Metal ion control of dimensionality and self-penetration in coordination polymers containing furandicarboxylate and dipyridylamide ligands

Article abstract of DOI:10.1016/j.ica.2016.07.026

Hydrothermal reaction of metal nitrates, 2,5-furandicarboxylic acid (H₂fdc) and the conformationally flexible dipyridylamide ligand 3-pyridylnicotinamide (3-pna) afforded three new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd₂(fdc)₂(3-pna)(H₂O)₄]·6H₂O}_n(1) exhibits a 1D ladder structural motif with tethering anti-conformation 3-pna ligands acting as the rungs. {[Ni(fdc)(3-pna)₂(H₂O)]·2.5H₂O}_n(2) displays a (4,4) rhomboid grid structure that resembles a rarer (3,6) triangular grid if supramolecular interactions provided by pendant syn-conformation 3-pna ligands are considered. [Co(fdc)(3-pna)(H₂O)]_n(3) manifests {Co₂(OCO)₂} anti-syn dimer-based 3-connected 4.8²layers pillared into a novel 3D 3,5-connected self-penetrated (4.6.8)(4.6⁵8³10) topology network by anti-conformation 3-pna ligands. The specific metal coordination environments, fdc binding mode, and 3-pna conformation act synergistically to enforce structure direction in this system. Thermal decomposition properties of these three new materials are also discussed.

Full text of DOI:10.1016/j.ica.2016.07.026

Inorganica Chimica Acta 451 (2016) 171–176
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Research paper
Metal ion control of dimensionality and self-penetration in coordination
polymers containing furandicarboxylate and dipyridylamide ligands
⇑
Charmaine L. White, Robert L. LaDuca
Lyman Briggs College and Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 8 June 2016
Received in revised form 11 July 2016
Accepted 15 July 2016
Available online 18 July 2016
Hydrothermal reaction of metal nitrates, 2,5-furandicarboxylic acid (H fdc) and the conformationally
flexible dipyridylamide ligand 3-pyridylnicotinamide (3-pna) afforded three new coordination polymers
2
which were structurally characterized by single-crystal X-ray diffraction. {[Cd
O} (1) exhibits a 1D ladder structural motif with tethering anti-conformation 3-pna ligands acting
as the rungs. {[Ni(fdc)(3-pna) (H O} (2) displays a (4,4) rhomboid grid structure that resembles
O)]ꢀ2.5H
a rarer (3,6) triangular grid if supramolecular interactions provided by pendant syn-conformation
2
(fdc)
2
(3-pna)(H
2
O)
4
]ꢀ
6H
2
n
2
2
2
n
Keywords:
3
3
-pna ligands are considered. [Co(fdc)(3-pna)(H
2 n 2 2
O)] (3) manifests {Co (OCO) } anti-syn dimer-based
Coordination polymer
Crystal structure
Cobalt
Cadmium
Nickel
-connected 4.82 layers pillared into a novel 3D 3,5-connected self-penetrated (4.6.8)(4.6 8 10) topology
5
3
network by anti-conformation 3-pna ligands. The specific metal coordination environments, fdc binding
mode, and 3-pna conformation act synergistically to enforce structure direction in this system. Thermal
decomposition properties of these three new materials are also discussed.
Ó 2016 Elsevier B.V. All rights reserved.
1
. Introduction
For instance, the interpenetrated 3-D metal-organic framework
0
[
Zn(tp)(bpy)0.5
]
n
(bpy = 4,4 -bipyridine) can act as a gas chromato-
Basic research efforts towards the synthesis and structural char-
graphic stationary phase for the industrially relevant separation of
linear and branched alkanes [13].
acterization of crystalline coordination polymers have continued
unabated over the past decade. These materials can possess diverse
applications in hydrogen storage [1], selective separations [2], ion
exchange [3], heterogeneous catalysis [4], non-linear optics [5],
and explosives residue detection [6]. The near limitless combina-
tion of divalent metal ions, anionic dicarboxylate ligands, and
ancillary neutral dipyridyl ligands continues to spur exploratory
synthetic investigations into coordination polymers. Research has
focused lately on their efficacious properties, but interest remains
in regard to their often strikingly beautiful structural aesthetics [7],
including interpenetrated [8] or self-penetrated frameworks [9].
