1160 R E G U L A R S T R U C T U R A L PAPERS

Lists of structure factors, anisotropic thermalparameters, H-atomcoor- tetrahedrally distorted. The two phosphite ligands of the
dinates, bond distances, bond angles and torsion angles have been de- Rh complex are deformed as a result of steric interactions.
posited with the British Library Document Supply Centre as Supple-
mentary Publication No. SUP 55862 (20 pp.). Copies may be obtained
through The Technical Editor, InternationalUnionof Crystallography,5
Abbey Square, Chester CH1 2HU, England. [CIF reference: HE1001] Comment
The hydroformylation of otherwise unreactive inter-
nal and branched alkenes can be achieved by using
References bulky phosphite-modified Rh catalysts (van Leeuwen &
Ivanca, M. A., Lappin, A. G. & Scheidt, W. R. (1991). Inorg. Roobeek, 1983; Tokitoh & Yoshimura, 1987, 1989; Billig,
Chem. 30, 711-718. Abatjoglou, Bryant, Murray & Maher, 1988; Polo, Real,
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Claver, Castillon & Bayon, 1990; Treqiak & Ziolkowski,
Ridge National Laboratory, Tennessee, USA. 1988). The title compound (1) is a precursor of one of
K6rber, F. C. F., Lindsay Smith, J. R., Prince, S., Rizkallah, P.,
Reynolds, C. D. & Shawcross, D. R. (1991). J. Chem. Soc. these catalysts, and therefore the steric conformation of
Dalton Trans. pp. 3291-3294. this bisphosphite Rh complex is of use in the study of the
Mansuy, D. (1987). Pure Appl. Chem. 59, 759-770. catalytic cycle of these catalysts. The triphenylphosphite
Mansuy, D., Battioni, P. & Battioni, J. P. (1989). Eur. J. Biochem. analogue (2) of the title compound has been crystallized
184, 267-285.
Meunier, B. (1986). Bull. Soc. Chim. Ft. pp. 578-594.
Pflugrath, J. W. & Messerschmidt, A. (1986). MADNES. A
program system for the evaluation of FAST data. Max Planck
Institute, Munich, Germany.
Sheldrick, G. M. (1976). SHELX76. Program for crystal structure
determination. Univ. of Cambridge, England.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473.
Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158-166.
(1)

by Leipoldt, Lamprecht & van Zyl (1985). Other bulky

Acta Cryst. (1993). C49, 1160-1163 phosphites, i.e. tri(2-tert-butylphenyl) phosphite (3)
(Jongsma, Challa & van Leeuwen, 1991), tri(2,4,6-tri-
methylphenyl) phosphite (4) (J. Jongsma, G. Challa
Structure of (2,4-Pentanedionato-O,O')- & P. W. N. M. van Leeuwen, unpublished results)
bis(phenyl 3,3',5,5'-tetra-tert-butyl- 1,1'- and bi(2-tert-butyl-6-methylphenyl) phenyl Phosphite (5)
biphenyl-2,2'-diyl phosphite-P)rhodium (Jongsma, Kimkes, Challa & van Leeuwen, 1992),
exclusively yielded the monophosphite Rh complex
AtmE Rh(acac)(CO)P (acac = 2,4-pentanedionato, CO = car-
bonyl and P = phosphite ligand).
Crystal Structure Center, Department of Chemical The identification of the atoms and the configuration
Physics, University of Groningen, Nijenborgh 4, are shown in the PLUTO drawing of Fig. 1. Each asym-
NL-9747 AG Groningen, The Netherlands metric unit contains one complete molecule of the ti-
tle compound with no atom sitting at a special posi-
TJEERD JONGSMAAND GER CHALLA tion and two half molecules of disordered toluene sol-
vent molecules. The triclinic unit cell contains two dis-
Laboratory of Polymer Chemistry, University of crete molecules of the title compound and two toluene
Groningen, Nijenborgh 4, NL-9747 AG Groningen, molecules separated by normal van der Waals distances
The Netherlands
(Bondi, 1964). Both toluene molecules possess a crystal-
PIEr W. N. M. VAN LEEUWEN lographically imposed centre of inversion. The square-
planar structure of the complex (1) is tetrahedrally dis-
Koninklijke/Shell-Laboratorium (Shell Research BV), torted [distances of atoms from root-mean-square (r.m.s.)
