Syntheses and structures of Ag(I)-containing coordination polymers and Co(II)-containing supramolecular complex based on novel fulvene ligands

Article abstract of DOI:10.1021/ic0495517

Three new rigid conjugated fulvene ligands L1-L3 were synthesized. L1 and L3 have been prepared by an aroylation reaction of cyclohexyl-substituted cyclopentadienyl anions. L2 was prepared by the reaction of L1 with PhNHNH ₂ in hot enthanol. Six new coordination polymers, namely [Ag(C ₂₅H₂₀N₂O₂)(ClO₄) ·3.5C₆H₆ (1), [Ag₂(μ-C ₃₁H₂₄N₄)(η²-C₆H ₆)(H₂O)](ClO₄)₂·(C ₆H₆)·(H₂O)_0.5 (3), [Ag(C ₃₁H₂₄N₄)]SbF₆·solvate (4), [Ag(C₃₁H₂₄N₄)](SbF₆) ₂·2C₆H₆·CH₂Cl ₂ (5), [Ag(C₂₅H₂₀N₂O ₂)₂]SbF₆ (6), and [Ag(C₂₅H ₂₀N₂O₂)₂]SbF₆ (7), and one seven-membered cobaltacycle-containing complex, namely Co(C ₂₅H₂₀N₂O₂)₂(C ₂H₅OH)₂ (2), were obtained through self-assembly based on these three new fulvene lignads. L2-L3 and compounds 1-7 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can bind metal ions not only through the terminal N-donors and fulvene carbon atoms into organometallic coordination polymers but also through the two chelating carbonyl groups into unusual seven-membered metallo-ring supramolecular complexes. In the solid state, ligands L1-L3 are luminescent. A blue-shift in the emission was observed between the free ligand L1 and the one incorporated into Co(II)-containing complex 2, and a red-shift in the emission was observed between the free ligand L3 and the one incorporated into Ag(I)-containing polymeric compounds 6 and 7.

Full text of DOI:10.1021/ic0495517

Inorg. Chem. 2004, 43, 4727−4739
Syntheses and Structures of Ag(I)-Containing Coordination Polymers
and Co(II)-Containing Supramolecular Complex Based on Novel Fulvene
Ligands
Yu-Bin Dong,* Peng Wang, and Ru-Qi Huang
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal UniVersity,
Jinan, 250014, P. R. China
Mark D. Smith
Department of Chemistry and Biochemistry, UniVersity of South Carolina,
Columbia, South Carolina 29208
Received April 5, 2004
Three new rigid conjugated fulvene ligands L1−L3 were synthesized. L1 and L3 have been prepared by an aroylation
reaction of cyclohexyl-substituted cyclopentadienyl anions. L2 was prepared by the reaction of L1 with PhNHNH
2
in hot enthanol. Six new coordination polymers, namely [Ag(C H N O )(ClO )]‚3.5C H (1), [Ag2(µ-C H N )(η2-
25 20
2
2
4
6
6
31 24 4
C H )(H O)](ClO ) ‚(C H )‚(H O)0.5 (3), [Ag(C H N )]SbF ‚solvate (4), [Ag(C H N )](SbF ) ‚2C H ‚CH Cl2 (5), [Ag-
6
6
2
4 2
6
6
2
31 24
4
6
31 24
4
6 2
6
6
2
(C H N O ) ]SbF (6), and [Ag(C H N O ) ]SbF (7), and one seven-membered cobaltacycle-containing complex,
25 20
2
2 2
6
25 20
2
2 2
6
namely Co(C H N O ) (C H OH)2 (2), were obtained through self-assembly based on these three new fulvene
25 20
2
2 2
2 5
lignads. L2−L3 and compounds 1−7 have been fully characterized by infrared spectroscopy, elemental analysis,
and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is
versatile. They can bind metal ions not only through the terminal N-donors and fulvene carbon atoms into
organometallic coordination polymers but also through the two chelating carbonyl groups into unusual seven-
membered metallo-ring supramolecular complexes. In the solid state, ligands L1−L3 are luminescent. A blue-shift
in the emission was observed between the free ligand L1 and the one incorporated into Co(II)-containing complex
2, and a red-shift in the emission was observed between the free ligand L3 and the one incorporated into Ag(I)-
containing polymeric compounds 6 and 7.
Introduction
ligands is the main theme. So far, a number of organic-
inorganic coordination polymers based on organodiamine
ligands1a-b (metal-heteroatom interaction) and organome-
tallic coordination polymers based on polycyclic aromatic
hydrocarbons1c (metal-carbon interaction) have been suc-
cessfully synthesized. In contrast, the chemistry of supramo-
lecular architectures based on fulvene molecules has received
considerably less attention. It is well-known that fulvene is
one of the most important classes of ligands in organometallic
Self-assembly of organic ligands and inorganic metal ions
is one of the most efficient and widely used approaches for
the construction of supramolecular architectures.1-3 Owing
to their potential as new functional solid materials, interest
in self-assembled coordination polymers with interesting
physical properties has grown rapidly.4 In this field, the
coordination chemistry of bidentate or multidentate organo-
diamine ligands and polycyclic aromatic hydrocarbons
* Author to whom correspondence should be addressed. E-mail:
yubindong@sdnu.edu.cn.
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M.; Li, G.; Li, H.; Groy, T. L. J. Am. Chem. Soc. 1996, 118, 9096.
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10.1021/ic0495517 CCC: $27.50 © 2004 American Chemical Society
Published on Web 06/24/2004
Inorganic Chemistry, Vol. 43, No. 15, 2004 4727

Dong et al.
Scheme 1. Synthesis of Compounds 1-7
chemistry and widely utilized in synthesis of organometallic
complexes based on metal-carbon interaction, such as
metallocene. In our previous studies, we reported some new
conjugated fulvene ligands, by the aroylation of substituted
cyclopentadienyl anions, with both aromatic rings and -CN
functional groups and several novel one-dimensional coor-
dination polymers and supramolecular complexes based on
them.9 A -CN functional group on the aromatic ring, as we
know, is a good candidate for coordination bonding as has
been exploited in the self-assembly of Ag-supramolecular
architectures. For example, a series of very attractive Ag-
coordination polymers based on 1,3,5-tris(4-cyanophenyl-
ethynyl)benzene,5 4,4′-biphenyldicarbonitrile,6 3,3′-dicyan-
odiphenylacetylene,7 and phenylacetylene nitriles with pendant
oligo (ethylene oxide) side chains8 has been reported by
Moore and Lee. Fulvene together with -CN functional group
would be a good candidate for synthesis of organometallic
coordination polymers or supramolecular complexes based
on both carbon-metal and heteroatom-metal interactions.
This encouraged us to undertake further studies on fulvene
ligands of this type and explore their interesting coordination
chemistry. Following this approach, we now expand this
chemistry with three new fulvene ligands (L1-L3). Six new
Ag(I) coordination polymers, namely [Ag(C25H20N2O2)-
(ClO4)]‚3.5C6H6 (1), [Ag2(µ-C31H24N4)(η2-C6H6)(H2O)]-
(ClO4)2‚(C6H6)‚(H2O)0.5 (3), [Ag(C31H24N4)]SbF6‚unknown
solvate (4), [Ag(C31H24N4)](SbF6)2‚2C6H6‚CH2Cl2 (5), [Ag-
(C25H20N2O2)2]SbF6 (6), and [Ag(C25H20N2O2)2]SbF6 (7), and
one H-bonded Co(II) supramolecular complex, namely Co-
(C25H20N2O2)2(C2H5OH)2 (2), (Scheme1) were successfully
isolated. In addition, luminescent properties of some of them
were investigated in the solid state.
(3) (a) Heintz, R. A.; Zhao, H.; Ouyang, X.; Grandinetti, G.; Cowen, J.;
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Results and Discussion
Synthesis and Structural Analysis of Fulvene Ligands.
Ligands L1 and L3 were prepared in moderate yield (61%
for L1 and 59% for L3) as deep-yellow crystalline solids
by the reactions of 4-cyanobenzoyl chloride and 3-cyanoben-
zoyl chloride with tert-butyl-substituted cyclopentadienyl
anions, which in turn were prepared from 6,6′-dimethylful-
vene and CH3Li in ether at 0 °C, respectively. L2 was
prepared in 80% yield as an orange crystalline solid by the
1
reaction of L1 with PhNHNH2 in hot enthanol. In the H
NMR spectrum of L1 and L3, a proton resonance was
observed at 17.85 ppm as a singlet, which was attributed to
the chelated proton, which is hydrogen bonded to the
carbonyl next to the 1-aroyl group. The IR spectrum of L1
and L3 showed a -CN absorption band at 2250 cm-1. It
did not, however, show absorptions above 1630 cm-1 in the
region normally assigned to organic carbonyl groups. The
strong absorption band around 1620 cm-1 is, however,
consistent with the hydrogen bonded enol structure, since it
has been shown that conjugation and chelation lead to a large
shift in the carbonyl infrared band.10
The structure of L2 and L3 were further confirmed by
single-crystal X-ray diffraction. The crystal structure of L3
reveals that the asymmetric unit contains two crystallo-
graphically and conformationally inequivalent molecules (a)
(9) (a) Dong, Y.-B.; Jin, G.-X.; Smith, M. D.; Huang, R.-Q.; Tong, B.;
zur Loye, H.-C. Inorg. Chem. 2002, 41, 4909. (b) Dong, Y.-B.; Ma,
J.-P.; Jin, G.-X.; Huang, R.-Q.; Smith, M. D. Dalton Trans. 2003, 22,
4324. (c) Dong, Y.-B.; Zhao, X.; Jin, G.-X.; Huang, R.-Q.; Smith, M.
D. Eur. J. Inorg. Chem. 2003, 22, 4017. (d) Dong, Y.-B.; Jin, G.-X.;
Zhao, X.; Huang, R.-Q.; Smith, M. D.; Stitzer, K. E.; zur Loye, H.-C.
Organometallics 2004, 23, 1604.
(10) William, J. L.; William, H. S. J. Am. Chem. Soc. 1957, 79, 4970.
4728 Inorganic Chemistry, Vol. 43, No. 15, 2004

