1426 [ReC12(Cz6H22P2)z].C6H 14 for absorption effects based on 0 scans using the empirical method of North, Phillips & Mathews (1968); Tmi,=0.6332, Tmax=0.9988. 3269 unique observed data [Fo2 > 30-(Fo2)] were obtained. Scattering factors, including anomalous-dispersion factors, were taken from International Tables for X-ray Crystallography (1974, Vol. IV). All computations were carried out using the MolEN (Fair, 1990) packa g e of programs on a VAX computer. From the systematic absences of hOl: l ~ 2n, 0k0: k # 2n and from subsequent least-squares refinement, the space group was determined to be P21/e. The structure was solved by the heavy-atom method based on the assumption that an Re atom must be located at the origin. The rest of the structure was revealed in successive cycles of least-squares refinement and difference Fourier maps. Three peaks located near an inversion point clearly defined a hexane molecule. All of the non-H atoms, except those belonging to the C6H14 molecule, were refined with anisotropic thermal parameters. The isotropic thermal parameters for two C atoms on the hexane molecule (C2 and C3) were Constrained to be the same as the third (C1) which was refined without constraint. H atoms were not included in the refinement, w R = {[Yw(IFolIF~I)2]/[Y.w(Fo)2]}1/2 was minimized, where w = 0-2(IFol2)-! and 0- is the e.s.d, in a single measurement; final R = 0.034, wR = 0.051, S = 1.88 for 278 variables. The largest shift/e.s.d, in the final leastsquares cycle was 0.02; the maximum and minimum residual electron density in the /iF map were 0.92 (located near Re) and - 0 . 2 3 e A-3, respectively. An ORTEP (Johnson, 1965) representation of the molecule (without the hexane entity) and the atomic labeling scheme is depicted in Fig. 1. Final positional and equivalent isotropic thermal parameters are listed in Table 1,* with important bond distances and angles in Table 2. * Lists of structure factors, anisotropic thermal parameters, H-atom parameters and a stereoscopic view of the unit-cell packing have been deposited with the British Library Document Supply Centre as Supplementary Publication No. SUP 71073 (43 pp.). Copies may be obtained through The Technical Editor, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. [CIF reference: HH1045] Related literature. The synthesis, by a different route, and the crystal structure of [ReCI2(Ph2PCHCHPPh2)2] (without the hexane molecule of solvation) has been reported (Bakir, Fanwick & Walton, 1987). This study was supported by means of start-up funds from The American University to R L L and the N I H to JVS. References BAKIR,M., FANWlCK,P. E. & WALTON,R. A. (1987). Polyhedron, 6, 907-913. FAIR, C. K. (1990). MolEN. An interactive structure solution procedure. Enraf-Nonius, Delft, The Netherlands. JOHNSON, C. K. (1965). ORTEP. Report ORNL-3794. Oak Ridge National Laboratory, Tennessee, USA. NORTH,A. C. T , PHILLIPS,D. C. & MATHEWS,F. S. (1968). Acta Cryst. A24, 351-359. Acta Cryst. (1993). C49, 1426-1428 Structure