Amsterdam, Badhuisweg 3, NL-1031 CM Amsterdam, plane of P1-P2-O2-Ol: P1 -0.096 (7), P2 0.096 (6), O1
The Netherlands 0.108 (7), 0 2 -0.110 (6) A]. The central Rh atom is in
the plane [distance from r.m.s, plane: Rh 0.004 (6) A].
(Received23 July 1992; accepted 17 December 1992) Steric hindrance of the two phosphite groups is demon-
strated by the large P 1 - - R h - - P 2 angle of 99.87 (3) °, ver-
sus 94.8 (2) ° for the triphenyl phosphite Rh complex (2)
Abstract (Leipoldt, Lamprecht & van Zyl, 1985). The O 1 - - R h - -
The crystal structure of the rifle compound has been deter- 02 angle [89.41 (2) ° ] is only slightly larger than that
mined. The square-planar coordination of the complex is of the triphenyl phosphite analogue (2) [88.8 (2)°]. The
0108-2701/93/061160-04506.00 © 1993 International Union of Crystallography
 REGULAR STRUCTURAL PAPERS 1161

steric hindrance has led to distortions within the phos- Data collection
phite ligands. The different P m O m C angles within the Enraf-Nonius CAD-4F 10706 observed reflections
ligands [ P I - - O 3 - - C 6 -- 126.4 (2) versus P l m O 4 - - C 2 0 single-crystal diffractome- [ / > 2.5cr(I)]
--- 120.1 (2) ° and P 2 - - O 6 - - C 4 0 = 118.7 (2) versus P 2 - - ter Rint -- 0.022
O 7 - - C 5 4 = 128.0 (2) °] are examples of this distortion. w/20 scans 0max = 26.00 °
The angles between the two bridged phenyl groups of the Absorption correction: h = 0 ---~ 14
none k = - 2 0 ~ 21
phosphite ligands are 49.7 (2) and 51.5 (2) °, respectively.
14851 measured reflections l = - 2 3 ~ 23
The cone angle (Tolman, 1977) for the 2,2'-bis(4,6-di- 3 standard reflections
14111 independent reflec-
tert-butylphenyl) phenyl phosphite calculated from this frequency: 180 min
tions
X-ray structure is 164 °. The high 7r-acidity of aryl phos- intensity variation: 0.3%
phites leads to the formation of strong 7r-coordination
bonds, which might explain the formation of the bisphos- Refinement
phite complex (1), even though the cone angle of the lig- Refinement on F Extinction correction:
and is too large to expect the formation of bisphosphite Rh Final R = 0.042 Zachafiasen (1967)
complexes. [Triphenylphosphine, cone angle 145 °, ex- wR = 0.046 Extinction coefficient:
clusively yields monophosphine complexes when reacted S = 1.842 0.63 (9) x 10 -4
with Rh(acac)(CO)2, even when a large excess of phos- 10706 reflections Atomic scattering factors
phine is used (Bonati & Wilkinson, 1964).] 1136 parameters from Cromer & Mann
Calculated weights w = (1968) [anomalous-
1/[cr2(F)] dispersion factors from
(A/or)max =0.77 Cromer & Liberman
Apmax = 0.99 e ,~-3 (1970)]
C36 C1~'~ C3V~
I .c0 c00 Apmin = 0.92 e ,/~-3

Data collection: CAD-4, version 5.0 (Enraf-Nonius, 1988). Cell

refinement: CAD-4, version 5.0; SET4 (de Boer & Duisenberg,
1984). Data reduction: EUCLID (Spek, 1982). Reduced-cell
calculations: LEPAGE (Spek, 1988). Extra metric symmetry-
element calculations: MISSYM (Le Page, 1987, 1988). Pro-
gram(s) used to solve structure: SHELXS86 (Sheldrick, 1990).
