The title compound, {4,5,9,10,14,15,19,20-octachloro-2,7,12, 17-tetrakis(pentafluorophenyl)-20,22,23,24-

tetraazapentacyclo[l6.2.l.1^(3·6).l^(8·11).l^(13·16)]tetracosa-1,3(21),4,6,8(22),9,11, 13(23), 14, 16, 18(24), 19-dodecaene}copper(II)(CuTFPPC1_8)dichloromethane solvate,

shows a large tetrahedral distortion or ruffling, with pairs of Cl atoms alternately averaging + 1.20 and -1.18 Å out of the plane of the four N atoms; the Cu atom is 0.01 Å out of the plane and the N atoms show a slight (±0.12 Å) tetrahedral distortion. A Cl atom of the solvent, at 3.515 (6) Å in an approximately axial position, is the closest non-bonded neighbor of the Cu atom

Ellis, Paul E., Jr.

Gray, Harry B.

Hodge, Julia A.

Hughes, Maureen E.

Lyons, James E.

Schaefer, William P.

Wagner, Richard W.

Caltech Authors - Main

1342 REGULAR STRUCTURAL PAPERS 
References 
Cromer, D. T. (1974). International Tables for X-ray Crystal-
lography; Vol. IV, pp. 149-,151. Birmingham: Kynoch Press. 
(Present distributor .Kluwer Academic Publishers, Dordrecht.) 
Cromer, D. T. & Waber; J. T. (1974). International Tables for 
X-ray Crystallography, Vol. IV, pp. 99-101. Birmingham: 
Kynoch Press. (Present distributor Kluwer Academic 
Publishers, Dordrecht.) 
Duchamp, D. J. (1964). CRYM Crystallographic Computing 
System. Am. Crystallogr. Assoc. Meet., Bozeman, Montana, 
Paper Bl4, p. 29. 
Johnson, C. K. (1976). ORTEPII. Report ORNL-3794. Oak 
Ridge National Laboratory, Tennessee, USA. 
Lyons, J. E. & Ellis, P. E. (1991). Cata/. Lett. 8, 45-51. 
Acta Cryst. (1993). C49, 1342-1345 
Copper(ll) Tetrakis(pentafluorophenyl)-
. j:1-octachloroporphyrin 
WILLIAM P. SCHAEFER, JULIA A. HODGE, 
MAUREEN E. HUGHES AND HARRY B. GRAY 
Division of Chemistry and Chemical Engineeringt 
and The Beckman Insitute, Mail Code 139-74, 
California Institute of Technology, Pasadena, 
California 91125, USA 
JAMES E. LYONS, PAUL E. ELLIS JR AND 
RICHARD W. WAGNER 
Research and Development Department, Sun Company, 
Inc., Marcus Hook, Pennsylvania 19061, USA 
(Received 6 May 1992; accepted 15 January 1993) 
Abstract 
The title compound, {4,5,9,10,14,15,19,20-octachloro-
2, 7, 12, 17-tetrakis(pentafluorophenyl)-20,22,23,24-
tetraazapentacyclo[l 6.2. l.13·6. l 8·u. l 13·16]tetracosa-
1,3(21),4,6,8(22),9,11, 13(23), 14, 16, 18(24), 19-dodeca-
ene }copper(II) ( CuTFPPC18) dichloromethane solv-
ate, shows a large tetrahedral distortion or ruffling, 
with pairs of Cl atoms alternately averaging + 1.20 
and -1.18 A out of the plane of the four N atoms; 
the Cu atom is 0.01 A out of the plane and the N 
atoms show a slight (±0.12 A) tetrahedral distor-
tion. A Cl atom of the solvent, at 3.515 (6) A in an 
approximately axial position, is the closest non-
bonded neighbor of the Cu atom. 
t Contribution No. 8623. 