of Tetraphenylphosphonium #-{[7/4-2,4-Bis(2-hydroxy-2-methylpropanamido)-2,4-dimethyl-3-oxopentane]cobalt(III)}tetranitratocerium(III) Dichloromethane BY TERRENCE J. CoLLINs* AND Jos~ M. WORKMAN Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA (Received 24 July 1992; accepted 25 February 1993) Abstract. Bis(tetraphenylphosphonium) Iz-{N,N'(2,4-dimethyl-3-oxo-2,4-pentanediyl) bis[(2-hydroxy1:2r20)-2-methylpropanamido-2xN]}-tetranitrato 1xao, 1x40'-cerate(III)cobaltate(III) dichlorome[P(C6Hs)4]2[Co(CI 5H24N2Os) {Ce(NO3)4}]._ thane, CH2C12, Mr = 1523.2, monoclinic, P21/c (C~), a = 22.168 (5), b = 13.266 (2), c = 24.330 (6) A, /3 = * Author to whom correspondence should be addressed. ©1993 International Union of Crystallography Printed in Great Britain - all rights reserved 105.17 (2) ° , V = 6905 (3)/~ 3, Z=4, Dx = 1.465 Mg m -3, A(Mo Ka) = 0.71073/~, /x = 1.09 m m - 1, T = 293 K, F(000) = 3108, R = 0.036, wR = 0.045 for 8166 independent reflections having 20(Mo Ka) < 50.7 ° and I > 30-(/). The title compound is a dinuclear complex in which a planar cobalt(III) complex is linked via secondary coordination to a cerium(III) center. The Ce nI atom has four bidentate nitrato ligands and is further bridged to the Acta Crystallographica Section C ISSN 0108-2701 ©1993 T E R R E N C E J. COLLINS A N D JOSI~ M. W O R K M A N bidentate planar cobalt(Ill) complex ligand which is coordinated through two alkoxide O atoms. The cobalt--cerium non-bonded distance is 3.449 (1)A. The cobalt(Ill) complex ligand remains planar on coordination to the Ce m atom. 1427 Table 1. Atomic coordinates (× 104) and equivalent isotropic thermal parameters (× 10) with e.s.d.'s in parentheses Boq= (1/3)Y,Y.jBija,* aj* ai .aj . Ce Co Ol 02 03 04 05 06 07 08 09 OI0 O11 OI2 NI N2 N3 N4 Ola O2a Olb O2b O Yla Nlb Cla C2a C3a C4a C5a C6a C7a Clb C2b C3b C4b C5b C6b C7b C8 x 3045 (1) 2505 (1) 4035 (2) 4139 (2) 4899 (2) 3191 (2) 3719 (2) 3892 (3) 2132 (2) 2843 (2) 2087 (3) 3041 (2) 2173 (2) 2286 (3) 4370 (2) 3608 (2) 2351 (2) 2498 (3) 1420 (3) 2286 (1) 3352 (2) 3121 (I) 1327 (2) 1966 (2) 2693 (2) 1693 (3) 1768 (2) 1874 (3) 1181 (2) 1939 (3) 2565 (4) 1400(5) 3184 (2) 3523 (2) 4124 (2) 3634 (3) 2304 (2) 2684 (3) 1970 (3) 1816 (3) y 6047 (I) 3607 (1) 7104(3) 6160 (3) 7132 (3) 6188 (3) 4991 (2) 5394 (3) 7107 (3) 7990 (3) 8712 (3) 6760(4) 6168 (3) 6805 (4) 6816 (3) 5518 (3) 7957 (3) 6586 (4) 3111 (3) 4729 (2) 2334 (3) 4357 (2) 1141 (4) 2887 (3) 2604 (2) 3440 (4) 4571 (3) 5089 (4~ 4972 (4) 1768 (4) 1354 (4) 1311 (5) 2831 (3) 3811 (3) 3544(4) 4440 (4) 1711 (3) 730 (4) 1914 (5) 1520(3) z 1240(I) 1234 (I) 1199 (2) 1928 (2) 1874 (2) 225 (I) 730 (I) - 76 (2) 618 (2) 1121 (2) 510 (3) 2230 (2) 1783 (2) 2626 (2) 1673 (2) 284 (2) 744(2) 2224 (2) - 264 (2) 786 (I) 2665 (I) 1693 (I) 1269 (2) 666 (2) 1771 (1) 204 (2) 305 (2) - 208 (2) 442 (3) 671 (2) 615 (3) 202 (3) 2230 (2) 2157 (2) 2003 (2) 2703 (2) 1809 (2) 1938 (3) 2273 (3) 1249 (2) Bcq (,~2) 27 (1) 29 (1) Experimental. The title compound, hereinafter refer60 (I) red to