z -6 1 -2 -4 1 -2 -3 1 - 2 - 2 1 -2 -1 1 - 2 0 1 - 2 1 1 - 2 2 1 -4 t4 5 6 :: 1; 2 1 - 2 3 1 - 2 4 5 1 - 2 6 1 - 2 9 1 -2 10 I -2 11 1 - 2 1 2 ::: 5; I -2 13 1 -2 16 1 -1 -15 1 - 1 - 4 I -1 -13 1 - 1 4 1 -2 15 1 -1 -12 1 -1 -11 1 -1 -10 1 -1 9 1 -1 -G 1 -1 -5 1 -1 -4 1 -1 -3 1 -1 3 1 -1 4 1 -1 5 1 -1 7 1 -1 C) 1 -1 10 i -1 14 1 -1 15 i -1 16 1 o -17 1 0 -16 i o -15 1 0 -14 1 0 -11 1 0 -10 1 0 -9 1 0 -8 1 0 -7 1 o -6 1 0 -5 1 -1 -2 IF01 9.: 29.0 41.8 7.5, 15.u 19.2 4.9 29.0 15.1 15.3 19.5 5 -7 4.6 9.5 14.7 14.0 19.0 16.9 45.1 15 4 15.6 29.8 8.6 62.4 23.0 4 -9 80.0 6.2 S.1 12-5 43.5 8.6 6.0 28.5 9.8 10.5 4.6 4.5 14.9 4-4 11.2 7.3 24.3 16.4 78.5 11.3 10.3 72 .o 37.8 42.3 4.6 13.1 61 .g 24.9 30.3 5.7 13.5 4.3 23 *9 5.b 6.6 10.2 6.9 8.3 8.0 9.8 7.2 9.4 9 -9 22.5 18.6 14.1 115.8 74.1 14.7 55 *7 12.1 27.2 10.6 8.5 38.6 12.7 16.6 6.7 3.8 11.7 6.0 .34.2 13 -4 21.9 10.5 15.2 AO.2 22.0 2:: 25/4 $2 3:; 11.0 39.4 Fc -9.1 31.b *3..1 -43.5 6.S -21.1 20.3 1.6 -29.1 -12.5 13.6 19.7 -7.5 -3.3 4.0 -5.0 10.3 -15.1 -17.8 22 a7 ,173 -48.1 -15.6 -13.4 29.3 -7.9 57.1 -21.8 -4.2 -25.3 -6.3 -12.z 43.0 -7.7 6.5 -26.3 8.6 10.4 4.0 3.9 -13.6 -6.2 12.7 6.9 -29.2 44.6 19.9 -18.8 -77 * 1 42 *9 72 -4 10.9 -7.4 -68.9 -3 0 2.5 12.5 -63.0 -22.3 30.1 -8.2 13.1 4.9 -24.1 5 0 0 -6.1 9.6 5.7 -7.6 -7.2 11.6 -7.6 10.5 -8.5 -21.9 18.6 15.6 -107.0 kj.0 -12.6 -52.6 -12.9 25.6 -14.36.5 -13.4 15.0 5.8 4.4 11.8 -13.3 -6.5 39.9 -14.0 -22.4 -11.6 -15. 8 30.6 46.6 it:; 5812 -9.4 1 0 -.I .I62 3.5 1 0 2 37.5 35.9 1 -0 3 9.2 -59.3 1 0 7 7.4 7.6 1 0 5 55.0 54.1 1 o 6 11.0 -10.4 1 0 8 254 -24.6 1 0 9 17.6 -17.5 1 o 10 20.6 20.0 1 o 12 5.6 6.4 1 o 13 14.6 -13.3 i o 14 13.b -13.4 1 0 15 8.1 9.0 1 i -15 8.0 -8.1 i i -13 24.1 -25.6 1 1 -12 s.4 9.4 1 1 "4 7.9 -9.0 1 1 3 7.3 -7.2 1 1 -1 52.x 49.3 I i o 14.0 14.6 1 i i 7.4 -5.2 1 1 3 9.4 -94.7 i i 4 46.b 45.9 i 1 5 30 0 30. 1 1 6 .8:2 7.2 1 1 7 37.9 35.5 i 1 y 7.8 -7.6 1 i 10 13.7 12.4 1 1 11 4.0 4.5 1 i iz 17.1 16.0 1 1 13 11.2 -11.7 i i 1 5.9 -6.2 i 2 -8 i ~ j .6 -18.4 1 2 -7 16.0 -17.2 1 2 -6 59.6 61.9 1 2 -5 30. -31.2 1 2 -3 2a.o 27.9 1 z -1 17.6 4 . 2 i 2 o 21.9 19.3 1 2 i 27.:; 27.6 1 2 2 21.9 20.0 1 2 3 61.2 -58.7 i 2 5 14.9 -15.8 '1 z 6 32.7 32.4 i 2 7 3.0 31.2 1 2 8 28.2 -6.q 1 2 12 16.2 1G.o 1 3 -10 16.2 17.4 1 1-12 8.3 9.: 1 1 -1b 15.7 10.5 1 1 2 7.7 -61.3 1 1 8 32.0 -33.7 1 2 -14 8.7 -10.9 1 2 -4 ly.8 113.2 1 2 10 13.5 -16.S 1 2 13 5.0 -6.0 1 3 -11 13.3 -15.8 ; ; 13 ;;:; 40.1 1 3 -7 20.9 :g$ 1 3 -6 21.2 -21.3 1 3 -4 70.5 68.3 1 3 -3 32.6 -3394 i 3 -2 4.1 -3.3 1 3 -1 37.5 -34.5 1 3 0 43.1 -41.3 1 3 1 42.6 42.5 1 3 2 7.0 7.4 1 3 3 5.7 -3.5 1 3 4 8.3 -9.4 1 3 6 17.4 17.8 1 3 7 14.4 14.9 1 3 10 25.9 -23.9 1 3 11 4.4 4.5 1 4.-12 7.3 -9.0 1 4 -11 14.9 -12.5 I 4 -10 15.0 14.5 1 3 5 30.0 -25.7 1 3 4 -13 12 8.9 0.6 -8.9 8.0 ; ; 1% 2:;t 2::; 1 1 4 - 7 4 -b 30 GO:$ -61:l 3 4 1 1 4 -1 -'L 17.5 6.2 -15.G -4.5 1 4 -5 13.6 14.9 1 4 -3 3.1 -2.9 1 4 I zti.6 27.1 1 4 2 21.1 -21.4 1 4 3 21.4 21.0 1 4 4 9.9 7.3 1 4 5 10.5 -ii,4 i r, 6 1z.q 11.4 i 4 S 13.a 12.4 1 4 10 15.0 -14.9 1 5 -18 7.0 7.4 1 5 -17 7.7 -6.7 1 ; -10 11.8 -12.8 1 1 5 5 -13 -15 5.7 0.1 2.4 '5.4 1 4 -4 27.4 27.0Inorg.Phys. Theor. h k l i 5 -11 1 5 -10 1 5 -5 1 5 -7 1 5 -G 1 15 -4 1 5 -3 1 5 4 1 5 -1 'I 5 0 1 5 2 1 5 3 1 5 4 1 5 1 5 3 .; 5 ; ; 212 1 3 -17 1 6 -16 "1 6 -14 1 G -9 1 6 -8 1 G -7 1 6 -6 1 6 -5 1 (1 -4 I. 6 -3 1 6 -2 1 G -1 1 6 1 1 6 3 1 6 7 1 7 -15 1 7 -13 1 7 -11 1 7 -9 1 7 -8 1 7 -G 1 7 -5 1 7 -4 1 7 - 2 1 7 -1 1 7 0 1 .7 1 1 8 -15 1 S -13 1 ii -11 1 8 -10 1 -9 1 3 -6 s 2 : : 1; 1 s -1 1 3 0 1 8 1 1 9 -11 1 cj -10 1 !) -9 1 9 -s 1 9 -6 1 9 - 2 2 -10 ' 2 -9 -1 2 - 9 1 2 -10 2 2 -9 9 2 4) 10 2 4 13 ' 2 -8 -3 2 -s -2 . 2 -8 -1 2 4 2 2 -s 3 2 -8 4 2 -ii 5 2 -8 I) 2 -8 s 2 -8 9 2 -1; 11 2 -8 1:: 2 -8 13 2 -7 -s . 2 -7 -7 2 -7 -6 2 -7 -5 2 -7, -+ 2 -7 -3 2 -7 -2 2 -7 -1 i -7 1 2 -7 2 2 -7 .3 : 1; 1:; 6 . - ,. ,. 1 O . t -10.7 3.0 4.0 19.1 21.4 31.8 32.0 8.5 -8.0 4.8 5.2 23.9. 23.8 25.2 -2G.G 7.6 -7.4 17.2 -16.5 20.6 20.9 70: -4.5 5.1 -4.4 7.9 -0.2 11.2 -10.3 33.2 14.6 2:; 2:; 8.0 -3.0 17.6 14.9 9.0 -ll.s 17.0 16.7 12.0 10.4 9.1 -7.1 13.9 -14.0 33.0 34.7 9.5 -9.2 20.3 -17.0 24.6 22.2 5.3 5.2 7.5 -8.4 10.2 -10.5 5.6 -4.9 15.3 16.6 5 . 0 6.4 13.8 13.2 5.8 7.3 l C ) . j -1g.h 8.1 , 9.1 6.9 6.1 7.4 8.3 20.1 -18.7 9.4 -9.0 4.4 3.8 12.9 14.2 7.2 -7.J 10.9 -10.9 3 -9 6.4 G.7 5.b -6.G 10.5 11.4 3.7 -3.9 5.0 -3.8 5.8 -5.6 z .7 12.5 41.3 -3:;.4 14.3 -15.9 2< a ld.9 -;;:; 16.0 -16.0 8.0 -8.1 13.4 -14.0 15.1 14.4 7.9 -2:; ;:g -2:; 8.0 -3.2 13.7 11.5 9.3 -10.2 4.0 -4.6 12.7 13.9 11.1 -11.2 5.0 5.6 G.3 5.5 9.6 -10.0 11.6 -12.5 15.5 1:j.o 11.4 -13.1 16.0 -10.1 12.2 12.7 9.5 10.9 6.5 7.4. 16.6 -1G.4 5.0 4.0 6.2 13.1 -10.3 11.9 -1:j.i$ 3.7 3.4 8.2 4.3 7.1 7.5 4.8 -f.l 8.1 3:: 5.0 4.7 15.5 -17.5 4.4 -5.; 1o.S 10.7 33.9 36.8 18.2 -19.g 12.0 -10.1 S.0 -9.5 8.1 S.1 20.5 -21.6 26.!, 24.5 h k 1 2 -7 'n (1.3 3 -7 l o 11.2 2 -7 11 8.6 2 -7 13 6.2 2 -6 -10 9.6 2 -G .