© 1993 International Union of Crystallography 
Printed in Great Britain - all rights reserved 
Comment 
Derivatives of halogenated porphyrins are active 
catalysts for oxygenation of light alkanes, requiring 
no added co-reductants or sacrificial 0-atom donors 
for their activity (Lyons, Ellis, Wagner, Thompson, 
Hughes, Hodge & Gray, 1992). The CuTFPPC18 
derivative was synthesized from the metal-free por-
phyrin and copper acetate in methanol solution and 
purified by elution from silica gel with hexane/ 
dichloromethane. Reddish prisms were grown by 
evaporation of CH2Cli solutions of the complex at 
room temperature over 7-10 d. The Cu atom has 
approximately square-planar coordination. The four 
N atoms show a slight tetrahedral distortion 
( ± 0 .12 A from their plane) and the nearest axial 
neighbor atom is a Cl of the solvent, 3.515 (5) A on 
one side of the plane. On the other side, Cl 3 of an 
adjacent molecule is 2.968 ( 4) A distant. The mol-
ecule is shown in Fig. 1. 
F54 
Fig. 1. An ORTEPII drawing of the porphyrin molecule with 75% 
probability ellipsoids showing the numbering system. 
The porphyrin molecule shows a strong tetra-
hedral distortion, reaching ± 0. 7 A for the pyrrole C 
atoms and ± 1.19 A for the Cl atoms (Fig. 2). This 
appears to be a steric effect caused by crowding 
between the pentafluorophenyl groups and the Cl 
atoms on the periphery of the porphyrin. The f3 C 
atoms have planar coordination, but the angles to Cl 
atoms at them are altered to move the Cl atoms 
away from the phenyl rings. The tetrahedral distor-
tion accomplishes the same effect, but even the com-
bination of the two leaves exceedingly close 
Acta Crysta/lographica Section C 
ISSN 0108-2701 © 1993 
REGULAR STRUCTURAL PAPERS 1343 
Cl···apical-C contacts: the closest is 2.97 A and the 
average of all eight is 3.00 (2) A. A van der Waals 
contact would be 3.45 A, so the crowding here is 
significant. The Cl· .. Cl contacts are similarly close -
3.20 (2) vs 3.60 A for a van der Waals contact - so 
nothing can be gained by moving the Cl atoms in the 
plane; it must deform. The phenyl rings have turned 
so their planes are perpendicular to the Cl-Cl vector 
of their close neighbors, implying other contacts to 
ortho C atoms or F atoms. It appears that the Cl .. ·C 
contacts are the more important; they average 
3.28 (9) A, still 0.17 A or more shorter than a van 
der Waals distance (3.45 A expected; one found at 
3.13, two 3.18 and all others at greater than 3.23 A). 
Thus the distortion from planarity appears to arise 
not primarily from the influence of the metal atom, 
but more from the crowding of the f3 Cl atoms and 
the meso phenyl groups. 
The packing drawing (Fig. 3) shows the solvent 
CH2Cl2 molecule with one Cl atom in an approxi-
mately axial position with respect to the Cu, but 
3.515 (5) A from it. Other intermolecular contacts 
are at van der Waals distances or greater. 
Fig. 2. A stereoview of the porphyrin molecule showing the 
pronounced smooth tetrahedral distortion. Note that the phenyl 
rings are approximately perpendicular to the vector between 
their close Cl neighbors. 
Fig. 3. An ORTEPII drawing showing the packing in the crystal. 
The contents of one unit cell is shown (50% probability ellip-
soids) with a unit cell outlined. H atoms on the CH2Cb mol-
ecule are not shown. The Cu atoms have shaded octants, the 
porphyrin atoms outlined octants and the solvent atoms are 
unadorned. The view is perpendicular to the be plane, with the c 
axis horizontal. 