as [(CoUl)-(CeIn)] 2-, was prepared by stirring 61 (1) 65 (1) one equivalent of an orange dichloromethane solu47 (1) 51 (1) tion of the cobalt(Ill) complex (Brewer, Collins, 81 (2) Smith & Santarsiero, 1988) over one equivalent of 64 (I) 94 (2) solid (NHa)2Ce(NO3)5. One equivalent of tetraphe98 (2) nylphosphonium chloride was added in dichlorome81 (2) 63 (1) thane and the red [(Com)-(Cem)] 2- compound was 96 (2) 44(1) isolated in good yield (70%) following filtration and 47 (I) evaporation of the CH2C12. A single red-orange 56 (2) 57 (2) crystal of dimensions 0.52 x 0.58 × 0.63 mm was 109 (2) mounted on a glass fiber and coated with epoxy 34 (I) 62 (I) cement. Data collection was performed on a Nicolet 30 (1) four-circle P1 autodiffractometer (Mo K a radiation, 87 (2) 40(1) graphite monochromator). From the least-squares fit 33 (I) 52 (2) of the angular settings of 15 reflections (12.6 < 0 < 39 (I) 17.7 °) final unit-cell parameters were obtained. The 52 (2) 59 (2) intensities were collected at 293 K using the w-scan 54 (2) technique to generate a total of two shells: 3.0 < 75 (3) 117 (4) 20 __ 43.0 ° (6.0 ° min- ~) and 43.0 ___20 -- 50.7 ° 38 (I) (3.0 ° min- 1). The index ranges were - 26 _< h __ 25, 32 (I) 47 (1) 0 ___k _< 15, 0 _< l _< 29. The six standard reflections 48 (2) measured every 300 reflections showed negligible 41 (1) 57 (2) intensity loss over the collection period. Of the 72 (2) 49 (2) 13 103 independent reflections collected with 2O(Mo K a ) < 50.7 °, 8166 had I > 3o"(1). The intensity data were corrected empirically for absorption effects using 0 scans for seven reflections having 20 Table 2. Selected bond distances (•) and angles (o) with e.s.d. 's in parentheses between 6.1 and 33.0 ° and were then reduced to relative squared amplitudes by means of standard Ce--O1 2.629 (4) Ce---O7 2.600 (4) 2.567 (3) Ce---O8 2.620 (6) Lorentz and polarization corrections. The range of Ce---O2 Ce---O4 2.582 (3) Ce---Ol0 2.589 (4) 2.591 (4) Ce--O11 2.615 (5) relative transmission factors was 0.62-1.00. The Ce--O5 2.476 (3) Ce--O2b 2.483 (3) structure was solved using heavy-atom Patterson Ce--O2a Co---O2a 1.833 (3) Co---O2b 1.817 (3) 1.840 (3) Co--Nlb 1.835 (3) techniques on a Data General Eclipse S-200 com- C o - - N l a Ola--Cla 1.221 (6) OIb---CIb 1.218 (5) puter with the Nicolet S H E L X T L (Sheldrick, 1990) O2a--C2a 1.425 (5) O2b--C2b 1.438 (4) 1.348 (6) Nlb---Clb 1.374 (5) software package as modified at Crystalytics Com- N l a - - C l a Nla--C5a 1.485 (6) Nl/'r--C5b 1.483 (6) pany. Function minimized was Y~w(IFoI-LFc[) 2 C l t r - C 2 a 1.522 (6) CIb---C2b 1.536 (6) 1.496 (7) C2b---C3b 1.516 (7) where w = [tr2(Fo) + (0.03Fo) 2]-1. The structure was C2a---C3a C2a--C4a 1.521 (8) C2b---C4b 1.534 (6) 1.532 (10) C5b---C6b 1.537 (7) refined by counter-weighted cascade-block-diagonal C5a---C6a C5a--C7a 1.544 (9) CSb---C7b 1.528 (10) least-squares techniques and a structural model C5a--C8 1.535 (8) C5b--C8 1.523 (6) 1.210 (8) which incorporated anisotropic thermal