Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II) generates coordination monomers not polymers: Crystal structure of 4-(2,6- dicarboxypyridin-4-yl)ethynylpyridine-2,6-dicarboxylatotriaqua cobalt(II) monohydrate

Article abstract of DOI:10.1007/s10870-006-9077-5

Reaction and crystallization of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II) produces crystals containing monomers of 4-(2,6-dicarboxypyridin-4- yl)ethynylpyridine-2,6-dicarboxylatotriaqua cobalt(II) monohydrate complex (1), [Co(C₁₆H₆N₂O₈)(H₂O) ₃]·H₂O, instead of a rigid 1-D metal-organic framework consisting of a linear coordination polymer. This complex crystallizes in the monoclinic space group C2/c with a=6.8028(9) A, b=36.781(5) A, c=7.5135(9) 2.474(2)° and Z=4. The complex sits on a symmetry axis such that the two halves of the molecule are related by two-fold rotation symmetry. The molecules form layers in which the molecules are joined by intermolecular O-H...O interactions involving hydrogen bonds between CO₂H...CO₂^-, H₂O...CO ₂^-, H₂O...CO₂H and H ₂O...H₂O groups.

Full text of DOI:10.1007/s10870-006-9077-5

Journal of Chemical Crystallography, Vol. 36, No. 6, June 2006 (ꢀC 2006)
DOI: 10.1007/s10870-006-9077-5
Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with
Co(II) generates coordination monomers not polymers:
Crystal structure of 4-(2,6-dicarboxypyridin-4-yl)
ethynylpyridine-2,6-dicarboxylatotriaqua cobalt(II)
monohydrate
(
1)
(1)
(1)
Mehmet V. Yigit, Christopher G. F. Cooper, Yu Wang,
(
2)
(1)∗
Brian Moulton, and John C. MacDonald
Received November 15, 2005; accepted January 17, 2006
Published Online May 6, 2006
Reaction and crystallization of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II) pro-
duces crystals containing monomers of 4-(2,6-dicarboxypyridin-4-yl)ethynylpyridine-2,6-
dicarboxylatotriaqua cobalt(II) monohydrate complex (1), [Co(C16H6N2O8)(H2O)3]·H2O,
instead of a rigid 1-D metal–organic framework consisting of a linear coordination poly-
˚
mer. This complex crystallizes in the monoclinic space group C2/c with a = 6.8028(9) A,
˚
◦
b = 36.781(5) A, c = 7.5135(9) 2.474(2) and Z = 4. The complex sits on a symmetry axis
such that the two halves of the molecule are related by two-fold rotation symmetry. The
molecules form layers in which the molecules are joined by intermolecular O–H· · ·O inter-
−
−
actions involving hydrogen bonds between CO2H· · ·CO2 , H2O· · ·CO2 , H2O· · ·CO2H
and H2O· · ·H2O groups.
KEY WORDS: 2,6-Dicarboxypyridine.
Introduction
application in storage, separation, and sensing
of molecules, for catalysis, ion and molecular
Porous crystalline solids that derive their
exchange, and for production of metal nanoparti-
27–47
porosity from rigid frameworks of molecules are
under rapid development because these materials
exhibit large pore volumes, permanent porosity,
high thermal stability and have pores with tunable
structures and sizes.
framework materials show great promise for
cles.
We currently are investigating the design
and synthesis of rigid poly(2,6-dicarboxypyridin-
4-yl) ligands that promote divergent assembly
for this purpose. Our goal is to make new types
of metal–organic frameworks by reacting these
ligands with transition or lanthanide metals in
order to generate 1-D, 2-D, and 3-D coordination
polymers. We have demonstrated previously that
1–26
Consequently, crystalline
(
1)
2)
Department of Chemistry & Biochemistry, Worcester Polytechnic
Institute, Worcester, Massachusetts 01609.
Department of Chemistry, Brown University, Providence Rhode
Island 02912.
To whom correspondence should be addressed; e-mail:
jcm@wpi.edu
2,6-dicarboxypyridine is a versatile tridentate
(
ligand that coordinates a range of divalent
first-row transition metals and that metal–ligand
coordination can be used to promote assembly
∗
3
71
1
074-1542/06/0600-0371/0 ꢀC 2006 Springer Science+Business Media, Inc.