Experimental 
Crystal data 
[Cu(C44ClsF20N4)].CH2Ch 
M, = 1396.58 
Dx. = 1.96 Mg m-3 
Mo Ka radiation 
Tri clinic 
PT 
a = 11.794 (5) A 
b = 14.492 (4) A 
c = 14.731 (2) A 
a = 87.51 (5) 0 
/3 = 73.48 (5) 0 
'Y = 78.40 (3)0 
v = 2364 (3) A3 
Z=2 
Data collection 
Enraf-Nonius CAD-4 
diffractometer 
0-20 scans 
Absorption correction: 
empirical 
Tmm = 0.953, Tmax = 
1.042 
>. = o.71073 A 
Cell parameters from 25 
reflections 
() = 16.5- 18° 
µ = 1.15 mm- 1 
T= 294 K 
Irregular five-sided prism 
0.63 x 0.52 x 0.33 mm 
Reddish 
Rmt = 0.016 
Omax = 25° 
h=-14-d4 
k= -17---+ 17 
l = -17---+ 17 
16705 measured reflections 
8290 independent reflections 
8290 observed reflections 
3 standard reflections 
frequency: 166.66 min 
intensity variation: within 
counting statistiC8 
[all relections used] 
Refinement 
Refinement on F2 w = 1/u2(F1) 
Final R = 0.052 (on F) for 
6908 reflections with 
FJ>3u(FJ) 
(!!:../u)rruu = 0.03 for por-
phyrin, 0.35 for solvent 
t1pmax = 1.36 e A - 3 
wR = 0.014 (on F2) 
s = 3.75 
8290 reflections 
582 parameters 
No H atoms included in 
model 
t1pmm = -1.29 e A-3 
Extinction correction: Larson 
(1967) 
Extinction coefficient (sec-
ondary): 0.61 (7) x 10-6 
Table 1. Fractional atomic coordinates and isotropic or 
equivalent isotropic displacement parameters cA2) 
A dagger indicates an isotrqeic B parameter; for the other atoms 
Ueq = ~2..;iL:pvaiaJai.aj. 
Cu 
Cll 
Cl2 
Cl3 
Cl4 
Cl5 
Cl6 
Cl7 
Cl8 
NI 
N2 
N3 
N4 
Cl 
C2 
C3 
x 
0.2200 (4) 
0.1502 (1) 
0.1485 (1) 
0.3138 (1) 
0.3000 (1) 
0.0840 (1) 
0.0844 (1) 
0.3341 (1) 
0.3747 (1) 
0.2238 (3) 
0.2238 (3) 
0.1922 (3) 
0.2361 (3) 
0.2172 (3) 
0.1868 (3) 
0.1853 (3) 
y 
0.46010 (3) 
0.3108 (I) 
0.5302 (1) 
0.8111 (1) 
0.8401 (1) 
0.6347 (1) 
0.4147 (1) 
0.0848 (1) 
0.0593 (1) 
0.4426 (3) 
0.5969 (2) 
0.4798 (2) 
0.3210 (2) 
0.3605 (2) 
0.3822 (3) 
0.4743 (3) 
z 
0.83050 (3) 
0.4943 (1) 
0.4548 (1) 
0.6452 (1) 
0.8604 (1) 
1.2058 (1) 
1.2421 (I) 
0.9803 (1) 
0.7574 (1) 
0.6950 (2) 
0.8080 (2) 
0.9700 (2) 
0.8506 (2) 
0.6552 (3) 
0.5671 (3) 
0.5508 (3) 
Bor Ueq 
0.0284 (1) 
0.0502 (3) 
0.0458 (2) 
0.0504 (3) 
0.0624 (3) 
0.0578 (3) 
0.0512 (3) 
0.0603 (4) 
0.0620 (4) 
2.3 (l)t 
2.3 (l)t 
2.4 (l)t 
2.3 (l)t 
2.3 (l)t 
2.5 (l)t 
2.5 (l)t 
1344 REGULAR STRUCTURAL PAPERS 
C4 0.2118 (3) 0.5126 (3) 0.6307 (3) 2.4 (l)t Cl7-Cl7 1.713 (4) Cl0-C31 1.500 (6) 
C5 0.2308 (3) 0.6032 (3) 0.6380(3) 2.3 (l)t Cl8-C18 1.704 (4) C11-C12 1.444 (6) 
