Syntheses and crystal structures of two cobalt carboxylate-phosphonates with 4,4′-bipyridine as a secondary metal linker

Article abstract of DOI:10.1002/ejic.200400212

The hydrothermal syntheses and crystal structures of two novel cobalt carboxylate-phosphonates with 4,4′-bipyridine (4,4′-bipy) as the secondary metal linker are reported. Compound 1, [Co₃(H ₂L)₂(H₂O)₄(4,4′-bipy)], where H₅L = 4-HO₂CC₆H₄CH ₂N(CH₂PO₃H₂)₂, crystallizes in the monoclinic space group C2/c with a = 25.9281(5), b = 9.76310(10), c = 17.3671(5) A, β = 103.290(2)°, V = 4278.6(2) A³, and Z = 4. Its structure contains a pillar-layered architecture in which Co^II octahedra are linked by carboxylate-phosphonate ligands to form a 2D layer and these layers are crosslinked further by 4,4′-bipy ligands to form a porous 3D network. Compound 2, [Co₂(PMIDA)(H₂O)₅(4,4′-bipy)] ·4H₂O, where H₄PMIDA = H₂O ₃PCH₂N(CH₂CO₂H)₂, crystallizes in the triclinic space group P1 with a = 7.8009(7), b = 13.4560(12), c = 13.5453(12) A, α = 65.207(2), β = 88.035(2), γ = 77.135(2)°, V = 1255.57(19) A³, and Z = 2. The crystal structure of compound 2 contains 1D zigzag chains in which two cobalt(II) ions are bridged by PMIDA ligand to form dimeric units, and these dimeric units are connected further by bridging 4,4′-bipy ligands. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400212

FULL PAPER
Syntheses and Crystal Structures of Two Cobalt Carboxylate؊Phosphonates
with 4,4Ј-Bipyridine as a Secondary Metal Linker
Jun-Ling Song,[a] Andrey V. Prosvirin,[b] Han-Hua Zhao,[b] and Jiang-Gao Mao*[a]
Keywords: Hydrothermal synthesis / Crystal structure / Cobalt phosphonates / Inorganic-organic hybrids / Open
frameworks
The hydrothermal syntheses and crystal structures of two
2, [Co2(PMIDA)(H2O)5(4,4Ј-bipy)]·4H2O, where H4PMIDA =
novel cobalt carboxylate−phosphonates with 4,4Ј-bipyridine
(4,4Ј-bipy) as the secondary metal linker are reported. Com- group P1 with a = 7.8009(7), b = 13.4560(12), c = 13.5453(12)
H2O3PCH2N(CH2CO2H)2, crystallizes in the triclinic space
¯
˚
pound 1, [Co3(H2L)2(H2O)4(4,4Ј-bipy)], where H5L
HO2CC6H4CH2N(CH2PO3H2)2, crystallizes in the monoclinic
space group C2/c with a = 25.9281(5), b = 9.76310(10), c = 1D zigzag chains in which two cobalt(II) ions are bridged by
=
4-
A, α = 65.207(2), β = 88.035(2), γ = 77.135(2)°, V = 1255.57(19)
3
˚
A , and Z = 2. The crystal structure of compound 2 contains
3
˚
˚
17.3671(5) A, β = 103.290(2)°, V = 4278.6(2) A , and Z = 4. Its
PMIDA ligand to form dimeric units, and these dimeric units
structure contains a pillar-layered architecture in which CoII are connected further by bridging 4,4Ј-bipy ligands.