-8 10.4 2 -7 12 8.8 2 -7 14 5.1 2 -7 15 10.4 2 -6 -7 6.3 2 -6 -G . 13.4 2 -6 -5 .Io.z 2 -6 -4 19.1 2 -G -3 25.0 2 -6 -2 4.3 2 -G 0 5.5 2 -6 1 24.5 2 -6 2 2 -6 4 27.4 2 -G 5 21.7 2 -6 6 34.5 2 -6 -1 21.5 2 -6 3 12::: q :g g 10.3 2.6 2 -G 9 15.4 2 -6 10 21.0 2 -6 11 14.7 2 -6 12 9.5 2 -6 15 14.1 2 -5 -11 5.3 2 -5 -10 18.7 ; 1; 3 ;:; 2 -5 -7 11.3 2 -5 -6 26.1 2 -5 -5 18.3 2 -5 -4 27.4 2 -5 -2 9.4 2 -5 -1 49.5 2 -5 0 27.3 2 -5 1 22.7 2 -5 2 b.1 2 -5 3 17.2 2 -5 4 33.3 2 -5 5 34.9 z -5 6 23.4 2 -5 8 30.0 2 -5 9 29.3 2 -5 10 16.3 2 -5 11 13.7 2 -5 12 2.8 2 -5 .13 14.8 2 -5 15 11.0 2 -4 -11 4.0 2 -4 -10 12.5 2 -4 -8 13.4 2 -4 -7 11.9 2 -4 -6 4.8 2 -4 -5 11.7 2 -4 -4 rz.7 2 -4 -3 40.0 2 -4 -1 75.9 2 -4 0 19.9 2 -4 1 3.4 2 -4 2 46.2 2 -4 3 2.9 -4 4 58.2 2 -4 5 29.9 2 -4 6 7.4 2 -4 7 3.1 2 -4 8 45.6 2 -4 10 10.3 2 -4 11 9.6 2 -4 12 3.9 2 -4 13 27.9 2 -4 16 4.4 2 -3 -13 7.5 2 -3 -12 12.4 2 -3 -9 7.1 2 -3 -8 37.9 2 -3 -7 31.7 2 -3 -6 28.9 2 -3 -5 2.7 2 -3 -4 16.8 2 -3 -3 79.5 2 -3 -2 29.2 -3 0 25.2 2 -3 2 25.0 2 -3 3 58.0 2 -3 5 26.0 2 -3 6 62.3 31.8 2 -3 10 i;.3 2 -3 11 1q.8 2 -:I 12 lj.0 2 -3 13 19.3 2 -4 -13 7.3 2 -4 -12 15.4 2 -4 9 23*4 2 -3 -1 10.2 2 -3 1 16.3 2 1; s 33.5 FC -11.7 -11.5 8.2 8.8 -5.5 3.3 -S.8 16.7 -11.3 -5.9 -13.7 11.1 20.5 -25.6 -5.2 -20.4 5.5 26.1 -5.8 17.1 -29.1 -22.4 34.5 12.9 1.5) 18.0 9.1 -11.9 -6.2 18.8 s.4 3.4 -12.G -28.5 16.9 30.0 10.8 -4s.5 28.6 20.3 0.7 19.5 -34.0 -24.7 23.7 29.9 -30.6 -17.0 14.5 2.6 13 .? -1o.b 6.7 -1G.G -6.8 14.8 14 *o -15.8 -43.8 10.7 17.3 40.9 -73.8 18.2 -2.3 44.7 2.6 -GO.l -3.0 -6.5 -5.5 48.9 -22.6 -9.6 -11.9 -4.1 25 *3 3.0 5.6 -12.4 3b.3 -31.S -29.8 -3.2 -16.9 82 .S 29.5 -7.1 -25.3, -15.b 24.8 59.1 28.5 -64.0 19.9 2:4, -:.4 31:27 -20.2 -12.9 16.8 TABLE 3 (Copttznued) k I Fc 2 -2 15 8.0 * i.i 2 -2 -15 6.5 -6.7 2 -2 -14 . 9.4 9.0 2 -2 -8 45.8 47.1 2 -2 -7 10.1 -9.0 2 -2 -6 4.3 7.4 2 -2 .-5 4.1 -41.0 2 -2 "-4 34.6 -33.4 2 -2 -3 94 95.7 2 -2 -1 71:2 64.5 2 -2 0 22.9 -2 2 2 -2 2 79.0 -73.4 2 -2 3 17.7 16.0 2 -2 -13 13.4 13.1 2 -2 -10 19.5 -22;3 2 -2 1 101.1 -9t2 2 -2 15.0 2 -2 g 7.2 5.8 z -2 10 22.0 23.0 2 -2 11 21.6 -21.3 2 -2 15 14.6 z -1 -16 4.G 2 -I -15 17.2 2 -1 -14 5.1 2 -I -13 4.4 2 -1 -11 8.3 5.5 2 -1 -10 42.4 -39.0 2 -1 -q 16.4 4 . 7 2 -1 -8 17.5 1S.9 2 -1 -7 8.9 7.7 2 -1 -5 54.:; -51.1 2 -1 -4 27.6 24.8 2 -1 -3 26.5 25.3 2 -1 o 38.7 -40.1 2 -1 1 .75.2 -19.9 2 -1 2 35.3 33.9 2 -1 3 43.3 -42.9 2 -1 5 23.5 21.3 2 -1 G 21.6 -21.3 2 -1 8 7.s -8.7 2 -1 g 15.~ 15.9 2 -1 10 20.4 19.3 2 -1 ii 12.3 -10.9 2 -1 13 15.7 -15.6 2 o -17 13.4 13.8 2 o -15 11.9 -11.4 2 o -13 13.5 -13.9 o -12 23.7 22.6 2 o -11 20.3 21.8 2 o -10 20.4 -18.2 o -8 37.3 -36.2 2 o -5 7.5 6.8 2 0 -4 30.5 -29.7 2 0 2 2 0 0 g:; 1%: 2 0 3 55.0 -55.9 2 0 4 77.7 77.2 2 o 5 15.1 16.2 2 o G 11.7 10.1 2 o 7 6.4 -6.0 2 o 8 47.3 -46.3 2 0 10 9.3 10.0 2 o it 4.0 4.3 2 1 -14 12.3. -12.7 2 i -5 15.9 16.4 2 1 -4 7.5 6.5 2 1 -3 118.2 -111.1 2 1 -1 46.8 46.7 2 1 0 50.9 4j.O 2 1 1 8.2 8.2 2 1 2 62.4 40.6 2 1 3 35.9 -34.5 2 1 8 29.7 -28.6 2 1 9 5.0 3.2 2 1 10 9.1 4j.9 2 i ii 23.2 2o.G 2 1 12 9.2 9.7 2 1 13 11.7 -11.7 2 2 3 10.2 -10.4 2 2 -8 30.9 -9.2 2 2 -7 4O.5 39.7 2 2 -5 39.1; 2 2 -4 65.9 g:: 2 0 13 21.2 -19.5 2 1 -17 12.9 13.7 2 1 ;5 49.6 45.2 2 1 58.5 55.2 2 2 -3 63.0 -59.1 2 2 -2 8.0 -8.7 2 2 -1 26.5 -26.1 2 2 o 31.3 30.1 2 2 1 42.7 40.5 2 2 2 30.6 -31.4 2 2 3 14.0 -13.0 2 2 4 3.4 3.4 2 2 5 1j.G -11.7 2 2 6 26.7 26.2 2 2 7 12.4 4 .9 2 2 8 2 2 10 22.3 -19.8 2 2 9 4:: 3:; 14.5 -4.8 -17.6 9.3 5 99 h k l 7.3 52.2 7.0 2:: 55.0 31.1 12.1 4.8 20.6 55.2 19.b 51.0 8.0 3 09 5 -5 7.7 1 ~ . 6 E%:2 4.7 13.0 11.9 10.7 4G.o 3.5 13 -9 24.4 35.9 34.0 9.0 15.7 51.4 12.5 24.7 20.4 8.2 36.3 5.2 11.9 10.2 15.5 7.4 34 -4 -26.2 -17.4 11.5 16.2 -11.5 -15.0 4.6 -3.7 9.2 17.5 -19.0 -15.1 16.2 -9.6 -14.5 -5.1 28.2 5.1 6.2 -21.6 13.1 5.6 5.5 -5.5 -10.2 ll.s 2 > -1; 13.5 l3.ti 2 7 -10 22.4 -22.3 2 7 41 4.1 4-5 2 7 -8 10.6 9.7 2 7 -6 5.0 4.4 2 7 -5 11.5 -14.2 2 7 -4 7.1 -7.9 2 7 -3 8.1 3.8 2 7 -1 6.7 6.9 2 7 0 9.7 -8.4 2 1 10.4 -10.3 2 0 -11 3.9 4.8 2 g -12 8.1 8.3 2 s -10 12.7 -12.1 9.4 8 .') 19.2 13.v -13.8 36.7 28.7 15.2 11.6 14.7 12.5 16.0 8.0 4.0 9.6 17.8 17.8 15.1 15.3 9.4 14.1 1%:: 7.0 -6.6 2%:: 8:; 23.6 14.5 5 92 6.4 6.4 9.3 12 .0 18.9 -17.3 -6.7 51.2 -6.5 -30.3 -G.O -55.4 33.8 -4.0 -17.2 - 9 .3 17*9 4 9 5 -6.3 3.6 -24.4 25.7 -5.8 6.3 -13.4 -10.0 -11.9 13.6 -12.9 44 -5 -3.3 13.9 44.3 -32.1 35.7 9.7 14.b -52 -8 11.7 21.5 19.2 9.3 -34.: 5.L 11.5 -10.0 -13.6 4 4 -9.b 9.8 -7.2 18.3 -21.2 10.0 2 B -8 3:; -3.4 2 3 -7 5.7 6.9 2 Z . -6 14.'; 13.6 2 s -5 9.8 -10. 7 -10 0 8.G -3.8 3 -10 3 3.3 4.9 3 -9 -1 9.2 7.4 3 -9 0 12.1 -11.0 :j -c> I 4 . 