3
72
Yigit, Cooper, Wang, Moulton, and MacDonald
2
Fig. 1. Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with CoBr followed by
crystallization gave crystals containing 1 (top) rather than a rigid 1-D metal–organic
framework consisting of a linear coordination polymer (bottom).
of molecules in solids48–53 and on surfaces.54,55
Accordingly, we are preparing a library of soluble
organic ligands substituted with two, three, or four
generate coordination networks in solution.56
Our attempts to prepare crystalline solids with
1-D metal–organic frameworks by reacting 1,2-
bis(2,6-dicarboxypyridin-4-yl)ethyne with Co
metal ions resulted in an unexpected monomeric
coordination compound. Here we present the
crystal structure of 4-(2,6-dicarboxypyridin-
4-yl)ethynylpyridine-2,6-dicarboxylatotriaqua
cobalt(II) monohydrate (1).
2
,6-dicarboxypyridine units attached covalently
to a central organic core by rigid arms that consist
of alkynyl groups and benzene rings. We chose
1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne as a
target ligand for generating linear frameworks for
several reasons. 1,2-Bis(2,6-dicarboxypyridin-
4-yl)ethyne contains two 2,6-dicarboxypyridine
Results and discussion
groups bonded at both ends of ethyne, as shown
in Fig. 1. The rigid ethyne group holds the 2,6-
dicarboxypyridine groups in a linear arrangement
with metal-binding sites at both ends of the ligand
oriented facing in opposite directions. This ligand
has been reported to bind lanthanide metals and
The molecular structure and ORTEP
representation with atomic numbering of 1 is
shown in Fig. 2. A view of crystal packing along
the a axis is shown in Fig. 3. A summary of the
crystallographic information is given in Table 1.
Fig. 2. ORTEP representation of 1, ellipsoids at 50% probability.

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II)
373
Fig. 3. A hydrogen-bonded layer in the crystal structure of 1 viewed along the a-axis. Dotted magenta lines represent
hydrogen bonds.
Selected bond lengths and bond angles are given
in Table 2.
charged carboxylate groups that balance the 2 +
charge of the Co metal ion. The two pyridine
rings and two carboxylic acid groups all are
Molecular structure of 1
coplanar, while the carboxylate groups rotate
◦
5.2 out of the plane of the pyridine ring. The
Reaction of 1,2-bis(2,6-dicarboxypyridin-
metal ion bonds to the ligand via one Co–N bond
˚
4
-yl)ethyne with cobalt(II) bromide in H O
[Co1–N1 = 2.044(3) A] to the pyridine ring and
2
gave the corresponding 4-(2,6-dicarboxypyridin-
-yl)ethynylpyridine-2,6-dicarboxylatotriaqua
cobalt(II) complex, 1. As shown in Fig. 2, this
complex has a structure in which the Co metal
ion is coordinated octahedrally to one ligand of
two symmetry equivalent Co–O bonds [Co1–
˚
4
O1 = 2.1362(18) A] to the carboxylate groups
ortho to the nitrogen atom on the pyridine ring.
To compare the Co–N and Co–O bond
distances and coordination in 1 to those re-
ported previously in the crystallographic liter-
ature, we searched the Cambridge Structural
Database (CSD) for complexes that contain Co
1
,2-bis(2,6-dicarboxypyridin-4-yl)ethyne in a
meridional arrangement and to three molecules
of water also in a meridional arrangement. In
addition, a fourth molecule of water is included
in the lattice that is not coordinated to Co.
This complex results when both carboxylic acid
groups at one end lose a proton to form negatively
57
and at least one 2,6-dicarboxypyridine moiety.
The search allowed for substituents other than hy-
drogen on carbons 3, 4, and 5 on the pyridine
ring. The search yielded 11 crystal structures of

3
74
Yigit, Cooper, Wang, Moulton, and MacDonald
Table 1. Crystallographic Data and Refinement Information for 1
complexes with no additional substituents on the
pyridine ring and that featured 18 Co–N bonds
and 36 Co–O bonds that were unique crystal-
lographically. The Co–N bond distances ranged
Empirical formula
CCDC deposit no
Formula weight
Crystal system
C16H14N2O12Co1
CCDC-289569
485.22
Monoclinic
C2/c
˚
from 2.010 to 2.070 A with an average distance
Space group
˚
of 2.025(14) A. The Co–O bond distances ranged
Crystal description
Pale red plate
˚
Unit cell dimensions
from 2.105 to 2.244 A with an average distance of
˚
a (A)
6.8028(9)
˚
2
.185(36) A. By comparison, the Co–N length in
˚
b (A)
36.781(5)
the structure of 1 [Co1–N1 = 2.044(3)] is longer
˚
c (A)
7.5135(9)
92.474(2)
1878.2(4)
˚
◦
than the average Co–N distance by 0.019 A, while
β ( )
˚
3
˚
Volume (A )
the Co–O bonds in 1 [Co1–O1 = 2.1362(18) A]
Z
4
are shorter than the average Co–O distance by
3
Density (calculated, g/cm )
Temperature (K)
F(000)
θ range for data collection ( )
Absorption coefficient (mm 1)
1.716
100(2)
988
1.11–28.28
˚
0
.049 A. It is noteworthy that 8 of the 11 struc-
tures from the CSD had Co coordinated to two
,6-dicarboxypyridine ligands; the other three had
◦
−
2
0.986
Co coordinated to one 2,6-dicarboxypyridine lig-
and and to other ligands that include water, 1,10-
Reflections collected
5328
Independent reflections
Reflections [I > 2σ (I)]
Data/restraints/parameters
2221 (Rint = 0.0530)
ꢁ
1736
phenanthrolene, 4,4 -bipyridyl, and chloride ion.