Some of the most commonly employed linking agents in the
construction of divalent metal coordination polymer or metal-
organic framework solids are terephthalate (tp, p-benzenedicar-
boxylate) or isophthalate (ip, m-benzenedicarboxylate), which
can provide the requisite charge neutrality and also the rigidity
needed for a stable crystalline phase [10–14]. Structural diversity
and functional properties can be enhanced through the inclusion
of other neutral co-ligands, such as dipyridines or bisimidazoles.
Compared to terephthalate and isophthalate, the related five-
membered aromatic derivative 2,5-furandicarboxylate (fdc,
Scheme 1) has seen relatively infrequent use in the self-assembly
of coordination polymers [15–19]. Recent work by Sen and Lin
showed that auxiliary dipyridyl ligands such as 1,2-bis(4-pyridyl)
ethylene (bpe) and 1,2-bis(4-pyridyl)ethane (bpee) could produce
intriguing twofold interpenetrated uninodal 7-connected networks
3
13 4
with 3 4 5 6 topology, in both [Ni(fdc)(bpe)]
n
and [Ni(fdc)
(bpee)] . These materials and their isostructural cobalt derivatives
n
all showed modest uptake of nitrogen gas [15]. Sen and Lin also
prepared a series of cadmium coordination polymers containing
fdc and various auxiliary dipyridyl ligands, in which {[Cd(fdc)
(bpy)(H
system of interlocked square nanotubes, while [Cd(fdc)(bpe)
(H O)] exhibited a 1D + 1D ? 3D system of interwoven ribbon
motifs [16].
Coordination polymers containing the fdc ligand and the
2
2 3 2 n
O) ]ꢀCH CH OH} manifested an intriguing 1D + 1D ? 2D
2
n
dipyridylamide 3-pyridylnicotinamide (3-pna) have not yet been
reported. In contrast to the well-used rigid-rod bpy ligand, 3-pna
can adopt syn or anti conformations (Scheme 1), resulting in differ-
⇑
Corresponding author at: Lyman Briggs College, E-30 Holmes Hall, 919 East
Shaw Lane, Michigan State University, East Lansing, MI 48825, USA.
ent metal-metal linkage distances. [Zn(ip)(3-pna)]
n
possessed
2
2 7
{
Zn (OCO) } dimer-based [Zn(ip)] chains linked into (4 6)(4 6 8)
2
2
n
E-mail address: laduca@msu.edu (R.L. LaDuca).
http://dx.doi.org/10.1016/j.ica.2016.07.026
0
020-1693/Ó 2016 Elsevier B.V. All rights reserved.

1
72
C.L. White, R.L. LaDuca / Inorganica Chimica Acta 451 (2016) 171–176
Thermogravimetric Analyzer with a heating rate of 10 °C/min up to
00 °C.
6
2 2 2
2.2. Preparation of {[Cd (fdc) (3-pna)(H O)
4 2 n
]ꢀ6H O} (1)
Cd(NO (115 mg, 0.38 mmol), 2,5-furandicarboxylic
3
)
2 2
ꢀ4H O
acid (59 mg, 0.38 mmol) and 3-pna (75 mg, 0.39 mmol) and
.0 mL of a 1.0 M NaOH solution were placed into 10 mL distilled
O in a Teflon-lined acid digestion bomb. The bomb was sealed
1
H
2
and heated in an oven at 150 °C for 4 d, and then cooled slowly
to 25 °C. Colorless crystals of 1 (116 mg, 67% yield based on Cd)
were isolated after washing with distilled water and acetone, and
Scheme 1. Ligands used in this study.
2 3
drying in air. Anal. Calc. for C23H34Cd N O21 1: C, 30.25; H, 3.75;
ꢁ1
N, 4.60%. Found: C, 29.98; H, 3.41; N, 4.41%. IR (cm ): 3198 (m),
1677 (w), 1579 (s), 1552 (s), 1489 (m), 1429 (w), 1359 (s), 1337
(w), 1306 (m), 1218 (w), 1197 (m), 1127 (w), 1031 (m), 1012
(m), 968 (m), 897 (w), 830 (m), 801 (m), 782 (s), 699 (s).
3
,5L2 topology layers by anti-conformation 3-pna ligands [20].