Program(s) used to refine structure: Xtal CRYLSQ (Olthof-
Hazekamp, 1990). Program(s) used for geometric calculations:
Xtal (Hall & Stewart, 1990); PLATON (Spek, 1990). Molecu-
lar graphics: PLUTO92 (Meetsma, 1992; Motherwell & Clegg,
1978). Software used to prepare material for publication: PLA-
TON92 (Spek, 1992). All calculations were performed on a
C14 C52(~) CDC-Cyber 962-31 computer at the University of Groningen.
The positional and anisotropic thermal displacement param-
Fig. 1. PLUTO drawing of the molecule of the title compound illustrating eters for the non-H atoms were refined with block-diagonal
the puckering and the adopted numbering scheme. H atoms have been least-squares procedures (CRYLSQ; Olthof-Hazekamp, 1990)
omitted to improve clarity. minimizing the function Q = ~atw(lFo I - IFcl)2]. Subsequent
Fourier summations showed density which could be correlated
to the disordered phenyl group (C68-C73) and the two solvent
Experimental molecules of toluene. Both toluene molecules were disordered
Crystal data over a crystallographic inversion centre, each in a different way.
[Rh(CsH702)(C34H4503P)2].- Mo K ~ radiation The disorder in the phenyl group is described by two positions
C7H8 -- 0.71073 ,~, with occupancy of 0.5 for C72 and C73. Following the inclusion
Mr = 1359.56 Cell parameters from 22 of the positional parameters and appropriate occupancies of 1.0
Triclinic reflections and 0.5, respectively, of the toluene residues, the remainder of
P1 0 -- 14.84- 18.83 ° the structure refined smoothly. High thermal displacement mo-
a = 11.624 (1) A # = 0.328 mm-1 tion was found for the disordered fragments. The overall geom-
b = 17.244 (2) ]k T-- 130K etry of the toluene molecules appeared rather distorted, suggest-
c = 18.877 (1) A Parallelepiped ing some degree of disorder. The H atoms of the non-disordered
c~ = 79.884 (8) ° 0.40 x 0.33 × 0.15 mm fragments were located in subsequent Ap maps. The H atoms of
= 84.812 (6) ° Yellow the disordered fragments were included in the final refinement
7 = 75.398 (9) ° Crystal source: by synthesis, riding on their carder atoms with their positions calculated by
v = 3600.4 (6) k 3 details are published else- using sp 2 or sp 3 hybridization at the C atom as appropriate with
Z=2 where (Jongsma, Fossen, a fixed C - - H distance of 0.96 ,~,. A final Ap map was essen-
Dx = 1.254 Mg m -3 Challa & van Leeuwen, tially featureless with the highest peaks in the vicinity of the
1992) disordered fragments.