2221/0/145
1.032
The fact that the majority of the complexes from
the CSD and all of the complexes with Co from
our previous work feature Co coordinated with
two 2,6-dicarboxypyridine ligands suggests that
2
Goodness-of-fit on F
R [I > 2σ (I)]
R indices (all data)
R1 = 0.0380, wR2 = 0.0911
R1 = 0.0535, wR2 = 0.1164
0.66 and − 0.46
Max. and min. peaks in final diff.
˚
−3
)
map (eA
˚
◦
Table 2. Selected Bond Lengths (A) and Angles ( ) for 1
˚
Bond lengths (A)
Co(1)–O(2W)
Co(1)–N(1)
Co(1)–O(1W)
Co(1)–O(1)
N(1)–C(2)
N(2)–C(9)
O(1)–C(1)
O(2)–C(1)
1.990(3)
2.044(3)
2.110(2)
O(4)–C(10)
C(1)–C(2)
C(2)–C(3)
1.207(4)
1.511(4)
1.379(4)
1.406(3)
1.429(5)
1.189(6)
1.439(5)
1.395(3)
1.378(4)
2.1362(18) C(3)–C(4)
1.334(3)
1.340(3)
1.265(3)
1.254(3)
1.318(4)
C(4)–C(5)
C(5)–C(6)
C(6)–C(7)
C(7)–C(8)
C(8)–C(9)
O(3)–C(10)
Bond Angles ( )
◦
O(2W)–Co(1)–O(1W)
N(1)–Co(1)–O(1W)
O(1W)–Co(1)–O(1W)
O(2W)–Co(1)–O(1)
N(1)–Co(1)–O(1)
86.04(5)
93.96(5)
172.09(10)
104.24(5)
75.76(5)
95.94(7)
151.51(10)
121.4(3)
119.28(17)
116.5(3)
116.27(17)
124.5(2)
119.7(2)
115.8(2)
N(1)–C(2)–C(3)
N(1)–C(2)–C(1)
C(3)–C(2)–C(1)
C(2)–C(3)–C(4)
121.5(3)
112.0(2)
126.5(2)
117.9(3)
119.8(4)
120.08(18)
118.3(4)
120.84(18)
118.4(3)
124.2(3)
117.4(3)
118.4(3)
125.1(3)
122.4(3)
a
a
C(3)–C(4)–C(3)
C(3)–C(4)–C(5)
C(8)–C(7)–C(8)
C(8)–C(7)–C(6)
C(9)–C(8)–C(7)
O(1W)–Co(1)–O(1)
a
a
O(1)–Co(1)–O(1)
C(2)–N(1)–C(2)
a
C(2)–N(1)–Co(1)
a
C(9)–N(2)–C(9)
N(2)–C(9)–C(8)
N(2)–C(9)–C(10)
C(8)–C(9)–C(10)
O(4)–C(10)–O(3)
O(4)–C(10)–C(9)
C(1)–O(1)–Co(1)
O(2)–C(1)–O(1)
O(2)–C(1)–C(2)
O(1)–C(1)–C(2)
a
−
x + 2, y, − z + 1/2.

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II)
375
this arrangement may be favored over coordina-
tion to a single 2,6-dicarboxypyridine ligand.
It was surprising to find Co coordinated
to just one end of the ligand with the sec-
ond 2,6-dicarboxypyridine group remaining
uncoordinated. We reported previously that
transition metals coordinate exclusively to two
using optical microscopy to verify visually
the homogeneity of bulk samples. Despite
differences in size, all crystals had the same habit
and color regardless of the initial stoichiometry
of components placed in solution. We did not
attempt to prepare crystals of 1 from solvents
other than water; therefore it is not known
what effect solvents other than water might
have on the composition of the final product.