However, {[Zn(mip)(3-pna)]ꢀ2H O} (mip = 5-methylisophthalate)
featured syn conformation 3-pna ligands, and thereby formed
2
n
3
2
rarely encountered 4-connected 1-D ribbon motifs with 3 4 5
topology and encapsulated single-file water molecule chains
within its incipient tubular channels [20]. In this contribution we
report the synthesis, single-crystal structures, and thermal proper-
ties of the first reported coordination polymers to contain both the
2.3. Preparation of {[Ni(fdc)(3-pna) (H O)]ꢀ2.5H O} (2)
2
2
2
n
Ni(NO ) ꢀ6H O (110 mg, 0.38 mmol), 2,5-furandicarboxylic acid
3
2
2
(60 mg, 0.38 mmol) and 3-pna (146 mg, 0.76 mmol) and 1.0 mL of
fdc and 3-pna ligands: {[Cd
fdc)(3-pna) (H O}
O)]ꢀ2.5H
2
(fdc)
2
(3pna)(H
2
O)
4
]ꢀ6H
2
O}
n
(1), {[Ni
O)] (3).
a 1.0 M NaOH solution were placed into 10 mL distilled H O in a
Teflon-lined acid digestion bomb. The bomb was sealed and heated
in an oven at 120 °C for 2 d, and then cooled slowly to 25 °C. Green-
blue crystals of 2 (132 mg, 51% yield based on Ni) were isolated
after washing with distilled water and acetone, and drying in air.
2
(
2
2
2
n
(2), and [Co(fdc)(3-pna)(H
2
n
2
. Experimental section
.1. General considerations
Metal nitrates (Fisher) and 2,5-furandicarboxylic acid (TCI
2
27 6
Anal. Calc. for C28H N NiO10.5 2: C, 49.88; H, 4.04; N, 12.47%.
ꢁ1
Found: C, 49.51; H, 3.93; N, 12.31%. IR (cm ): 3259 (w), 1666
(m), 1587 (m), 1543 (m), 1478 (m), 1431 (w), 1420 (s), 1389 (w),
1358 (s), 1328 (s), 1293 (s), 1190 (m), 1119 (m), 1046 (m), 1032
(m), 962 (w), 901 (m), 785 (s), 730 (w), 696 (s).
America) were purchased commercially. The 3-pna ligand was pre-
pared via condensation of nicotinoyl chloride hydrochloride and
one molar equivalent of 3-pyridylamine in dry pyridine solvent,
in a manner similar to that used for the preparation of 4-
2 n
2.4. Preparation of [Co(fdc)(3-pna)(H O)] (3)
pyridylisonicotinamide [21]. Water was deionized above 3 MX-
cm in-house. IR spectra were recorded on powdered samples using
a Perkin Elmer Spectrum One instrument. Thermogravimetric anal-
Co(NO
3
)
2
ꢀ6H
2
O (108 mg, 0.38 mmol), 2,5-furandicarboxylic acid
(60 mg, 0.38 mmol) and 3-pna (75 mg, 0.39 mmol) and 0.75 mL of
ysis was performed under flowing N
2
on a TA Instruments TGA Q50
2
a 1.0 M NaOH solution were placed into 10 mL distilled H O in a
Table 1
Crystal and structure refinement data for 1–3.
Data
1
2
3
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
23
H
34Cd
2
N
3
O
21
C
28
H
27
N
6
NiO10.5
C
17
H
13CoN
3 7
O
913.33
Triclinic
P1ꢀ
8.9382(5)
9.9664(6)
674.26
Monoclinic
P2 /c
10.4593(13)
28.321(4)
430.23
Monoclinic
C2/c
21.984(2)
10.0481(8)
1
b (Å)
c (Å)
10.0591(6)
74.8476(6)
83.3062(6)
66.2266(6)
791.47(8)
1
10.8203(14)
90
113.1484(14)
90
2947.1(6)
4
1.520
0.729
14.7669(12)
90
90.5741(17)
90
3261.9(5)
8
1.752
a
(°)
b (°)
(°)
c
3
V (Å )
Z
D
calc (g cmꢁ3)
1.916
1.439
ꢁ
1
l
(mm
)
1.104
Min./max. trans.