C6 0.2432 (3) 0.6398 (3) 0.7206(3) 2.3 (l)t Nl-Cl 1.374 (5) Cl2-C13 1.347 (6) 
C7 0.2727 (3) 0.7301 (3) 0.7300 (3) 2.6 (l)t Nl-C4 1.371 (5) C13-C14 1.447 (5) 
cs 0.2674 (3) 0.7421 (3) 0.8211 (3) 2.8 (l)t N2-C6 1.385 (5) C14-Cl5 1.393 (5) 
C9 0.2332 (3) 0.6592 (3) 0.8719 (3) 2.5 (l)t N2-C9 1.373 (5) C15-C16 1.392 (5) 
ClO 0.2041 (3) 0.6473 (3) 0.9698 (3) 2.6 (l)t N3-Cll 1.375 (5) C15-C41 1.504 (5) 
C11 0.1740 (3) 0.5650(3) 1.0150 (3) 2.6 (l)t N3-C14 1.376 (5) C16-C17 1.451 (5) 
Cl2 0.1328 (4) 0.5522 (3) 1.1160 (3) 2.9 (l)t N4-C16 1.387 (5) C17-Cl8 1.350 (6) 
C13 0.1325 (3) 0.4599 (3) 1.1310 (3) 2.8 (l)t N4-C19 1.371 (5) Cl8-Cl9 1.449 (5) 
C14 0.1753 (3) 0.4130 (3) 1.0393 (3) 2.4 (l)t Cl-C2 1.448 (5) C19-C20 1.401 (5) 
C15 0.2087 (3) 0.3161 (3) 1.0227 (3) 2.5 (l)t Cl-C20 1.394 (5) C20-C51 1.498 (5) 
C16 0.2457 (3) 0.2743 (3) 0.9331 (3) 2.5 (l)t N2-Cu-Nl 90.3 (1) C7-C8-Cl4 122.l (3) 
C17 0.2932 (4) 0.1751 (3) 0.9100 (3) 2.9 (l)t N3-Cu-Nl 172.3 (1) C9-C8-Cl4 130.3 (3) 
C18 0.3084 (4) 0.1635 (3) 0.8165 (3) 2.9 (l)t N4-Cu-Nl 90.5 (1) C9-C8-C7 107.6 (3) Cl9 0.2660(3) 0.2544 (3) 0.7801 (3) 2.4 (l)t N3-Cu-N2 90.4 (1) C8-C9-N2 108.4 (3) 
C20 0.2467 (3) 0.2710 (3) 0.6907 (3) 2.4 (l)t N4-Cu-N2 173.7 (1) C10-C9-N2 125.0 (3) 
C21 0.2368 (3) 0.6654 (3) 0.5532 (3) 2.7 (l)t N4-Cu-N3 89.7 (1) C10-C9-C8 126.3 (3) 
C22 0.1373 (4) 0.7286(3) 0.5455 (3) 0.0458 (11) Cl-Nl-Cu 125.6 (2) C11-C10-C9 124.0 (4) 
F22 0.0327 (2) 0.7326 (2) 0.6132 (2) 0.0592 (7) C4-Nl-Cu 126.3 (2) C31-C10-C9 117.9 (3) 
C23 0.1391 (6) 0.7873 (3) 0.4692(4) 0.0651 (14) C4-Nl-Cl 107.1 (3) C31-C10-Cll 117.7 (3) 
F23 0.0398 (4) 0.8477 (2) 0.4642(3) 0.1041 (11 C6-N2-Cu 125.5 (2) C10-C11-N3 124.7 (3) 
C24 0.2440(7) 0.7813 (4) 0.3985 (4) 0.0777 (18) C9-N2-Cu 125.7 (2) C12-Cll-N3 108.8 (3) 
F24 0.2471 (5) 0.8389 (3) 0.3234 (3) 0.1272 (14) C9-N2-C6 107.6 (3) C12-Cll-C10 126.1 (4) 
C25 0.3458 (6) 0.7201 (4) 0.4029 (3) 0.0682 (17) Cll-N3-Cu 125.9 (2) Cll-C12-Cl5 129.4 (3) 
F25 0.4501 (4) 0.7160 (3) 0.3338 (2) 0.1140 (15) C14-N3-Cu 126.7 (2) Cl3-C12-Cl5 122.9 (3) 
C26 0.3425 (5) 0.6610(3) 0.4803 (3) 0.0492 (12) C14-N3-Cll 107.1 (3) Cl3-C12-Cll 107.6 (3) 
F26 0.4423 (3) 0.6016 (2) 0.4850 (2) 0.0731 (9) C16-N4-Cu 126.1 (2) C12-C13-Cl6 122.8 (3) 
C31 0.2205 (4) 0.7224 (3) 1.0290(3) 3.1 (l)t C19-N4-Cu 125.1 (2) C14-C13-Cl6 130.0 (3) C32 0.3285 (5) 0.7155 (3) 1.0480(3) 0.0524 (12) C19-N4-Cl6 107.5 (3) C14-Cl3-C12 1072 (3) 
F32 0.4153 (3) 0.6390 (2) 1.0180 (2) 0.0709 (8) C2-Cl-Nl 108.9 (3) C13-C14-N3 108.8 (3) 