Our earlier investigation of bis(imidazolium
2,6-dicarboxypyridine) M(II) dihydrate com-
2
2
,6-dicarboxypyridine ligands in bis(imidazolium
,6-dicarboxypyridine) M(II) dihydrate
bis(2-methylimidazolium 2,6-
50–53
complexes,
49
dicarboxypyridine) M(II) dihydrate complexes
50–53
and bis(imidazolium 2,4,6-tricarboxypyridine)
M(II) trihydrate complexes (where M: Mn, Co,
Ni, Cu, or Zn).48 These studies showed that
plexes
interestingly revealed that water was
included in all structures regardless of whether
DMSO, water, or a mixture of DMSO and water
was used as the solvent for crystallization. It is
likely that coordination of water to Co will occur
in other solvents to give monomers of 1 unless
water is excluded rigorously.
2,6-dicarboxypyridine is a versatile ligand that
reliably coordinates to a variety of first-row
transitions metal ions in an octahedral arrange-
ment in which the metal ion is encapsulated
by two ligands. Consequently, we expected
the
1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne
Crystal packing and hydrogen bonding in 1
ligand to coordinate Co at both ends, thereby
forming a linear coordination polymer instead
of the observed monomeric structure. It is worth
noting that a 2:1 ratio of ligand to metal was
used to prepare crystals of 1. In our previously
reported work with 2,6-dicarboxypyridine and
Complex 1 crystallizes in the monoclinic
space group C2/c with the asymmetric unit
consisting of half the complex. The complex
sits on a symmetry axis such that the two
halves of the compound are related by two-fold
rotation. Packing in the solid is dominated by
hydrogen bonding involving water, carboxylic
acid groups, and carboxylate groups. Each
molecule is joined to adjacent molecules by two
O–H· · ·O interactions between carboxylic acid
2,4,6-tricarboxypyridine metal complexes, we
found that the presence of excess ligand gave
crystals of higher quality with larger dimensions
than those that formed in the absence of excess
ligand. Those studies also showed that varying
the ratio of ligand to metal in solution did not
affect the composition of the metal complexes
that formed. Accordingly, crystallization of 1
was carried out with a 1:1 ratio of ligand and
metal to test whether a stoichiometric ratio of
˚
and carboxylate groups (O3· · ·O2 = 2.595(3) A,
◦
˚
H3O· · ·O2 = 1.816 A, O3–H3O· · ·O2 = 152.86 )
that form hydrogen-bonded rings with graph set
2
58,59
R (26).
These interactions form on both
2
sides of each molecule, thereby generating chains
2
2
1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne ligand
of molecules with graph set C (16)[R (26)].
2 2
and Co would give the desired coordination
polymer. The resulting pale red rectangular plates
had the same habit and powder X-ray diffraction
pattern as crystals of 1 (calculated from the single
crystal data) prepared from a 2:1 ratio of ligand to
metal. Thus, varying the ratio of ligand to metal
did not result in a different mode of coordination
or a complex of different composition. Batches
of crystals isolated from solution were examined
Adjacent chains are joined into layers (20-4
plane) via two different O–H· · ·O hydrogen
bonds between coordinated molecules of water
and carboxylate groups. Water coordinated cis
to the pyridine forms O–H· · ·O interactions
to the carboxylate oxygen atom proximal
˚
to the Co ion (O1W· · ·O1 = 2.770(3) A,
˚
H1OB· · ·O1 = 1.967
A,
O2W–
◦
H1OB· · ·O1 = 169.15 ) that generate hydrogen-

3
76
Yigit, Cooper, Wang, Moulton, and MacDonald
2
bonded chains with graph set C(4)[R (8)].
OH
N
Br
2
1
. PBr , 100 °C
5
Water coordinated trans to the pyridine forms
O–H· · ·O interactions to the carboxylate oxygen
atom distal to the Co ion (O2W· · ·O2 =
2
. EtOH, 0 °C
HO C
CO H
EtO C
N
i
CO Et
2
2
2
2
˚
˚
acetylene (g)
2
.701(3) A, H2O· · ·O2 = 1.875 A, O2W–
◦
2
PdCl , CuI, PPh3
H2O· · ·O2 = 177.16 ) that form hydrogen-
Et N
3
2
2
bonded chains with graph set C(6)[R (12)].