3 h k l 3 -9 2 3 -s 21 3 -8 2 3 -8 3 3 -8 4 3 -7 -7 3 -7 -5 3 -7 -2 3 -7 -1 3 -7 0 3 . - 7 2 3 -7 3 3 -7 4 3 -6 -7 3 -6 -6 3 -6 -5 3 -6 -2 3 -6 -1 3 -6 2 3 -6 4 3 -5 -7 3 -j -6 3 '-5 -5 3 -5 -2 3' -j 0 3 -.5 2 3 -5 3 3 -5 4 3 -4 -7 3 -4 -6 3 -4 -2 3 -4 -1 3 -4 0 3 -4 1 3 -4 2 3 -4 3 3 -4 4 3 -3 -7 3 -5 -6 3 -5 -.5 3 -J -1 3 -3 0 3 -3 1 3 -3 2 3 -3 3 3 -2 -6 3 -2 -j 3 -2 0 3 -G 2 3 -1 -7 3 -1 -6 3 -1 -5 3 -1 -1 3 -1 0 3 -1 1 3 -1 2 3 -1 3 3 -1 4 3 0 -7 3 o -6 3 0 -1 3 0 0 3 0 1 3 0 2 3 0 3 3 0 4 3 1 -7 3 I -6 3 1 -5 3 1 -1 3 1 0 3 1 1 3 1 2 3 1 3 3 1 4 3 2 -7 3 2 -G 3 2 -5 3 2 - 2 3 2 -1 3 2 0 3 2 1 .3 2 2 3 2 4 3 3 -7 3 3 -6 3 3 -5 3 3 -2 3 3 -1 3 3 0 3 3 1 3 3 2 3 3 3 3 3 4 3 4 -z 3 4 -b 3 4 -5 3 Lj J2 ; :i 4 3 -6 O 3 -j -1 1 -2 P o l 1 3 15-7 10.9 21.8 G.2 993 4.9 14.7 3 25.1 21.5 8.2 4.9 14.5 :>. j 19.4 11.1 19.8 41 -0 17.2 20.6 13.6 14.4 33.5 4S.G 17.5 "9.0 13.7 1.; .2 48.3 44.4 2 05 17.4 3:;.7 20.8 13.9 56.9 12.4 20.5 13.9 37.9 40.7 15.5 40.6 19.3 67.9 12.6 4.2 52 *9 4"4 22.4 25.7 35.1 51.5 53.5 70.4 75.5 10.7 3.7 39.3 (a .O 78.1 21.6 17.3 Rz.5 3 -5 47.4 zo.5 24.8 19.1 Y.7 7.3 8.5 30.6 6.8 % .7 38.5 ti:; 40.8 S.9 8.1 16.4 37.0 15.7 17.1 zg.7 FC -5.7 14.3 14.5 b.7 -22.1 8.9. 9.9 4.0 15.6 G.5 -2.1 24 -7 -21.7 10.1 -5.5 -10.9 -10.1 24-4 -11.0 -17.5 39.9 -19.1 -20.1 -12.8 -16.3 37.; -43.6 -16.0 27.8 12.8 -lG.A< -55.4 -40.3 -2.5, -16.b -36.5 -19.5 -1 .4 j2.0 -12.8 -24.3 -41.3 40.8 -46.5 -15.2 -34.9 -20.0 64.7 15.7 1.4 -58.1 30.1 4 .5 36.9 dz4.8 -23.7 34.9 -51.0 50.0 -57.6 44.7 79.6 73.7 -40.0 3.8 -36.7 59.6 -72.2 21.3 20.4 40.3 33.7 33.5 45.9 -19.9 22.7 16.3 -17.9 6.3 7.0 -10.0 7.9 63.0 61.3 9.0 -S.8 5.9 -4.7 09.0 65.5 15.2 -12.0 40.8 -38.1 38.9 -38.3 24.9 -25.1 43.8 4b.5 36.4 -38.4 10.4 -17.0 9.0 -12.6 -20.2 -38.9 1 G .q 15.5 -31.6J. Chem. SOC. (A), 1970 TABLE 3 (Continued) h k I 3 4 -A : : 2 3 4 3 3 4 4 3 5 -7 3 5 -6 3 5 -5 3 5 -2 3 5 0 3 5 1 3 5 2 3 5 3 3 6 -5 3 6 -1 3 6 0 3 6 . 2 3 7 -7 3 7 -5 3 7 0 4 -10 0 4 -10 3 4 -10 4 4 -10 5 4 -9 -1 4 -9 1 4 -9 2 4 -9 3 4 -9 4 4 -8 -6 4 -8 - 2 . 4 :; -; :: -8 1 $ 1; ; 4 -8 2 4 -7 -7 4 -7 -1 4 -7 0 4 -7 1 4 -7 2 4 -7 5 4 -6 -9 4 -6 -7 4 -6 -2 4 -6 O -G 1 -6 2 4 -6 3 4 - 6 . 4 4 -6 5 4 -5 -9 4 -5 -8 4 -5 -7 4 -5 -2 4 -5 -1 4 -5 0 4 -5 1 4 -5 2 4 -5 3 4 -5 4 4 -5 5 4 -4 -9 4 -4 -8 4 -4 -7 4 -4 -2 4 -4 1 4 -4 2 4 -4 5 4 -3 --o 4 -3 -7 4 -3 -2 4 -3 -1 4 -3 0 4 -3 1 4 -3 2 4 -3 3 4 -3 4 4 -2 -9 4 -2 -7 4 - 2 - 2 4 -2 -1 4 -2 0 4 -2. 3 4 - 2 4 4 -1 -2 4 -1 -1 4 -1 0 4 -1 1 4 -1 2 4 -1 3 4 -1 4 4 -1 5 0 4) 4 0 - 2 4 0 -1 4 -3 -2 4 -2 -8' : 0 -3 IF01 Fc 25.3 -25.8 21.0 21.4 14.6 -14." 13.9 -15.0 2.7 2.9 j.2 -5.7 17.9 -18.0 10.4 -9.5 6.3 -3.7 13.0 -13.2 6.2 5.6 17.5 -15.4 9.7 10.3 8.2 7.9 16.5 -15.8 12.4 -12.0 10.4 -8.2 10.7 11.6 7.2 -5.4 7.1 -6.7 .9.1 -8.9 8.6 9.2 4.5 6.1 4.8 3.6 9.8 9.0 6.7 8.5 2z.G -20.9 11.1 -10.6 17.5 18.9 5.4 5.1 3.2 -2.1 13.6 10.9 23.7 24.3 28.2 -29.6 10.6 -13.1 1s.1 22.2 11.2 -10.9 10.7 -11.5 39.6 -36.3 32.5 31.7 4.7 3.2 7.8 7.1 30.5 -30.5 9.2 -10.1 29.2 36.2 7.3 4.9 3.9 -5.6 19.1 -22.1 h.3 -54.0 12.2 -11.3 6 1.1 l& 17.5 26.1 25.5 51.3 -56.8 15.8 -17.1 6.9 b.7 22.9 28.0 16.3 -19.6 33.0 -30.9 63.0 -58.2 25.1 26.3 28.9 33.8 24.2 -25.8 44.1 42.9 12.3 -13.8 11.1 14.0 34.7 -30.2 19.8 -20.7 6z.o -61.2 43.b 51.2 21.3 20.8 14.2 13.1 3 ~ .1 34.2 10.7 10.1 14.; 13.6 14.4 -1b.7 23.7 22.7 10.8 -10.6 2:; -::i 14.9 13.7 26.7 25.4 d.5 -5.4 46. s 5 4 4 -52.3 24.5 -@ 34.0 35.2 34.0 35.9 45.0 -55.2 43.7 44.9 9 . 6 51.6 13.0 -10.9 7-0 7.5 18.5 19.3 38.9 -36.8 7:; 2: 11.4 -13.G 48.4 -55.8 .54.') 35.7 9.7 41.7 51.0 46.6 h k l 4 0 3 4 0 4 4 0 5 4 1 -9 4 1 -7 4 1 0 4 1 1 4 1 2 4 1 3 4 1 ' 4 4 1 5 4 2 -9 4 2 . 4 4 2 -7 .4 2 -2 4 2 -1 4 2 0 4 2 1 4 2 2 4 2 3 4 2 4 4 2 5 4 3 -9 4 3 -8 4 3 -7 4 3 - 2 4 3 -1 4 3 0 4 3 1 4 3 2 4 3 3 4 3 4 1 - 2 :: 1 -1 4 3 ,5 44 :: -8 4 4 7 :: :3 4 4 -7 4 4 4 4 2 4 4 3 4 5 -7 4 5 - 2 4 5 0 4 . 5 1 4 5 2 4 G -3 4 6 -9 4 6 0 f : r: ; ; 12 1 g ri; 2 ::: : 5 -11 5 5 -10 4 5 -9 -1 5 -9 1 5 -9 2 5 -9 G -8 -2 5 -s 1 5 -8 4 -3 5 2 -8 G 5 -7 -10 5 -7 -9 5 -7 -1 5 -7 1 5 -7 2 5 -7 4 5 -7 6 5 -G -10 5 -6 4) 5 -6 -2 5 -G -1 5 -G 0 5 -6 2 5 -6 4 5 -5 -11 5 -5 -9 5 -5 5 -5 5 -5 1 -ij -1 Ab.4 48.5 1.2.3 4 9 20.2 11.0 16.7 3 3 4 15.9 37.4 31.6 25.9 12.1 4 -2 24.2 31.4 6.0 8.1 34.2 30.3 38.4 18.1 9.8 26.8 8 *4 17.7 10.9 6.8 36.7 47.6 42.S 8.5 8.5 29.0 7.4 9.7 11.1 2: 20.2 43.7 16.0 7.0 2s.4 11.2 12 .$ 6.1 3.4 8.2 11.2 FC -25.4 -21.2 50.2 4 .6 15.7 -49.3 21.7 32.6 12.9 35.2 -30.2 -22.4 11.4 29.5 -31.4 -9.3 -7.5 -j.Z -33.1 30.7 36.6 -17.0 -7.4 -26.1 43.2 22.1 -12.3 -7.1 -35 -4 -51.9 12.9 3G.6 5.3 0.7 -30.0 5.5 11.4 4.b -7.8 -20.3 -44. s 16.8 7.1 -27.9 13.0 -1G.2 - -8 -8.1 8: 9 -23 -15.1 12.4 4 . 6 10.6 -11.1 -11.8 7.9 5.4 8.9 7.0 -7.7 -3.8 4 . 