hkl ranges
Total reflections
Unique reflections
R(int)
0.8906
0.8875
0.8834
ꢁ11 6 h 6 11, ꢁ12 6 k 6 12, ꢁ12 6 l 6 12
ꢁ12 6 h 6 12, ꢁ34 6 k 6 34, ꢁ13 6 l 6 13
ꢁ26 6 h 6 26, ꢁ12 6 k 6 12, ꢁ17 6 l 6 17
13,984
3125
0.0386
255
47,814
5403
0.0612
437
12,780
2973
0.0343
260
Parameters
R
R
wR
wR
1
(all data)
(I > 2 (I))
(all data)
(I > 2 (I))
0.0324
0.0279
0.0652
0.0624
1.008/ꢁ0.431
1.065
0.1293
0.1198
0.2450
0.2414
1.411/ꢁ1.195
1.285
0.0449
0.0383
0.0961
0.0919
0.544/ꢁ0.544
1.068
1
r
2
2
r
ꢁ
3
Max/min residual (e /Å )
G.O.F.

C.L. White, R.L. LaDuca / Inorganica Chimica Acta 451 (2016) 171–176
173
Fig. 1. (a) Coordination environment of 1, with thermal ellipsoids at 50% probability and partial atom numbering scheme. The symmetry codes are as in Table 2. (b)
Cd (fdc) (3-pna)(H O) 1D ladder-like coordination polymer pattern in 1. (c) Supramolecular slab motif in 1. Hydrogen bonding patterns between bound water molecules
[
2
2
2
4 n
]
and fdc carboxylate oxygen atoms are shown as dashed lines.
Table 2
Teflon-lined acid digestion bomb. The bomb was sealed and heated
in an oven at 120 °C for 2 d, and then cooled slowly to 25 °C. Pink
crystals of 3 (80 mg, 49% yield based on Co) were isolated after
washing with distilled water and acetone, and drying in air. Anal.
Selected bond distance (Å) and angle (°) data for 1.
O3–Cd1–O7#1
Cd1–O2
Cd1–O5
Cd1–O3
Cd1–O4
2.606(2)
2.324(2)
2.289(2)
2.277(2)
2.319(2)
2.430(2)
2.429(2)
89.33(7)
95.63(7)
84.67(7)
52.96(7)
91.11(7)
137.85(8)
138.37(7)
86.14(7)
89.65(8)
177.91(8)
89.74(8)
92.75(9)
84.99(8)
97.30(8)
84.97(8)
85.34(8)
83.71(8)
134.97(8)
167.22(7)
138.57(7)
53.89(7)
O4–Cd1–O2
O4–Cd1–O5
O4–Cd1–O3
O4–Cd1–N1
Calc. for C17
H
13CoN
3
O
7
3: C, 47.45; H, 3.05; N, 9.77%. Found: C,
ꢁ1
4
7.09; H, 3.16; N, 9.62%. IR (cm ): 3271 (w), 1675 (s), 1614 (m),
Cd1–N1
Cd1–O6#
1
#1
#1
1547 (s), 1489 (m), 1472 (w), 1401 (m), 1353 (s), 1334 (s), 1299
(m), 1224 (w), 1196 (m), 1113 (w), 1032 (w), 1014 (s), 972 (m),
898 (w), 803 (s), 781 (s), 699 (s).
O4–Cd1–O6
O4–Cd1–O7
N1–Cd1–O2
N1–Cd1–O5
N1–Cd1–O6
N1–Cd1–O7
Cd1–O7#1
O5–Cd1–O2
O5–Cd1–O6
#1
O5–Cd1–O7#1
O3–Cd1–O2
O3–Cd1–O5
#1
#
1
3. X-ray crystallography
#1
O6 –Cd1–O2
#1
O3–Cd1–N1
O7 –Cd1–O2
O3–Cd1–O6#1
#1
#1
Single crystal X-ray diffraction on crystals of 1–3 was
performed using a Bruker-AXS ApexII CCD instrument at 173 K.
Reflection data were acquired using graphite–monochromated
O7 –Cd1–O6
Symmetry transformations: #1 x, y, z + 1.