HO C
N
CO H
EtO C
N
CO Et
2
2
2
2
A free molecule of water resides in the cleft
between the two carboxylic acids and forms
two O–H· · ·O interactions with the oxygen
atoms in the OH groups of the carboxylic
NaOH
H O, EtOH
2
˚
acids (O3W· · ·O3 = 2.953(3) A). The resulting
2
2
HO C
N
iii
CO H
EtO C
N
ii
CO Et
2
2
2
2
hydrogen-bonded ring has graph set R (10).
Although the hydrogen atoms on the free water
were not located in the electron density difference
maps during refinement of the crystal structure,
the geometry of hydrogen bonds involving
this molecule of water was determined with
confidence based on the O· · ·O distance. The free
water also forms O–H· · ·O interactions with water
coordinated cis to the pyridine in complexes in
Scheme 1.
4
(
-yl)ethyne was synthesized in three steps
Scheme 1) by adapting procedures reported pre-
viously by Latva et al. as described later.
56
Acetylene (30% in acetone) was purchased from
Mattheson Gas, Inc. Phosphorous pentabromide
was prepared freshly via addition of bromine
and phosphorous tribromide. The resulting yel-
low solid was reslurried in tert-butyl methyl ether
several times, until the filtrate was no longer yel-
low in color, and was used immediately after.
NMR spectra were obtained with a 400 MHz
Avance Bruker spectrometer. Mass spectra were
measured by SynPep Corporation. Ionization was
performed using electrospray, with acetonitrile as
the carrier solvent, and nitrogen as a curtain gas
˚
neighboring layers (O1W· · ·O3W = 2.819(3) A,
˚
H1OA· · ·O3W = 2.191
A,
O1W–H1OA· · ·O3W =
◦
1
59.57 ). These O–H· · ·O interactions form
1
2
hydrogen-bonded chains with graph set C (6)
that connect adjacent layers as they stack.
Conclusions
Our attempts to prepare a crystalline solid
containing a 1-D metal organic framework by re-
acting 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne
with Co(II) metal ions resulted in an unexpected
monomeric complex, 1. Instead of forming a lin-
ear coordination polymer composed of alternating
(Scheme 1).
Preparation of diethyl
-bromopyridine-2,6-dicarboxylate (i)
4
1
,2-bis(2,6-dicarboxypyridin-4-yl)ethyne ligands
Chelidamic acid (23.9 g, 100 mmol)
was combined with phosphorous pentabromide
and Co(II) metal ions as expected, the ligand co-
ordinates a Co(II) metal ion at just one of the two
2
(
43.1 g, 100 mmol) under an N atmosphere. The
2
,6-dicarboxypyridine groups.
◦
mixture was heated gently at 100 C for 0.5 h.
The reaction was cooled to RT, and the solid
was dissolved in ether (150 mL). The ethereal
solution was then added dropwise to a stirred so-
Experimental
All reagents and solvents were purchased
◦
lution of absolute ethanol (100 mL) at 0 C. Re-
from Aldrich or Acros and were used without
further purification. Bis(2,6-dicarboxypyridin-
crystallization of the product from 30% nitric acid

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II)
377
yielded 22.0 g (66.1% yield) of i as white needles.1
H NMR (d6-DMSO) δ (ppm) 1.30 (t, 6H), 4.29
Preparation of 4-(2,6-dicarboxypyridin
-4-yl)ethynylpyridine-2,6-dicarboxylatotriaqua
(q, 4H), 9.0 (s, 2H).
cobalt(II) monohydrate (1)
Compound iii (5.0 mg, 0.014 mmol) and
Preparation of bis[2,6-bis(ethoxycarbonyl)
pyridin-4-yl]ethyne (ii)
CoBr (1.6 mg, 0.0074 mmol) were dissolved in
2
◦
2
mL of H O at 50 C with stirring for 20 min.
2
The resulting mixture was then injected into a
previously prepared 3 mL glass tube (pipet sealed
at one end) to occupy approximately 1/3 of the
volume. The tube was then sealed by flame and
Compound i (22.0 g, 66.1 mmol) was dis-
solved in triethyl amine (200 mL) under an N2
atmosphere, and PdCl (1.1 g, 6.6 mmol), CuI
2
(
(
2.5 g, 13.2 mmol), and triphenyl phosphine
1.7 g, 6.6 mmol) were added. Acetylene was bub-
◦
placed in an oven at 110 C. Crystals of 1 formed
as pale red rectangular plates in solution after 48 h.