0 2 0 3:: -10.1 3.7 -10.3 S.1 9.9 -25.7 12.2 8.8 -20.3 -12.3 -5.5 27.7 -35.7 4.7 23.2 -14.3 -14.1 2.1 -23.6 34.1 -3.0 -3.1 29.0 5.5 10.6 7.3 G .2 9.5 6.3 6.G 3.3 7.0 4.1 10.0 4.1 9.7 7.9 13.2 2b.G 11.4 S.4 18.3 11.5 5.5 33.3 34.7 4.1 22 .o l2.0 13.:; 3 -3 25 .o 35.2 3.5 3.9 25 -7 6.4 7.9 32.9 -41.4 0.3 8.7 42.1 38.7 9.: 5 -5 2 21.2 -22.9 d.1 5 -4 -11 6.1 -4.7 5 -4 -10 11.0 11.3 7.0 s.3 0 9.; 10.7 144 i 60.: 60.0 5 -4 r", 12.5 -1q.1 5 -4 5 -4 2 4.2 7.3 j -4 4 8 . c ; -9.9 5 -4 5 I.>..% -13.2 5 -3 -11 3.4 -5.: 5 - 3 -10 19.0 20." S -.3 -9 17.: 16.6 5 -3 -2 10.0 10.6 5 -.; -1 h.,7 4 . G 5 -3 4 4.3 -17.5 5 -3 5 43.4 -45.1 5 -2 -11 28.2 -27.0 5 -55 -2 19.5 21.:; 5 -2 -1 72.7 -74.2 j -2 0 22.5 24.S 5 -2 2 3.ti 12.2 5 -2 4 450" -49.: 5 -2 5 13.3 -16.0 5 -1 -11 17.6 -l:.?, 5 -1 -10 4.7 .,.<> 5 -1 -2 22.4 25.9 5 -1 -1 34.j -36.5 5 -1 0 17.0 17.0 5 -1 1 9.5 -11.<) 5 -1 2 22.3 24.1 5 -1 -251.1 5 o -10 2i.i1 +L.Z 5 0 -2 7.5 7.9 5 0 -1 7.0 -7.5 5 o o 3o.t 26.1 5 0 1 W.4 -jG.7 5 0 2 qd; 13.0 5 0 4 13.8 13.j 5 0 5 10.3 lo.!- 5 " 6 22.4 - 5 i -11 15.G 16.1 5 1 -10 37.2 -:;3.9 5 1 -0 9.1 -7.:; 5 1 -2 10.9 -12.3 j 1 -1 39.6 40.8 5 1 1 37.3 -35.5 5 1 4 13.2 15.1 5 1 5 7.3 3.6 5 1 G 16.3 e 2 h 5 z -11 17.2 18.8 5 3 -10 35.7 -32.2 5 2 -9 12.1 -u.s 5 2 22 20.4.-21.5 2 2 -1 31.4 33.5 :) 2 0 5.b -5.2 5 2 1 4.9 2.9 5 2 2 7.9 -6.3 5 2 4 1j.I 16.2 5 2 b :;.0 4j.z 5 3 -it 17.4 iR.5 5 3 -10 3.3 5.4 5 3 -2 14.9 -14.4 5 3 -1 20.8 20.9 5 3 2 9.0 -G.l 5 3 4 9.0 9.3 5 4 -10 d.9 3.5 5 -2 -10 2:j.4 20.7 5 -2 -9 b.4 11.7 5 -1 ;t 2:; -37.1 5 2 5 i'.5 7.8 5 3 1 20.'[ 17.5 5 3 s 5.5 4.: 5 4 -11 z-4 7.0 5 4 -2 2;:t 9.0 5 4 19.j 5 4 2 13.7 -12.2 5 4 5 5.2 -4.7 5 5 -11 3.:: -3.5 5 5 -10 21.5 1S.5 5 5 -9 4.0 4.5 5 5 -1 8.G - 1 o . G 5 5 0 10.3 1 17.9 f;:8 2 -11 7.7 -9.0, 5 G -10 i3.g 19.7 6 -10 1 6.4 -4.0 G -9 o i:$.i -13.4 6 -u 1 11.6 -10.7 6 -0 2 16.3 13.7 2 7 -10 5.2 -10 0 2:: - 5 4 ; -9 5 6.6 -5.4 i) 4; -1 2:; 12:; G -8 o cj.3 -?-? G -10 2 G . 1 -5.5 G -10 G 5.: -5.9 -\J 6 1:<.6 -14.1 G -9 7 8.7 10.2 6 -s -2 (i -3 1 12.7 -I,.& 6 -7 .n, 8.; 7.3 ti -7 -1 30.9 28.0 G -7 0 12.9 -1o.G b -7 i 5.0 -4.0 5.0 -1J.6 1; 3 15.~4. -15.6 6 -7 5 -d'4 c, -7 7 13.2 -14.0 h k l b -0 -12 G -6 I! 6 -6 -1 6 -G 2 (i -6' 5 G -ti 6 G -6 7 6 -,5 -12 6 -5 -11 (i -5 -2 6 -5 -1 6 -5 0 ( 1 -5 1 6 -5 2 tj -5, 6 f i -4 -13 6 -4 -11 G -4 -1 0 -'I 0 -4 5 6 -4 0 6 -3 -U ti -I; -11 6 -3 -2 ti -3 -1 G -3 o G -3 G 6 -:j 7 .G -2 -12 6. -2 -11 6 - 2 - 2 6 -2 -1 G -2 0 6 - 2 1 6 - 2 2 6 - 2 5 ti -2 6 G -2 7 6 -1 -12 6 -1 -2 0 -1 -1 6 -1 0 6 -1 1 6 -1 2 G -I 5 6 -1 6 C -1 jr 6 o -13 ti 0 -12 6 0 - 2 6 0 -1 G o o G o 1 G o 2 6 0 6 2 -4 1 : ;-2 6 I -12 6 1 -11 G 1 - 2 G 1 -1 6 1 0 6 1 1 6 1 2 6 1 5 6 1 6 G 2 -13 6 2 -12 G 2 -11 G 2 - 2 6 2 -1 6 2 0 6 2 1 G z z G 3 -13 G 3 -12 6 3 -11 6 3 - 2 3 1 6 3 2 6 4 -13 G 4 -12 G 4 -11 G 4 o 6 4 1 6 5 -13 G 5 -12 G 5 -11 7 -10 0 7 -10 1 7 -9 2 7 -9 7 7 -8 -2 7 -s -1 7 4 0 2 3 O : 2 -12" ; -:; : 7 , -s 2 25.1 -2'!.2 11.7 1o.b 17.8 -14.6 54.; 52.1 -9.4 -1l.j 17.1 24.5 29.4 -29.3 18.1 -17.9 45.5 -42.2 9.9 -11.2 18.3 -17.8 52.4 47.8 14.3 -14.0 1s.s -19.2 1b.1 20.9 2'7 -4.0 ib.7 -19.4 4.4 5.1 12.0 13.0 36.1 -34.3 16.2 -1O.b 21.5 19.2 17.2 -16.6 11.7 12.9 3.4 1.0 13.1 17.2 11.1 -10.8 3.9 5.6 31.1 33.5 34.7 -31.O 11.0 -10.2 1S.7 -15.0 6.1 -7.3 16.7 -13.9 4.4 -4.1 15.2 17.2 7.0 -7.4 13.7 15.7 15.2 ij.7 3.b -5.1 5.6 5.2 15.8 -15.2 4.7 -5.6 ib.8 18.4 9.1 s.5 6.0 6.3 12.3 11.5 22.5 -19.7 4.4 -6.0 4.9 5.s 9.0 s.7 8.9 6.9 2.0 -3.5 G.4 -0.4 7.3 6.3 13.5 13.5 7.7 -9.5 7.7 -7.6 4.5 3.7 10.2 12.3 18.7 -15.4 11.7 9.5 9.3 11.5 12.4 10.1 b.3 G.G 13.j -12.9 8.7 -8.1 18.2 17.3 22.2 17.3 h k l 7 4; b 7 -8 8 7 -7 -2 7 -7 0 7 -7 2 7 -7 6 7 -7 7 -7 0 7 -G -2 7 -6 0 7 -G 1 7 -6 2 7 -6 7 7 -5 -Y 7 -5 -13 7 -5 -2 7 -5 -1 7 -5 0 7 -5 1 7 -5 2 7 -5 6 7 -5 7 7 -4 -14 5 1; 9 ; 1; : 7 -3 -15 7 -3 -13 7 -3 -2 7 -3 -1 7 -3 0 7 -3 6 7 -3 7 7 -2 -14 7 -2 -13 7 22 -2 7 - 2 0 7 - 2 1 7 - 2 2 7 4 6 7 - 2 7 7 - 2 8 7 -I -15 7 -1 -14 7 -1 -2 7 -1 -1 7 -1 0 7 -1 1 7 -1 7 7 0 -15 7 0 -14 7 0 - 2 7 0 0 7 0 1 7 0 2 7 0 7 7 1-14 7 1 -1-3 7 1 - 2 .7 1 -1 7 1 0 7 1 1 7 1 2 7 1 7 7 2 -4 7 2 -13 7 2 - 2 7 2 -1 7 2 2 7 3 -14 7 3 -13 7 3 - 7 3 -1 7 3 0 7 3 1 7 4 -1.5 7 4 -4 7 4 0 8 -10 0 8 -10 1 8 -9 -2 8 -9 -1 ; r: : : 1: ; 8 8 :i -8 -1 8 -8 0 3 -8 1 s -8 7 8 -8 8 8 -7 -2 s -7 1 -7 2 <> -7 7 8 -7 s S -G -2 S -6 o 8 -G 1 3 -6 2 8 3 -2 g'.G -ij.2 6.3 8.0 9.1 -0.1 22.8 -21.1 22.9 2E.S 10.0 G.3 -17.9 -4.7 5.7 7.5) y.3 40.h 3.0 -3.8 22.1 -2.3.0 19.2 -19.9 17.0 -1S.7 11.0 -11.3 3.; 5.1 21.2 23.7 s.4 6.:; 2S.l 29.2 24.7 -20.9 15.0 -15.9 4.:; 4.7 7.:; 4 . 2 9.7 -9.0 33.9 -32.6 9.3 9.6 4s.2 49.9 3.4 3.9 4.:' -6.4 8.6 ' -7.1 50.5 -54.:; 13.8 11.7 4.:; -5.4 13.6 14.0 14.6 13.5 5.0 5.1 18.2 -16.2 44.5 1 -8 -15.5 -45.9 22.3 23.1' 21.4 23.5 2.7 -2.0 22.; 21.8 G.3 -7.3 11.1 11.8 14.3 15.8 14.5 -16.2 11.0 -11.5 31.3 -33.3 12.0 lO.<J 32.7 31.5 7.5 7.0 19.8 19.1 7.6 8.3 16.7 18.0 25.J 24.3 s.5 9.9 6.3 4.7 5.6 5.2 7.3 7.9 3.7 4." 