1162 R E G U L A R S T R U C T U R A L PAPERS

Table 1. Fractional atomic coordinates and equivalent C62 0.8298 (4) -0.2204 (2) 0.2626 (2) 0.0413 (14)
C63 0.9423 (4) --0.1188 (2) 0.2741 (2) 0.0369 (12)
isotropic thermal parameters ( A 2) C64 0.3760 (3) --0.0334 (2) 0.27887 (17) 0.0258 (11)
Ueqffi ~1 Y]~i~]jUija i* aj* ai.aj. C65 0.3126 (4) 0.0299 (2) 0.3264 (2) 0.0304 (12)
C66 0.3786 (4) --0.1176 (2) 0.3219 (2) 0.0397 (16)
x y z Ueq C67 0.3033 (4) -0.0247 (3) 0.2126 (2) 0.0402 (14)
R_hl 0.24589 (2) 0.25048 (2) 0.25092 (I) 0.0167 (1) C68 0.3578 (3) 0.1891 (2) 0.04307 (16) 0.0223 (10)
P1 0.33686 (7) 0.29811 (5) 0.32160 (4) 0.0160 (2) C69 0.4510 (4) 0.1582 (5) 0.0050 (3) 0.135 (4)
P2 0.39402 (7) 0.20136 (5) 0.18155 (4) 0.0181 (2) C70 0.4449 (6) 0.1207 (4) -0.0521 (3) 0.110 (3)
O1 0.09006 (19) 0.30273 (14) 0.30461 (12) 0.0270 (8) C71 0.3488 (5) 0.1135 (3) --0.0715 (2) 0.073 (2)
02 0.1490 (2) 0.19744 (14) 0.19480 (12) 0.0284 (8) C721 t 0.2671 (6) 0.1159 (5) --0.0222 (4) 0.034 (3)
03 0.30218 (17) 0.39500 (12) 0.32417 (10) 0.0169 (6) C722 t 0.2385 (8) 0.1922 (6) --0.0537 (4) 0.055 (4)
04 0.48010 (17) 0.27538 (12) 0.31838 (10) 0.0167 (6) C731 t 0.2645 (6) 0.1578 (4) 0.0353 (4) 0.027 (2)
05 0.30010 (19) 0.26871 (12) 0.40434 (10) 0.0206 (7) C732 t 0.2528 (7) 0.2226 (6) 0.0080 (4) 0.044 (3)
06 0.52260 (18) 0.21956 (12) 0.18494 (10) 0.0173 (6) C78 0.9090 (5) 0.5265 (4) 0.0303 (3) 0.068 (2)
07 0.42558 (19) 0.10493 (12) 0.17982 (11) 0.0213 (7) C79 0.8838 (11) 0.5992 (7) -0.0078 (6) 0.077 (5)
08 0.3615 (2) 0.23240 (13) 0.09835 (11) 0.0235 (7) C80 0.9811 (7) 0.6133 (4) -0.0667 (3) 0.090 (3)
C1 --0.0135 (3) 0.2967 (2) 0.29351 (18) 0.0308 (11) C81 ~ 0.9320 (8) 0.4532 (7) 0.0693 (5) 0.051 (4)
C2 --0.0410 (3) 0.2478 (2) 0.2497 (2) 0.0330 (11) C82 ~ 0.9945 (10) 0.4624 (7) 0.0273 (5) 0.054 (4)
C3 0.0390 (3) 0.2009 (2) 0.20515 (19) 0.0318 (12) C74 0.0236 (4) 0.0708 (4) 0.4655 (4) • 0.090 (3)
C4 --0.1145 (4) 0.3488 (3) 0.3326 (2) 0.0504 (18) C75 0.0049 (4) 0.0594 (5) 0.5396 (4) 0. I00 (3)
C5 --0.0098 (5) 0.1508 (3) 0.1629 (3) 0.0577 (19) C76 0.0192 (4) 0.0092 (5) 0.4277 (4) 0.100 (3)
C6 0.3679 (3) 0.45048 (18) 0.29268 (15) 0.0161 (8) C77 ~ 0.0516 (9) 0.1373 (5) 0.4359 (5) 0.056 (3)
C7 0.4822 (3) 0.44022 (17) 0.31606 (15) 0.0160 (9)
C8 0.5480 (3) 0.49647 (18) 0.28499 (15) 0.0170 (9) t Occupancy 0.5.
C9 0.5037 (3) 0.56079 (18) 0.23294 (15) 0.0176 (9)
C10 0.3852 (3) 0.57138 (19) 0.21464 (16) 0.0190 (9)
CI1 0.3143 (3) 0.51840 (18) 0.24363 (15) 0.0171 (9)