Self-Assembled Polymers Based on NoWel FulWene Ligands
Figure 1. Molecular structure of L3 (30% probability displacement
ellipsoids).
and (b). For example in molecule (a), as shown in Figure 1,
two aroyl groups on the tetracarbon-substituted cyclopeta-
dienyl ring are adjacent. The C-C bond lengths on the
substituted Cp-ring and also C(1)-C(5) and C(5)-C(14)
range from 1.384 (2) to 1.420(2) Å, which is significantly
shorter than a normal C-C single bond distance. Evidently,
L3 exists in the fulvene form.10 The enol hydrogen atom
(H(1)) is hydrogen bonded to the carbonyl oxygen atom
(O(2), dO(2)‚‚‚H(1) ) 1.34(2) Å, O(1)-H(1)‚‚‚O(2) ) 177(2)°,
and dO(1)‚‚‚O(2) ) 2.4379(17) Å) to provide a hydrogen bonded
seven-membered ring. It is worth pointing out that the two
-C6H4-CN-p rings and hydrogen bonded seven-membered
ring are not in the same plane. The dihedral angles between
-C6H4-CN-p rings and the hydrogen bonded seven-
membered ring are 55.0(2)° and 52.3(2)°, respectively. The
terminal (-CN) N‚‚‚N separations in L3 are 12.52 (cis
conformation) and 14.67 (trans-conformation) Å, respec-
tively. It is significantly longer than the terminal N‚‚‚N
separations of 7.122(4), 9.385(5), and 9.685(4) Å found in
4,4′-bipyridine,11 trans-1,2-bis(4-pyridyl)ethene,12 and 1,2-
bis(4-pyridyl)ethyne,13 respectively. There are two indepen-
dent L2 molecules (a) and (b) present in the asymmetric
unit, too. For example in molecule (a), as shown in Figure
2, the hydrogen bonded seven-membered ring in L1 was
replaced by a six-membered phenyl-substituted pyridazine
in L2. The contact between two terminal N-donors is
16.41(3) Å, which is slightly longer than the corresponding
distances found in L3. In addition, L2 could be considered
as an angular ligand with a bite angle between one terminal
-CN (N(4)) donor and one Npyridazine donor around 60°,
which has a strong tendency to form cyclic moieties with
inorganic metal ions.13c Such a kind of geometric configu-
Figure 2. Molecular structure of L2 (30% probability displacement
ellipsoids).
Figure 3. ORTEP figure of compound 1 with 30% probability ellipsoids.
ration together with the other terminal N-donor would be
expected to form metallacycle-containing coordination poly-
mers or supramolecular complexes.
Synthesis and Structural Analysis of 1. Reaction of L1
with AgClO4‚xH2O (1:2 ratio) in benzene at room temper-
ature afforded compound 1 as orange cubic crystals in 54%
yield. Compound 1 loses guest solvent molecules quickly
and is not stable outside of the mother liquor. Single-crystal
analysis revealed, as shown in Figure 3, compound 1
crystallizes in the triclinic system P1h. The asymmetric unit
-
consists of one Ag(I) center, one L1 ligand, one ClO4
counterion, three full benzene molecules of crystallization,
and another half-benzene located on an inversion center.
Ag(I) center adopts a {AgN2O} (Ag-N(1) ) 2.139(2),
Ag(1)-N(2)#1 ) 2.169(2), Ag(1)-O(11) ) 2.5463(19) Å)
coordination sphere, which is commonly observed in Ag(I)
complexes. In addition, one guest benzene molecule is
located close to the Ag(I) metal center. The shortest
Ag(I)‚‚‚C contact (Ag‚‚‚C(31)) is only 3.070(3) Å, which is
beyond the bond length limits (2.47 to 2.80 Å) commonly
observed in Ag(I) aromatic complexes.14
(11) (a) Fujita, M.; Kwon, Y. J.; Wsahizu, S.; Ogura, K. J. Am. Chem.
Soc. 1994, 116, 1151. (b) Lloret, F.; Munno, G. D.; Miguel, J.; Cano,
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Champness, N. R.; Gill, P. M. W.; O’Neill, D. P.; Teat, S. J.; Wilson,
C.; Schro¨der, M. J. Am. Chem. Soc. 2003, 125, 6753.
In the solid state, Ag(I) metal centers are connected to
each other by bidentate ligands L1 through the terminal -CN
nitrogen atoms into a one-dimensional linear chain extended
(14) (a) Griffith, E. A. H.; Amma, E. L. J. Am. Chem. Soc. 1974, 96, 5407.
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Inorganic Chemistry, Vol. 43, No. 15, 2004 4729

Dong et al.
3:1, the compound 2 is always isolated as the only product.
Compound 2 crystallizes in the triclinic system. As shown
in Figure 8, Co(II) center lies in an octahedral coordination
environment defined by four O-donors from two bidentate
ligands L1 and two O-donors from two coordinated ethanol
solvent molecules. The octahedral coordination polyhedron
is slightly distorted, where all angles around the copper center
deviate significantly from 90° (O(1)-Co-O(2) ) 91.32(7)°,
O(1)-Co-O(3) ) 95.29(9)°, O(2)-Co-O(3) ) 90.82(9)°).
The Co-O bond distances on the basal plane are 2.0022-
(16) and 2.0052(16) Å, respectively, which compare well
with the Co-O distances found in cobalt-oxygen com-
plexes.19 The distances between the cobalt center and the
two axial O-donor atoms are the same (dCo-O ) 2.137(3)
Å), again consistent with corresponding bond lengths in those
complexes with similar coordination envoronment.19 It is
well-known that neutral or deprotonated 1,2-diketone or 1,3-
diketone compounds can be the chelating ligands to bind
transition metal ions into five- or six-membered metallo-
ring systems which engender less strain,20a because the atoms
on the rings are allowed to adopt more closely their natural
bond angles. It is much less known that seven-membered
metallo-ring complexes can be generated from neutral or
deprotonated 1,4-diketone-containing ligands and transition
metal ions probably due to the conformational strain effect.20a
However, some interesting seven-membered metallacycle
complexes were reported recently, such as metal complexes
generated from TADDOL,20b diazoacetate,20c bis(phosphane)
ligands,20d and related bidentate chelating ligands.20e Some
of them are demonstrated to be very useful catalysts in metal-
catalyzed stereoselective syntheses. Owing to its specific
molecular geometry, ligand L1 reported herein presents an
additional perfect example for the synthesis of seven-
membered metallo-ring transition metal complexes. The four
-CN groups in 2 are uncoordinated and every two of them
aligned along the same axis, but are oriented in the reverse
directions. The IR spectrum of 2 shows that the sCtN
stretch (2255 cm-1) was essentially unchanged from free
ligand L1, which can be taken as evidence for the nitrile
nitrogen not entering the coordination sphere of the Co(II)
center. A similar phenomenon occurs in the reaction of Ru2-
Figure 4. One-dimensional double chain in 1.
along crystallographic [111h] direction. The intrachain
Ag‚‚‚Ag separation is 21.00(3) Å. As shown in Figure 4,
weakly coordinated ClO4- counterions are located between
these one-dimensional chains and, moreover, they link these
one-dimensional polymer chains into a double chain motif
via weak inter-polymer Ag(I)-O interactions. The correspond-
ing Ag-O (Ag(1)-O(13)) bond distance is 2.742(3) Å.1b
The shortest interchain Ag‚‚‚Ag separation is 4.80(4) Å,
which is longer than the sum of the van der Waals radii of
two silver atoms, 3.44 Å.15 In addition, π-π interactions16
are present in 1 (Figure 5). Chain pairs are linked into two-
dimensional layers through π-π interactions of {C15‚‚‚
C20}-{C15*‚‚‚C20*} across an inversion center (dcentroid-centroid
) 3.599 Å). As shown in Figure 6, benzene guest molecules
are located between layers and give rise to an interesting
ordered arrangement due to their edge-to-face interactions
commonly observed in the crystal structure of benzene
(Figure 7).17 The shortest intermolecular C-C separation is
3.472 Å, which is similar to those reported for related
compounds, such as pyrene and 1-propynylpyrene.18
Synthesis and Structural Analysis of 2. As shown in
Figure 1, fulvene ligands of this type have not only terminal
-CN coordination sites but also cis-1,4-diketone moiety. The
specific geometry herein affords a scarce opportunity to
synthesize seven-membered metallo-ring complexes that are
not achievable easily by other kinds of 1,4-diketone-type
ligands. The complex 2 was synthesized by reaction between
L1 and Co(OAc)2‚2H2O in hot ethanol. When a solution of
L1 in ethanol was treated with Co(OAc)2‚2H2O, in a metal-
to-ligand molar ratio of 1:2, compound 2 was obtained as
the neutral molecular compound with seven-membered
metallo-rings. It is worth pointing out that the coordination
chemistry of L1 with transition metal templates Co(II) are
independent of the metal-to-ligand mole ratio. For example,
when the metal-to-ligands ratio changed from 1:1 to 2:1, even
Figure 5. Two one-dimensional double chains linked by π-π interactions.
4730 Inorganic Chemistry, Vol. 43, No. 15, 2004

