Structure of C O ~ ( C O ) ~ ( C ~ H ~ ~ ) ~
Inorganic Chemistry, Vol. 17, No. 7, 1978 1995 Contribution from the Research School of Chemistry, Australian National University, Canberra, A.C.T., Australia 2600
Isolation of Intermediates in the Co2(CO)&atalyzed Cyclotrimerization of Cyclooctyne. Crystal and Molecular Structure of a Cobaltacyclopentadiene Complex M. A. BENNETT* and P. B. DONALDSON
Received October 21, 1977 Dicobalt octacarbonyl reacts with cyclooctyne at room temperature to give an orange air-stable complex CO2(C0)5(C8H12)2 as the major organocobalt product together with the pcyclooctyne complex C O ~ ( C O ) ~ ( C and ~ H ~the~ )aromatic cyclotrimer tris(hexamethy1ene)benzene. The crystal and molecular structure of C O ~ ( C O ) ~ ( C has ~ H been ~ ~ ) determined ~ by threedimensional X-ray structural analysis using 4682 reflections, with p > 3 0 ( p ) , collected on a four-circle diffractometer. Crystals of C02(C0)5(C8H12)2 are triclinic, space group Pi,with a = 13.529 (3) %.,b = 8.587 (2) A, c = 9.848 (2) A, a = 103.92 ( l ) " , p = 100.44 (l)', y = 102.16 (l)', and Z = 2. The structure was solved by conventional heavy-atom methods and was refined to final weighted and unweighted R factors of 0.031 and 0.044. In its general features the structure resembles those of the well-known ferracyclopentadiene complexes Fe2(C0)6(alkyne)2.Two cyclooctyne units are joined in a metallacyclopentadiene unit containing one cobalt atom carrying three carbon monoxide groups, and the ring is T bonded to the second cobalt atom which carries two carbon monoxide groups. The Co-Co distance of 2.4738 (7) 8, is in the range expected for a metal-metal bond. The cobaltacyclopentadiene ring is approximately planar and the near equality H , ~Co2(C) of C-C bond lengths [ 1.423 average] indicates extensive electron delocalization Both C O ~ ( C O ) ~ ( C ~and 0)5(C8H,2)2 catalyze cyclotrimerization of cyclooctyne at room temperature, apparently independently of each other.
Introduction
Dicobalt octacarbonyl, C O ~ ( C O )reacts ~ , with acetylenes (ac) to give a wide variety of organometallic and organic The first complex formed under mild conditions is Co2(C0),(ac) (I), which contains a bridging acetylene
7'
R
' C e C
eliminated the possibility that an intermediate cyclobutadiene metal complex is i n v ~ l v e d . ~Cyclooligomerization of the simplest unsubstituted isolable cyclic alkyne, cyclooctyne (CxHIZ),is catalyzed by a number of transition metal compounds, e.g., NiBr2,10Ni(CN),," Ni(CH2=CHCN),,l1 Pt(PPh3)2(C8H12),11 TiC14,12and Fe(C0)513under very mild conditions, and we have therefore investigated the reaction of cyclooctyne with C O ~ ( C Oto) ~see if intermediates in cyclooligomerization could be isolated.