8.7 -8.0 15.0 -14.8 5.1 -3.0 9.3 -10.2 9.3 -9.4 5.8 -6.0 10.1 9.2 z8.G 30.1 5.6 -5.1 14.6 -12.9 12.3 -12.7 17.5, 4.B 21.7 25.3 11.7 9.7 4 f l s:7 * -2:$ 12.9 11.4 4.7 -4.0 3.0 -2.9 7.2 -9.0 12.4.11.7 3.7 -4.9 11.4 9.7 7.7 7.9 11.4 4 . 6 5.3 -6.0 6.1 5.9 4.4 4.9 13.5 11.3 8.7 -0.6 6.5 -7.0 0.3 -4.9 3.6 -3.0 9.6 10.3 20.3 21.6 27.7 -25.5 . 5.1 -3.5 7.3 -8.8 13.2 13.9 10.0 16.0 6.2 4.4 33.5 -32.1 12.2 -11,lInorg. Phys. Theor. 43 8 -6 7 7.8 8 -G S 8.0 S -5 -I 26.4 8 -5 0 3.6 -5 8 6.5 h -4 -1b (1.1 S -4 -1 3S.G s -.' 7 7.4 -s- -? s 1i.1 s -3 -2 30.1 5 .:i -3 1 25.0 0 -3 2 s.7 S -3 7 q.7 s -3 s 12.4.8 -2 -1; 5.2 s -2 -2 13.0 S -2 -1 15.1 s -2 0 7.5 8 -2 1 30.0 8 -'$ -2 22.5 2 -3 -15 7.7 ; 1; -; 11.7 ; ; g ::; 8 -I -IG 2.9 D -1 * 4.9 :: -1 -1 17.6 -24.4 37.7 6.1 -l&8 -7.4 -33.1 12.S 5 .O 23.9 -8.G 10.2 3.3 -13.7 2.6 -14.5 -10.9 2b.6 3.:: -7.0 -2.5 -4.5 -q..; -1 0 -1 1 -1 2 0 -16 0 -1 0 0 0 1 1 -16 1 -15 1 -2 1 -1 1 1 2 -16 2 - 2 2 -1 2 0 2 1 3 -15 4 -1i) -9 -1 -9 0 -6 -1 -8 1 -s 2 -7 0 -7 1 -7 2 -10 0 U.1 p .2 5.') 7 4 24-3 13.7 15.5 10.4 10.5 22.1 21.1 3.9 3.7 11 .o s.7 s..+ 17.2 9.8 2.6 7.0 14.6 7.2 13.2 9.7 13.2 15.2 11. 3.2 -13.0 29.7 4.6 -7.1 24.4 -9.5 11.6 -12.0 .'10.1 23.0 -20.6 -8.6 -5.3 11.4 -6.9 5 *4 -14.3 .-gS 3.s 7.6 -14.1 .7.0 -10.0 -5.6 ii.2 -0.5 -12 .z 12 .<> TABLE 4 Molecular geometry (a) Intramolecular distances (A) Fe(1)-Fe(2) 2*645(2) C(2)-C(3) Fe(1)-C(11) 2.02(1) C(3) -c (4) Fe(2)-C(1) 2.29(1) C(4)-C(5) Fe(2)-C(10) 2.17(1) c (5)-C(6) Fe(2)<(11) 1-96(1) C(6)-C(7) Fe(l)-C(12) 1-81(1) C(7)-C(8) Fe( 1)-C(13) 1.77(2) C(8)-C (9) Fe(l)-C(14) 1.83(1) C( 9)-c ( 1 0) Fe(1)-C(15) 1.79(1) c ( 1 O)-c (1 1) Fe(2)-C(16) 1*76(1) C(11)-C(1) C(13)-O(13) 1.16(2) H(l)-H(3) Fe(2)-C(17) 1.80(1) 0 (1 2)-0 ( 17) Fe(2)-C(18) 1.77(1) 0(12)-H(2') C(12)-O(12) 1*13(1) O( 14)-H ( 10) C(14)-O(14) 1*11(1) C(l5)-O(l5) 1*14(2) C(16)-O(16) 1.16(1) C 17)-O(17) 1*13(1) C( 1)-C(2) 1-52(1) C 11 8)-0 (1 8) 1.16 (1) H (61-H (9) (b) Intramolecular angles (") Fe ( 1 )-C ( 1 1 )-Fe (2) 8 3.1 (4) Fe ( 1)-Fe (2)-C ( 1 8) C( 1 1 )-Fe ( 1) -Fe (2) 47.4 (3) C( 16)-Fe (2)-C( 1) F e ( 1)-C( 1 1)-C( 1) 120*5( 7) C( 16)-Fe (2)-C( 10) F e ( 1)-C ( 1 1)-C (1 0) 1 1 6.8 (6) C( 16)-Fe (2)-C ( 17) C(1)-Fe(1)-C(l1) 23*9(3) C( 16)-Fe(2)-C(18) C(10)-Fe(1)-C( 11) 25*4(3) C( 1)-Fe(2)-C(17) Fe (2)-C ( 1 1 )-C ( 1) 79- 6( 7) C( 1 7)-Fe (2)-C ( 1 8) Fe(2)-C(ll)-C(lO) 78-3(6) C(lO)-Fe(2)-C(18) C(l)-Fe(2)-C(ll) 39.1(4) C(ll)-Fe(2)-C(16) C( 10)-Fe (2)-C (1 1) 39.7 3) C ( 1 1)-Fe (2)-C (1 7) C(l)-Fe(2)-C(lO) 65.914) C( 11)-Fe(2)-C( 18) Fe(2)-Fe( 1)-C(12) 77.9(3) F e l)-C( 12)-O(12) Fe(2)-Fe( 1)-C(13) 142.6(4) Fe[l)-C(13)-0(13) Fe(2)-Fe( 1)-C(14) 97*7(4) Fe(1)-C(14)-0(14) Fe(2)-Fe(l)-C(15) 112.8(4) Fe(1)-C(15)-O(15) C( 1 1)-Fe ( l ) - C (1 2) 96*0(4) Fe (2)-C( 1 6)-0 (1 6) C( 1 1)-Fe( l)-C( 13) 97.7 (5) Fe( 2)-C( 17)-O( 17) C ( 1 1 )-Fe ( 1 )-C (1 4) 89.7 (5) F e (2)-C ( 18)-0 (1 8) C(11)-Fe( 1)-C( 15) 159.2(5) C(l)-C(2)-C(3) C(12)-Fe( 1)-C(13) 96.5(6) C(2)-C(3)-C(4) C ( 12)-Fe (1) -C (1 4) 1 66-9 (6) C( 3)-C (4) -C (5) C( 1 2)-Fe (1 )-C ( 15) 83.6 (5) C( 4)-C (5)-C( 6) C ( 1 3)-Fe ( 1 )-C ( 1 4) 94-6 (6) C( 5)-C( 6)-C (7) C (1 3)-Fe (1)-C ( 15) 103- 1 (6) C(6)-C( 7)-C(8) C(14)-Fe(l)-C(15) 86.8(5) C(7)-C(8)-C(9) Fe ( 1) -Fe (2)-C ( 1) 75.8 (2) C( 8)-C( 9)-C( 10) Fe(l)-Fe(B)--C(lO) 74-7(2) C(9)<(10)-C(ll) Fe( 1 )-Fe (2)-C ( 1 6) 1 62.3 (4) C ( 1 0)-C ( 1 1 )-C (1) Fe( l)-Fe(2)<(17) 105.7(3) C(l l)-C(l)-C(2) -6 -2 $ -6 -1 -6 o 2 -0 I 9 '-6 z 9 -6 9 9 -5 -2 9 -5 -1 -5 0 9 -4 -2 9 -4 -1 9 -4 " 9 -3 -2 9 -3 -1 9 -3 3.9 -3 2 L 5 9 ; 2 : ;:2 :: -1 0. -1 -1 'f 0 -1 9 0 0 9 1 - 2 1*53(2) 1 -53 (2) 1*55(2) 1*55(2) 1-51(2) 1-53(2) 1 -5 0 (2) 1.56(1) 1.42( 1) 1.41(1) 3.1 O( 1) 2-67 2.68 2.67 2.73 2.01 2.31 2.18 2.16 83.0(3) 100-8(5) 88*3(5) 91*5(5) 96*1(5) 1 0 1 -2 (5) 97-8(5) 117.9(5) 126.5 4) 11 7-2[5) 168-7 (9) 174-6(13) 174-3(12) 177*4(13) 176.6 (1 0) 174*2( 11) 176-6(11) 115.5 11) 115*3[13) 114-0( 15) 117*0( 1 1) 114.4(11) 115q 10) 112*6( 9) 124.8 (8) ll4-6(8) 127-1 (8) 95*4( 5) 108.9(10) 4.7 0.0 12.2 22.6 7.9 b.2 8.0 25.2 8.1 :: .2 5 ** 17.2 4.6 4.1 14.2 0.9 22.3 10.0 la.? "$1," 24.3 12 .o 20.3 3.7 2G.2 5.3 4-0 -4.5 5.1 -14.3 -20.5 8.1 7.9 9.7 25.3 53.1 s.7 4.8 14.5 5.1 13.1 9.9 -19.9 12.5 17.5 -20.2 -9.5 -22.g 12.8 17.6 -1.3 -24.5 -5.1 -2.0 4.9 g 1 -1 9 1 0 9 1 1 9 2 0 10 -5 0 10 -z -2 10 -8 -1 10 -8 2 10 =7 0 10 -7 2 10 -6 -2 10 -0 0 10 -5 -2 10 -5 -1 10 -5 0 10 -4 -2 10 -4 0 10 -4 2 10 -3 -2 10 -3 0 10 -3 1 10 -3 2 10.-2 -1 10 -2 0 10 -1 -2 10 -1 -1 10 -10 0 10 -j- -1 10 -4 -1 10.1 ::: I . J 13.6 10.5 7.2 11.1 6.2 13.4 b.3 19.9 22.0 13 -0 13.8 23.: 12.0 12 .O 5.0 12.3 5 09 23.1 10.2 17.4 5 02 15.5 2:2 15.8 5.1 -0.2 2.6 -7.2 -10.1 9.6 5.5 -1v.j 4 . 