octahedra are linked by carboxylate−phosphonate ligands to
form a 2D layer and these layers are crosslinked further by
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
4,4Ј-bipy ligands to form a porous 3D network. Compound
Germany, 2004)
Introduction
rare.[12,13] We selected two carboxylateϪphosphonic acids,
H5L [H5L
ϭ
4-HOOCC6H5CH2N(CH2PO3H2)2] and
H2O3PCH2N(CH2COOH)2]
H4PMIDA [H4PMIDA
ϭ
Recently, many research studies have been devoted to the
synthesis of metal phosphonates with open-framework or
microporous structures because of their potential appli-
cations in ion-exchange, catalysis and sensors.[1Ϫ6] Further-
more, interesting magnetic properties have been observed in
some of these systems. For example, weak ferromagnetic or
canted antiferromagnetic behavior has been observed in
some MnII, FeII, CuII and CoII compounds.[3,7Ϫ14] The
strategy of attaching functional groups such as carboxylic
acids, crown ethers and amines to the phosphonic acid mol-
ecule has been found to be an effective method for the prep-
aration of metal phosphonates with open-framework and
microporous structures. For example, a series of novel
microporous materials has been synthesized by hydrother-
mal reactions of different metal salts with carboxylate-func-
tionalised phosphonic acids H2O3PCH2CH2CO2H and
H2O3PCH2CO2H.[15Ϫ17] The use of additional bidentate
metal linkers, such as 1,10-phenanthroline, 2,2Ј-bipyridine,
piperazine and 4,4Ј-bipyridine, results in various mixed-me-
tal hybrids of V and Mo.[13,18] Reports regarding the corre-
sponding divalent transition metal compounds are
(Scheme 1), in combination with 4,4Ј-bipyridine (4,4Ј-bipy)
as the secondary metal linker. Zinc() and cobalt() com-
pounds prepared from H4PMIDA have been reported pre-
viously.[19] Hydrothermal reactions of the metal salts with
the above phosphonic acids and 4,4Ј-bipy led to two new
cobalt carboxylateϪphosphonates, namely [Co3(H2
L)2(H2O)4(4,4Ј-bipy)] (1) and [Co2(PMIDA)(H2O)5(4,4Ј-
bipy)]·4H2O (2). Herein we report their syntheses and crys-
tal structures.
[a]
State Key Laboratory of Structural Chemistry, Fujian Institute
of Research on the Structure of Matter, The Chinese Academy
of Sciences,
Fuzhou 350002, P. R. China
[b]
Department of Chemistry, Texas A&M University,
P. O. Box 30012, College Station, TX 77843-3012, USA
E-mail: mjg@ms.fjirsm.ac.cn
Scheme 1. The structure of H5L and H4PMIDA
3706
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400212
Eur. J. Inorg. Chem. 2004, 3706Ϫ3711

Syntheses and Crystal Structures of Two Cobalt CarboxylateϪPhosphonates
FULL PAPER
cobalt()
phosphonates.[13,14,20]
The
carboxylateϪ
Results and Discussion
phosphonate ligand is hexadentate and occupies three coor-
dination sites on one CoII ion and also bridges three CoII
ions. The phosphonate group containing P(2) is tridentate,
whereas the one containing the atom P(1) is bidentate. It
should be noted that the benzoic acid moiety does not coor-
dinate to metal ions and remains protonated (O2). The
atom O(11) in the P(1)O3 group is also noncoordinating.
This PO3 group is singly protonated based on PϪO dis-
tances and charge balance. The noncoordinating car-
boxylate (O2) and phosphonate (O11) oxygen atoms are hy-
drogen-bonded to an aquo ligand (O1W) (Table 1). The
[CoN2O4] and [CoO6] octahedra are interconnected by
bridging carboxylateϪphosphonate ligands in the plane
Crystal Structure Descriptions for Compounds 1 and 2
As shown in Figure 1, the asymmetric unit of compound
1 contains two unique CoII atoms. The Co(1) atom is octa-
hedrally coordinated by the tridentate phosphonate ligand
(1 N and 2 O), two phosphonate oxygen atoms from two
other phosphonate ligands, and one nitrogen atom from a
4,4Ј-bipy ligand. The Co(1)ϪO bond lengths are in the
˚
range from 2.036(7) to 2.087(6) A, and the Co(1)ϪN bond
˚
lengths are in the range from 2.154(8) to 2.348(8) A. The
OϪCoϪO and OϪCoϪN bond angles deviate from the
values for an ideal octahedron (Table 1). The atom Co(2)
lies on a twofold symmetry axis and is octahedrally coordi-
nated to two phosphonate oxygen atoms from two
Co(1)(H2L) units, and four water ligands. The CoϪO bond
˚
{400} (Figure 2). The interlayer distance is 12.9 A (1/2a).