Self-Assembled Polymers Based on NoWel FulWene Ligands
Figure 9. Hydrogen-bonded one-dimensional chain motif found in
compound 2. Hydrogen bonds are shown as thin lines.
and polymers.22,23 It appears that the nitrile N-donor atom
has a poor coordinating ability to effectively link 3d metal
ions. For example, in [(Cu(4-cyanopyridine)4(H2O)(ClO4)2)n,
the nitrile nitrogen only weakly coordinates with copper
centers through a “semi-coordinated” bond (CusNtC is
2.649(4) Å), which is much longer than a normal Cu-N
coordinative bond.24 It is worth noting that 2 contains
uncoordinated N-donors, and could be used as a potential
new metal-containing building block, as suggested recently.25
These building blocks could be connected by other suitable
metal ions (Ag+ or Cd2+, for example) or unsaturated metal
complexes via bonding interactions with the free nitrile
nitrogen atoms in 2, a direction we are pursuing. The shortest
Co‚‚‚Co distance is 12.66(3) Å.
Figure 6. Crystal packing of 1.
In the solid state, as shown in Figure 9, the neutral building
blocks of 2 arrange parallel to the crystallographic c axis,
and moreover are bound together by strong intermolecular
N‚‚‚O-H hydrogen bonds in a hand-in-hand fashion to create
a one-dimensional chain motif along crystallographic b axis.
The hydrogen bonding system in 2 consists of the one
uncoordinated nitrogen atom N(1) on -CN group with the
hydrogen atom H(3A) on the coordinated ethanol molecule
O(3) of a neighboring Co(II) complex. The N(1)‚‚‚H(3)
Figure 7. Edge-to-face arrangement of benzene guest molecules in 1.
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Inorg. Chem. 1994, 33, 324.
(20) (a) Guerriero, P.; Tamburini, S.; Vigato, P. A. Coordination Chem.
ReV. 1995, 139, 17. (b) Charette, A. B.; Molinaro, C.; Brochu, C. J.
Am. Chem. Soc. 2001, 123, 12168. (c) Louie, J.; Grubbs, R. H.
Organometallics 2001, 20, 481. (d) Kadyrov, R.; Bo¨rner, A.; Selke,
R. Eur. J. Inorg. Chem. 1999, 705. (e) Kim, Y. H. Acc. Chem. Res.
2001, 34, 955.
(21) Wesemann, J. L.; Chisholm, M. H. Inorg. Chem. 1997, 36, 3258.
(22) (a) Hung, H. Y.; Chen, W. J.; Yang, G. C.; Yeh, A. Inorg. Chem.
1997, 30, 1862. (b) Benaltabef, A.; Degllo, S. B. R.; Folquer, M. E.;
Katz, N. E. Inorg. Chim. Acta 1991, 188, 67. (c) Almaraz, A. E.;
Gentil, L. A.; Baraldo, L. M.; Olabe, J. A. Inorg. Chem. 1996, 35,
7718.
(23) (a) Bailey, R. D.; Hook, L. L.; Pennington, W. T. Chem. Commun.
1998, 1181. (b) Carlucci, L.; Ciani, G.; Proserpio, D. M.; Sironi, A.
J. Chem. Soc., Chem. Commun. 1994, 2755.
(24) Zhang, W. R.; Jeitler, J. R.; Turnbull, M. M.; Landee, C. P.; Wei, M.
Y.; Willet, R. D. Inorg. Chim. Acta 1997, 256, 183.
(25) (a) Dong, Y.-B.; Smith, M. D.; zur Loye, H.-C. Angew. Chem., Int.
Ed. 2000, 39, 4271. (b) Dong, Y.-B.; Smith, M. D.; zur Loye, H.-C.
Solid State Sci. 2000, 2, 335. (c) Dong, Y.-B.; Smith, M. D.; zur Loye,
H.-C. Inorg. Chem. 2000, 39, 1943.
Figure 8. ORTEP figure of compound 1 with 30% probability ellipsoids.
(O2C(CH2)6CH3)4 in toluene and Cu(hfacac)2‚H2O (hfacac
) hexafluoroacetylacetonate) in methylene chloride with
4-cyanopyridine and 3-cyanopyridine, respectively.21 The
discrete molecular 1:2 adduct Ru2(O2C(CH2)6CH3)4(4-cyan-
opyridine)2 and Cu(hfacac)2(3-cyanopyridine)2 are obtained
instead of the expected 4-cyanopyridine and 3-cyanopyridine
bridged transition metal complexes. It is known that 4-cy-
anopyridine and 3-cyanopyridine spacers have been used as
bridging ligands to link transition metal species into dimers
Inorganic Chemistry, Vol. 43, No. 15, 2004 4731

Dong et al.
Figure 11. One-dimensional organometallic ladder-like chain in 3.
Figure 10. Molecular structure of 3.
distance is 2.18(2) Å. The corresponding O(3)‚‚‚N(1)
distance is 2.909(3) Å, and the corresponding O(3)-
H(3)‚‚‚N(1) angle is 173(4)°. The existence and structural
importance of strong hydrogen-bonding interactions gener-
ated from -CN (as the hydrogen bond acceptor) are now
well established and observed in many compounds.26 It is
no doubt that these strong hydrogen bonding interactions
contribute significantly to the alignment of the molecules of
2 in the crystalline state.
Figure 12. Crystal packing of 3. Benzene and water solvent molecules
and ClO4 counterions are omitted for clarity.
-
η2 instead of an η1 bonding mode, which is normally
observed in arene-silver complexes.28
In the solid state, as shown in Figure 11, Ag(2) centers
are connected to each other by L2 ligands through two
terminal N-donors into one-dimensional chains along the
crystallographic a axis. The shortest intrachain Ag(2)...Ag(2)
distance is 20.85(4) Å. These one-dimensional chains are
further linked together by five-membered ring-Ag(2) (C(2)-
Ag(1)) linkages into an interesting ladder-like motif.29 The
Ag(I)-benzene moieties are located outside the ladder and
bound to it through Ag(1)-Npyridazine bond interaction. The
shortest intrachain Ag(1)‚‚‚Ag(1) distance is 20.56(4) Å.
These chains stack together along the crystallographic b axis
and generate channels along the crystallographic c axis. The
benzene and water solvent molecules and ClO4- counterions
are located in the channels as the guest (Figure 12). To date,
a number of Ag(I)-containing coordination polymers have
been successfully generated from inorganic silver salts and
various types of rigid and flexible organic spacers based on
Ag-heteroatom1a-b or Ag-π interactions,1c,3 g respectively.
To our knowledge, silver coordination polymers or supramo-
lecular networks based on both metal-heteroatom and metal-
carbon interactions are still unusual, especially for Cp-metal-
containing ones.9d Fulvene organic spacers reported herein
are good candidates for preparation of Cp-Ag(I) moiety-
containing organometallic coordination polymers or su-
pramolecular complexes.
Synthesis and Structural Analysis of 3. Compound 3
was obtained as red-orange crystals by combination of L2
with Ag(ClO4)‚xH2O in CH2Cl2/C6H6 mixed solvent system.
Crystals of 3 lose solvent molecules and turn opaque within
several minutes under ambient atmosphere. Single-crystal
analysis revealed, as shown in Figure 10, that there are two
different Ag(I) centers in 3. The coordination sphere around
the first silver atom is distorted tetrahedral, being made of
two N-donors (N(1) and N(2)) from two ligands L2 (Ag-
N(1) ) 2.166(10) and Ag-N(2) ) 2.165(10) Å), one
O-donor (O(1)) from ClO4- counterion (Ag-O(1) ) 2.6122-
(2) Å),27 and one carbon atom (C(2)) from the substituted
Cp group on the third ligand L2. The Ag-C distance is
2.679(9) Å, while the remaining Ag-C contacts are greater
than 2.80 Å which is beyond the limits (2.47 to 2.80 Å)
commonly observed in Ag(I)-aromatic complexes.14 Thus,
the substituted five-membered ring in L2 coordinates to the
Ag(I) ion with an η1 bonding mode, which is normally
observed in arene-silver complexes.28 The second Ag(2)
center adopts a {AgC2NO} oragnometallic pseudotetrahedral
coordination environment, which consists of two carbon
atoms (C(41) and C(42)) from solvent benzene molecule,
one aquo oxygen atom (Ag(2)-O(11) ) 2.290(13) Å), and
one nitrogen donor (N(2)) from six-membered phenyl-
substituted pyridazine moiety (Ag(2)-N(2) ) 2.317(8) Å).
For the Ag(2) center, the two Ag-Cbenzene bond distances
(2.444(16)-2.571(15) Å) lie in the range of normal Ag-C
bond distances 2.47-2.76 Å, while the remaining Ag-C
contacts are greater than 2.86 Å, which is beyond the limits
commonly observed in Ag(I)-aromatic complexes.14 Thus,
the benzene ring in 1 coordinates to the Ag(I) ion with an
Synthesis and Structural Analysis of 4 and 5. When a
solution of L2 in CH2Cl2 was treated with AgSbF6 in
benzene, compounds 4 and 5 were obtained successively as
yellow and red crystals, respectively. Compounds 4 and 5
are not air stable. As shown in Figure 13, compound 4
crystallizes in the tetragonal system with the space group
P4/n. The asymmetric unit consists of the Ag(I) center, one
L2 ligand, and an SbF6- anion disordered over two closely
(26) Inoue, K.; Hayamizu, T.; Iwamura, H.; Hashizume, D.; Ohashi, Y. J.
Am. Chem. Soc. 1996, 118, 1803.
(27) Choe, W.; Kiang, Y.-H.; Xu, Z.; Lee, S. Chem. Mater. 1999, 11, 1776.
(28) Munakata, M.; Wu, L. P.; Ning, G. L. Coord. Chem. ReV. 2000, 198,
171.
(29) (a) Losier, P.; Zaworotko, M. J. Angew. Chem., Int. Ed. Engl. 1996,
35, 2779. (b) Hennigar, T. L.; MacQuarrie, D. C.; Losier, P.; Rogers,
R. D.; Zaworotko, M. J. Angew. Chem., Int. Ed. Engl. 1997, 36, 972.
4732 Inorganic Chemistry, Vol. 43, No. 15, 2004

