The coordination geometry of the cations in the red form of aquatricarbonyl(1,10-phenanthroline-N, N')rhenium(I) trifluoromethanesulfonate hydrate, [Re(C_(12)H_8N_2)(CO)_3-

(H_2O)]CF_3SO_3•H_2O, is approximately octahedral, with a facial arrangement of the linearly coordinated carbonyl ligands. The phenanthroline (phen) ligands interleave to form a columnar r-stacked structure

Connick, William B.

Di Bilio, Angel J.

Gray, Harry B.

Schaeffer, William P.

Caltech Authors - Main

The red form of [Re(phen)(CO)_3(H_2O)]CF_3SO_3•H_2O

LJILJANA KARANOVI(~ et al. 913 
Table 2. Hydrogen-bonding geometry (A, o) 
D--H. • .A D--H H. • .A D. • .A D--H. • .A 
O5--H5...07 1.20 (4) I.t9 (4) 2.384 (3) 171 (4) 
OI- -HI . . .07 0.80 (3) 1.96 (3) 2.764 (2) 178 (4) 
O2--H2...O9' 0.75 (3) 1.99 (3) 2.729 (3) 170 (2) 
O3--H3...04" 0.77 (3) 2.00 (3) 2.748 (3) 166 (3) 
O8--H8-- .04'" 0.82 (4) 2.08 (5) 2.856 (3) 158 (4) 
O9--H7...05" 0.87 (3) 1.90 (3) 2.764 (2) 178 (2) 
Symmetry codes: (i) -x ,  -y ,  -z ;  (ii) x -  ½, y -  ½, z; (iii) ½ +x, y -  ½, z; 
(iv) ½ - x, ½ - y, -z .  
Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473. 
Sheldrick, G. M. (1993). SHELXL93. Program for the Refinement of 
Crystal Structures. University of Grttingen, Germany. 
Usubaliev, B. T., Shnulin, A. N. & Mamedov, H. S. (1982). Koord. 
Khim. 8, 1532-1538. 
Ward, D. L. & Luehrs, D. C. (1983). Acta Cryst. C39, 1370-1372. 
Zou, J. Z., Liu, Q., Xu, Z., You, X. Z. & Huang, X. Y. (1998). 
Polyhedron, 17, 1863-1869. 
The structure was solved by heavy-atom and difference- 
Fourier methods, and refined by the full-matrix least-squares 
method. All H atoms were found in AF maps, but those con- 
nected to C atoms were placed at calculated positions using 
a riding model [C--H = 0.93 A and Uiso(H) = 1.2U~(C)]. H 
atoms from the H20 molecules and COOH groups were re- 
fined isotropically. The intensities were corrected for absorp- 
tion with the program ABSORB (DeTitta, 1985). 
Data collection and cell refinement: CAD-4 Software 
(Enraf-Nonius, 1989). Data reduction: a local modification 
of MoIEN (Fair, 1990). Program used to solve structure: 
SHELXS86 (Sheldrick, 1990). Program used to refine struc- 
ture: SHELXL93 (Sheldrick, 1993). Molecular graphics: OR- 
TEX5f (McArdle, 1994). Software used to prepare material 
for publication: SHELXL93. Weighted least-squares planes: 
PARST (Nardelli, 1983, 1995). 
This work was supported financially by the Ministry 
for Science and Technology of the Republic of Serbia. 
Acta Cryst. (1999). C55, 913-916 
The red form of [Re(phen)(CO)3(H20)]- 
CF3SO3-H20 
WILLIAM B. CONNICK, ANGEL J. DI BILIO, WILLIAM P. 
SCHAEFER AND HARRY B. GRAY 
Beckman Institute, Mail Code 139-74, California 
Institute of Technology, Pasadena, CA 91125, USA. E-mail: 
bill. connick@ uc. edu 
(Received 14 September 1998; accepted 26 January 1999) 
Supplementary data for this paper are available from the IUCr 
electronic archives (Reference: NA1397). Services for accessing these 
data are described at the back of the journal. 
Re ferences  
Adiwidjaja, G. & Ktippers, H. (1978). Acta Cryst. B34, 2003-2005. 
Bartl, H. & K/Jppers, H. (1980). Z. Kristallogr. 152, 161-167. 
Biagini Cingi, M., Guastini, C., Musatti, A. & Nardelli, M. (1969). 
Acta Cryst. B25, 1833-1840. 
Biagini Cingi, M., Manotti Lanfredi, A. M. & Tiripicchio, A. (1984). 
Acta Cryst. C40, 56-58. 
Chen, W., Tioh, N. H., Zou, J.-Z., Xu, Z. & You, X.-Z." (1996). Acta 
Cryst. C52, 43-45. 
Cousson, A. (1985). Acta Cryst. C41, 1758-1761. 