The 2D layers are further crosslinked by 4,4Ј-bipy ligands
˚
lengths fall between 2.049(6) and 2.152(7) A, and the
OϪCoϪO bond angles are in the range from 84.5(3) to
95.6(3)°. These bond lengths and angles are similar to those
in Co2[PMIDA]2(H2O)5·H2O,[19] as well as for other
Figure 2. A Ͻ400Ͼ cobalt carboxylateϪphosphonate layer in 1;
the CPO3 tetrahedra and CoN2O4 octahedra are represented by
medium and light gray, respectively; the CH2C6H5COOH moiety
of the ligand has been omitted for clarity
Figure 1. ORTEP representation of the asymmetric unit of com-
pound 1; thermal ellipsoids are drawn at the 50% probability level
˚
Table 1. Selected bond lengths [A] and angles [°] for compound 1
Co(1)ϪO(12)
Co(1)ϪO(23)
Co(1)ϪO(13)#1
Co(1)ϪO(21)#2
Co(1)ϪN(2)
Co(1)ϪN(1)
Co(2)ϪO(22)
2.036(7)
2.063(7)
2.082(6)
2.087(6)
2.154(8)
2.348(8)
2.049(6)
Co(2)ϪO(22)#3
Co(2)ϪO(2W)#3
Co(2)ϪO(2W)
Co(2)ϪO(1W)#3
Co(2)ϪO(1W)
C(10)ϪO(1)
2.049(6)
2.121(7)
2.121(7)
2.152(7)
2.152(7)
1.209(15)
1.290(14)
C(10)ϪO(2)
Hydrogen bonds:
O(1w)···O(1)#6
2.735(11)
92.2(3)
90.0(3)
177.7(3)
178.0(3)
89.8(3)
88.0(3)
87.9(3)
92.0(3)
88.7(3)
92.0(3)
O(1W)···O(11)#5
2.992(10)
180.0(3)
O(12)ϪCo(1)ϪO(23)
O(12)ϪCo(1)ϪO(13)#1
O(23)ϪCo(1)ϪO(13)#1
O(12)ϪCo(1)ϪO(21)#2
O(23)ϪCo(1)ϪO(21)#2
O(13)#1ϪCo(1)ϪO(21)#2
O(12)ϪCo(1)ϪN(2)
O(23)ϪCo(1)ϪN(2)
O(13)#1ϪCo(1)ϪN(2)
O(21)#2ϪCo(1)ϪN(2)
O(22)ϪCo(2)ϪO(22)#3
O(22)ϪCo(2)ϪO(2W)#3
O(22)#3ϪCo(2)ϪO(2W)#3
O(22)ϪCo(2)ϪO(2W)
84.5(3)
95.5(3)
95.5(3)
84.5(3)
180.0(6)
91.8(3)
88.2(3)
89.5(3)
90.5(3)
O(22)#3ϪCo(2)ϪO(2W)
O(2W)#3ϪCo(2)ϪO(2W)
O(22)ϪCo(2)ϪO(1W)#3
O(22)#3ϪCo(2)ϪO(1W)#3
O(2W)#3ϪCo(2)ϪO(1W)#3
O(2W)ϪCo(2)ϪO(1W)#3
Symmetry transformations used to generate equivalent atoms: #1: Ϫ x ϩ 1/2, y Ϫ 1/2, Ϫz ϩ 1/2; #2: Ϫx ϩ 1/2, Ϫy Ϫ 3/2, Ϫz; #3: Ϫx
ϩ 1/2, Ϫy Ϫ 1/2, Ϫz; #4: Ϫ x ϩ 1, y, Ϫz ϩ 1/2; #5: Ϫx ϩ 1/2, y ϩ 1/2, Ϫz ϩ 1/2; #6: x, Ϫy Ϫ 1, Ϫz.
Eur. J. Inorg. Chem. 2004, 3706Ϫ3711
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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J.-L. Song, A. V. Prosvirin, H.-H. Zhao, J.-G. Mao
FULL PAPER
not involved in metal coordination. This type of coordi-
nation
mode
is
different
from
that
for
Co2[PMIDA]2(H2O)5·H2O,[19] in which the phosphonate
group is tridentate and one carboxylate group is bidentate.
The PMIDA ligand in compound 1 has been fully depro-
tonated based on charge balancing.