Experimental Section Starting Materials. Hydrocarbon solvents were stored over sodium wire and degassed before use. Chromatographic separations were carried out on columns (100 cm X 4 cm) containing degassed Florisil I (60-100 mesh) using degassed n-pentane or benzene as eluent. Samples were collected under nitrogen. ligand, but on heating with an excess of acetylene organoDicobalt octacarbonyl (Strem) was used as received, and cyclooctyne metallic complexes of formulas C O , ( C O ) ~ ( ~ C or) ~Cozwas prepared by heating cycloocteno-1,2,3-selenadiazolein v ~ c u o . ~ ~ , ~ ~ ( C O ) , ( ~ C are ) ~ produced, in addition to cyclopentadienones, Physical Measurements. The following instruments were used: a quinones, benzenes, and polymer^.^ The relative amounts of PE457 grating instrument calibrzted in the v(C0) region with DCl these products depend on reaction conditions and on the alkyne (IR), an AEI MS902 operating at 70 eV (mass spectra), a Varian substituents. Cobalt carbonyl complexes such as C O ~ ( C O ) ~ , HA100 ('H N M R ) , and a Jeol FX-60 F T spectrometer operating H ~ [ C O ( C O ) ~ and ] , , Co,(CO),(ac) also catalyze the cycloat 15.02 M H z (13C NMR). Microanalyses were carried out by the trimerization of acetylenes to benzenes. It has been Microanalytical Unit of this University. Melting points were measured on a Gallenkamp hot-stage apparatus in capillaries sealed under suggested5,, that the Coz(CO),(ac), complexes are cyclopentadienone cobalt carbonyls (11), and the C 0 ~ ( C 0 ) , ( a c ) ~ nitrogen and are uncorrected. Reaction of Dicobalt Octacarbonyl with Cyclooctyne. A solution of C O ~ ( C O(0.401 )~ g, 1.17 mmol) in n-pentane (150 mL) contained in a 250-mL Schlenk flask at room temperature (22 "C) was treated under nitrogen with cyclooctyne (0.752 g, sixfold molar excess) from a syringe. On stirring the mixture, carbon monoxide was rapidly evolved. The reaction gradually subsided but gas evolution continued over a 2-h period. Nitrogen was then bubbled through the solution I1 until the volume was ca. 50 mL and the brownish yellow mixture was (substituents on cyclopentadlenone omitted for clarity) chromatographed in n-pentane on Florisil; other adsorbents caused complete decomposition. The faster running brown band contained complexes are known from X-ray studies to contain a bridging a mixture of C O ~ ( C O ) ~ ( C ~ H and ~ , colorless ) tris(hexamethy1ene)unit of three linked alkyne units in a so-called "fly-over'' benzene, C24H36, while the slower moving orange band contained arrangement (III).73x Although the latter compounds do give C O ~ ( C O ) ~ ( C and ~ H C24H36. ~ ~ ) ~ The organocobalt complexes were separated from the aromatic compound by repeated chromatography. The first band gave p-cyclooctyne-hexacarbonyldicobalt,Co2(C0)6(C8H12)(0.1 1 g, 22%), as moderately air-sensitive, red-brown waxy crystals, mp 36-38 "C, from n-pentane at -10 "C: IR (cm-I) (thin film) 2086 (m), 2045 (s), 2024 (vs), 2010 (s) [v(CO)], 1625 (m) [v(C=C)]; (C6HI4) 2087 (m), 2045 (s), 2025 (vs), 2012 (s) I11 [v(CO)]; mass spectrum m / e (relative intensity) 394 (6), 366 (28), (substituents on carbon chain omitted for clarity) 338 (14), 310 (34), 282 (30), 254 (28), 226 (14), 117 (34), 115 (28), aromatic trimers on chemical o r thermal degradation, they 105 (40), 103 (42), 101 (36), 91 (60), 89 (54), 87 (40), 77 (loo), do not catalyze alkyne cyclotrimerization. The mechanism 75 (69); ' H N M R (CD,C12) 6 1.64, 3.00 (br, m, CH2) I3C N M R of the catalytic process is unknown, although a study of the (CD2C12) 6 27.0, 27.4, 36.5 (s, CH2), 99.9 (s, C=C), (overlapping, C ~ ~ ( C O ) ~ - c a t a l y zcyclotrimerization ed of CH3C2CD3has br, s, 0 ) . Anal. Calcd for C14H1206C02:C, 42.64; H, 3.04; Co,