parameters O--C8 OI--NI 1.256 (5) O7--N3 1.234 (5) for all non-H atoms and isotropic thermal param- O2--N1 1.254 (6) O8--N3 1.230 (6) O3--N1 1.222 (5) O9--N3 1.223 (6) eters for all H atoms. The eight methyl groups (C3a, O4---N2 1.263 (6) O10---N4 1.224 (7) C4a, C6a, C7a, C3b, C4b, C6b, C7b and their H O5--N2 1.260 (5) Ol I - - N 4 1.254 (6) 1.213 (7) O12--N4 1.225 (8) atoms) were refined as rigid rotors with sp a, O6---N2 48.5 (1) O4--Ce----O10 153.5 (1) hybridized geometry and a C - - H bond lengths of OI---Ce---O2 O4--Ce---O5 49.3 ( I ) O4---Ce--OI 1 140.7 ( 1) 47.1 ( 1) O4--Ce---O2a 82.3 ( 1) 0.96/k. The initial orientation of each methyl group O7--Ce---O8 1 47.6 (1) O4---Ce--O2b 118.6 (I) was determined from difference Fourier positions for OI0--Ce---OI O2a--Ce---O2b 61.3 (1) O5--Ce---O7 118.2 (1) 67.0 ( I ) O5---Ce--O8 125.6 (2) the H atoms. The final orientation of each methyl O 1- - C e - - O 4 OI--Ce--O5 71.2 (1) O5--Ce---OI0 141.8 (1) group was determined by three rotational param- OI--Ce---O7 102.7 (1) O5---Ce--OI 1 150.6 (I) 65.8 ( 1) O5--Ce---O2a 79.3 ( 1) eters. The refined positions for the rigid-rotor methyl O l--Ce---O8 [CO(el5H24N2Os)Ce(NO3)4][P(C6Hs)412.CH2C12 1428 Table 2 (cont.) Ol---Ce---Ol0 O1~11 Ol----42e---O2a O1--Ce---O2b O2---Ce---O4 O2--Ce--O5 O2--Ce--O7 O2---Ce---O8 O2---Ce--Ol0 O2--Ce--~l I O2--Ce--O2a O2--Ce--O2b (M---Ce----4)7 O4---Ce---O8 O2a--Co--O2b O2a---Co---Nla O2a--Co---Nlb Ce--OI--N1 Ce--O2--NI C_.e---q34---N2 Ce---O5---N2 Co---4)2a---Ce Co---O2a--C2a C_.e---~2a--C2a OI--N1--O2 OI--N1-----O3 O2--N1-----O3 O4--N2-----O5 (M---N2---O6 O5---N2--O6 Co---Nla---Cla Co---Nla---C5a Cla---Nla--C5a Ola----Cltr-Nla Ola---Cla--C2a Nla---Cla--C2a O2a--C~a--Caa O2a---C2a---C4a Cla--C2a--Caa Cla--C2a--C4a Caa--C2a---C4a N I a---C5a---C6a Nla---C5a--CTa NIa---C5a--C8 C6a--C5a--C7a C6a--C5a--C8 C7a--C5a--C8 O---C8---C5a O---C8--C5b C5a--CS---C5b 92.6 (1) 136.1 (1) 146.7 (1) 122.5 (1) 106.6 (1) 77.2 (1) 143.8 (1) 96.8 (1) 66.7 (1) 111.3 (1) 138.4 (1) 79.7 (I) 71.2 (1) 83.3 (2) 87.7 (1) 87.5 (1) 170.9 (1) 95.8 (3) 98.9 (2) 96.5 (3) 96.1 (3) 105.3 (1) 113.6 (2) 141.0 (2) 116.6 (4) 122.6 (4) 120.8 (4) 117.4 (4) 121.0 (4) 121.6 (4) 113.9 (3) 122.2 (3) 122.7 (4) 126.1 (4) 120.6 (4) 113.3 (4) 110.5 (4) 108.6 (4) 110.6 (4) 108.4 (4) 110.7 (4) 108.6 (5) 114.3 (4) 103.8 (4) 109.7 (5) 112.7 (4) 107.7 (5) 120.2 (5) 117.9 (5) 122.0 (5) O5---Ce---O2b O7--Ce----~10 O7--Ce--O11 O7--Ce--O2a O7--Ce--O2b OS--Ce--Ol0 O8--Ce---OI 1 O8---Ce---O2a O8--Ce--O2b Ol0--Ce--O2a Ol0--Ce--O2b Ol 1---Ce---O2a O1 l--Ce---O2b 75.2 (1) 98.8 (1) 72.3 (1) 77.8 (1) 134.3 (1) 72.6 (2) 82.4 (2) 124.7 (1) 158.0 (2) 120.4 (I) 86.2 (l) 76.3 (I) 78.8 (1) O2b----Cty--Nla O2b--Cty--Nlb Nla---Co---Nlb Ce----O7--N3 Ce---O8--N3 Ce---OI0---N4 Ce--O 1I--N4 Co---O2b---Ce Co---O2b--C2b Ce---q92b----C2b O7--N3--O8 O7--N3--O9 O8--N3---O9 OI0--N4---OI 1 O10---N4--O12 Ol 1--N4---O12 Co---Nlb--Clb Co~Nlb--C5b Clb--Nlb-----CSb Olb---Clb---Nlb Olb---Clb---C2b Nlb--Clb--C2b O2b--C2b---Clb O2b--C2b----C3b