C12 0.5770 (3) 0.62082 (19) 0.19592 (16) 0.0207 (10) Table 2. Selected geometric parameters (A, o)
C13 0.5271 (3) 0.7034 (2) 0.22064 (19) 0.0257 (11)
C14 0.7079 (3) 0.5915 (2) 0.2139 (2) 0.0275 (11) Rhl--P1 2.1566 (9) O5--C34 1.400 (4)
C15 0.5697 (4) 0.6315 (2) 0.11402 (18) 0.0295 (11) Rhl--P2 2.1549 (9) O6--C40 1.412 (4)
C16 0.1840 (3) 0.53467 (19) 0.22311 (16) 0.0205 (9) Rhl--Ol 2.070 (2) O7--C54 1.395 (4)
C17 0.1698 (3) 0.4712 (2) 0.1796 (2) 0.0286 (12) Rhl--O2 2.074 (2) O8--C68 1.395 (4)
C18 0.1000 (3) 0.5355 (2) 0.2909 (2) 0.0304 (11) P1--O3 1.625 (2) C1--C2 1.388 (5)
C19 0.1432 (3) 0.6181 (2) 0.1759 (2) 0.0296 (11) P1--O4 1.610 (2) C1--C4 1.508 (6)
C20 0.5413 (2) 0.29299 (18) 0.37240 (15) 0.0166 (9) P1--O5 1.609 (2) C2--C3 1.394 (5)
C21 0.5373 (2) 0.37358 (18) 0.37321 (15) 0.0155 (8) P2--O6 1.612 (2) C3--C5 1.508 (7)
C22 0.5945 (3) 0.39233 (18) 0.42765 (15) 0.0148 (8) P2 --O7 1.616 (2) C6--C7 1.397 (5)
C23 0.6558 (3) 0.33225 (18) 0.47912 (15) 0.0164 (9) P2 - - 0 8 1.614 (2) C7--C21 1.488 (4)
C24 0.6624 (3) 0.25153 (18) 0.47299 (16) 0.0180 (9) O1--C1 1.273 (4) C40--C45 1.387 (4)
C25 0.6078 (3) 0.22856 (18) 0.41997 (15) 0.0174 (9) O2--C3 1.264 (4) C45--C55 1.486 (4)
C26 0.7113 (3) 0.35231 (18) 0.54281 (16) 0.0183 (9) O3--C6 1.392 (4) C54--C55 1.389 (5)
C27 0.7300 (4) 0.4384 (2) 0.5276 (2) 0.0290 (11) O4--C20 1.410 (3)
C28 0.6248 (4) 0.3462 (2) 0.60861 (19) 0.0313 (11) P1--Rhl--P2 99.87 (3) O3--C6--Cll 119.5 (3)
C29 0.8299 (3) 0.2931 (2) 0.5603 (2) 0.0307 (12) P1--Rhl--O1 86.43 (7) C7--C6--C 11 122.0 (3)
C30 0.6298 (3) 0.13875 (18) 0.41099 (17) 0.0234 (10) P1--Rhl--O2 172.67 (7) C6--C7--C8 118.4 (3)
C31 0.6996 (3) 0.0827 (2) 0.4726 (2) 0.0281 (11) P2--R_h 1--O1 171.94 (7) C6--C7--C21 123.6 (3)
C32 0.5149 (4) 0.1118 (2) 0.4088 (3) 0.0427 (14) P2--Rhl--O2 84.83 (7) C8--C7--C21 118.0 (3)
C33 0.7048 (4) 0.1274 (2) 0.3410 (2) 0.0384 (14) OI--Rhl--O2 89.41 (9) C7--C8--C9 122.2 (3)
C34 0.2576 (3) 0.31423 (18) 0.45992 (16) 0.0184 (9) RhI--P1--O3 119.52 (8) C8--C9--C10 117.1 (3)
C35 0.1380 (3) 0.3527 (2) 0.46415 (18) 0.0265 (11) Rhl--P1--O4 119.18 (8) C8--C9--C12 122.7 (3)
C36 0.0943 (3) 0.3924 (2) 0.52235 (19) 0.0283 (11) Rhl--Pl--O5 110.17 (9) C10--C9--C12 120.1 (3)
C37 0.1674 (3) 0.3943 (2) 0.57478 (18) 0.0282 (11) O3--P1--O4 103.25 (11) C9--C10--Cll 123.7 (3)
C38 0.2867 (3) 0.3559 (2) 0.56916 (17) 0.0286 (11) O3--P1--O5 97.30 (11) C6--Cll--C10 116.2 (3)
C39 0.3327 (3) 0.3160 (2) 0.51139 (16) 0.0212 (10) O4--P1--O5 104.37 (11) C6--C11--C16 122.5 (3)
C40 0.6094 (3) 0.20035 (18) 0.12925 (15) 0.0174 (9) RhI--P2--O6 121.07 (8) C10--Cli--C16 121.3 (3)