5 13.1 4 . s -10.3 11.:; 15.2 -23.4 14.3 10.9 -3.7 i3.G 6.6 -21.2 17.7 17.6 -j.Z -15-7 -4.4 21.4 -16.2 -5 .b 18.3 10 -1. o i2.4 14.3 10 0 "2 22.b -22.0 10 o o 7.1 4.7 10 1 0 11.9 -9.7 11 -9 0 7.3 7.4 11 4; -1 4.:; -1.4 11 -3 1 14.0 12.5 11 -2 1 19.2 8.1 11 -0 JL 12.0 U.!) 11 ?b. -1 7.4 -5.7 11 -G o 5.1 -7.0 11 -5 -2 15.;; 14.:; 11 - 5 ' -1 s.5 -7.9 11 -4 -2 l2.J 12.5 11 -4 0 G,;; 8.1 11 -4 i 2u.t) -17.0 11 - 3 -1 6.6 5.1 11 -3 0 ti.2 9.7 11 -2 -1 13.0 12.0 ii'.-i -1 10.b 10.4 11 -7 0 1CJ.t.) -12.0 11 -3 1 15.1 -14.3 1 1 -1 0 7.4 6.7 12 -8 0 4.7 3.3 11.9 -11.6 13.:: -12.7 12 -4 -1 10.6 s.5 12 12 IZ 1; TABLE 4 (continued) (c) Least-squares planes * defined by atomic positions and, in parentheses, distances of the atoms (A) from these planes Plane (i) : C(1), C(lO), and C(11) 0.9765X + 0.0099Y - 0.21522 + 2.0544 = 0 [Fe(l) 0.94, Fe(2) 1.83, C(2) -0.27, C(9) -0.771 Plane (ii): C(1), C(2), C(9), C(10), and C(11) 0.8066X - 0.0341Y - 0.59012 + 2.8421 = 0 [Fe(l) 0.00, Fe(2) 1-82, C(l) 0-24, C(2) -0.11, C(9) -0.09, C(l0) 0.09, C(11) -0.141 Plane (iii): Fe(2), C(11), C(13), and C(15) -0.1277X - 0.9496Y + 0.28642 - 2.5694 = 0 [Fe(l) 0.06, Fe(2) -0.14, C(11) 0.19, C(13) -0.13, C(15) 0.09, O(13) -0.35, O(15) 0.09, C(12) -1.70, C(14) 1.891 Plane (iv) : C(1)-( 11) 0.0044X - 0.0288Y + 0.99962 - 2.6149 = 0 [Fe(l) 2.22, Fe(2) -0-32, C(l) -0.33, C(2) -0.20, C(3) -0.46, C(4) 0.61, C(5) 0.08, C(6) -0.47, C(7) 0.53, C(8) -0.09, C(9) -0.71, C(10) 0.33, C(11) 0.711 * X, Y, and 2 refer t o orthogonal co-ordinates obtained by the transformation a b , cos y 0 b .sin y --c . cos a* . sin C. cos /I c . sin /I. sin a* 1 [311 El= 0 0 (d) Torsion angles ( O ) for the eleven-membered carbon ring C(l)-C(2)<(3)-C(4) 68.6 C(7)-C(S)-C(9)-C( 10) 61.3 C(2)-C(3)<(4)-C(5) - 128.7 C(S)-C(9)-C(lO)-C( 11) - 84.7 C(3)-C(4)-C(5)-C(6) 69.5 C(9)-C( 10)-C(l1)-C(1) - 37.1 C (4) -C (5)-C (6)-C (7) 1 6 7 *3 C f6kC I7)-C (8)-C (9) 68.6 68.6 C (1 0) -C (1 1) -C ( 1) -C (2) C(5)-C(B)-C(7)-C(8) - 163.8 C(l l)-C(l)--C(2)-C(3) - 105.7 metal-ally1 bond lengths are also shown in the di- meric complex bromo-2-carbox yethyl-x-allylnickel10 [Ni-C(ally1) 2.05(2), 1.90(2), and 2.06(3)], and in the complexes c yclopent adiene (1 -c yclopentadienyl-l,2,3,4- tetramethylcyclobuteny1)nickel l1 [Ni-C(ally1) 2.00( 1) , 149( l), and 1-98( l)], and azulenepentacarbonyldi-iron 12 10 M.R. Churchill and T. A. O'Brien, Inorg. Chem., 1967, 6, 1386. 11 L. F. Dahl and W. E. Oberhansli, Inorg. Chem., 1965, 4, 160. M. R. Churchill, Inorg. Chem., 1967, 6, 190.44 J. Chem. SOC. (A), 1970 [Fe-C(ally1) 2-20(1), 2.05(1) , and 2-14(1)] ; no significant variation is found, however, in bis(methylally1)nickel l3 [Ni-C(ally1) 2.01(1), 1.98(1), and 2*03(1)], or bromo- met hylallyl[bis-l,2- (diphenylphosphino) e t hane] nickel l4 [Ni-C(ally1) 2.06(1), 2.02(1), and 2.05(1) A].The vari- ation in the metal-ally1 bond-lengths in the azulene- pent acarbonyldi-iron complex has been explained in terms of an overall strain in the molecule, whereas for the mono-nuclear x-ally1 palladium complexes it has been suggested that the variation is indicative of 6-x bonding.15 Fe(1) lies on the same side of the plane defined by the allylic carbon atoms as Fe(2) and is 0.94 A from it. The vector Fe(1)-C(11) makes an angle of ca. 30" with this plane. This displacement probably arises from the metal-metal bonding, but in other 2-substituted x-ally1 metal complexes the substituent has been found to be displaced in either direction. Thus, in bis(methy1- allyl)nickel,13 chloro(tripheny1phosphine)methylallyl- palladium,15 and bromo(methylally1)bis-[ 1,2-(diphenyl- phosphino)ethane]nickel l4 the 2-methyl substituent is displaced towards the metal atom by 0.3,O 5, and 0.3 A, whereas in cyclopentadienyl-( 1-cyclopentadienyl-l,2,3,4- tetramethylcyclobuteny1)nickel l1 and chloro-( 1- ethoxy-l,2,3,4-tetraphenylcyclobutenyl)palladium di- mer16 the methyl and phenyl 2-ally1 substituents are both displaced by 0.1 A from the metal atom; in the bromo-(2-carboxyethyl-x-allyl)nickel dimer the 2-car- boxyethyl group lies in the plane.These displacements may result from non-orthogonality of the metal d orbitals and the B framework of the allyl ligand,14 but it is possible in the case of the tetraphenylcyclobutenyl complex, for example, that steric hindrance between the phenyl group and one of the chlorine atoms on the other side of the metal atom plays a part.It has been found that for several x-ally1 complexes of nickel, palladium, and iron the C-C-C allyl bond angle is close to the value of 120" required by an sp2- hybridised carbon atom. However, in the cyclobutenyl complexes where the allyl group comprises three members of a strained four-membered ring this angle reduces to ca. 90". In the present complex the value is 114.6" and whilst this value might be explained in terms of ring strain pulling the atoms C(l) and C(11) together, this explanation is not consistent either with the value of 11 6.0" observed in pallyl-hexacarbonyltriphenyl- phosphinedi-ironJ6 or with the values of 119.0 and 122.8" observed in acetylacetonato(cyclo-octa-2,4- dieny1)palladium and azulenepentacarbon yldi-iron.12 The values of the allyl C-C bond-lengths in n-ally1 complexes have been found to vary between 1-38 A in chloro-(x-ally1)palladium and 1.48 A in chloro- (1 -e thoxy- 1,2,3,4-tet raphen ylc yclobut en yl) palladium di- mer.16 In general the values axe larger in the strained 13 H.Dietrich and R. Uttech, Naturwiss., 1963, 50, 613. 