C33 0.3553 (6) 0.7860(4) 1.0938 (3) 0.0671 (15) C20-Cl-Nl 124.5 (3) C15-C14-N3 124.6 (3) 
F33 0.4629 (4) 0.7762 (3) 1.1104 (3) 0.1064 (12) C20-Cl-C2 126.4 (3) C15-C14-C13 126.1 (3) C34 0.2710 (8) 0.8667 (4) 1.1204 (4) 0.0773 (19) Cl-C2-Cll 129.5 (3) Cl6-Cl5-Cl4 123.9 (3) 
F34 0.2965 (4) 0.9375 (2) 1.1613 (2) 0.1116 (13) C3-C2-Cll 122.7 (3) C41-C15-C14 118.1 (3) C35 0.1596 (7) 0.8747 (3) 1.1064(3) 0.0709 (19) C3-C2-Cl 107.7 (3) C41-C15-C16 118.0 (3) 
F35 0.0764 (4) 0.9541 (2) 1.1320 (3) 0.1129 (14) C2-C3-Cl2 122.9 (3) C15-C16-N4 124.8 (3) 
C36 0.1342 (5) 0.8031 (3) 1.0617 (3) 0.0557 (13) C4-C3-Cl2 130.0 (3) C17-C16-N4 108.3 (3) F36 0.0257 (3) 0.8127 (2) 1.0478 (2) 0.0792 (9) C4-C3-C2 107.0 (3) C17-C16-C15 126.8 (3) C41 0.2076 (3) 0.2529 (3) 1.1066(3) 2.7 (l)t C3-C4-Nl 108.9 (3) C16-C17-Cl7 129.6 (3) C42 0.1113 (4) 0.2106 (3) 1.1482 (3) 0.0420 (10) C5-C4-Nl 125.1 m C18-C17-Cl7 122.7 (3) F42 0.0158 (3) 0.2278 (2) 1.1148 (2) 0.0670 (8) C5-C4-C3 125.8 (3) C18-C17-C16 107.6 (3) C43 0.1096 (5) 0.1516 (3) 1.2244 (3) 0.0559 (14) C6-C5-C4 123.5 (3) C17-C18-Cl8 123.2 (3) F43 0.0142 (3) 0.1129 (2) 1.2622 (2) 0.0882 (10) C21-C5-C4 118.1 (3) C19-C18-Cl8 129.3 (3) C44 0.2062 (6) 0.1356 (4) 1.2610(3) 0.0689 (17) C21-C5-C6 118.4 (3) C19-C18-C17 107.4 (3) F44 0.2039 (4) 0.0791 (3) 1.3361 (2) 0.1153 (14) C5-C6-N2 125.6 (3) C18-C19-N4 108.9 (3) C45 0.3026 (5) 0.1755 (4) 1.2230(4) 0.0654 (14) C7-C6-N2 108.4 (3) C20-Cl9-N4 124.8 (3) F45 0.3967 (4) 0.1587 (3) 1.2585 (3) 0.1169 (13) C7-C6-C5 125.9 (3) C20-C19-C18 126.0 (3) C46 0.3029 (4) 0.2341 (3) 1.1454 (3) 0.0490 (11) C6-C7-Cl3 129.6 (3) C19-C20-Cl 123.8 (3) F46 0.4000 (3) 0.2726 (2) 1.1070(2) 0.0759 (9) C8-C7-Cl3 122.4 (3) C51-C20-Cl 117.7 (3) C51 0.2593 (3) 0.1880 (3) 0.6289 (3) 2.4 (l)t C8-C7-C6 107.9 (3) C51-C20-C19 118.5 (3) C52 0.3594 (4) 0.1634 (3) 0.5518 (3) 0.0345 (9) 
F52 0.4449 (2) 0.2148 (2) 0.5311 (2) 0.0538 (6) The two H atoms on CH2Ch were ignored. The structure was C53 0.3734 (4) 0.0868 (3) 0.4957 (3) 0.0407 (10) 
solved by MULTAN88 (Debaerdemaeker, Germain, Main, Re-F53 0.4724(3) 0.0641 (2) 0.4216 (2) 0.0627 (8) 
C54 0.2877 (4) 0.0329 (3) 0.5155 (3) 0.0451 (11) faat, Tate & Woolfson, 1988) which located the Cu and Cl atoms 
F54 0.3029 (3) -0.0439(2) 0.4622 (2) 0.0729 (9) of the porphyrin and 15 light atoms. F2 magnitudes were used 
C55 0.1864 (4) 0.0554 (3) 0.5904(3) 0.0455 (11) in full-matrix least-squares refinement of 582 parameters: posi-F55 0.1018 (3) 0.0025 (2) 0.6088 (2) 0.0717 (8) 