Cousson, A., Stout, B., Nectou×, ~F., Pages, M. & Gasperin, M. (1986). 
J. Less Common Met. 125, 111-115. 
DeTitta, G. T. (1985). J. Appl. Cryst. 18, 75-79. 
Enraf-Nonius (1989). CAD-4 Software. Version 5.0. Enraf-Nonius, 
Delft, The Netherlands. 
Fair, C. K. (1990). MolEN. An Interactive Intelligent System for 
Crystal Structure Analysis. Enraf-Nonius, Delft, The Netherlands. 
Gonschorek, W. & KiJppers, H. (1975). Acta Cryst. B31, 1068-1072. 
Jessen, S. M. & K~ippers, H. (1990). Acta Co'st. C46, 2351-2354. 
KiJppers, H. (1978). Acta Cryst. B34, 3763-3765. 
McArdle, P. (1994). J. Appl. Cryst. 27, 438-439. 
Nardelli, M. (1983). Comput. Chem. 7, 95-98. 
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. 
Nectoux, A., Abazli, H., Jove, J., Cousson, A., Pages, M., Gasperin, 
M. & Chopin, G. (1984). J. Less Common Met. 97, 1-10. 
Poleti, D. & Karanovi~, Lj. (1989). Acta Cryst. C45, 17 i 6-17 i 8. 
Poleti, D., Stojakovir, D. R., Prelesnik, B. V. & Herak, R. M. (1988). 
Acta Cryst. C44, 242-245. 
Robl, Ch. (1987). Z. Anorg. Allg. Chem. 554, 79-86. 
Abstract 
The coordination geometry of the cations in the red form 
of aquatricarbonyl(1,10-phenanthroline-N, N')rhenium(I) 
trifluoromethanesulfonate hydrate, [Re(Cl2 HsN2)(CO)3- 
(H20)]CF3SO3.H20, is approximately octahedral, with 
a facial arrangement of the linearly coordinated carbonyl 
ligands. The phenanthroline (phen) ligands interleave to 
form a columnar r-stacked structure. 
Comment 
The water-soluble [Re(phen)(CO)3(H20)] + trifluoro- 
methanesulfonate salt is a useful reagent for coupling 
[Re(phen)(CO)3] + to an imidazole group of a protein 
histidine (Connick et al., 1995). We have found that 
the aqua complex forms both yellow and red crystalline 
solids, and that both materials dissolve to give spec- 
troscopically indistinguishable yellow solutions. How- 
ever, the room-temperature mission spectrum of the 
red crystals exhibits maxima near 550 and 670 nm. The 
high-energy yellow-green emission is characteristic of 
rhenium diimine tricarbonyl complexes and evidently 
arises from a film of yellow material formed on the 
surface of the red crystals. However, the red color and 
low-energy emission are less common for these com- 
plexes (Schanze et al., 1993; Wrighton & Morse, 1974). 
In order to elucidate the origins of these spectroscopic 
properties, we have undertaken a structural study of the 
red form of this salt, (I). 
© 1999 International Union of Crystallography 
Printed in Great Britain - all rights reserved 
Acta Crystallographica Section C 
ISSN 0108-2701 © 1999 
914 [Re(CI 2H8N2)(CO)3(H20)]CF3 SO3 .H20 
f 
C,  ........ Re '"" N ~  
OH 2 
(I) 
cv3so3.Hzo 
The red crystals contain two crystallographically dis- 
tinct cations, A and B (corresponding to Re l and Re2, 
respectively), with nearly identical geometries (Fig. 1). 
The coordination geometry is approximately octahe- 
dral, with a facial arrangement of the linearly coor- 
dinated carbonyl ligands. Distances and angles in the 
phenanthroline (phen) ligand are normal (Orpen et al., 
1989). The structure of the cation is very similar to 
that of [Re(phen)(CO)3(imidazole)] ÷ and related com- 
plexes (Connick et al., 1995; Wallace et al., 1995). As 
c,2  
~--~~ ~o2 
(~C15 
(a) 
TM 
(b) 
Fig. 1. ORTEPII (Johnson, 1976) drawings of the two independent 
cations, (a) A and (b) B, showing the atom-numbering system and 
50% probability ellipsoids. H atoms are not shown. 
expected, the Re----C distance trans to the water lig- 
and [1.887 (10) and 1.868 (10) ~,] is slightly shorter than 