0020-1669/78/1317-1995$01 .OO/O
0 1978 American Chemical Society
1996 Inorganic Chemistry, Vol. 17, No. 7 , 1978 29.95; mol wt 393.9299. Found: C, 42.54; H , 3.25; Co, 29.66; mol wt 393.9296 (P', mass spectrometry). Evaporation of the more slowly moving orange band gave air-stable, orange crystals of dicarbonyl[2-5-q-2,3:4,5-bis( hexamethylene)(tri-
M. A. Bennett and P. B. Donaldson Table I. Crystal Data for Co,(CO),(C,H,,), a = 13.529 (3) A ' * b ~ c
a = 103.92 (1)"
b = 8.587 (2) A c = 9.848 (2) A
0= 100.44 (1)"
244 (42), 216 (loo), 201 (20), 173 (55), 159 (65), 145 (87), 131 (95), 117 (off scale), 105 (off scale), 91 (off scale), 79 (96), 77 (95); ' H NMR (c&) 6 1.0-3.05 (overlapping multiplets, CH,; main peaks at 6 1.50, 2.55, and 2.95); I3CNMR (CD2CI2,-90 "C) 6 25.06, 26.75, 29.61, 32.34,41.04 (s, CH2), 138.43, 180.89 (s, C=C), 201.94, 204.79 (s, CO). Anal. Calcd for C2,HZ405C02:C, 53.16; H, 5.06; Co, 24.89; mol wt 474.0287. Found: C, 53.38; H , 5.10; Co, 24.35; mol wt 474.0286 (P', mass spectrometry). Other accurate mass measurements were as follow. P - CO+: calcd, 446.0037; found, 446.0038. P 2C0': cdcd, 418.0388; found, 418.0386. P - 3CO': calcd, 390.0439; found, 390.0439. (C&!2)2+: calcd, 216.1877; found, 216.1877. The most slowly moving band eluted with n-pentane gave on evaporation and recrystallization from n-pentane colorless needles of Tris(kexasnethylene)benzene, C24H36 (0.45 g, 59% or ca. 90% of available excess of cyclooctyne): mp 199-200 "C (lit.l6 mp 197-198 "C); mass spectrum m/e (relative intensity) 324 (loo), 281 (98), 253 (23), 241 (15), 239 (18), 211 (34), 199 (21), 185 (37), 171 (28), 157 (24), 155 (26), 143 (31), 141 (27), 129 (26), 128 (25), 91 (26), 79 (16), 77 (19). Anal. Calcd for C24H36:C, 88.81; H, 11.19. Found: C, 88.95; H , 11.08. Elution with benzene gave two bands, the faster moving of which afforded yellow plates identified as bis(hexamethylene)-l,4-benzoquinone, [CsHl2C0I2(0.045 g, 5%): mp 148-149 "C ( M I 3 mp 148 "C); IR (Nujol) 1640 cm-' [v(C=O)] 1640 cm-'); mass spectrum m/e (relative intensity) 274 (67), 272 (loo), 244 (lo), 229 (14), 216 (9), 215 (lo), 203 (12), 201 (9), 189 (12), 187 (14), 175 (13), 173 ( l l ) , 161 (14), 159 (lo), 147 (9), 145 ( l o ) , 131 ( l l ) , 117 (12), 105 (18), 91 (59), 79 (30), 71 (34). Anal. Calcd for C18H2402: C, 79.41; H , 8.82; mol wt 272.1174. Found: C, 79.38; H, 8.79; mol wt 272.1775 (P', mass spectrometry). The more slowly moving orange band eluted with benzene gave a 3 4 % yield of a red organocobalt complex of empirical formula C O ~ ( C O ) ~ ( C ~ which H I ~ ) is~ still being studied. Catalysis of Cyclooctyne Trimerization. (i) A solution of Co2(CO)6(C8Hl2) (0.04 g, 0.1 "01) in n-hexane (100 mL) was stirred under nitrogen with cyclooctyne (1.22 g, 3.77 mmol) at room temperature. No gas was evolved and after 8 h, needles of tris(hexamethy1ene)benzene (1.16 g, 94%) had deposited. The IR spectrum of the solution in the v(C0) region showed that Co2(C0)6(C&12) was still present, and there was no evidence for the formation of CO2(C0)5(C&12)2 or any other cobalt carbonyl complexes. (ii) A solution of C O ~ ( C ~ ) ~ ( C(0.025 ~ H , ~g,) 0.05 ~ mmol) was treated with cyclooctyne (0.98 g, 3.02 mmol) as in (i). After 8 h, 0.941 g (96%) of tris(hexamethy1ene)benzene was isolated and the IR spectrum of the solution in the v(C0) region showed that unchanged C O ~ ( C O ) ~ ( C was ~ H ~the ~ )only ~ organocobalt carbonyl complex present.