C41 0.6422 (3) 0.26343 (18) 0.08031 (15) 0.0177 (9) Rhl--P2--O7 117.76 (9) C9--C12--C13 109.6 (3)
C42 0.7188 (3) 0.23897 (19) 0.02319 (16) 0.0204 (9) Rhl--P2--O8 109.76 (9) C9--C12--C14 111.9 (3)
C43 0.7634 (3) 0.15786 (19) 0.01381 (16) 0.0210 (9) 06--P2--07 103.23 (12) C9--C12--C15 lo9.8 (3)
C44 0.7377 (3) 0.09886 (19) 0.06779 (16) 0.0199 (9) 06--P2--08 103.80 (12) C13--C12--C14 108.3 (3)
C45 0.6601 (3) 0.11885 (18) 0.12697 (15) 0.0190 (9) 07--P2--08 98.04 (12) C13--C12--C15 108.9 (3)
C46 0.6045 (3) 0.35297 (18) 0.09087 (16) 0.0198 (9) Rhl--Ol--Cl 125.2 (2) C14--C12--C15 108.2 (3)
C47 0.6574 (3) 0.3594 (2) 0.16075 (18) 0.0272 (11) R_hl--O2--C3 125.3 (2) Cll--C16--C17 110.4 (3)
C48 0.4693 (3) 0.3868 (2) 0.0957 (2) 0.0277 (11) P1--O3--C6 126.46 (19) Cl1--C16--C18 110.6 (3)
C49 0.6540 (3) 0.4070 (2) 0.02873 (19) 0.0273 (11) P1--O4--C20 120.07 (17) Cll--C16--C19 111.8 (3)
C50 0.8371 (3) 0.1391 (2) -0.05558 (17) 0.0248 (10) P1--O5--C34 129.79 (19) C17--C16--C18 110.7 (3)
C51 0.7661 (4) 0.1858 (2) -0.12076 (18) 0.0311 (11) P2--O6--C40 118.72 (19) C17--C16--C19 106.8 (3)
C52 0.9526 (3) 0.1657 (3) -0.0566 (2) 0.0351 (14) P2--O7--C54 128.0 (2) C18--C16--C19 106.4 (3)
C53 0.8643 (4) 0.0484 (2) -0.0611 (2) 0.0337 (11) P2--08--C68 130.8 (2) O4--C20--C21 117.4 (2)
C54 0.5229 (3) 0.04575 (18) 0.20837 (16) 0.0197 (9) 01--CI--C2 126.6 (3) O4--C20--C25 119.1 (3)
C55 0.6368 (3) 0.05231 (18) 0.18369 (15) 0.0188 (9) 01--CI--C4 115.2 (3) C21--C20--C25 123.4 (3)
C56 0.7342 (3) -0.00838 (19) 0.21093 (16) 0.0199 (9) C2--C I--C4 118.2 (3) C7--C21--C20 122.9 (3)
C57 0.7195 (3) -0.07524 (19) 0.26058 (16) 0.0227 (10) CI--C2--C3 126.3 (3) C7--C21--C22 118.8 (3)
C58 0.6019 (3) -0.0811 (2) 0.27983 (17) 0.0247 (10) 02--C3--C2 126.6 (3) C40--C45--C44 117.8 (3)
C59 0.5018 (3) --0.02250 (19) 0.25557 (16) 0.0223 (10) O2--C3--C5 115.9 (3) C44--C45--C55 118.8 (3)
C60 0.8243 (3) --0.1420 (2) 0.29257 (18) 0.0288 (I1) C2--C3--C5 117.5 (4) C45--C55--C54 123.0 (3)
C61 0.8060 (4) --0.1581 (2) 0.3749 (2) 0.0354 (12) O3--C6--C7 118.3 (3) C45--C55--C56 118.3 (3)
 REGULAR STRUCTURAL PAPERS 1163

P2--Rhl--PI--O3 117.84 (9) RhI--P2--O7--C54 - 108.5 (2) Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473.
P2--RhI--P1--04 -- 10.32 (10) O6--P2--O7--C54 27.8 (3) Spek, A. L. (1982). The EUCLID Package. In Computational Crystal-
P2--Rhl--P1--O5 -- 130.85 (9) O8--P2--O7--C54 134.1 (2)
OI--RhI--PI--O3 --57.10(11)
lography, edited by D. Sayre. Oxford: Clarendon Press.