Self-Assembled Polymers Based on NoWel FulWene Ligands
Figure 13. ORTEP figure of compound 4 with 30% probability ellipsoids.
Figure 15. Crystal packing of 4.
Figure 16. Molecular structure of 5.
Figure 14. Two-dimensional net in 4.
etrating square-grid coordination polymers, such as 4, can
have reduced porosity due to the stacking of the nets. In the
case of 4 the ABAB stacking of the layers generates reduced,
yet still large, infinite channels of dimensions of 12.36 ×
12.36 Å (Figure 15). The solvent-accessible region calculated
with the PLATON program31 is 654.1 Å3 or 10.0% of the
total unit cell volume. A series of binuclear metallacycle-
containing polymeric compounds were reported recently,13c
wherein those Cd(II)-metallacyclic building blocks are con-
nected to each other through coordinated NO3- counterions
into extended structures. Compared to 2,4′-bipyrindyl type
ligands,13c L2 is more suitable to generate binuclear, even
multinuclear, metallacyclic polymeric complexes.
spaced positions. The final occupancy values are 0.925/0.075.
The Ag(I) centers in 4 lie in a distorted trigonal coordination
environment4f which consists of two terminal CN-donors
(Ag(1)-N(1)#2 ) 2.327(4) and Ag(1)-N(4)#1 ) 2.203(5)
Å) from two L2 ligands and one phenyl-substituted py-
ridazine nitrogen donor (N(2), Ag(1)-N(2) ) 2.199(4) Å)
from the third L2 ligand.
In the solid state, as shown in Figure 14, L2 ligands bind
Ag(I) centers through one pyridazine nitrogen donor (N(2))
and one terminal nitrile N-donor (N(1)) into a binuclear
metallacycle. These binuclear metallacycles are further linked
together by the other terminal nitrile N-donor (N(1)) into a
novel two-dimensional net extended in crystallographic ab
plane. It is worth pointing out that this two-dimensional net
consists of three different kinds of metallacyacles, i.e., big
square-like quadrinuclear, medium square-like quadrinuclear,
and small rectangle-like binuclear metallacycles. Their
crystallographic square-grid dimensions30 are 20.83 × 20.83
and 12.37 × 12.37 Å, respectively, and the rectangle-grid
dimension is 9.15 × 3.14 Å. These two-dimensional sheets
stack together in ABAB fashion along crystallographic c axis
to generate a noninterpenetrating square-channels containing
network. It is well-known that interpenetrating square-grid
polymers are typically nonporous since all available spaces
are filled by the interpenetration; even large noninterpen-
Compound 5 was obtained as red crystals at only 9% yield.
Single-crystal analysis revealed that 5 crystallizes in the
monoclinic space group P21/c. All species reside on positions
of general crystallographic symmetry. The tert-butyl sub-
stituent of the L2 ligand is rotationally disordered over two
orientations, and was refined with the aid of 10 C-C same-
distance restraints. Occupancies for each disorder component
were initially refined but subsequently fixed near the final
refined values (0.65/0.35) for stability. As shown in Figure
16, Ag(I) center adopts a linear coordination environment
which consists of two terminal nitrile N-donors from two
(31) PLATON. (a) Spek, A. L. Acta Crystallogr., Sect. A: Found.
Crystallogr. 1990, 46, C34. (b) Spek, A. L. PLATON, A Multipurpose
Crystallographic Tool; Utrecht University: Utrecht, The Netherlands,
2002.
(30) The pore dimensions described here are crystallographic scalar
quantities, and do not account for the van der Waals radii of the atoms
defining the pore.
Inorganic Chemistry, Vol. 43, No. 15, 2004 4733

Dong et al.
Figure 17. One-dimensional chain found in 5.
L2 ligands (N(1)-Ag(1)-N(4)#1 ) 172.4(2)°, Ag(1)-N(1)
) 2.123(5) Å, and Ag(1)-N(4)#1 ) 2.147(5) Å). In addition,
there are two benzene and one methylene chloride solvent
molecules for every Ag atom and they are located very close
to the Ag(I) centers (Ag(1)-Cl(1A) ) 3.397(2), Ag(1)-
C(41) ) 3.002(7), Ag(1)-C(42) ) 3.018(7), Ag1-C(52A)
-
) 3.204(7), and Ag(1)-C(53A) ) 3.283(7) Å). The SbF6
Figure 18. ORTEP figure of compound 6 with 30% probability ellipsoids.
counterion coordinates to Ag(I) center very weakly with the
32
shortest Ag‚‚‚F contact 2.705(5) Å.
Phenyl-substituted
pyridazine nitrogen donor is not involved in the Ag(I)
coordination sphere, which is quite different from that of
compound 4. In the solid state, as shown in Figure 17, Ag-
(I) centers are bound together by L2 ligands into a one-
dimensional chain along the [101] crystallographic direction.
The intrachain Ag(I)‚‚‚Ag(I) distance is 20.61(7) Å. It is
worth pointing out that the two substituted benzonitriles show
a dihedral angle of 100.4° whereas ones in free L2 ligand
are slightly twisted, showing a dihedral angle of 23°. Those
uncoordinated SbF6- counterions and solvent molecules are
located between chains.
Synthesis and Structural Analysis of 6. The idea behind
the use of ligand L3 is to control supramolecular motifs
through 3,3′-dicyano-type ligands.33 It is well-known that
the relative different orientations of the nitrogen donors and
also the different bridging spacing might result in unusual
building blocks, and then lead to the construction of
supramolecular motifs which have not been achieved using
normal rigid linear bidentate organic ligands. We earlier
reported a series of novel coordination polymers generated
from rigid bidentate 4,4′-bipyridine- and 3,3′-bipyridine-type
Schiff-base ligands.34 Indeed, our previous studies demon-
strated that the relative different orientation of the coordinat-
ing sites is one of the most important factors to control the
polymeric motifs. Compound 6 was obtained as orange
crystals by combination of L3 and AgSbF6 in a benzene and
methylene chloride mixed solvent system at 37% yield.
Single-crystal X-ray analysis revealed that 6 crystallizes in
the triclinic crystal system in the space group P1h. The
asymmetric unit contains two independent ligands per Ag-
(I) atom and SbF6- unit. The Ag(I) center lies in a distorted
tetrahedral coordination sphere which consist of four N-
donors (Ag-N(3)#1 ) 2.294(4), Ag-N(4) ) 2.301(4), Ag-
N(2)#2 ) 2.316(4), and Ag-N(1) ) 2.338(4) Å) from four
L3 ligands (Figure 18).
Figure 19. View perpendicular to one 2-D layer.
In the solid state, distorted tetrahedral Ag(I) centers are
connected to each other by two crystallographically inde-
pendent L3 ligands through the phenyl-CN groups into
infinite two-dimensional square sheets parallel to the crystal-
lographic [001] plane. It is worth pointing out that L3 ligands,
as noted above, adopt cis conformation to coordinate Ag(I)
centers in 6. Cis conformation orients the two -CN groups
in the same direction, and would allow them to bind at the
neighboring metal center in the two-dimensional net. As
shown in Figure 19, each square unit consists of four Ag(I)
atoms and four L3 ligandssin fact, it is a 64-membered ring
structure (Figure 19). The effective cross section of ca. 16
× 16 Å,30 which is significantly larger than those related
compounds generated from 4,4′-bipyridine and transition
metals (M ) Cd, Zn, Ni, Cu) with the similar square pattern
(the square dimension is ca. 8 × 8 Å).35 There are two sets
of such two-dimensional sheets in 6 and they interpenetrate
together to form a layer with SbF6- anions stuffed in. These
interpenetrated layers stack upon one another along [001].
(32) Carlucci, L.; Ciani, G.; Proserpio, D. M.; Sironi, A. J. Am. Chem.
Soc. 1995, 117, 4562.
(33) Hirsch, K. A.; Wilson, S. R.; Moore, J. S. Inorg. Chem. 1997, 36,
2960.
(34) (a) Dong, Y.-B.; Smith, M. D.; Layland, R. C.; zur Loye, H.-C. Chem.
Mater. 2000, 12, 1156. (b) Dong, Y.-B.; Smith, M. D.; zur Loye, H.-
C. Inorg. Chem. 2000, 39, 4927. (c) Ciurtin, D. M.; Dong, Y.-B.;
Smith, M. D.; Barclay, T.; zur Loye, H.-C. Inorg. Chem. 2001, 40,
2825.
(35) (a) Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem.
Soc. 1994, 116, 1151. (b) Gable, R. W.; Hoskins, B. F.; Robson, R.
J. Chem. Soc., Chem. Commun. 1990, 1677. (c) Robson, R.; Abrahms,
B. F.; Batten, S. R.; Gable, R. W.; Hoskins, B. F.; Liu, J. In
Supramolecular Architecture; Bein, T., Ed.; ACS Symposium Series
499; American Chemical Society: Washington, DC, 1992; Chapter
19. (d) Biradha, K.; Domasevitch, K. V.; Moulton, B.; Seward, C.;
Zaworotko, M. J. Chem. Commun. 1999, 1327.
4734 Inorganic Chemistry, Vol. 43, No. 15, 2004