O2b---C2b--C4b Clb---C2b--C3b Clb---C2b--C4b C3b--C2b-----C4b Nlb---C5b---C6b N lb-----C5b--C7b NIb--C5b--C8 C6b--C5b--C7b C6b--C5b--C8 C7b-----C5b-----C8 169.0 (2) 88.0 (1) 98.0 (1) 98.9 (3) 98.0 (3) 99.4 (3) 97.2 (4) 105.6 (1) 114.7 (2) 139.4 (2) 115.6 (4) 121.7 (4) 122.7 (4) 115.8 (5) 121.9 (5) 122.3 (6) 113.9 (3) 126.6 (3) 118.3 (3) 125.8 (4) 120.8 (4) 113.4 (3) 107.2 (3) 109.2 (4) 109.4 (3) 108.6 (4) 109.3 (4) 112.9 (4) 113.2 (4) 108.0 (4) 111.4 (4) 110.1 (5) 105.4 (4) 108.8 (5) groups gave C---C--H angles which ranged from 105 to 114 °. The remaining H atoms were included in the structure-factor calculations at idealized positions (assuming sp2- or spa-hybridization of the C atoms and a C - - H bond length of 0.96/~) 'riding' on their respective C atoms. The isotropic thermal parameter of each H atom was fixed at 1.2 times the equivalent isotropic thermal parameter of the C atom to which it is covalently bonded. The refinement of 863 parameters converged with R = 0.036, wR = 0.045 and S - - 1.1. The maximum shift for all parameters was 0.12trp and the average shift for all parameters was 0.03o-p. There were no peaks present in the final difference Fourier map above the background level. The maximum and minimum electron density in the final difference Fourier map were 0.55 and - 0 . 4 9 e / ~ - 3 , respectively. Atomic scattering factors were taken from International Tables for X-ray Crystallography (1974, Vol. IV) as contained in SHELXTL (Sheldrick, 1990). ~3 -09 Fig. 1. Thermal ellipsoid drawing of the dinuclear complex shown to encompass 50% of the electron density with the atomnumbering scheme. A thermal ellipsoid drawing of the dinuclear complex with the atom-numbering scheme is shown in Fig. 1. Atomic coordinates and final equivalent isotropic thermal parameters of all non-H atoms included in the refinement are given in Table 1.* Selected interatomic distances and angles are listed in Table 2. Related literature. The title compound is the first known dinuclear coordination complex involving a planar cobalt(III) complex and a lanthanide metal ion. A related planar cobalt(III) complex coordinated to a sodium cation (Collins, Richmond, Santarsiero & Treco, 1986) has been structurally characterized. * Lists of structure factors, anisotropic thermal parameters, complete bond distances and angles, H-atom parameters and non-bonded distances have been deposited with the British L i b r a r y Document Supply Centre as Supplementary Publication N o . S U P 5 5 9 7 0 (70 p p . ) . Copies may be obtained through The Technical Editor, International Union of Crystallography, 5 A b b e y Square, Chester C H 1 2 H U , England. [CIF reference: A B 1 0 3 6 ] References BREWER, J. C . , COLLINS, T. J., SMITH, M . R . & SANTARSIERO, B. D . (1988). J. Am. Chem. Soc. 110, 4 2 3 - 4 2 8 . COLLINS, T . J., RICHMOND, T. G . , SANTARSIERO, B. D . & TRECO, B. G . R. T . (1986). J . Am. Chem. Soc. 108, 2 0 8 8 - 2 0 9 0 . SHELDRICK, G . M . (1990). Acta Cryst. A 4 6 , 4 6 7 - 4 7 3 .