Rh 1 - - P 2 - - O 8 - - C 6 8 -- 121.4 (3)
OI--RhI--PI--O4 174.74(11) O6--P2--O8--C68 107.9 (3)
Spek, A. L. (1988). J. Appl. Cryst. 21,578-579.
OI--RhI--P1--O5 54.21 (11) O7--P2--O8--C68 2.0 (3) Spek, A. L. (1990). Acta Cryst. A46, C-34.
PI--RhI--P2--O6 - 9 . 4 4 (I0) Rhl--O1--C1--C2 7.4 (5) Spek, A. L. (1992). PLATON92. Unpublished.
PI--RhI--P2--O7 118.81 (10) RhI--OI--CI--C4 - 172.6 (2) Tokitoh, Y. & Yoshimura, Y. (1987).Jpn. Kokai TokyoKoko. Jpn. Patent
PI--RhI--P2--O8 - 130.27 (10) Rh 1 - - O 2 - - C 3 - - C 2 7.8 (5) 01/29 335, Jpn. Patent Appl. 85/2 486 466 and Jpn. Patent 62/201 881.
O2--Rh 1--P2--O6 176.23 (11) Rh 1 - - O 2 - - C 3 - - C 5 - 174.2 (3) Tokitoh, Y. & Yoshimura, Y. (1989). Jpn. Patent 64/26 530 (Kuraray).
O2--RhI--P2--O7 - 5 5 . 5 2 (12) P I - - O 3 - - C 6 - - C 11 123.6 (3) Tolman, C. A. (1977). Chem. Rev. 77, 3, 313-348.
O2--RhI--P2--O8 55.40 (11) P 1- - O 3 - - C 6 - - C 7 - 62.1 (3)
PI--RhI--OI--CI - 176.5 (3)
Treqiak, A. M. & Ziolkowski, J. J. (1988). J. Mol. Catal. 48, 319-325.
PI--O4--C20--C21 -70.8 (3)
O2--Rhl--O1--CI - 2 . 5 (3) PI--O4--C20--C25 112.4 (3)
Zachariasen, W. H. (1967). Acta Cryst. 23, 558-564.
P2--RhI--O2--C3 - 179.0 (3) PI--O5--C34--C39 - 102.4 (3)
O1--RhI--O2--C3 - 4 . 6 (3) PI--O5--C34--C35 81.5 (4)
RhI--PI--O3--C6 - 104.0 (2) P2--O6--C40--C45 -71.2 (3)
O4--PI--O3--C6 31.2 (2) P2--O6--C40--C41 110.2 (3)
O5--PI--O3--C6 137.8 (2) P2--O7--C54--C59 126.7 (3)
RhI--PI--O4--C20 - 1 6 8 . 3 2 (17) P2--O7--C54--C55 -59.7 (4) Acta Cryst. (1993). C49, 1163-1 169
O3--P1--O4--C20 56.3 (2) P2--O8--C68--C731 80.5 (5)
O5--PI--O4--C20 - 4 4 . 9 (2) P2--O8--C68--C732 132.8 (4)
RhI--PI--O5--C34 - 1 2 7 . 9 (3) P2--O8--C68--C69 -82.6 (5) Structures of two Cobalt(III) Sepulchrate
O3--PI--O5--C34 - 2 . 7 (3) OI--C1--C2--C3 -5.4 (6)
O4--PI--O5--C34 103.0 (3) C44--C45--C55--C54 -129.3 (3) Complexes*
RhI--P2--O6--C40 - 1 6 7 . 2 6 (17) C40--C45--C55--C54 50.9 (5)
07--P2--06--C40 58.3 (2) C40--C45--C55--C56 -132.1 (3)
O8--P2--O6--C40 - 4 3 . 6 (2) C44--C45--C55--C56 47.7 (4) ALESSIA BACCHI

Lists of structure factors, anisotropic thermal parameters, H-atom coor- Istituto di Chimica Generale ed lnorganica, Universitd
dinates and complete geometry, as well as a molecular packing diagram, degli Studi di Parma, Centro di Studio per la Struttu-
have been deposited with the British Library Document Supply Centre ristica Diffrattometrica del CNR, Viale delle Scienze
as Supplementary Publication No. SUP 55972 (97 pp.). Copies may be 78, 1-43100 Parma, Italy
obtained through The Technical Editor, International Union of Crystal-
lography, 5 Abbey Square, Chester CH 1 2HU, England. [CIF reference: FRANCESCO FERRANTI
AB1032]
Dipartimento di Chimica Fisica ed lnorganica, Univer-
sitd degli Studi di Bologna, Viale del Risorgimento 4,
References 1-40136 Bologna, Italy
Billig, E., Abatjoglou, A. G., Bryant, D. R., Murray, R. E. & Maher, J.