14 M. R. Churchill and T. A. O'Brien, Chem. Comm., 1968, 15 R. Mason and D. R. Russell, Chem. Comm., 1966, 26. 16 L. F. Dahl and W. E. Oberhansli, Inorg. Chem., 1966, 4, 246. 629. cyclobutenyl complexes than in the other x-ally1 com- plexes and within experimental error have the same length in any particular complex in agreement with a delocalisation of electron density over the three atomic centres of the allyl group.Exceptions have been reported 1 5 9 1 7 with allyl C-C bond-lengths l5 of 1.40 and 1.47 A; the mean length for the present complex is 1.42 A. Iron-iron separations in bridged bi-nuclear organo- metallic complexes vary over a wide range dependent on the nature of the bridging species, e.g. 2.37 A in a nitrogen-bridged complex l8 to 2-65 A in di-p-seleno- tri~(tricarbonyliron).~9 The distance found in the present complex, 2.65 A, is thus at the long end of this range. It is not possible to advance unequivocal reasons for this value. The bridging allyl group in- volves B--x co-ordination ; this by itself is insufficient to account for the length since other 6-r bridging ligands FIGURE 2 A projection of part of the molecule perpendicular to the plane defined by the atoms Fe(2), C(11), C(13), and C(l5), showing the configuration about Fe(1) occur with shorter separations, e.g.2.49 A in 7t-tri- carbonyl(2,5-dihydroxy-3,4-dimethylf erracyclopent a- diene) tricarbonyliron.20 Three types of iron-carbon bonds are present in this molecule: the c-bond between Fe(1) and C(11), the x-bonds between Fe(2) and C(1), C(lO), and C(11), and the partial double bonds between both iron atoms and their respective carbonyl groups. The length of an Fe-C single bond is hard to predict if it has indeed any mean- ing. According to the value used for the radius of the iron atom, together with 0-74A for an sp2-hybridised carbon atom, one might expect it to lie in the range 1.98-2.04 A which spans the observed value of 2.02 A.Of the five carbon atoms which surround Fe( 1), C (12), and C(14) most nearly form with it a linear arrangement. Figure 2 shows the projection of this part of the molecule along this direction. Depending on whether or not Fe(2) is included in the co-ordination sphere, the arrangement may be described as involving either a grossly distorted octahedral or trigonal bi-pyramidal co-ordination ; the angle C (13)-Fe (1)-C( 15), 103.1 O , lies D. Bright and 0. S. Mills, 2nd Internat. Symposium Organo- P. E. Baikie and 0. S. Mills, Chem. Comm., 1966, 707. L. F. Dahl and P. W. Sutton, Inorg. Chem., 1963, 2, 1067. 20 A. A. Hock and 0. S. Mills, Acta Cryst., 1961, 14, 139. metallic Chem., Madison, Wisconsin, U.S.A., 1965.Inorg. Phys. Theor. 45 approximately half-way between the values of 90 and 120" expected for octahedral and trigonal bi-pyramidal co-ordination respectively.The co-ordination poly- hedron of Fe(2) may be regarded as a distorted trigonal prism with the three carbonyl groups, Fe(1) , and the two allylic partial double bonds forming the co-ordination 4 I I FIGURE 3 The conformation of the carbon ring. (a) A pro- jection parallel to the least-squares plane defined by all eleven ring atoms and (b) a projection perpendicular to the least- squares plane defined by the ring atoms framework in an arrangement similar to that observed in x-tricarbonyl-(2,5-dihydroxy-3,4-dimethylferracyclo- pent adiene) tricarbonyliron .20 The seven iron-carbonyl groups show Fe-C and C-0 bond lengths (mean values are 1-79 and 1-14w re- spectively), closely similar to those observed in other typical iron carbonyl complexes.However, one of these groups, Fe(1)-C0(12), deviates by over 11" from linearity. The Fe( 1)-CO( 12) vector is approximately parallel to the vector Fe(2)-C0(17) ; the C(12)-C(17) and O(12)-O(17) separations are 2.80 and 3010A. If the Fe(1)-C(l2)-O(12) angle was 180" the O(12)-O(17) separation would decrease to 2.94& a distance only slightly greater than 2.80 A, the van der Waals' diameter of the oxygen atom. It would therefore appear that repulsive forces between these two oxygen atoms may be responsible for the non-linearity of the Fe(1)-CO(12) group. The slight deviations from linearity in the remaining Fe-CO groups (average Fe-C-0 angle 175.5"), may be a result of the molecular packing.21 Chem. SOC. Special Publ., No. 11, 1958. z2 H. M. M. Shearer and V. Vand, Acta Cryst., 1956, 9, 379. ~4 J. D. Dunitz and H. M. M. Shearer, Helv. Chim. Acta, 1960, 43, 18. The conformation of the eleven-membered carbon ring is shown in Figures 3(a) and (b) by projections per- pendicular and parallel to the least-squares plane defined by all eleven ring atoms. The torsion angles around the ring are listed in Table 4. The C-C bond lengths (average 1.53&, within the non-allylic section of the ring are not significantly different from the values observed between two sp3- hybridised carbon atoms in other ring and chain com- pounds, e.g. 1.545 in diamond,21 1-53 in n-hexatria- contane,22 and 1.54 A in cycl~dodecane.