found for related complexes with pyridyl [1.90 (2)~; 
Wallace et al., 1995] and imidazole ligands [1.915 (6) A; 
Connick et al., 1995]. The co~esponding Re--O dis- 
tance [2.214(6) and 2.210(6)A] is longer than found 
for complexes with negatively charged O-donor lig- 
ands; 2.18 A in [Re(bpy)o(CO)3(CF3SO3) ] (Calabrese 
& Tam, 1987), 2.188 (13) A in [Re(bpy)(CO)3(PO2F2)] 
(Guilhem et al., 1989) and 2.19A in [Re(bpy)(CO)3- 
(HCO2)] (Horn & Snow, 1980). The coordination geom- 
etry within the equatorial plane exhibits approximate 6"2 
symmetry, with similar equatorial Re--C bond lengths 
[1.911(10), 1.910(11), 1.902(10)and 1.909 (10) ~,], 
as well as similar equatorial C---O bond leng~s 
[1.149(14), 1.152(13), 1.154(13)and 1.157(13)A]. 
In the case of [Re(phen)(CO)3(imidazole)](SO4)2.4H20, 
steric and electronic effects due to twisting of the imida- 
zole group about the Re--N bond result in significantly 
dissimilar equatorial Re--C bond lengths [1.907 (6) and 
1.953 (6)A], as well as dissimilar C--O bond lengths 
[1.149(7) and 1.116 (8) ,~]. 
Close intermolecular contacts (< 3.0 A) between the 
O atoms of the trifluoromethanesulfonate nion and 
the coordinated and solvent water molecules suggest 
extensive hydrogen bonding linking the cations, anions 
and water of crystallization. However, due to solvent 
disorder, this network was not fully elucidated. 
The phenanthroline groups of the rhenium cations in- 
terleave to form a 7r-stacked columnar structure paral- 
lel to the c axis, with the equatorial carbonyl groups 
thrust to the periphery of the column. The cations 
are sequentially positioned along this chain forming 
an . . .A iAB i iB  . . .  motif [symmetry codes: (i) -x+ 1, 
-y+ 1, -z; (ii) -x+ 1, -y+ 1, - z+ 1] (Fig. 2). The 
interplanar spacing between the centrosymmetrically re- 
lated °(and hence parallel) phen ligands B and B ii is 
3.45 A, with closest contacts C21...C26 [3.466 (13)~,] 
and C23...C30 [3.504 (12) ,~,]. The spacing between the 
A and A i phen ligands is slightly larger (3.53 ~,). Con- 
secutive A and B" (as well as A i and B) phen groups 
along the chain are not quite parallel, making a di- 
hedral angle of 12.2(1)°; the shortest intermolecular 
contacts are C12...C30 [3.373 (12)~,] and C16---C26 
[3.384 (14) A]. Whereas there are ten intermolecular 
contacts less than 3.65 ,~, between consecutive B and 
B i~ phen ligands, and seven contacts between consecu- 
tive A and B ii phen ligands, there are only two contacts 
as short between the A and A i phen groups (Table 2). 
Thus, this one-dimensional 7r-stacked structure may be 
regarded as a chain of ABi iBA ii tetrameric units with 
shortest phen..-phen contacts between cations B and 
B ii" 
This packing arrangement suggests that the red color 
of these crystals is related to the interactions between 
phen ligands of adjacent cations. Similar r-stacked 
structures have been proposed to account for the per- 
WILL IAM B. CONNICK et al. 915 
( )  
) 
() 
Fig. 2. A view showing four cations (AiABiiB) stacked along the c 
axis. Intermolecular contacts <_ 3.50 A between phen ligands are 
shown as dashed lines. H atoms are not shown. 
turbed absorption and emiss ion properties of  [Ru(3,3'-  
bi isoquinoline)3](PF6)2 crystals (Kato et al., 1992) and 
plat inum(I I)  d i imine complexes (Bai ley et al., 1995; 
Kato et al., 1996). The effects on the spectroscopy 
appear more pronounced for the extended 7r-stacked 
structure of  [Re(phen)(CO)3(H20)]CF3SO3.H20 than in 