Collection and Reduction of X-ray Intensity Data Chunky orange crystals of C O ~ ( C O ) ~ ( Csuitable ~ H ~ ~for ) ~X-ray diffraction studies were grown from n-hexane by slow evaporation a t 4 O C . The crystal selected for the experiment was an eight-sided prism with faces (loo), (TOO), (OlO), (OTO), (OOl), (OOT), ( l o r ) , and (101). Preliminary photographs indicated that the complex crystallizes in the triclinic crystal system; there was no evidence of diffraction symmetry higher than C,(T). The choice of the centrosymmetric triclinic space group PI (C,,, No. 2) was confirmed by the successful solution and refinement of the structure. The crystal was mounted on a Picker FACS-1 automated diffractometer with the crystal b axis approximately coincident with the diffractometer r$ axis. Unit cell dimensions and the crystal orientation matrix were obtained from the least-squares refinement" of the setting angles obtained for 12 carefully centered high-angle reflections (20 > 45"). Full crystal data are listed in Table I. The experimental conditions and data collection methods used are described in Table TI. No crystal decomposition was observed and the reflection intensities were reduced to lFol values, each reflection being assigned an individual estimated standard deviation. Formulas
Cryst dimensions 0.029 0.019 cmd
X
0.014
102.16 (1)" Cell vol 1052.6 A 3 Mol wt 474.03 dcalcd= 1.495 g cm-3 z=2 p(Mo Ka) = 16.67 cmi* y=
carbonylcobalta)cyclopentadiene]cobalt( CpCo), CO~(CO)~(C~H~~)~: Temp 22.5 f 1 "C mp 101-103 "c (0.36 g, 66%); IR (cm-') (C6HI4)2070 (m), 2014 Formula C,,W,,O,Co, (vs), 2006 (m), 1966 (vs); mass spectrum m/e (relative intensity) 474 dobsd = 1.492 g cm-3 (6), 446 (8), 418 (lo), 390 (8), 388 (15), 362 (6), 360 (14), 332 (18), Space group PT (Ci' , No. 2) X
'Estimated standard deviations (in parentheses) in this and the following tables, and also in the text, refer to the least significant digit(s). The "reduced" cell obtained from a Delaunay reduction [B.Delaunay, 2. Kristallogr., Kristallgeom., Kristallphys., Kristallchem., 84,109 (1933)j agreed with these cell parameters. No significant variation in cell dimensions was evident after data collection. Crystal dimensions are parallel to a*, b*, and c * , respectively. Table 11. Details of X-ray Data Collection Radiation Wavelength Monochromator Tube takeoff angle Cryst-counter dist Scan technique Scan speed Scan width
Mo Ka 0.7093 A Graphite cryst (002 reflecting plane) 3.0" 28.5 cm Coupled w/20 scans 2" min-' From 0.88" below the Mo K a , max to 0.88" above the Mo KO, max of each peak Scan range limits 3" d 2e d 60" Total bkgd counting time' 20 s "Standard" reflctn indices (006), (350), (800), measd after every 100 reflctns Form of data collected hkl, Kkl, Kkl; hkT Total data collected 6760 Data withI/u(lJ ? 3,O 4682 Data withI/u(l) 6.0 3970
' 10-s stationary background counts were taken at the limits of the scan and the background was assumed to be linear between these two points. used in the data reduction programs have been described elsewhere.lS The instrumental uncertainty factor (p)I9 was set at a value of 0.0021/2. After sorting of reflection data and averaging of equivalent reflections, data with I 5 3u(I) were discarded as being unobserved and those reflections for which the individual background measurements differed significantly ( B 1 / B 2> 4.00) were also discarded. The statistical R factor for the 4682 reflections of the final data set was 0.020.