tional and isotropic displacement parameters for the light atoms C56 0.1733 (4) 0.1327 (3) 0.6462 (3) 0.0393 (10) 
F56 0.0734 (2) 0.1551 (2) 0.7189(2) 0.0631 (7) of the porphyrin ring and the phenyl C atoms bonded to it, po-
C(Sl) 0.4144 (11) 0.4448 (10) 0.2258 (10) 0.2054 (50) sitional and anisotropic displacement parameters for all other Cl(Sl) 0.4351 (2) 0.3873 (3) 0.3268 (3) 0.2286 (15) 
atoms, a scale factor and a secondary-extinction parameter. A Cl(S2) 0.4720(4) 0.5382 (3) 0.2089 (4) 0.2479 (19) 
population parameter for the solvent molecule refined to 1.0 
Table 2. Selected bond lengths (A) and angles (°) within 2.5 e.s.d. and it was set to 1.0 for the final cycles. The weights were taken as 1/u2(FJ); variances [u2(FJ)] were de-
Cu-Nl 2.010 (3) C2-C3 1.342 (5) rived from counting statistics plus an additional term, (0.0141)2; 
Cu-N2 2.003 (3) C3-C4 1.459 (5) variances of the merged data were obtained by propagation of Cu-N3 2.011 (3) C4-C5 1.388 (5) 
error plus another additional term, (0.014/)2. Atomic scatter-Cu-N4 2.003 (3) C5-C6 1.405 (5) 
Cll-C2 1.717 (4) C5-C21 1.502 (5) ing factors and values for I were taken from Cromer & Waber 
Cl2-C3 1.719 (4) C6-C7 1.441 (5) (1974) and Cromer (1974). The largest peaks and valleys in the 
Cl3-C7 1.712 (4) C7-C8 1.343 (5) final difference map were all within 1.5 A of the solvent atom. Cl4-C8 1.707 (4) C8-C9 1.453 (5) 
The programs used were those of CRYM (Duchamp, 1964) and Cl5-C12 1.714 (4) C9-C10 1.395 (5) 
C16-C13 1.719 (4) ClO-Cll 1.400 (5) ORTEPIT (Johnson, 1976). 
REGULAR STRUCTURAL PAPERS 1345 
This work was supported by the US Department of En-
ergy, Morgantown Energy Technology Center, the Gas 
Research Institute, and the Sun Company, Inc. 
Lists of structure factors, anisotropic displacement parameters and com-
plete geometry have been deposited with the British Library Document 
Supply Centre as Supplementary Publication No. SUP 71020 (40 pp.). 
Copies may be obtained through The Technical Editor, International 
Union of Crystallography, 5 Abbey Square, Chester CHl 2HU, Eng-
land. [CIF reference: HH1022] 
References 
Cromer, D. T. (1974). International Tables/or X-ray Crystallogra-
phy, Vol. IV, pp. 149-151. Birmingham: Kynoch Press. (Present 
distributor Kluwer Academic Publishers, Dordrecht.) 
Cromer, D. T. & Waber, J. T. (1974). International Tables for 
X-ray Crystallography, Vol. IV, pp. 99-101. Birmingham: 
Kynoch Press. (Present distributor Kluwer Academic 
Publishers, Dordrecht.) 