Self-Assembled Polymers Based on NoWel FulWene Ligands
Figure 20. Each layer made up of two interpenetrated sheets.
The tert-butyl group from one interpenetrated double layer
stick into the adjacent double layersinterdigitation. When
viewed down the crystallographic c axis, the Ag(I) centers
in one set occupy the center of the channels formed by the
other sets (Figure 20). Such interpenetration effectively
reduces the volume of the cavities and channels and no guest
molecules are found in 6.
Synthesis and Structural Analysis of 7. It is worth
pointing out that the coordination chemistry of L3 with Ag(I)
metal template appears to be quite versatile, with the products
dependent on the choice of solvent system, and largely
independent of the metal-to-ligand mole ratio. However,
increasing the ligand-to-metal ratio resulted in somewhat
higher yield and higher crystal quality. When a solution of
L3 in the nonpolar solvent benzene was treated with AgSbF6
in the same solvent with the same metal-to-ligand mole ratio,
the only product yielded was [Ag(C25H20N2O2)2]SbF6 (7),
which crystallizes with a novel three-dimensional diamondoid
motif distinctly different from the polymeric motifs found
in compound 6. In other words, the proper selection of
solvent system and template ions in the synthetic process is
critical in directing the self-assembly of coordination poly-
mers, an observation which has been borne out by many
previous studies.36 Single-crystal X-ray analysis revealed that
7 crystallizes in the monoclinic crystal system in the space
group C2/c. As shown in Figure 21, the Ag(I) metal ion in
7 lies in a distorted tetrahedral coordination environment
defined by four N-donors from four L3 ligands. For 7, the
Ag-N bond lengths range from 2.253(4) to 2.410(4) Å,
which are well comparable with bond lengths found in 6.
In the solid state, Ag(I) centers are connected to each other
Figure 21. ORTEP figure of compound 7 with 30% probability ellipsoids.
Figure 22. One independent framework shown of 7.
by L3 ligands into a three-dimensional diamondoid structure
(Figure 22).1b It is noteworthy that two independent frame-
-
works interpenetrate to produce channels occupied by SbF6
counterions. In addition, L3 ligand adopts transoid confor-
mation to coordinate Ag(I) centers in 7, which is different
from that in 6. Trans-conformation orients the two -CN
groups in two different directions, and allows them to bind
metal centers into higher dimensional framework. It is well-
known that the diamondoid structure is the motif that can
be observed for three-dimensional structures based on
tetrahedral building blocks. Several polymeric complexes
(36) (a) Lu, J.; Paliwala, T.; Lim, S. C.; Yu, C.; Niu, T.; Jacobson, A. J.
Inorg. Chem. 1997, 36, 923. (b) Munakata, M.; Ning, G. L.; Kuroda-
Sowa, T.; Maekawa, M.; Suenaga, Y.; Harino, T. Inorg. Chem. 1998,
37, 5651. (c) Power, K. N.; Hennigar, T. L.; Zaworotko, M. J. New J.
Chem. 1998, 22, 177. (d) Jung, O. S.; Park, S. H.; Kim, K. M.; Jang,
H. G. Inorg. Chem. 1998, 37, 5781. (e) Losier, P.; Zaworotko, M. J.
Angew. Chem., Int. Ed. Engl. 1996, 35, 2779. (f) Gudbjartson, H.;
Biradha, K.; Poirier, K. M.; Zaworotko, M. J. J. Am. Chem. Soc. 1999,
121, 2599. (g) Carlucci, L.; Ciani, G.; Proserpio, M. J. Chem. Soc.,
Dalton Trans. 1999, 1799. (h) Furusho, Y.; Aida, T. J. Chem. Soc.,
Chem. Commun. 1997, 2205.
Inorganic Chemistry, Vol. 43, No. 15, 2004 4735

Dong et al.
Figure 24. Photoinduced emission spectra of 2, 6, and 7 in the solid state
at room temperature.
Figure 23. Photoinduced emission spectra of L1-L3 in the solid state at
room temperature.
Conclusions
such as Cu(bpe)2BF4,37 Cu(bpy)2PF6,38 Ag(bpy)CF3SO3,39 and
Cu(dzp)2PF6 were reported and their interpenetration
40
Three new fulvene ligands were synthesized. L1 and L3
were synthesized by an aroylation reaction of cyclohexyl-
substituted cyclopentadienyl anions. L2 was prepared by the
reaction of L1 with PhNHNH2 in hot enthanol. The
coordination chemistry of L1-L3 were investigated systemi-
cally. The results indicate that the coordination chemistry
of new fulvene ligands is versatile. They can bind metal
centers not only through the terminal N-donors and fulvene
carbon atoms into organometallic coordination polymers but
also through the two chelating carbonyl groups into unusual
seven-membered metallo-ring supramolecular complexes. In
the solid state, ligands L1-L3 are luminescent. A blue-shift
in the emission was observed between the free ligand L1
and the one incorporated into Co(II)-containing complex 2,
and a red-shift in the emission was observed between the
free ligand L3 and the one incorporated into Ag(I)-containing
polymeric compounds 6 and 7. We are currently extending
this result by preparing additional fulvene-type ligands of
this kind that have different substituted organic functional
groups. We anticipate this approach to be useful for the
construction of a variety of new transition metal complexes
and luminescent coordination polymers with novel structures
that have the potential of leading to new fluorescent
materials.
reduced from 5-fold to 3-fold, which suggests that the steric
bulk of the ligands could prevent the interpenetration
effectively. The steric influence of big substituted groups
on L3 could be the reason that compound 7 reported herein
exhibits only 2-fold interpenetrating diamondoid motif.
Luminescent Properties. Aromatic organic molecules, all-
organic polymers, and mixed inorganic-organic hybrid
coordination polymers have been investigated for fluores-
cence properties and for potential applications as light-
emitting diodes (LEDs).41 Owing to the ability of affecting
the emission wavelength of organic materials, syntheses of
inorganic-organic coordination polymers by the judicious
choice of organic spacers and transition metal centers can
be an efficient method for obtaining new types of electrolu-
minescent materials.42 The luminescent properties of free
ligands L1-L3, and their metal complexes 2, 6, and 7, were
investigated in the solid state. The spectra of L1-L3 in solid
state are shown in Figure 23. L1, L2, and L3 exhibit one
emission maximum at 539, 572, and 354 nm, respectively.
The emission band of Co(II)-containing complex 2 is blue-
shifted to 532 nm compared to the emission color of L1,
however, the emission bands of Ag(I)-containing polymeric
compounds 6 and 7 are red-shifted to 533 and 531 nm,
respectively (Figure 24). No enhancement of the fluorescence
intensity is realized. Because of their instability, the lumi-
nescent properties of 1 and 3-5 could not be investigated.
The emission colors of free L1 and L3 were significantly
affected by its incorporation into the M-containing (M )
Co(II) and Ag(I)) complexes, as evidenced by the large shift
in the emission.
Experimental Section
Materials and Methods. 4-Cyanobenzoyl chloride, 3-cyanoben-
zoyl chloride, 6,6′-dimethylenefulvene, and CH3Li were prepared
according to literature methods. Inorganic metal salts were pur-
chased from Acros and used without further purification. Infrared
(IR) samples were prepared as KBr pellets, and spectra were
obtained in the 400-4000 cm-1 range using a Perkin-Elmer 1600
1
FTIR spectrometer. H NMR data were collected using a JEOL
(37) Blake, A. J.; Champness, N. R.; Chung, S. S. M.; Li, W.-S.; Schro¨der,
M. Chem. Commun. 1997, 1005.
(38) MacGillivrary, L. R.; Subramanmian, S.; Zaworotko, M. J. J. Chem.
Soc., Chem. Commun. 1994, 1325.
FX 90Q NMR spectrometer. Chemical shifts are reported in δ
relative to TMS. Element analyses were performed on a Perkin-
Elmer model 240C analyzer.
(39) Carlucci, L.; Ciani, G.; Proserpio, D. M.; Sironi, A. J. Chem. Soc.,
Chem. Commun. 1994, 2775.
(40) Blake, A. J.; Champness, N. R.; Chung, S. S. M.; Li, W.-S.; Schro¨der,
M. Chem. Commun. 1997, 1339.
(41) Bunz, U. H. F. Chem. ReV. 2000, 100, 1605.
(42) (a) Ciurtin, D. M.; Pschirer, N. G.; Smith, M. D.; Bunz, U. H. F.; zur
Loye, H.-C. Chem. Mater. 2001, 13, 2743. (b) Cariati, E.; Bu, X.;
Ford, P. C. Chem. Mater. 2000, 12, 3385. (c) Wu¨rthner, F.; Sautter,
A. Chem. Commun. 2000, 445.
Safety Note. Perchlorate salts of metal complexes with organic
ligands are potentially explosive and should be handled with care.
Synthesis. Preparation of L1. A solution of 4-cyanobenzoyl
chloride (2.00 g, 12.5 mmol) in anhydrous ether (20 mL) was added
dropwise to a solution of tert-butyl-substituted cyclopentadienyl
anions (16.2 mmol) in anhydrous ether at 0 °C, which derived from
6,6′-dimethylenefulvene (18.8 mmol) and CH3Li (18.8 mmol) in
4736 Inorganic Chemistry, Vol. 43, No. 15, 2004