the case of  7r-stacked dimers of  plat inum(I I)  d i imine 
complexes (Kato et al., 1997; Miskowski  & Houlding, 
1989). 
Experimental 
Crystals of (I) were grown by slow evaporation of an aqueous 
solution of [Re(phen)(CO)3(HzO)]CF3SO3 (Sullivan & Meyer, 
1984). 
Crystal data 
[Re(CI2H8 N~)(CO)3 (H20)]- 
CF3SO3"H20 
Mr = 635.54 
Triclinic 
PT 
a = 12.922 (2) ,4, 
b = 13.914 (2) ,4, 
c = 14.263 (6) ,~, 
a = 65.05 (2) ° 
/3 = 73.30 (3) ° 
"7 = 64.59 (1)° 
V = 2082.4 (11 ) ,&3 
Z=4 
Dx = 2.027 Mg m -3 
D,, not measured 
Mo Ka radiation 
A = 0.7107 ]k 
Cell parameters from 25 
reflections 
0 = 10-11 ° 
# = 6.01 mm - l  
T-- 295 K 
Irregular 
0.41 x 0.26 × 0.22 mm 
Red-orange 
Data collection 
Enraf-Nonius CAD-4 
diffractometer 
o,, scans 
Absorption correction: 
scan (North et al., 
1968) 
Tmi, = 0.172, Tmax = 0.267 
14 739 measured reflections 
7218 independent reflections 
5421 reflections with 
I > 2o'(/) 
Ri,t = 0.034 
0max -" 25 ° 
h = -13  ~ 15 
k=-13- -~ 15 
l = -15  ~ 16 
3 standard reflections 
frequency: 150 min 
intensity decay: 1.2% 
Refinement 
Refinement on F 2 
R(F) = 0.058 
wR(F 2) = 0.075 
S = 1.66 
7218 reflections 
560 parameters 
H atoms: see below 
w = 1/[o.2(Fo2)] 
(m/o . )max = 0.04 
Apmax = 2.06 e ,~-3 
Apmin = - -1 .86  e/~-3 
Extinction correction: 
(Larson, 1967) 
Extinction coefficient: 
1.4(14) x 10 -7  
Scattering factors from 
International Tables for 
Crystallography (Vol. C) 
o 
Table 1. Selected geometric parameters (A, o) 
ReI- -N1 2.171 (7) Re2--N3 2.164(7) 
Re l - -N2  2.183 (7) Re2--N4 2.178 (7) 
Re 1---O7 2.214 (6) Re2--O8 2.210 (6) 
Rel---C1 1.887 (10) Re2---C4 1.868 (10) 
Re 1---C2 1.911 (10) Re2----C5 1.902(10) 
Re 1---C3 1.910(11) Re2--C6 1.909(10) 
N l - -Re  I - -N2  75.9 (2) N3- -Re2- -N4 75.8 (3) 
N I - -Re l - -O7  82.1 (2) N3- -Re2- -O8 79.4 (2) 
N2- -Re l - -<)7 80.3 (2) N4---Re2--O8 80.7 (2) 
C2- -Re l - -N2  98.2 (4) C5- -Re2- -N4  98.0 (4) 
C2- -Re l - -O7  95.7 (3) C5--Re2--4)8 95.2 (3) 
C2--Rel - - -C3 88.4 (4) C5--Re2---C6 87.8 (4) 
C2- -Re l - -C I  87.1 (4) C5- -Re2- -C4  87.2 (4) 
C3- -Re I - -N I  97.3 (4) C6---Re2--N3 98.3 (4) 
C3- -Re 1 - -07  93.1 (4) C6--Re2---O8 96.0 (3) 
C3- -Re l - -C I  88.5 (4) C6---Re2--C4 88.6 (4) 
C 1--Re I - -N  1 95.0 (3) C4- -Re2- -N3 97.8 (4) 
C1- -Re I - -N2  97.9 (3) C4---Re2--N4 94.5 (4) 
Table 2. Intermolecular phen...phen contacts less than 
3.65,4 
A- • -A i A. • .B ii 
C10. • -C18 i
CI3. • .C17' 
B.  • .B ii 
C2 I. • -C26" 
C22- .C25" 
C22 . .C26  ii 
C23. .C25" 
C23- .C30" 
C24. -C29 i' 
C24. .C30 'i 
3.561 (13) 
3.645 (13) 
3.466 (13) 
3.497(12) 
3.534 (13) 
3.644(12) 
3.504(12) 
3.514 (12) 
3.574(12) 
CI0- .C29 'i 
C l l .  -C30 'i 
C12. -C25" 
C12- .C30 ~i 
C I 3. .C25" 
C15- -C26" 
C15. -C27" 
C16. -C26 'i 
N2. -C26 i' 
C I7 . .C29  ii 
Symmetry  codes: (i) 1 - x, 1 - y, - z ;  (ii) 1 - x, 
3.531 (12) 
3.476 (12) 
3.626(12) 
3.373 (12) 
3.583(12) 
3.537(14) 
3.535 (14) 
3.384 (14) 
3.603(12) 
3.624(13) 
1 - -y ,  1 - -  z .  
The Re-atom positions were found from a Patterson map and 
the remaining heavy-atom coordinates were obtained from 
subsequent s ructure-factor Fourier calculations. H atoms were 
positioned by calculation (C--H 0.95 ,~,), assigned B values 
916 [Re(C 12H8N2)(CO)3(H20)]CF3 SO3 .H20 
1.1 times the average of the bound C atoms, and repositioned 
twice during refinement. The H atoms of the water molecules 
were ignored. Modeling the disordered water molecules was 
difficult and a three-site model was eventually adopted. The 
corresponding O atoms were assigned populations based on 