Fig. 2. (a) Distorted {NiO
Table 3. (b) Face on view of the [Ni(fdc)(3-pna)
3
N
3
} coordination octahedron in 2, with thermal ellipsoids at 50% probability and partial atom numbering scheme. The symmetry codes are as in
(H O)] coordination polymer layer in 2. The tethering pna-A and monodentate pna-B ligands are drawn in blue and green,
2
2
n
respectively, in the online version of this article. (c) Side on view of the layer motif in 2, showing hydrogen bonding between the unligated pna-B pyridyl nitrogen atoms and
the aqua ligands. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

1
74
C.L. White, R.L. LaDuca / Inorganica Chimica Acta 451 (2016) 171–176
Table 3
Selected bond distance (Å) and angle (°) data for 2.
Ni1–O5
2.019(5)
2.059(5)
2.055(6)
2.124(8)
2.125(6)
2.113(8)
172.1(2)
97.6(2)
O6#1–Ni1–N1
87.8(3)
85.5(2)
92.5(3)
89.1(2)
90.2(3)
173.9(2)
89.3(3)
92.4(3)
179.4(3)
88.2(3)
Ni1–O6#1
Ni1–O7
O6 –Ni1–N4
#1
#1
#2
O6 –Ni1–N6
O7–Ni1–O6#
O7–Ni1–N1
O7–Ni1–N4
1
Ni1–N1
Ni1–N4
Ni1–N6#2
O5–Ni1–O6#1
O5–Ni1–O7
O5–Ni1–N1
O5–Ni1–N4
O5–Ni1–N6#2
#2
O7–Ni1–N6
N1–Ni1–N4
#2
87.9(3)
88.1(2)
91.8(3)
N6 –Ni1–N1
#2
N6 –Ni1–N4
Symmetry transformations: #1 x, y, z + 1; #2 x ꢁ 1, y, z.
Mo-K
a radiation (k = 0.71073 Å). The data was integrated via SAINT
Fig. 4. Distorted {CoO
0% probability and partial atom numbering scheme. The symmetry codes are as in
Table 4.
4 2
N } coordination octahedron in 3, with thermal ellipsoids at
[
22]. Lorentz and polarization effect and empirical absorption cor-
5
rections were applied with SADABS [23]. The structures were solved
using direct methods and refined on F using SHELXTL [24] within the
2
OLEX2 crystallographic software suite [25]. All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were placed
in calculated positions and refined isotropically with a riding
model. The amide groups within the 3-pna ligands in 1 and 3 were
disordered over two sets of positions and refined satisfactorily
with partial occupancies. Relevant crystallographic data for 1–3
are listed in Table 1.
amide moiety is disordered across a crystallographic inversion cen-
ter, two bound water molecules, and three unbound water mole-
cules. The coordination environment around cadmium is
a
{CdO N} pentagonal bipyramid (Fig. 1a), with the axial positions
6
filled by the bound water molecules. In the equatorial plane are
located chelating carboxylate groups from two fdc ligands, and a
3
-pna pyridyl nitrogen donor atom. Bond lengths and angles
within the coordination environment are listed in Table 2.
Bis(chelating) fdc ligands connect cadmium atoms into [Cd(fdc)
4
. Results and Discussion
(
H
2
O)
2
]
n
chain submotifs, with a Cdꢀ ꢀ ꢀCd distance of 10.0591(7) Å,
4
.1. Synthesis and Spectral Characterization
which marks the c lattice parameter. In turn the chain submotifs
are bridged by tethering anti-conformation 3-pna ligands
(
(
Compounds 1–3 were prepared by hydrothermal reaction of the
Nꢀ ꢀ ꢀCꢀ ꢀ ꢀCꢀ ꢀ ꢀN torsion angle = 180°) to form [Cd
2 2
(fdc) (3-pna)
requisite metal nitrate, 2,5-furandicarboxylic acid, and 3-pna. Their
infrared spectra were consistent with structural components
determined by single-crystal X-ray diffraction. Intense, slightly
broadened asymmetric and symmetric carboxylate CAO stretching
bands for the dicarboxylate ligands were observed at 1579 and
H
2
4 n
O) ] 1D ladder-like coordination polymer patterns (Fig. 1b).
The dipyridylamide ligands form the rungs of the ladder, with a
Cdꢀ ꢀ ꢀCd distance of 11.669(4) Å. Adjacent ladder motifs aggregate
by means of hydrogen bonding donation between aqua ligands
and bound fdc carboxylate oxygen atoms (Table S1), thereby form-
ing supramolecular slabs aligned along the ac crystal planes
(Fig. 1c). Additional hydrogen bonding patterns involving the aqua
ligands and other fdc carboxylate oxygen atoms provide the
supramolecular impetus for stacking of the slab motifs (Fig. S1).