~~ The C-C-C valence angles (average 114.2") , differ significantly from the tetrahedral angle.This discrepancy has been observed in many ring and chain carbon compounds since first predicted by I n g ~ l d , ~ ~ e.g. 112.0" in n-hexa- triacontane 22 and 116.5" in 1,6-trans-diaminocyclo- dodecane hydrochloride.25 In the final stages of the structure refinement, the positions of the hydrogen atoms in the molecule were calculated assuming a H-C-H valence angle of 104.0" in order to compensate for the observed opening out of the C-C-C angles. A feature common to several of the medium-sized saturated carbon ring systems is that they are built up from nearly planar zig-zag chain units each containing four carbon atoms, with an atom shared between successive units. Thus cyclododecane * is comprised of four such units with torsion angles of ca.160" (anti- 9eripZanar) about the central bond of each unit and approximately - 70" (syn-cZinaZ) about the bonds either side of the common atoms. In the present molecule carbon atoms C(2)-(5) and C(5)-(8) form two such chain units with C(5) as the common atom, although the former chain is distorted from planarity due to ring closure via the ally1 group. The torsion angles are shown in Figure 3. The conformation of the carbon ring gives rise to several close H-H non-bonded separations. Hydrogen atoms H(1), H(3), H(6), and H(9), which are on the same side of the ring as Fe(2), are directed inside the ring and have tvans-annular separations ranging from 2.01- 2-68 A, whereas H(4') and H(7') on the opposite side of the ring are separated by 2-18A. trans-Annular separations of ca. 2.0-2.1 A have also been observed in the cyclododecane molecule.23 The non-bonded separation C(9)-H( I), 2.67 A, would seem to indicate that the formation of an analogous ptetramethylallyl-complex would not be favoured be- cause of the possibility of steric hindrance between the methyl groups occupying the C(9) and H(l) positions. The reaction between tetramethylallene and ennea- carbonyliron has so far yielded only the mono-nuclear complex, Me2C:C:CMez*Fe(CO), in agreement with this suggest ion. The molecular packing is shown in Figure 4 in pro- jection along the b axis, and the shortest intermolecular separations are listed in Table 5. The rather short 24 C. K. Ingold, J . Chem. SOC., 1921, 305. 26 E. Huber-Buser and J. D. Dunitz, Helv. Chim. Acta, 1960, 43, 760.46 J. Chem. SOC. (A), 1970 separation between O(17) and H(5V1rr) may result from the uncertainty of the position of this hydrogen atom rather than from any degree of hydrogen-bonding. a 111.11 0 5 A‘ FIGURE 4 The molecular packing and projection along the b axis TABLE 5 Closest intermolecular approaches (A) O(12) - * * O(13I) 3.47 O(16) * * H(6‘1X) O(12) * * * O(15I) 3.31 O(16) * * - H SIX) O(12) - - * 0(1811) 3.40 O(17) - - - H[lvIII) O(13) * - * O(14UI) 3-22 O(17) * * - H(5x) O(13) * - * O(15’) 3.40 O(17) - - H(8vI) O(14) * * * O(15IV) 3.20 O(18) * * * H(2’XI) O(15) * * * 0[15IV) 3.31 O(18) * * H(7X) O(15) * * * O(18IV) 3.05 H(3’) * * * H(9’11) O(16) * - - O(16V) 3-44 H(3’) * * * H(10II) O(16) * - * O(18V) 3.15 H(4) * * * H(1OII) O(12) * - H(8‘vI) 2-82 H(8) * - * H(91X) O(13) * * H(4VII) 2.82 O(13) * - - H(8’In) 2.89 O(14) * - * H(7’IU) 2.92 O(16) * - * H(2V’II) 2-68 2.67 2.92 2.49 2-71 2.97 2.87 2.68 2-43 2.2 1 2.59 2.69 The Roman numerals as superscripts refer to the equivalent positions : 1 1 - x , l - y , l - z VII - x , l - y , l - z 11 x, 1 + y, z vrrr -x, -y, -2 111 - x , -y, 1 - z IX -1 - x , -1 - y, -2 IV 1 - x, --y, 1 - z x 1 + x , rs v -x,-1-y, -2 XI x , -1 +r, z VI 1 3 - x , 1 + y , z We thank the Computing Machine Laboratory, University of Manchester, for computing facilities, N.A.T.O. for the award of a fellowship (to P. F. L.), and Professor R. Pettit for providing the crystal sample. Some of the programmes used in this work were contributed to by Drs. L. I. Hodgson, F. S. Stephens, J. P. Nice, and A. D. Redhouse. [9/443 Received, March 14th, 19691

ISSN:0022-4944    

DOI:10.1039/J19700000038

出版商:RSC    

年代:1970

数据来源: RSC