Single crystals were removed from solution and
dried on filter paper.
bled through the reaction mixture, and the mix-
ture stirred for 18 h at RT. The resultant mixture
was poured into water (400 mL), and extracted
three times with ethyl acetate (900 mL total). The
organic fractions were combined, washed twice
with citric acid, dried over anhydrous sodium sul-
fate, and evaporated under reduced pressure. The
resulting crude product was purified over silica
gel (40% ethyl acetate:hexane) to give 10.2 g of
Crystal structure determination
A crystal of 1 having approximate dimen-
sions 0.30 mm × 0.25 mm × 0.05 mm was
placed on a glass fiber that was mounted on a
Siemens SMART/CCD diffractometer equipped
with an LT-II low temperature device. Diffrac-
tion data were collected at 100(2) K using
graphite monochromated Mo-Kα radiation with
the omega-scan technique. Diffraction data were
corrected for absorption using the SADABS pro-
1
ii (33.0% yield) as a white powder. H NMR (d6-
DMSO) δ (ppm) 1.25 (t, 12H), 4.38 (q, 8H), 8.6
s, 4H).
(
Preparation of bis(2,6-dicarboxypyridin
4-yl)ethyne (iii)
-
60
gram. The unit cell and space group were deter-
60
Compound ii (10.2 g, 21.7 mmol) was dis-
mined using the SAINT + program. The struc-
ture was solved by direct methods and refined
by full-matrix least-squares using the SHELXTL
solved in 10% aqueous ethanol (300 mL), and
sodium hydroxide (3.5 g, 87.5 mmol) was added.
The reaction mixture was heated to reflux for 3 h,
with progress being monitored via TLC. The re-
action mixture was cooled to RT, and solvent re-
moved under reduced pressure. The crude product
was dissolved in water (500 mL), and extracted
twice with TBME (500 mL total). The pH of
the aqueous layer was adjusted to 6 with am-
monium chloride, and the product was extracted
three times with methylene chloride (250 mL
per wash). The organic fractions were combined,
dried over anhydrous sodium sulfate, and concen-
60
program on a PC platform. Refinement was
2
based on F using all reflections. All non-
hydrogen atoms were refined anisotropically. Hy-
drogen atoms on oxygen atoms were located and
refined with isotropic thermal parameters. Hydro-
gen atoms on oxygen atoms on the molecules of
water bonded to Co were located in the difference
Fourier map, the coordinates constrained to ride
on the coordinates of the bonded oxygen atom,
and refined isotropically with thermal parame-
ters based upon the corresponding attached oxy-
trated under reduced pressure to give 6.2 g of iii
gen atoms [U(H) = 1.2 U (O)]. Hydrogen atoms
eq
1
(
80% yield) as a white solid. H NMR (d6-DMSO)
were not located in the difference map on the
free molecule of water and are not included in
the structure. The remaining hydrogen atoms on
δ (ppm) 9.3 (s, 4H), 12.6 (bs, ∼ 4H). ESI–MS, m/z
∗
∗
[
M + H] = 357.1, [M + Na] = 379.8.

3
78
Yigit, Cooper, Wang, Moulton, and MacDonald
carbon were fixed in calculated positions and re-
fined isotropically with thermal parameters based
upon the corresponding attached carbon atoms
17. Du, M.; Guo, Y.-M.; Chen, S.-T.; Bu, X.-H.; Batten, S.R.; Ribas,
J.; Kitagawa, S. Inorg. Chem. 2004, 43, 1287–1293.
18. Kondo, M.; Irie, Y.; Shimizu, Y.; Miyazawa, M.; Kawaguchi, H.;
Nakamura, A.; Naito, T.; Maeda, K.; Uchida, F. Inorg. Chem.
2
004, 43, 6139–6141.
9. Saied, O.; Maris, T.; Wuest, J.D. J. Am. Chem. Soc. 2005, 125,
4956–14957.
0. Liao, Y.-C.; Liao, F.-L.; Chang, W.-K.; Wang, S.-L. J. Am. Chem.
Soc. 2004, 126, 1320–1321.
[
U(H) = 1.2 U (C)].
eq
1
2
2
1
Supplementary material CCDC-289569 contains the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/data request/cif,
by e-mailing data request@ccdc.cam.ac.uk or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 IEZ, UK; fax: +44(0)1223-336033.
1. Rowsell, J.L.C.; Yaghi, O.M. Micropor. Mesopor. Mater. 2004,
7
3, 3–4.
2
2
2. Rosseinsky, M.J. Micropor. Mesopor. Mater. 2004, 73, 15–30.
3. Burrows, A.D.; Cassar, K.; Friend, R.M.W.; Mahon, M.F.;
Rigby, S.P.; Warren, J.E. CrystEngComm 2005, 7, 548–550.