Discrete chains of three unbound water molecules with D(3) clas-
sification [26] also play an ancillary structure-directing role.
ꢁ
ꢁ
1
1
ꢁ1
1
1
359 cm
for 1, 1543 and 1358 cm
for 2, and 1547 and
353 cm for 3. Sharp and medium intensity bands in the range
ꢁ
1
ꢁ1
of ꢂ1600 cm to ꢂ1300 cm were attributed to stretching mode
of the pyridyl rings of the dipyridylamide ligands and the fdc furan
rings in 1–3. Broad weak spectral bands in the vicinity of
ꢂ3000 cm to ꢂ3500 cm indicate the presence of NAH bonds
within the dipyridylamide ligands and any bound or unbound
water molecules in 1–3. The C@O stretching band of the carbonyl
ꢁ1
ꢁ1
ꢁ
1
groups of the 3-pna ligands in are seen at 1677 cm
1
(for 1),
4.3. Structural description of {[Ni(fdc)(3-pna) (H O)]ꢀ2.5H O} (2)
2
2
2
n
ꢁ1
ꢁ1
666 cm (for 2), and 1675 cm (for 3).
The asymmetric unit of compound 2 contains a divalent nickel
4
.2. Structural Description of {[Cd
2
(fdc)
2
(3-pna)(H
2
O)
4
]ꢀ6H
2
O}
n
(1)
atom, an fdc ligand, two crystallographically distinct 3-pna ligands
(
pna-A, pna-B), an aqua ligand, and net two and one half water
molecules of crystallization. A distorted {NiO } coordination
octahedron is evident at nickel, with a mer arrangement of oxygen
The asymmetric unit of compound 1 contains a divalent cad-
3
N
3
mium atom, an fdc ligand, half of a 3-pna ligand whose central
Fig. 3. (a) Schematic perspective of the (3,6) triangular net of 2, including the pna-B mediated hydrogen bonding patterns as connectors. (b) Schematic perspective of the (4,4)
rhomboid net of 2, considering only fdc and pna-A ligands as connectors. In both graphics, the spheres represent the nickel atoms.

C.L. White, R.L. LaDuca / Inorganica Chimica Acta 451 (2016) 171–176
175
Table 4
Niꢀ ꢀ ꢀNi distance of 10.459(2) Å, about 1.2 Å shorter than the
metal-metal distance connected by the anti-conformation 3-pna
ligands in 1. This distance marks the a lattice parameter. Pendant,
monodentate syn-conformation pna-B ligands (Nꢀ ꢀ ꢀCꢀ ꢀ ꢀCꢀ ꢀ ꢀN tor-
sion angle = 19.7°) project off of one side of the layer motif (Fig. 2c),
with the 3-pyridylamine side of the ligand remaining unligated.
The even more extreme syn conformation of the pna-B monoden-
tate ligands places the unbound pyridyl nitrogen donor atom
directly in position to accept hydrogen bonding from the aqua
ligands (Table S1). If this hydrogen bonding interaction within
Selected bond distance (Å) and angle (°) data for 3.
Co1–O3
2.1072(17)
2.0509(17)
2.1238(18)
2.0823(18)
2.192(2)
2.232(2)
87.30(7)
89.41(8)
91.70(7)
O5#1–Co1–O7#2
93.01(7)
91.29(8)
87.61(8)
92.93(8)
86.57(8)
85.31(7)
170.57(7)
92.85(7)
87.79(8)
178.75(8)
Co1–O5#1
Co1–O6
O5 –Co1–N1
O5 –Co1–N3
O6–Co1–N1
#1
#1
#3
Co1–O7#2
#
3
Co1–N1
O6–Co1–N3
Co1–N3#3
#2
O7 –Co1–O3
O7 –Co1–O6
O7 –Co1–N1
#2
O3–Co1–O6
O3–Co1–N1
O3–Co1–N3
#2
#3
#2
#3
O7 –Co1–N3
#1
#3
O5 –Co1–O3
178.21(7)
94.30(7)
N1–Co1–N3
#1
the full [Ni(fdc)(3-pna)
treated as a connecting linker, the topology becomes that of a
-connected (3,6) triangular lattice (Fig. 3a). If only the fdc and
pna-A ligands are considered connectors, then the topology is that
of a standard (4,4) grid (Fig. 3b). Adjacent [Ni(fdc)(3-pna) (H O)]
n
2 2 n
(H O)] coordination polymer layer is
O5 –Co1–O6
Symmetry transformations: #1 ꢁx + 1/2, y ꢁ 1/2, ꢁz + 3/2; #2 x, ꢁy + 1, z + 1/2; #3
x + 1/2, y ꢁ 1/2, z.