Self-Assembled Polymers Based on NoWel FulWene Ligands
Table 1. Crystallographic Data for L2, L3, and 1-3
C32H27N4O0.50
C25H20N2O2
L3
C46H41AgClN2O6
C54H50CoN4O6
C43H39Ag2Cl2N4O9.5
formula
formula weight
crystal system
space group
a (Å)
L2
1
2
3
475.58
monoclinic
P21/n
11.3927(6)
29.4124(16)
15.7412(9)
90
105.5330(10)
90
5082.0(5)
8
1.243
0.075
150(1)
380.43
triclinic
P1h
861.13
triclinic
P1h
909.91
triclinic
P1h
1050.42
monoclinic
C2/c
42.289(3)
18.2148(13)
11.1327(8)
90
103.677(2)
90
8332.3(10)
8
9.7027(9)
12.8883(12)
16.8118(16)
74.200(2)
89.116(2)
84.894(2)
2014.8(3)
4
1.254
0.080
150(1)
7122
10.3433(5)
14.3521(7)
15.5484(8)
65.4250(10)
87.3260(10)
72.9880(10)
1999.72(17)
2
1.430
0.623
150(1)
8179
7.8699(5)
12.6649(8)
12.8184(8)
92.5710(10)
98.2910(10)
106.9780(10)
1204.06(13)
1
1.255
0.410
294(1)
4271
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
F calc (g/cm3)
1.675
1.131
150(1)
6639
µ (mm-1
)
temperature (K)
no. refl.
10421
R1; wR2 (I > 2∑(I))
0.0586; 0.1600
0.0496; 0.1158
0.0391; 0.0831
0.0492; 0.1200
0.0979; 0.2516
Table 2. Crystallographic Data for 4-7
C31H24AgF6 N4Sb
C44H38AgCl2F12N4Sb2
C50H40AgF6N4O4Sb
C50H40AgF6N4O4Sb
formula
formula weight
crystal system
space group
a (Å)
4
5
6
7
796.16
Tetragonal
P4/n
26.2633(7)
26.2633(7)
9.3983(5)
90
90
90
6482.6(4)
8
1.632
1273.05
Monoclinic
P21/c
19.3530(9)
15.0315(7)
17.8900(8)
90
112.9510(10)
90
4792.3(4)
4
1104.48
triclinic
P1h
1104.48
Monoclinic
C2/c
34.7405(19)
9.1035(5)
31.9219(18)
90
111.2640(10)
90
9408.3(9)
8
8.9189(4)
13.5085(6)
19.1073(9)
86.3540(10)
85.0180(10)
84.0390(10)
2277.51(18)
2
1.611
1.097
150(1)
8004
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
F calc (g/cm3)
1.430
1.718
150(1)
8462
1.560
1.063
293(2)
8372
µ (mm-1
)
1.498
150(1)
5171
temperature (K)
no. refl.
R1; wR2 (I > 2∑(I))
0.0479; 0.1262
0.0536; 0.1255
0.0474; 0.0870
0.0435; 0.1176
anhydrous ether. The mixture was stirred overnight at room
temperature. The solvent was then reduced to about 10 mL under
vacuum. Hexane was added and an orange solid precipitated. The
solid was washed with hexane several times and stirred in HCl
(5% in water) overnight. The final product was purified by column
chromatography on silica gel (CH2Cl2/hexane, 2:1) to afford an
orange crystalline solid (1.45 g, 61%). IR (KBr pellet) ν (cm-1) )
3140 (s), 2970 (s), 2880 (s), 2250 (vs), 1620 (vs), 1600 (vs), 1510
(vs), 1410 (vs), 1365 (s), 1350 (s), 1180 (s), 1110 (s), 1015 (s),
940 (s), 845 (s), 745 (s). 1H NMR (90 MHz, CDCl3, 25 °C, TMS):
δ ) 17.85 (s, 1H, -OH), 7.84 (s, 8H, -C6H4), 7.07 (s, 2H, -C5H2),
1.21 (s, 9H, -CH3). Elemental analysis (%) calcd for C25H20N2O2:
C, 78.95; H, 5.26; N, 7.37. Found: C, 78.90; H, 5.30; N, 7.38.
Preparation of L3. L3 was prepared following the procedure
described for L1 except by using 3-cyanobenzoyl chloride (2.00
g, 12.5 mmol) instead of 4-cyanobenzoyl chloride to afford orange
crystalline solid (1.41 g, 59%). IR (KBr pellet) ν (cm-1) ) 3105
(s), 2995 (s), 2880 (s), 2250 (vs), 1630 (vs), 1605 (vs), 1550 (vs),
1515 (vs), 1415 (vs), 1365 (vs), 1350 (vs), 1170 (s), 1120 (s), 935
1
(s), 800 (m), 730 (s), 675 (m). H NMR (90 MHz, CDCl3, 25 °C,
TMS): δ ) 17.85 (s, 1H, -OH), 7.8 (m, 8H, -C6H4), 7.09 (s,
2H, -C5H2), 1.25 (s, 9H, -CH3). Elemental analysis (%) calcd
for C25H20N2O2: C, 78.95; H, 5.26; N, 7.37; O, 8.42. Found: C,
78.91; H, 5.28; N, 7.39.
Preparation of 1. A mixture of L1 (7.6 mg, 0.02 mmol) and
Ag(ClO4)‚H2O (6.0 mg, 0.03 mmol) in benzene (20 mL) was stirred
for 5 min. The clear orange solution was allowed to stand for a
week at room temperature to afford orange crystals (6.3 mg, 54%,
based on L1). IR (KBr pellet) γ (cm-1) ) 3145 (s), 2990 (s), 2850
(m), 2290 (m), 2255 (s), 1620 (s), 1600 (vs), 1520 (vs), 1415 (vs),
1370 (vs), 1350 (s), 1185 (m), 1110 (vs), 1090 (vs), 945 (s), 850
(m), 750 (w), 680 (w). Elemental analysis (%) calcd for
AgC46H41O6N2Cl: C, 64.10; H, 4.76; N, 3.25. Found: C, 64.28;
H, 5.00; N, 3.35. Crystals of 1 lose solvent molecules and turn
opaque within several minutes under ambient atmosphere. Because
of its instability, the host-guest chemistry of 1 could not be
investigated.
Preparation of L2. A solution of L1 (0.76 g, 2.0 mmol) in
anhydrous EtOH (80 mL) was heated to reflux for about 5 h. After
cooling to room temperature, the solvent was removed under
reduced pressure to give a yellow solid. The product was recrystal-
lized from EtOH to give orange crystals of L2. Yield, 80%. IR
(KBr pellet) ν (cm-1) ) 3100 (s), 2990 (s), 2850 (m), 2250 (vs),
1620 (m), 1595 (m), 1580 (s), 1530 (m), 1485 (vs), 1460 (s), 1385
(s), 1340 (vs), 1295 (s), 1225 (s), 1115 (s), 1020 (s), 960 (m), 920
1
(m), 845 (s), 805 (m), 780 (m), 745 (m), 700 (s). H NMR (90
MHz, CDCl3, 25 °C, TMS): δ ) 8.17-7.18 (m, 13H, -C6H4 and
-C6H5), 6.94 (s, 2H, -C5H2), 1.33 (s, 9H, -CH3). Elemental
analysis (%) calcd for C31H24N4: C, 83.30; H, 5.31; N, 12.39.
Found: C, 83.14; H, 5.28; N, 12.25.
Preparation of 2. A mixture of L1 (19.1 mg, 0.05 mmol) and
Co(OAc)2‚2H2O (5.3 mg, 0.025 mmol) in anhydrous EtOH (15 mL)
was refluxed for 10 min and allowed to cool. The clear red-brown
Inorganic Chemistry, Vol. 43, No. 15, 2004 4737