4. Zhang, J.-P.; Lin, Y.-Y.; Zhang, W.-X.; Chen, X.-M. J. Am.
Chem. Soc. 2005, 127, 14162–14163.
5. Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour,
J.; Surble, S.; Margiolaki, I. Science 2005, 309, 2040–2042.
6. Sun, D.; Ke, Y.; Mattox, T.M.; Ooro, B.A.; Zhou, H.-C. Chem.
Commun. 2005, 5447–5449.
2
2
2
2
Acknowledgments
Acknowledgement is made to the U.S. Army
Research Office (grant # W911NF-05-0293)
and to the Donors of The Petroleum Research
Fund (grant # 34604-B3), administered by the
American Chemical Society, for support of
this research at Worcester Polytechnic Institute.
The authors would like to thank Dr. Dumas for
insightful comments.
7. Snurr, R.Q.; Hupp, J.T.; Nguyen, S.T. AIChE J. 2004, 50, 1090–
1095.
2
2
8. Cheetham, A.K.; Rao, C.N.R. MRS Bull. 2005, 30, 93–98.
9. Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.;
O’Keeffe, M.; Yaghi, O.M. Science 2002, 295, 469–472.
0. Ward, M.D. Science 2003, 300, 1104–1105.
3
3
1. Rosi, N.L.; Eckert, J.; Eddaoudi, M.; Vodak, D.T.; Kim, J.;
O’Keeffe, M.; Yaghi, O.M. Science 2003, 300, 1127–1129.
2. Halder, G.J.; Kepert, C.J.; Moubaraki, B.; Murray, K.S.; Cash-
ion, J.D. Science 2002, 298, 1762–1765.
3
3
3. Liu, S.Q.; Konaka, H.; Kuroda-Sowa, T.; Suenaga, Y.; Ito, H.;
Ning, G.L.; Munakata, M. Inorg. Chim. Acta 2004, 357, 3621–
3
631.
4. Hu, A.; Ngo, H.L.; Lin, W. Angew. Chem. Int. Ed. 2003, 42,
000–6003.
5. Maji, T.K.; Uemura, K.; Chang, H.-C.; Matsuda, R.; Kitagawa,
S. Angew. Chem. Int. Ed. 2004, 43, 3269–3272.
36. Moon, H.R.; Kim, J.H.; Suh, M.P. Angew. Chem. Int. Ed. 2005,
44, 1261–1265.
37. Rowsell, J.L.C.; Eckert, J.; Yaghi, O.M. J. Am. Chem. Soc. 2005,
127, 14909–14910.
38. Seo, J.S.; Whang, D.; Lee, H.; Jun, S.I.; Oh, J.; Jeon, Y.J.; Kim,
K. Nature 2000, 404, 982–986.
39. Wang, Z.; Zhang, B.; Kurmoo, M.; Green, M.A.; Fujiwara,
H.; Otsuka, T.; Kobayashi, H. Inorg. Chem. 2004, 44, 1230–
1237.
3
3
References
6
1
2
3
4
5
. Kitagawa, S.; Kitaura, R.; Noro, S.-I. Angew. Chem. Int. Ed.
2
004, 43, 2334–2375.
. Rao, C.N.R.; Natarajan, S.; Vaidhyanathan, R. Angew. Chem.
Int. Ed. 2004, 43, 1466–1496.
. Kitaura, R.; Seki, K.; Akiyama, G.; Kitagawa, S. Angew. Chem.
Int. Ed. Engl. 2003, 42, 428–431.
. Ishii, Y.; Takenaka, Y.; Konishi, K. Angew. Chem. Int. Ed. 2004,
4
3, 2702–2705.
. Serre, C.; Millange, F.; Surble, S.; Ferey, G. Angew. Chem. Int.
Ed. 2004, 43, 6286–6289.
6
7
8
. Wu, C.-D.; Lin, W. Angew. Chem. Int. Ed. 2005, 44, 2–5.
. Bowes, C.L.; Ozin, G.A. Adv. Mater. 1986, 8, 13–28.
. Eddaoudi, M.; Moler, D.B.; Li, H.; Chen, B.; Reineke, T.M.;
O’Keeffe, M.; Yaghi, O.M. Acc. Chem. Res. 2002, 34, 319–
40. Dybtsev, D.N.; Chun, H.; Yoon, S.H.; Kim, D.; Kim, K. J. Am.
Chem. Soc. 2004, 126, 32–33.
41. Uemura, K.; Kitagawa, S.; Fukui, K.; Saito, K. J. Am. Chem.
Soc. 2004, 126, 3817–3828.