6
2
2
donor atoms (Fig. 2a). Two of these ligated oxygen atoms are pro-
vided by carboxylate groups from two fdc ligands in a trans fash-
ion, with the third being the bound water molecule. Pyridyl
nitrogen donor atoms from two pna-A ligands rest in cis positions,
with the coordination sphere rounded out by a pyridyl nitrogen
donor atom from a pna-B ligand. Bond lengths and angles within
the octahedral coordination environment are listed in Table 3.
Bis(monodentate) fdc ligands connect nickel atoms into
coordination polymer layers stack along the b crystal direction in
an ABCD pattern (Fig. S2), mediated by water molecules of crystal-
lization that are bound to pna-A C@O amide groups in neighboring
layers. The disordered water molecules of crystallization are
located within the interlamellar regions.
4.4. Structural description of [Co(fdc)(3-pna)(H O)] (3)
2
n
[
Ni(fdc)(H
with a Niꢀ ꢀ ꢀNi distance of 10.820(3) Å. These are pillared into
Ni(fdc)(3-pna)(H O)] coordination polymer grids parallel to the
ac crystal planes (Fig. 2b) by twisted syn-conformation 3-pna
pna-A) ligands (Nꢀ ꢀ ꢀCꢀ ꢀ ꢀCꢀ ꢀ ꢀN torsion angle = 59.3°), that span a
2
O)]
n
chains oriented parallel to the c crystal direction,
The asymmetric unit of compound 3 contains a divalent cobalt
atom, an fdc ligand, a 3-pna ligand, and a bound water molecule.
There are no unligated species in 3. Although the coordination
environment is octahedral, as seen in the nickel derivative 2, the
arrangement of donors is different. Here in 3, the environment is
[
2
n
(
2 n
O)]
coordination polymer layer motif in 3. (b) Schematic perspective of the 4.82 layer formed by 3-connected cobalt atoms and exotridentate fdc
Fig. 5. (a) [Co(fdc)(H
ligands, which are represented by the large and small spheres, respectively.
5
3
Fig. 6. (a) 3D [Co(fdc)(3-pna)(H
the online version of this article, the [Co(fdc)(H
For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
2
O)]
n
network motif in 3. (b) Schematic perspective of the self-penetrated (4.6.8)(4.6 8 10) topology 3,5-connected binodal network in 3. In
2
O)] coordination polymer layer motifs are shown in red, and the anti-conformation 3-pna ligands represented as blue rods.
n
(

1
76
C.L. White, R.L. LaDuca / Inorganica Chimica Acta 451 (2016) 171–176
a distorted {CoO
4
N
2
} octahedron, with pyridyl nitrogen donor
3-pna ligands in the nickel derivative are ligated in a cis fashion,
resulting in a layered topology. Meanwhile, in the cobalt analog,
the anti-conformation 3-pna ligands in the cobalt derivative are
bound in a trans disposition. As a result, an intriguing self-pene-
trated 3-D topology comprising pillared metal dicarboxylate slab
motifs is observed.
atoms from two 3-pna ligands in trans positions (Fig. 4). The nom-
inal equatorial plane is comprised of single carboxylate oxygen
donor atoms from three fdc ligands, and the ligated water mole-
cule. Bond lengths and angles within the octahedral coordination
environment at cobalt are listed in Table 4.
The fdc ligands in 3, in contrast to those in 1 and 2, adopt an
exotridentate binding mode, with one carboxylate group bridging
two cobalt atoms in an anti-syn fashion, and the other serving as
a simple monodentate donor. Pairs of bridging carboxylate groups
Acknowledgments
C.L.W. thanks the Lyman Briggs College (MSU) Undergraduate
Research Fellowship Program for funding her participation in this
work. We thank Ms Cassi LaRose for obtaining the analytical data
for the compounds under study.
form {Co
Å. These are connected to other dimeric units by the other fdc car-
boxylate termini into [Co(fdc)(H O)] coordination polymer layer
2 2
(OCO) } dimeric units with a Coꢀ ꢀ ꢀCo distance of 4.832(2)
2
n
motifs (Fig. 5a). Within this layer, both the cobalt atoms and the
exotridentate fdc ligands can be considered 3-connected nodes.