The two types of cobalt() octahedra are bridged by a
PMIDA ligand to form a dimeric unit, and such dimeric
units are further interconnected by bridging 4,4Ј-bipy li-
gands to form a 1D chain (Figure 5). These chains are held
together by hydrogen bonds among noncoordinating car-
boxylate (O12 and O10) and phosphonate(O1) oxygen
atoms as well as aquo ligands, resulting in a porous 3D
network (Figure 6, Table 2). The lattice water molecules are
located in the pores and are also involved in hydrogen
bonding (Table 2, Figure 6).
Figure 3. A view of the crystal structure of complex 1 along the b
axis; the CPO3 tetrahedra and CoN2O4 octahedra are represented
by medium and light gray, respectively; C and O atoms are rep-
resented by black and crossed circles, respectively
to form a pillar-layered structure (Figure 3), which contains
˚
channels with a size of about 9 ϫ 11 A based on the crystal
structure. The benzoic acid moieties are located in these
channels.
Figure 5. A 1D zigzag chain along the diagonal axis b and the
Ϫc axis in 2; the CPO3 tetrahedra and CoN2O4 octahedra are
represented by medium and light gray, respectively
Compound 2 features a 1D zigzag chain structure. There
are two independent CoII ions in the asymmetric unit of
compound 2 (Figure 4). Co(1) is octahedrally coordinated
to a tetradentate PMIDA ligand, an aquo ligand and a ni-
trogen atom from a 4,4Ј-bipy ligand, whereas Co(2) is octa-
hedrally coordinated by one 4,4Ј-bipy N atom, one phos-
phonate oxygen atom from a neighboring Co(1)(PMIDA)
chelating unit as well as four aquo ligands. The CoϪO dis-
˚
tances are in the range from 2.082(4) to 2.181(4) A, and the
˚
CoϪN distances fall in the range 2.115(3) to 2.156(4) A.
These bond lengths are similar to those in other CoII com-
plexes with O- and N-containing ligands.[13,14,19,20] The
PMIDA ligand is pentadentate, occupying four sites on a
CoII ion (1 N, 3 O) and bridging to another CoII ion. O(1)
and O(3) atoms of the carboxylate groups remain noncoor-
dinating. The phosphonate group adopts a bidentate and
bridging coordination mode, with one oxygen atom (O11)
Figure 6. A view of the crystal structure of 2 along the a axis; the
CPO3 tetrahedra and CoN2O4 octahedra are represented by me-
dium and light gray, respectively; C and O atoms are represented
by black and crossed circles, respectively
TGA Studies
The TGA diagram of compound 1 shows three main
stages of weight loss. The first stage begins at 138 °C and
is complete at 342 °C, and corresponds to the loss of four
water molecules. The observed weight loss of 6.4% is in
good agreement with the calculated value of 6.7%. The se-
cond stage, occurring between 347 and 820 °C, corresponds
to the combustion of 4,4Ј-bipy and diphosphonate ligands.
The third stage, which overlaps with the second, continues
up to 1000 °C and corresponds to further decomposition
of the compound. Assuming the final product is a mixture
Figure 4. An ORTEP representation of the asymmetric unit of 2;
thermal ellipsoids are drawn at the 30% probability level
3708
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 3706Ϫ3711

Syntheses and Crystal Structures of Two Cobalt CarboxylateϪPhosphonates
FULL PAPER
˚
Table 2. Selected bond lengths [A] and angles [°] for compound 2
Co(1)ϪO(11)
Co(1)ϪO(13)
Co(1)ϪN(2)
Co(1)ϪO(3)
Co(1)ϪO(2W)
Co(1)ϪN(3)
2.082(4)
2.085(4)