Dong et al.
Table 3. Interatomic Distances (Å) and Bond Angles (deg) with
Estimated SDs () for L2-L3 and 1-7
Elemental analysis (%) calcd for C54H50CoN4O6: C, 71.22; H, 5.50;
N, 6.15. Found: C, 71.23; H, 5.30; N, 6.09.
L2
Preparation of 3. Compound 3 was synthesized by laying a
benzene solution (7 mL) of Ag(ClO4)‚H2O (11.0 mg, 0.055 mmol)
over a methylene chloride solution of (5 mL) of L2 (12.4 mg, 0.028
mmol) in 55% yield. IR (KBr pellet) γ (cm-1) ) 2980 (s), 2850
(m), 2280 (s), 2250 (m), 1610 (m), 1580 (s), 1490 (s), 1460 (s),
1390 (m), 1340 (s), 1290 (m), 1220 (m), 1100 (vs), 845 (s), 690
(s). Elemental analysis (%) calcd for C43H39Ag2Cl2N4O9.50: C,
49.12; H, 3.71; N, 5.33. Found: C, 49.14; H, 3.54; N, 5.28. Crystals
of 3 lose solvent molecules and turn opaque within several minutes
under ambient atmosphere. Because of its instability, the host-
guest chemistry of 3 could not be investigated.
C(1)-C(6)
1.372(2) C(1)-C(2)
1.410(2)
1.390(2)
1.390(2)
1.445(2)
1.143(3)
118.99(15)
118.31(15)
114.15(13)
C(1)-C(5)
1.460(2) C(2)-C(3)
C(3)-C(4)
1.424(2) C(4)-C(5)
C(14)-N(3)
1.328(2) C(22)-N(2)
N(2)-N(3)
1.361(2) C(21)-N(4)
C(6)-C(1)-C(2)
C(2)-C(1)-C(5)
C(6)-N(2)-N(3)
132.76(16) C(6)-C(1)-C(5)
108.19(15) N(2)-C(6)-C(1)
125.34(14) N(3)-N(2)-C(22)
L3
C(1)-C(2)
1.408(2) C(1)-C(5)
1.384(2)
1.402(2)
1.420(2)
C(4)-C(14)
1.395(2) C(2)-C(3)
C(3)-C(4)
1.468(2) C(4)-C(5)
C(6)-O(1)
1.273(2) C(13)-N(1)
106.65(16) C(5)-C(1)-C(22)
110.67(16) C(2)-C(3)-C(6)
113.46(11) O(1)-C(6)-C(7)
1.149(3)
C(5)-C(1)-C(2)
C(3)-C(2)-C(1)
O(1)-C(6)-C(7)
127.38(16)
125.44(16)
114.54(15)
Preparation of 4 and 5. A solution of AgSbF6 (12.0 mg, 0.035
mmol) in benzene was layered onto a solution of L2 (15.8 mg,
0.035 mmol) in CH2Cl2 (5 mL). The solution was left for about
one week at room temperature, and yellow crystals of 4 were
obtained. Yield, 46%. IR (KBr, cm-1): 2955 (s), 2850 (m), 2255
(s), 1580 (s), 1490 (s), 1394 (s), 1348 (s), 845 (s), 657 (vs). Anal.
Calcd for C31H24AgF6N4Sb‚0.5C6H6 (4): C, 48.85; H, 3.23; N, 6.71.
Found: C, 49.19; H, 3.30; N, 6.71. Above solution was left to stand
at room temperature for about two weeks, affording 5 as red crystals.
Yield, 9%. IR (KBr, cm-1): 2960 (s), 2850 (m), 2362 (m), 2333
(m),1628 (s), 1491 (s), 1397 (vs), 1022 (s), 847 (s), 660 (vs). Anal.
Calcd for C44H38AgCl2F12 N4Sb2 (4): C, 41.48; H, 2.98; N, 4.40.
Found: C, 41.39; H, 3.05; N, 4.48.
1
Ag-N(1)
Ag-O(11)
N(1)-Ag-N(2)#1
N(2)#1-Ag-O(11)
2.139(2) Ag-N(2)#1
2.169(2)
2.5463(19)
166.83(9)
78.90(7)
N(1)-Ag-O(11)
C(2)-C(1)-C(5)
114.11(8)
106.9(2)
2
Co-O(1)#1
Co-O(2)
O(1)#1-Co-O(1)
O(2)-Co-O(2)#1
O(2)#1-Co-O(3)
2.0022(16) Co-O(1)
2.0052(16) Co-O(3)
2.0022(16)
2.129(2)
88.68(7)
84.71(9)
180.0
180.00(5)
180.0
89.18(9)
O(1)#1-Co-O(2)
O(1)#1-Co-O(3)
O(3)-Co-O(3)#1
3
Ag(1)-N(4)#1
Ag(1)-C(2)#2
Ag(2)-N(2)
2.165(10) Ag(1)-N(1)
2.679(9) Ag(2)-O(11)
2.317(8) Ag(2)-C(42)
2.571(15)
2.166(10)
2.290(13)
2.444(16)
Preparation of 6. A solution of L3 (15.2 mg, 0.04 mmol) in
benzene (15 mL) was mixed with a solution of AgSbF6 (14.0 mg,
0.041 mmol) in CH2Cl2. The solutions were left for about three
weeks at room temperature, and yellow crystals were obtained.
Yield, 36%. IR (KBr, cm-1): 3015 (m), 2970 (s), 2850 (m), 2300
(m), 2250 (vs), 1625 (vs), 1600 (vs), 1555 (vs), 1520 (vs), 1440
(vs), 1425 (vs), 1365 (vs), 1170 (m), 1120 (s), 930 (m), 800 (m),
750 (m), 725 (m), 665 (vs). Anal. Calcd for C50H40AgF6N4O4Sb
(6): C, 54.32; H, 3.62; N, 5.07. Found: C, 54.35; H, 3.65; N, 5.03.
Ag(2)-C(41)
N(4)#1-Ag(1)-N(1) 160.5(4)
N(4)#1-Ag(1)-C(2)#2 101.8(3)
N(1)-Ag(1)-C(2)#2
O(11)-Ag(2)-C(42)
O(11)-Ag(2)-C(41)
C(42)-Ag(2)-C(41)
N(2)-Ag(2)-C(31)
C(41)-Ag(2)-C(31)
94.0(3)
113.0(6)
137.0(6)
31.2(5)
70.0(2)
90.7(4)
O(11)-Ag(2)-N(2)
N(2)-Ag(2)-C(42)
N(2)-Ag(2)-C(41)
O(11)-Ag(2)-C(31)
C(42)-Ag(2)-C(31)
C(1)-C(2)-Ag(1)#2
112.7(5)
133.5(4)
108.8(5)
93.0(5)
115.5(5)
84.4(5)
4
Ag(1)-N(2)
Ag(1)-N(1)#2
2.199(4) Ag(1)-N(4)#1
2.203(5)
2.327(4)
N(2)-Ag(1)-N(4)#1 145.63(17) N(2)-Ag(1)-N(1)#2
N(4)#1-Ag(1)-N(1)#2 89.59(16) N(2)-Ag(1)-C(22)
124.55(15)
50.77(14)
Preparation of 7. A solution of L3 (15.2 mg, 0.04 mmol) in
benzene (15 mL) was mixed with a solution of AgSbF6 (14.0 mg,
0.041 mmol) in benzene. The solutions were left for about one week
at room temperature, and yellow crystals were obtained. Yield, 60%.
IR (KBr, cm-1): 2970 (s), 2850 (m), 2300 (vs), 2250 (m), 1620
(vs), 1555 (vs), 1520 (vs), 1415 (vs), 1365 (vs), 1350 (s), 1174 (s),
1124 (s), 935 (m), 800 (m), 725 (m), 655 (vs). Anal. Calcd for
C50H40AgF6N4O4Sb (6): C, 54.32; H, 3.62; N, 5.07. Found: C,
54.50; H, 3.46; N, 5.12.
N(4)#1-Ag(1)-C(22)
N(2)-Ag(1)-N(3)
94.96(16) N(1)#2-Ag(1)-C(22) 174.94(14)
23.23(12) N(4)#1-Ag(1)-N(3)
122.66(15)
27.71(12)
N(1)#2-Ag(1)-N(3) 147.73(13) C(22)-Ag(1)-N(3)
5
Ag(1)-N(1)
Ag(1)-F(11)
N(1)-Ag(1)-N(4)#1 172.4(2)
N(4)#1-Ag(1)-F(11)
N(4)#1-Ag(1)-C(41)
N(1)-Ag(1)-C(42)
F(11)-Ag(1)-C(42)
N(1)-Ag(1)-Cl(1)#2
2.123(5) Ag(1)-N(4)#1
2.147(5)
2.705(5)
N(1)-Ag(1)-F(11)
N(1)-Ag(1)-C(41)
F(11)-Ag(1)-C(41)
N(4)#1-Ag(1)-C(42)
C(41)-Ag(1)-C(42)
85.39(19)
90.0(2)
169.1(2)
85.7(2)
88.2(2)
95.6(2)
97.3(2)
144.8(2)
26.3(2)
Crystallography. Suitable single crystals of L2, L3 and 1-7
were selected and mounted onto thin glass fibers. X-ray intensity
data were measured on a Bruker SMART APEX CCD-based
diffractometer (Mo KR radiation, λ ) 0.71073 Å). The raw frame
data for L2, L3 and 1-7 were integrated into SHELX-format
reflection files and corrected for Lorentz and polarization effects
using SAINT.43 Corrections for incident and diffracted beam
absorption effects were applied using SADABS.43 There was no
evidence of crystal decay during data collection for any compound.
The final unit cell parameters were determined by the least-squares
refinement of all reflections from each data set with I > 5σ(I) (5944
for 1, 4588 for 2, 5142 for 3, 7259 for 4, 7825 for 5, 7562 for 6,
and 8511 for 7). Space groups were determined by a combination
of systematic absences in the intensity data, intensity statistics, and
the successful solution and refinement of the structures. All
88.53(16) N(4)#1-Ag(1)-Cl(1)#2 85.08(16)
F(11)-Ag(1)-Cl(1)#2 64.77(13) C(41)-Ag(1)-Cl(1)#2 105.33(16)
C(42)-Ag(1)-Cl(1)#2 80.22(17)
6
Ag-N(3)#1
Ag-N(2)#2
N(3)#1-Ag-N(4)
N(4)-Ag-N(2)#2
N(4)-Ag-N(1)
2.294(4) Ag-N(4)
2.316(4) Ag-N(1)
92.08(16) N(3)#1-Ag-N(2)#2
150.49(16) N(3)#1-Ag-N(1)
99.73(15) N(2)#2-Ag-N(1)
2.301(4)
2.338(4)
107.37(15)
121.29(16)
89.08(15)
7
Ag-N(1)
Ag-N(3)
N(1)-Ag-N(2)#1
N(2)#1-Ag-N(3)
N(2)#1-Ag-N(4)#2
2.253(4) Ag-N(2)#1
2.385(4) Ag-N(4)#2
143.38(15) N(1)-Ag-N(3)
105.39(14) N(1)-Ag-N(4)#2
82.48(14) N(3)-Ag-N(4)#2
2.296(3)
2.410(4)
94.23(15)
108.56(14)
129.47(15)
solution was allowed to stand for a week at room temperature. Deep
brown crystals were collected, washed with hexane, and dried in
air (20.7 mg, 85%). IR (KBr pellet) γ (cm-1) ) 3500 (br), 2980
(m), 2850 (m), 2260 (s), 1610 (m), 1580 (s), 1550 (s), 1535 (s),
1417 (s), 1365 (w), 1330 (s), 1170 (s), 870 (m), 845 (m), 760 (w).
(43) SMART Version 5.624, SAINT Version 6.02, SADABS, and SHELX-
TL Version 5.1. Bruker Analytical X-ray Systems, Inc.: Madison,
WI, 1998.
4738 Inorganic Chemistry, Vol. 43, No. 15, 2004