Debaerdemaeker, T., Germain, G., Main, P., Refaat, L. S., Tate, 
C. & Woolfson, M. M. (1988). MULTAN88. A System of 
Computer Programs for the Automatic Solution of Crystal Struc-
tures from X-ray Diffraction Data. Univs. of York, England, 
and Louvain, Belgium. 
Duchamp, D. J. (1964). CRYM Crystallographic Computing 
System. Am. Crystallogr. Assoc. Meet., Bozeman, Montana, 
Paper B14, p. 29. 
Johnson, C. K. (1976). ORTEPII. Report ORNL-3794. Oak 
Ridge National Laboratory, Tennessee, USA. 
Larson, A. C. (l 967). Acta Cryst. 23, 644-665. 
Lyons, J. E., Ellis, P. E., Wagner, R. W., Thompson, P. E., 
Hughes, M. E., Hodge, J. A. & Gray, H. B. (1992). ACS 
Division of Petroleum Chemistry Symposium, ACS National 
Meeting, April 1992. 
Acta Cryst. (1993). C49, 1345-1347 
Trimeric Bis( cyclopentadienyl)oxo-
zirconium(IV) Benzene Solvate 
OLGA A. MIKHAILOVA, MARIA H. MINACHEVA, 
VLADIMIR v. BURLAKOV, VLADIMIR B. SHUR, 
ALEXANDER P. PISAREVSKY, ALEXANDER I. Y ANOVSKY 
AND YURI T. STRUCHKOV 
Institute of Organoelement Compounds, 28 Vavilov St., 
Moscow 117813, Russia 
(Received 1 August 1992; accepted 22 December 1992) 
Abstract 
The title compound, cyclo-tri-µ-oxo-tris[bis( 775 -cyclo-
pentadieny l)zirconium] benzene solvate, obtained from 
the reaction of zirconocene hydride with C02, is shown 
to contain planar Zr30 3 cycles with comparatively short 
© 1993 International Union of Crystallography 
Printed in Great Britain - all rights reserved 
Zr-0 distances [1.959 (5)-1.976 (5) A] as a result of par-
tial double bonding. 
Comment 
Oxo complexes of zirconocene are of interest as interme-
diates in carbon monoxide and carbon dioxide fixation 
processes. Cp2Zr0 units are often found to be associated 
in trimeric molecules where Zr30 3 six-membered cycles 
are planar owing to additional d7r -p7r interaction between 
0 and Zr atoms. In previous studies, a toluene solvate of 
oxo-zirconocene trimer (I) was obtained via CJ>2Zr(C0)2 
reaction with C02 and characterized by means of X-
ray structure analysis (Fachinetti, Floriani, Chiesi-Villa & 
Guastini, 1979). 
(I) 
Our investigations of carbon dioxide interaction with 
zirconocene and hafnocene hydrides have shown that 
[Cp2ZrH2]n readily reacts with C02 at room temperature 
and atmospheric pressure yielding the benzene solvate of 
the oxo-zirconocene trimer, (II). Its cystal structure was 
determined and compared with that of (I) and that of ( TJ2-
formaldehyde )zirconocene trimer (III) (Kropp, Skibbe & 
Erker, 1983), which turns into (II) on thermolysis. 
Crystals of (II) consist of trimeric bis( cyclopentadien-
y l )oxozirconium complexes [CJ>2Zr0h and solvating 
benzene molecules. The Zr30 3 cycle is planar within 
0.023 A; the Zr-0 bond lengths range from 1.959 (5) to 
1.976 (5) A, which is almost the same as in (I) (l.950-
1.968 A) and significantly shorter than in (III) (2.133-
2.178 A). Rather short Zr-0 bond distances in (µ-oxo )-
complexes (I) and on result from the partial double bond-
ing which is absent in (772-CH20)-complex (III) and(µ-
hydroxo )(µ3-oxo )cyclopentadienylzirconium complexes 
reported in recent publications (Babcock, Day & Klem-
perer, 1989; Thewalt, Doppert & Lasser, 1986). The three 
Zr-0-Zr angles [142.6 (2), 142.4 (1) and 142.1 (2)0 ] 
are amost equal and close to those observed in (I) (average 
Acta Crystallographica Section C 
ISSN 0108-2701 © 1993 
