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 .