Self-Assembled Polymers Based on NoWel FulWene Ligands
structures were solved by direct methods followed by difference
Fourier synthesis, and refined against F2 by the full-matrix least
squares technique, using SHELX.43 L2 crystallized in the space
group P21/n. Two independent L2 molecules are present in the
asymmetric unit. The tert-butyl group of one is rotationally
disordered over two positions in a 50:/50 ratio. An EtOH molecule
of crystallization is also present, also disordered equally over two
positions. L3 crystallizes in the space group P1h. The asymmetric
unit contains two crystallographically and conformationally in-
equivalent molecules. Compound 1 crystallizes in the space group
P1h. The asymmetric unit consists of one Ag(I) center, one L1 ligand,
one ClO4- counterion, three full benzene molecules of crystalliza-
tion, and another half-benzene located on an inversion center.
Compound 2 also crystallizes in the space group P1h. The complex
lies on a crystallographic inversion center. The tert-butyl substituent
of the L1 ligand is rotationally disordered over two orientations in
the refined ratio 0.69(2):0.31(2). Compound 3 crystallizes in the
space group C2/c. In general, precise refinement was hindered by
the low quality of the available crystals and by extensive disorder,
as reflected in the high R-factors. The present structural results
should be regarded accordingly. Two Ag centers, one L2 ligand,
an η2-coordinated C6H6 molecule, and a coordinated H2O molecule
were readily located in the asymmetric unit and refined anisotro-
pically. The water hydrogen atoms could not be located and were
component, and all atoms of the minor component were refined
isotropically. Additionally, the tert-butyl substituent of the ligand
is rotationally disordered over two orientations in the refined ratio
0.80(2):0.20(2). The minor component of this group was refined
isotropically. All other atoms except those noted were refined with
anisotropic displacement parameters. Hydrogen atoms were placed
in idealized positions and included as riding atoms. After location
and refinement of the species described above, channels parallel
to the c-axis containing many diffuse electron density peaks
remained, at (x,y) ) (1/4,1/4). No satisfactory disorder model was
attained for these peaks, assumed to be solvent species disordered
about 4-fold axes, and therefore the program SQUEEZE was used.44
SQUEEZE calculated a solvent-accessible region of 654.1 Å3
(10.0% of the total unit cell volume), corresponding to 351 e-/cell.
The contribution of these regions of electron density was removed
from the structure factor calculations. The final reported F(000),
FW, and density reflect crystallographically identifiable species
only. Compound 5 crystallizes in the space group P21/c. The tert-
butyl substituent of the L2 ligand is rotationally disordered over
two orientations, and was refined with the aid of 10 C-C same-
distance restraints. Occupancies for each disorder component were
initially refined but subsequently fixed near the final refined values
(0.65/0.35) for stability. Compound 6 crystallizes in the triclinic
crystal system in the space group P1h. The asymmetric compound
contains two independent ligands per Ag and SbF6- unit. The tert-
butyl group of one ligand is disordered over two orientations in
the refined ratio 0.66(1):0.34. Compound 7 crystallizes in the space
group C2/c. All atoms are on positions of general crystallographic
symmetry. Crystal data, data collection parameters, and refinement
statistics for L2, L3, and 1-7 are listed in Tables 1 and 2. Relevant
interatomic bond distances and bond angles for them are given in
Table 3.
-
not calculated. There are three independent ClO4 counterions in
the asymmetric unit. Perchlorate Cl(1), near Ag(1), was located
and refined anisotropically; however, the inflated displacement
parameters for this species indicate unresolved disorder. Cl(2) was
modeled as being disordered together in the same region with a
C6H6 and a water molecule. The disorder model used was 50%
occupancy ClO4-/H2O and 50% C6H6. The C6H6 was refined as a
rigid group, the ClO4- was restrained to adopt the same geometry
as perchlorate Cl(1), and no H atoms were located or calculated
for the water. All species of this disorder assembly were refined
isotropically. Cl(3) is disordered about a 2-fold axis, and was refined
surrounded by eight-half-occupied oxygen atoms. Occupancies and
isotropic displacement parameters were fixed for the oxygen atoms.
Half of another C6H6 molecule of crystallization on an inversion
center completes the asymmetric unit. Compound 4 crystallizes in
the space group P4/n. The asymmetric unit consists of the Ag center,
Acknowledgment. We are grateful for financial support
from the National Natural Science Foundation of China
(20371030 and 20174023), and Open Foundation of State
Key Lab of Crystal Materials.
Supporting Information Available: Crystallographic informa-
tion files for the title compounds (cif). This material is available
free of charge via the Internet at http://pubs.acs.org.
-
one L2 ligand, and an SbF6 anion disordered over two closely
-
IC0495517
spaced positions. Occupancies of each SbF6 disorder component
were adjusted manually until reasonable displacement parameters
were achieved for each, whereupon they were fixed. The final
occupancy values are 0.925/0.075. The geometry of the minor
component was restrained to be similar to that of the major
(44) PLATON. (a) Spek, A. L. Acta Crystallogr., Sect. A: Found.
Crystallogr. 1990, 46, C34. (b) Spek, A. L. PLATON, A Multipurpose
Crystallographic Tool; Utrecht University: Utrecht, The Netherlands,
2002.
Inorganic Chemistry, Vol. 43, No. 15, 2004 4739