2.099(4)
2.115(3)
2.125(4)
2.156(4)
Co(2)ϪN(1)#1
Co(2)ϪO(3W)
Co(2)ϪO(5W)
Co(2)ϪO(2)
Co(2)ϪO(1W)
Co(2)ϪO(4W)
2.148(4)
2.181(4)
2.075(4)
2.091(4)
2.120(4)
2.122(4)
Hydrogen bonds:
O(1W)···O(1)
O(1W)···O(3W)
O(3W)···O(4W)#2
O(3W)···O(1)#3
O(4W)···O(2)
O(5W)···O(12)#4
O(6W)···O(8W)#6
O(7W)···O(8W)#7
O(8W)···O(1)#6
O(13)ϪCo(1)ϪN(3)
N(2)ϪCo(1)ϪN(3)
O(3)ϪCo(1)ϪN(3)
O(2W)ϪCo(1)ϪN(3)
2.675(5)
2.973(5)
2.756(5)
2.628(5)
2.910(5)
2.747(5)
2.611(13)
2.786(9)
2.851(7)
79.75(15)
171.75(17)
86.69(15)
96.13(16)
O(2W)···O(10)#5
O(3W)···O(4W)
O(3W)···O(10)#3
O(3W)···O(5W)
O(4W)···O(5W)
O(6W)···O(6W)#6
O(6W)···O(9W)
O(7W)···O(9W)#6
2.789(6)
2.927(5)
2.865(6)
2.953(5)
2.936(5)
2.655(12)
2.633(2)
2.904(16)
O(2)ϪCo(2)ϪO(3W)
O(1 W)ϪCo(2)ϪO(3W)
O(4 W)ϪCo(2)ϪO(3W)
91.57(14)
87.46(14)
85.73(14)
Symmetry transformations used to generate equivalent atoms: #1: x, y ϩ 1, z Ϫ 1; #2: Ϫx ϩ 1, Ϫy ϩ 1, Ϫz ϩ 2; #3: Ϫx, Ϫy ϩ 1, Ϫz
ϩ 2; #4: x, y ϩ 1, z; #5: x ϩ 1, y, z; #6: Ϫx, Ϫy ϩ 1, Ϫz ϩ 1; #7: x Ϫ 1, y, z.
of Co(PO3)2 and Co2P2O7 in a molar ratio of 1:1, the total microporous materials can be developed by self-assembly or
weight loss should be 52.8%. On the other hand, if com- by structure-directed synthesis of other metal phosphonate
pound 1 completely decomposes to CoO, the total weight building blocks with secondary metal linkers such as 4,4Ј-
loss is calculated to be 79.2%. The observed weight loss bipy or acidic carboxylic acid. In the latter case, the car-
(70.2%) is between these two theoretical values, and indi- boxylate ligand may remain protonated and noncoordi-
cates the partial decomposition of Co(PO3)2 and Co2P2O7 nated, in other words, it can act as an intercalated species
to CoO. The TGA weight loss curves of compound 2 also between two metal phosphonate layers. Such compounds
exhibit three stages. The first stage (24Ϫ269 °C) corre- may have good ion-exchange properties and could exhibit
sponds to loss of the four water molecules of crystallisation proton conductivity.
and five aquo ligands. The observed weight loss of 24.8%
is in good agreement with the calculated value of 24.9%
based on the loss of a total of nine H2O molecules. The
second loss occurs at 330Ϫ570 °C, and corresponds to the
decomposition of the 4,4Ј-bipy and carboxylateϪ
Experimental Section
Materials and Instrumentation: All chemicals were obtained from
phosphonate ligand. The third stage, occurring between 620
and 1000 °C, corresponds to further decomposition of the
organic groups. If the residue is assumed to be a mixture of
CoO and Co2P2O7 in a molar ratio of 2:1, the total weight
loss is calculated to be 66.5%. On the other hand, if the
final residue is CoO alone, the total weight loss is calculated
to be 88.6%. The observed weight loss (74.8%) is between
these two theoretical values, indicating that some Co2P2O7
has decomposed to CoO.
commercial sources and used without further purification. Elemen-
tal analyses were performed with a Vario EL III elemental analyzer.
Thermogravimetric analyses were carried out with a NETZSCH
STA 449C unit at a heating rate of 15 °C/min under nitrogen. IR
spectra were recorded with a Magna 750 FT-IR spectrophotometer
on KBr pellets in the range 4000Ϫ400 cmϪ1 1H and 31P NMR
.
spectra were recorded with a Varian Unity 500 NMR spectrometer
using D2O as solvent. H3PO4 (85%) was used as 31P standard refer-
ence.