Structure Solution and Refinement The positions of the two cobalt atoms were found from a threedimensional Patterson map. The remaining carbon and oxygen atoms were located on successive electron density difference maps. The structure was refined by block-diagonal least-squares methods to final unweighted and weighted R factors of R I = 0.033 and R2 = 0.049. Atomic scattering factors for the nonhydrogen atomsZowere corrected for real and imaginary contributions from anomalous scattering.21x22 Although most hydrogen positions could be located on a difference Fourier map ( R , = 0.045), all hydrogen atoms were included at calculated positions assuming a C-H distance of 1.0 A, and equivalent fixed isotropic temperature factors were set at 1Wo greater than those of the attached atom. The positional and thermal parameters were not refined but recalculated after each refinement cycle. Scattering factors for hydrogen were obtained from the analytical fit of those of Stewart et Full details of the refinement sequence are given in Table 111. Four full-matrix refinement cycles were then done on the model as described (R,= 0.031, R2 = 0.044). No individual parameter shift was greater than 0.1 of the corresponding parameter esd. A final difference Fourier map showed no positive maxima >0.3 e A". The standard deviation of an observation of unit weight [Cw(lFol IFcl)2/(m- n)]"' (where m is the number of observations and n is the number of parameters varied) is 1.40; cf. 1.0 for ideal weighting. There is no evidence of serious extinction effects and no dependence of the minimized function on either lFol or A-l sin 0. The computer
Inorganic Chemistry, Vol. 17, No. 7, 1978 1997 Table 111. Least-Squares Refinement Sequence Set no. 1
1 1 2 2 2 2
No. of cycles R~~
Conditions Two Co atoms included All non-H atoms included; temp factors invariant B's varied; anomalous dispersion Absorption-corrected datab l3 Anisotropic temp factorscpd H atoms included Full-matrix refinement
1
~
,
0.335 0.183
0.206
1
0.120 0,099
0.139 0.112
3
0.045 0.033 0.031
0.061 0.049 0.044
4
2
4
b
0.414
'R, =ZIIFoI- IF,II/~IF,IandR,= {w[lF,I- IF,I]z/ Zw lFolz}l'z, where F, is the observed and F, is the calculated structure factor and w is the weight. The function ZW( IFoI IFc1)' was minimized. The transmission factor applied to IFoI 2 averaged 0.896 and ranged from 0.834to 0.927. Anisotropic temperature factors of the form exp[-(P lh* + Ol2kZ+ p J 2 + 2PlZhk + 201,hZ + 2OZ3kl)]were used. Weights of the form u = uz were also introduced, where uz = [ ( ~ r , / L pt) PFo4]1/1/2Fo, ~ and u1= [peak count + (peak time/background time)2]'/2 x total background time. L p is the Lorentz-polarization factor, and P i s
the instrumental uncertainty factor. programs used have been described elsewhere.18 Calculations were performed on the Univac-1108 computer of the Australian National University Computer Centre. Final atomic positional and thermal parameters are listed in Table IV. A list of observed and calculated structure factor amplitudes (X 10) is available as supplementary material.