M. (1988). US Patent 4 717 775 (Union Carbide). GtANCARLO PELIZZI
Boer, J. L. de & Duisenberg, A. J. M. (1984). Acta Cryst. A40, C-410.
Bonati, F. & Wilkinson, G. (1964). J. Chem. Soc. pp. 3156-3160. Istituto di Chimica Generale ed Inorganica, Universitgt
Bondi, A. (1964). J. Phys. Chem. 68, 441-451.
Cromer, D. T. & Liberman, D. (1970). J. Chem. Phys. 53, 1891-1898. degli Studi di Parma, Centro di Studio per la Struttu-
Cromer, D. T. & Mann, J. B. (1968). Acta Cryst. A24, 321-324. ristica Diffrattometrica del CNR, Viale delle Scienze
Emaf-Nonius (1988). CAD-4 Manual, version 5.0. Enraf-Nonius, Sci- 78, 1-43100 Parma, Italy
entific Instruments Division, Delft, The Netherlands.
Hall, S. R. & Stewart, J. M. (1990). Editors. Xtal3.0 Reference Manual. (Received 13 July 1992; accepted 20 November 1992)
Univs. of Western Australia, Australia, and Maryland, USA.
Jongsma, T., Challa, G. & van Leeuwen, P. W. N. M. (1991). J.
Organomet. Chem. 421, 121-128.
Jongsma, T., Fossen, M., Challa, G. & van Leeuwen, P. W. N. M. (1992). Abstract
J. Mol. Catal. Submitted. The complex (1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]-
Jongsma, T., Kimkes, P., Challa, G. & van Leeuwen, P. W. N. M. (1992). icosane)cobalt(III) perchlorate thiosulfate, [Co(C12HB0-
Polymer, 33, 161-165. N8)](C104)($203), crystallizes in the hexagonal
Leeuwen, P. W. N. M. van & Roobeek, C. F. (1983). J. Organomet.
Chem. 258, 343-350. space group P6322. Cations and anions occupy special-
Leipoldt, J. G., Lamprecht, G. J. & van Zyl, G. J. (1985). Inorg. Chim. site positions with the anions disordered as a result
Acta, 96, 31-35. of s y m m e t r y requirements. Co(sep) 3÷ (sep = C12H30N8)
Le Page, Y. (1987). J. Appl. Cryst. 20, 264-269. adopts the optically active D3 crystallographic geom-
Le Page, Y. (1988). J. Appl. Cryst. 21, 983-984.
etry. The packing consists of layers of interacting
Meetsma, A. (1992). Extended version of the program PLUTO (unpub-
lished). Univ. of Groningen, The Netherlands. Co(sep) 3÷ and $ 2 0 ~ - ions, intercalated by isolated C104--
Motherwell, W. D. S. & Clegg, W. (1978). PLUTO.Program for plotting anions. The second complex, rac-(1,3,6,8,10,13,16,19-
molecular and crystal structures. Univ. of Cambridge, England. octaazabicyclo[6.6.6]icosane)cobalt trichloride m o n o h y -
Oithof-Hazekamp, R. (1990). CRYLSQ. In Xtal3.0 Reference Manual, drate, rac-Co(C12H3oN8)]C13.H20, crystallizes in the
edited by S. R. Hall & J. M. Stewart. Univs. of Western Australia,
Australia, and Maryland, USA.
Polo, A., Real, J., Claver, C., Castillon, S. & Bayon, J. C. (1990). J. * In honour of Professor Antonio Indelli, who passed away un-
Chem. Soc. Chem. Commun. pp. 600-601. timely in September 1990.

0108-2701/93/061163-07506.00 © 1993 International Union of Crystallography