42. Rowsell, J.L.C.; Millward, A.R.; Park, K.S.; Yaghi, O.M.
J. Am. Chem. Soc. 2004, 126, 5666–5667.
43. Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2004,
127, 8940–8941.
3
30.
9
. Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F. Acc.
Chem. Res. 2005, 38, 217–225.
1
1
1
0. Shmilovits, M.; Diskin-Posner, Y.; Vinodu, M.; Goldberg, I.
Cryst. Growth Des. 2003, 3, 855–863.
44. Hermes, S.; Schroter, M.-K.; Schmid, R.; Khodeir, L.; Muhler,
M.; Tissler, A.; Fischer, R.W.; Fischer, R.A. Angew. Chem. Int.
Ed. 2004, 44, 6237–6241.
1. Lu, J.; Shen, E.; Li, Y.; Xiao, D.; Wang, E.; Xu, L. Cryst. Growth
Des. 2005, 5, 65–67.
2. Lu, K.-L.; Chen, Y.-F.; Liu, Y.-H.; Cheng, Y.-W.; Liao, R.-T.;
Wen, Y.-S. Cryst. Growth Des. 2005, 5, 403–405.
3. Ferey, G. Chem. Mater. 2001, 13, 3084–3098.
4. Zheng, X.-J.; Wang, Z.-M.; Gao, S.; Liao, F.-H.; Yan, C.-H.; Jin,
L.P. Eur. J. Inorg. Chem. 2004, 2968–2973.
45. Matsuda, R.; Kitaura, R.; Kitagawa, S.; Kubota, Y.; Belosludov,
R.V.; Kobayashi, T.C.; Sakamoto, H.; Chiba, T.; Takata, M.;
Kawazoe, Y.; Mita, Y. Nature 2005, 436, 238–241.
46. Mori, W.; Takamizawa, S.; Kato, C.N.; Ohmura, T.; Sato, T.
Micropor. Mesopor. Mater. 2004, 73, 31–46.
47. Schichte, K.; Kratzke, T.; Kaskel, S. Micropor. Mesopor. Mater.
2004, 73, 81–88.
48. Yigit, M.V.; Biyikli, K.; Moulton, B.; MacDonald, J.C. Cryst.
Growth Des.2006, 6, 63–69.
1
1
1
5. Dybtsev, D.N.; Chun, H.; Kim, K. Angew. Chem. Int. Ed. Engl.
2
004, 43, 5033–5035.
6. Ma, J.-F.; Yang, J.; Zheng, G.-L.; Li, L.; Liu, J.-F. Inorg. Chem.
003, 42, 7531–7534.
1
2

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II)
379
4
5
5
5
5
5
9. MacDonald, J.C.; Luo, T.-J.M.; Palmore, G.T.R. Cryst. Growth
Des. 2004, 4, 1203–1209.
0. MacDonald, J.C.; Dorrestein, P.C.; Pilley, M.M.; Foote, M.M.;
Lundburg, J.L. J. Am. Chem. Soc. 2000, 122, 11692–11702.
1. MacDonald, J.C.; Dorrestein, P.C. ACA Trans. 1998, 33, 121–
55. Soto, E.; MacDonald, J.C.; Cooper, C.G.; McGimpsey, W.G. J.
Am. Chem. Soc. 2003, 125, 2838–2839.
56. Latva, M.; Takalo, H.; Simberg, K.; Kankare, J. J. Chem. Soc.
Perkin Trans. 1995, 2, 995–999.
57. Allen, F.H. Acta Crystallogr. 2002, B58, 380–388.
58. Bernstein, J.; Davis, R.E.; Shimoni, L.; Chang, N.-L. Angew.
Chem. Int. Ed. Engl. 1995, 34, 1555–1573.
59. Etter, M.C.; MacDonald, J.C.; Bernstein, J. Acta Crystallogr. B
1990, 46, 256–262.
1
31.
2. Luo, T.-J.M.; MacDonald, J.C.; Palmore, G.T.R. Chem. Mater.
004, 16, 4916–4927.
3. Luo, T.-J.M.; MacDonald, J.C.; Palmore, G.T.R. ACA Trans.
004, 39, 1–10.
2
2
60. Bruker (1997). SAINT (Version 6.12), SHELXTL (Version
6.12) for WNT/2000. Bruker AXS Inc., Madison, Wisconsin,
USA.
4. Cooper, C.G.F.; MacDonald, J.C.; Soto, E.; McGimpsey, W.G.
J. Am. Chem. Soc. 2004, 126, 1032–1033.