Results and Discussion Although the reaction of cyclooctyne, CsH12,with dicobalt octacarbonyl, C O ~ ( C O )gives ~ , the expected p-alkyne complex
C O ~ ( C ~ ) ~ ( Cin~about H , ~ 20% ) yield, the main organocobalt complex, formed in 66% yield, is an orange-red crystalline air-stable solid of formula C O ~ ( C O ) ~ ( C ~Single-crystal H~~)~. X-ray diffraction analysis shows this to be a metallacyclopentadiene complex, IV, a type which has not been isolated hitherto from cobalt carbonyl-acetylene reactions. However, the structure is similar to that proposed on the basis of 19F NMR spectroscopy for the complexes Rh,(PF,),(ac), isolated from the reaction of Rh2(PF3)8with dimethyl acetylenedicarboxylate or methyl p r ~ p i o l a t e . ~ ~ The mass spectra of both organocobalt complexes show parent ions and successive loss of CO groups, a feature which is also observed in the case of the metallacyclopentadiene complexes M2(CO)6(ac)2(M = Fe, Ru, Os);25peaks due to CH2 loss from the eight-membered rings are also observed, the pattern being similar to that for cyclooctyne and tris(hexamethy1ene)benzene (see Experimental Section). The IR spectrum of C O ~ ( C O ) ~ ( C shows ~ H ~ ~four ) strong u(C0) bands in the 2000-cm-' region which resemble in position and intensity those of other C O ~ ( C O ) ~ (com~C) plexes.26-28The latter generally show five terminal v(C0) bands and we suggest that the lowest frequency u(C0) absorption in Co2(C0)6(CaH12)at 2010 cm-' consists of two overlapping bands which correspond to those at 2016 and 2005 cm-' in the IR spectrum of C O ~ ( C ~ ) ~ ( C H , C ~ CThe H~).~~ u(C=C) band at 2210 cm-' in free c y c l o ~ c t y n eis~shifted ~ to 1625 cm-I in C O ~ ( C O ) ~ ( C ~ Hthe , , ) , decrease in frequency being similar to that observed in forming the 2-butyne complex C O ~ ( C ~ ) ~ ( C H ~ C ~The C H 'H ~ ) .N~M~R spectrum of exhibits two broad areas of methylene
Table IV. Atomic Positional and Thermal Parameters x/a
dl0Y
YIR
~ ~ 1 1 2 2
:IC
L(ETA33
BETA13
SfTAl?
BETA23
C O I I I
3.15931121
0.00025131
-0.72922
o.ni29n151
'1 9 1 0 8 0 R 1 3 I
o.no203121
0.0005nizi
0.00111131
c0121
0~32093121
r1.12~63131
-0.13190171
C.OOYb014 I
n.1084013i
D.00152121
O.@005512I
0.002U9131
C I I I
3.30041 1 I
-n.0251131
-0.334i121
0.01 30 13 I
9.ncnoizi
0.'1016121
0.001911l
0~003012l
CIZI
0.3510121
-3.001614I
-0.4551131
0.C224151
0.0129131
n.ooqo121
O.@OV912 I
o.ooa2131
C t 3 l
1 . 3 0 3 9 1 31
-0.1417151
-0.5945151
0,0353 I 6 I
3.w92 131
0 . 0 0 7 1 I4 I
0.009612I
C14I
1.2983 13 I
-3.3218151
-n.5iii131
0.1295171
o.ni 3 5 1 4 I
O.OClb14I
0.@029131
-i].oot21u1
CIS1
C.3919 1 3 1
-0.3535151
-'I.E142141
0.0399181
'1.0117151
0.nO9bl4 I
0.0053131
-0.0005151
Clbl
n.qitsizi
-U.3426141
-n, 3 5 1 9 1 3 1
U.020515
I
1.nlb9141
0.0074131
0.004612)
0.001114l
C l l l
0 . 9 3 9 4 I2 I
-0.lb01131
-0.2463 1 3 1
0.318714 I
n.0129131
0.0046121
O.PO~SIZI