their heights in a Fourier map with fixed isotropic B values. 
The maximum (2.06 e ,~-3) and minimum (-71.86 e,~-3) 
peaks in the final difference map are within 0.4 A of the Re2 
atom. Individual variances 0-2(/) were derived from counting 
statistics plus an additional term (0.014I) 2, while variances 
of the merged intensities included propagation of error plus 
another additional term (0.014(1)) 2 .
Data collection: CAD-4 Software (Enraf-Nonius, 1989). 
Cell refinement: CAD-4 Software. Data reduction: CRYM 
(Duchamp, 1964). Program(s) used to solve structure: CRYM. 
Program(s) used to refine structure: CRYM. Molecular graph- 
ics: ORTEPII (Johnson, 1976). Software used to prepare ma- 
terial for publication: CRYM. 
Acta Cryst. (1999). C55, 916-918 
Dibenzylbis(tert-butylimido )molyb- 
denum(VI), containing both r/1- and 
r/2-benzyl igands 
WILLIAM CLEGG, a MARK R. J. ELSEGOOD, a PHILIP W. 
DYER, b VERNON C. GIBSON b AND EDWARD L. MARSHALL b 
aDepartment of Chemistry, University of Newcastle upon 
Tyne, Newcastle upon Tyne NE1 7RU, England, and 
bDepartment of Chemistry, Imperial College of Science, 
Technology and Medicine, South Kensington, London 
SW7 2AY, England. E-mail: w.clegg@ncl.ac.uk 
(Received 11 February 1999; accepted 2 March 1999) 
We thank L. M. Henling for expert assistance and 
helpful discussions. This work was supported by the 
National Science Foundation and the National Institutes 
of Health. 
Supplementary data for this paper are available from the IUCr 
electronic archives (Reference: BK1449). Services for accessing these 
data are described at the back of the journal. 
References 
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1003. 
Abstract 
The title compound, [Mo(CH2Ph)z(C4H9N)2], contains 
two slightly bent imido ligands and two benzyl ligands. 
One of these benzyl ligands is coordinated as a sim- 
ple r/l-alkyl ligand, while the other is r/2-coordinated 
through the CHE group and the ipso-C atom, i.e. 
dibenzyl-nCO; n2C t , C~-bis(tert-butylimido-nN)molyb - 
denum(VI). Considering the r/2-benzyl ligand as oc- 
cupying one coordination site, this gives a tetrahedral 
geometry around molybdenum, the main angular dis- 
tortion being a mutual repulsion of the two strongly 
n-donating imido ligands. This complex is not crystal- 
lographically isostructural with its chromium analogue, 
but the two molecular structures are very similar. 
Comment 
As part of our work directed towards the develop- 
ment of new alkene polymerization catalysts based 
on complexes of imido ligands (Coles & Gibson, 
1994), we have already reported the synthesis and 
crystallographic characterization of the chromium di- 
benzyl complex [Cr(CH2Ph)z(NtBu)2], (1) (Coles et al., 
1995). Although the possibility of a-agostic interac- 
tions between chromium and the CH2 H atoms of the 
benzyl ligands was envisaged in this study, the struc- 
ture revealed instead the presence of one 77 l- and one 
r/2-benzyl ligand. In subsequent investigations of related 
complexes of chromium and molybdenum with different 
imido and alkyl ligands, we have prepared the molyb- 
denum analogue of (1), complex (2), and report here its 
structure. 
Mo~NCMe3 
'~NCMe 3
(2) 
© 1999 International Union of Crystallography 
Printed in Great Britain - all rights reserved 
Acta Crystallographica Section C 
ISSN 0108-2701 © 1999 


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The red form of [Re(phen)(CO)_3(H_2O)]CF_3SO_3•H_2O

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