Preparation of H5L and H4PMIDA: H5L was prepared by a Man-
nich-type reaction using 4-(aminomethyl)benzoic acid (15.1 g, 0.1
mol), hydrochloric acid (16 mL), deionized water (20 mL), phos-
phoric acid (32.8 g, 0.4 mol) and paraformaldehyde (9.0 g, 0.3
mol), according to known procedures.[16,21] The 31P NMR spec-
Conclusion
In summary, the hydrothermal syntheses and crystal
structures of two novel cobalt carboxylateϪphosphonates
containing 4,4Ј-bipy as the secondary metal linker have
been described. The interconnection of the metal
carboxylateϪphosphonate layer in compound 1 by 4,4Ј-
bipy leads to a pillar-layered architecture. In compound 2,
the dinuclear metal carboxylateϪphosphonate units are
crosslinked by 4,4Ј-bipy ligands resulting in a 1D chain. We
1
trum shows a single peak at δ ϭ 7.69 ppm. H NMR (D2O) : δ ϭ
3.50 (d, JH,P ϭ 12.5 Hz, 4 H, NCH2PO3), 4.74 (s, 2 H, 3-H), 7.73
(d, JH,H ϭ 5.5 Hz, 2 H, 2-H), 8.13 (d, JH,H ϭ 5.5 Hz, 2 H, 1-H)
ppm (see Scheme 1 for atomic labeling). IR (KBr): ν˜ ϭ 3423 (w),
2995 (m), 2771 (m), 2657 (m), 1720 (s), 1618 (w), 1583 (w), 1458
(m), 1435 (w), 1417 (w), 1327 (m), 1232 (m), 1138 (s), 1107 (s),
1022 (s), 939 (s), 862 (w), 810 (w), 746 (m), 710 (m), 580 (s), 519
(w), 494 (m), 451 (m) cmϪ1. H5L: C10H15NO8P2 (339.18): calcd. C
believe that a wide range of new open-frameworks and 35.53, H 4.34, N 4.22; found C 35.41, H 4.46, N 4.13. H4PMIDA
Eur. J. Inorg. Chem. 2004, 3706Ϫ3711
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J.-L. Song, A. V. Prosvirin, H.-H. Zhao, J.-G. Mao
FULL PAPER
1%. Both data sets were corrected for Lorentz and polarization
factors as well as for absorption using the SADABS program.[23]
Both structures were solved by direct methods and refined by full-
matrix least-squares fitting on F2 using SHELX-97.[23] All non-
hydrogen atoms were refined with anisotropic thermal parameters.
Hydrogen atoms were located at geometrically calculated positions
and refined with isotropic thermal parameters. Crystallographic
data and structural refinements for compounds 1 and 2 are summa-
rized in Table 3. Selected bond lengths and angles are listed in
Tables 1 and 2, respectively. CCDC-233617 (1) and -233618 (2) con-
tain the supplementary crystallographic data for this paper. These
data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.)
ϩ 44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
Table 3. Crystal data and structure refinements for compounds 1
and 2
1
2
Empirical formula
Formula mass
Space group
C30H40Co3N4O20P4 C15H32Co2N3O16P
1077.33
C2/c
25.9281(5)
9.76310(10)
17.3671(5)
90.0
103.290(2)
90.0
4278.55(15)
4
659.27
P1
¯
˚
a [A]
7.8009(7)
13.4560(12)
13.5453(12)
65.207(2)
88.035(2)
77.135(2)
1255.57(19)
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
Dcalcd. [g·cmϪ3
]
1.672
1.381
1.744
1.466
µ [mmϪ1
]
Measured reflections
Independent reflections
6367
3699
6417
4356
335
1.066
0.0533/0.1132
0.0828/0.1308
Acknowledgments
No. of parameters refined 279
GOF on F2
1.214
0.0728/0.1326
0.1326/0.2037
This work was supported by the National Natural Science Foun-
dation of China (20371047). We thank Prof. Kim Dunbar and John
Bacsa for their great help with the manuscript. K. R. D. gratefully
acknowledges the Department of Energy (DE-FG03-02ER45999),
the National Science Foundation (NIRT-NSF DMR-0103455), the
Welch Foundation A1449, and Texas A&M University (TITF) for
funding of this research.
R1, wR2 [I Ͼ 2σ(I)][a]
R1, wR2 (all data)
[a]
R1 ϭ |Fo| Ϫ |Fc|/|Fo|, wR2 ϭ {w[(Fo)2 Ϫ (Fc)2]2/w[(Fo)2]2}1/2, I Ͼ
4σ(I) for compound 1.
was also synthesized by a Mannich-type reaction according to pro-
cedures described previously.[22]
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3711