0.003613I
Cl'il
0.34?311 I
-0.1099IZI
-3.~410121
0.010813l
0 I OOR 612 I
0.~n20111
0.0013111
~.COlb121
(191
7.2841111
-7.1287I21
-3.1351121
0.009V 1 3 I
o.no12121
O.qO1711 I
0.000911 I
0.0019121
c1101
S.SIR~I~I
-C.1992131
-3.1115121
0.0146141
1.DC99
0.0029121
0.0014121
0.0053121
CI11I
3.2664 12 I
-n.3srb13'
-0. nu06 1 3 1
0.3195141
n.ni741~1
o.no3n121
0.00251 2 I
o.oon1isi
CI12I
0.1509131
-0.421513
- 0 , 0 3 3 9 1 31
J.Olbtl4 I
0.0164191
o.no09131
0.0040 I 3 1
0.0075 1 9 I
Cl13l
0.0118121
-0.404hl31
-'1.113513I
I.Olbbl4I
-1.ni531~1
-c.r1011~21
O~OO3312I
0.0026131
c1191
0.0315121
-0.1414131
-9.1165131
0.0210151
?.O137131
0.0010121
0.0045121
0.0052131
C1151
C.1221121
-0.0833131
-i.r531121
o.ni5aiui
0.0099 121
n.co111zi
C.003912 I
0.0032121
Cl161
9.19b6llI
-0~0b23121
-9.15r9121
0.0198131
3.rlC69121
0.0014III
0.CJ1511 I
0.001a121
c1111
1.1731121
9~1419141
-0.Ulb8131
0.9237161
0.nleb
141
n.no35121
0.001b121
0.0121141
')llll
~.1811121
C.2343IYl
-1.5003131
3.nuui171
0,1388 161
0.0334161
1 . 0 5 6 9 12 I
3.0192131
-0.2695121
C.0200 15 I
0.0106131
n.no80131 @.OO51121
0.C05913 I
r i i 8 i
0.000412 I
0.0036111
01181
.O.~OQ~IZI
0.1215131
-n.2366121
0.0311161
1.O151131
n.wi30131
O.CO34121
0.0062131
C1191
0.0903121
-C.20151.11
-1.4472121
3.0168141
n, noev I2 I
0.noi9121
01191
l.rIY5112 I
-0.3293131
-3.5188121
0.019414 I
n.~iqi131
-0.1005121
3.2371131
r.0319121
a.ni24131
n.ri13131
n.ooi91~1
0.0011121
O.300?131
0~1494121
0.0219141
~ . o i ~ a 1 3 1
0.0034131
J.CO50121
n.noii121
O.COOSI2I
0.00'451 31
o.no261~1
0.0091 131
I3I
I21
c1201
1.3156121
0I:II
fi
C121I
~.419812I
3.279501
-I.I5141JI
C~013R141
n.01351~1
01211
o.qeu2121
0.3197131
-C.l647IJI
0.0214141
0.P252141
'lie
2IC
ATOH
3097 I 2 I
XI*
ATOM
Xlb
-0.10271
YIE
2I
O.C30611 I -0.C003121
2IC
0.00~0i n i
0~302713l
-0~0009131 0.0001 131 - 0 , 0 0 2 a Is
Flb*t71
HI211
z.421
0.0lD
-1.424
H I 101 I
1.3C2
-5.135
0.07c
4.U
HI'II
n.1ui
0.103
-0.41~
~ 1 1 0 2 1
7.396
-0.184
0."03
4.4
5.8
HI311
0.347
-C.133
-9.hbS
HI1111
1.306
-0.92q
n.nu
HI321
n.211
-C.l4h
-0.634
MI1121
0.711
-0.446
-0.138
HI911
1.269
-0.402
-0.176
Ull211
0.146
-9.356
1,159
$97
HI421
!1.25P
-0.3~0
-0.519
HI1221
1.130
-9.540
-7.'130
6.1
HI511
l.457
-J.'eP
-0.521
HI131I
0.011
-0.5UZ
-n.ia~
6.0
"1521
".I98
-5.467
-0.5b9
HI1321
0.107
-0.403
-0.236
6.0
Hlhll
fl.qe-
-0.385
-0.127
HI1911
-1.005
-13.251
-0.044
5.4
HI621
1.351
-0.415
-0.337
H1142I
[email protected])
-0.242
-q.'ol
5.4
HI711
0.489
-0.088
-n. 7 7 6
HI1511
3.161
-J.O62
111721
n.412
-0.173
-0.148
HIlSII
D.OBP
u.011
n.043 -".74l
5.8
4.3
4.3
i
1998 Inorganic Chemistry, Vol. 17, No. 7, 1978 R
n
M. A. Bennett and P. B. Donaldson
C5
Figure 2. Unit cell contents. Table VI. Selected Interatomic Angles (deg)
W
Figure 1. General view of C O ~ ( C O ) ~ ( C ~ H ~ ~ ) ~ . Table V. Selected Interatomic Distances (A) Co(l)-C0(2) Co(l)-C(l) C0(l)-C(16) CO(l)-C(17) C0(l)-C(18) C0(l)-C(19) C0(2)-C(l) C0(2)