The resulting layer topology is that of a 4.82 net featuring 4- and
Appendix A. Supplementary data
8
-membered circuits (Fig. 5b).
Adjacent [Co(fdc)(H O)] slab motifs are pillared by twisted
anti-conformation 3-pna
angle = 151.3°) to form a neutral 3D [Co(fdc)(3-pna)(H
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ica.2016.07.026.
2
n
ligands
(Nꢀ ꢀ ꢀCꢀ ꢀ ꢀCꢀ ꢀ ꢀN
O)]
torsion
n
coordi-
2
nation polymer network (Fig. 6a). The through-ligand Coꢀ ꢀ ꢀCo dis-
References
tance across the full span of the dipyridylamide component is
[
1] (a) L.J. Murray, M. Dinca, J.R. Long, Chem. Soc. Rev. 38 (2009) 1294;
b) S.S. Han, J.L. Mendoza-Cortes, W.A. Goddard, Chem. Soc. Rev. 38 (2009)
460.
[2] J.R. Li, R.J. Kuppler, H.C. Zhou, Chem. Soc. Rev. 38 (2009) 1447.
1
2.086(1) Å, over 1.5 Å longer than that seen in the nickel congener
(
1
2
that contained syn-conformation 3-pna ligand tethers. Including
the 3-pna ligands results in each cobalt atom becoming a 5-con-
nected node. Thus, the overall Schlafli symbol for the 3,5-con-
[
3] (a) Q.R. Fang, G.S. Zhu, M. Xue, J.Y. Sun, S.L. Qiu, Dalton Trans. (2006) 2399;
b) X.M. Zhang, M.L. Tong, H.K. Lee, X.M. Chen, J. Solid State Chem. 160 (2001)
18;
(
1
5
3
nected net in 3 is (4.6.8)(4.6 8 10) according to TOPOS [27], with
self-penetration of the anti-conformation 3-pna tethers through
(c) O.M. Yaghi, H. Li, T.L. Groy, Inorg. Chem. 36 (1997) 4292.
4] (a) J. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Chem. Soc.
Rev. 38 (2009) 1450;
[
2 n
the windows within the [Co(fdc)(H O)] slab motifs.
(
b) L. Ma, C. Abney, W. Lin, Chem. Soc. Rev. 38 (2009) 1248.
4
.5. Thermogravimetric analysis
[5] O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511.
6] (a) S.S. Nagarkar, B. Joarder, A.K. Chaudhari, S. Mukherjee, S.K. Ghosh, Angew.
Chem., Int. Ed. 52 (2013) 2881;
[
Thermogravimetric analyses were carried out on compounds
–3 to investigate their degradation behavior. For compound 1,
(
b) G. Liu, Y. Qin, L. Jing, G. Wei, H. Li, Chem. Commun. 49 (2013) 1699.
1
[7] V.A. Blatov, L. Carlucci, G. Ciani, D.M. Proserpio, CrystEngComm 6 (2004) 377.
[8] L. Carlucci, G. Ciani, D.M. Proserpio, Coord. Chem. Rev. 246 (2003) 247.
9] X. Ke, D. Li, M. Du, Inorg. Chem. Commun. 14 (2011) 788.
10] W. Yuan, F. Xiong, H. Zhang, W. Tang, S. Zhang, Z. He, L. Jing, D. Qin,
CrystEngComm 16 (2014) 7701.
ejection of the bound water molecules occurred between ꢂ150
and ꢂ300 °C, with a mass loss of 6.5% corresponding roughly to
the predicted value of 7.9%. All of the water of crystallization was
apparently released upon standing at room temperature for
ꢂ60 d. Ligand combustion occurred above 300 °C. Dehydration of
compound 2 occurred between ꢂ150 and ꢂ250 °C, with a mass
loss of 6.4% matching closely with the predicted value of 6.7%.
Ligand combustion occurred above 270 °C. For compound 3, a mass
loss of 4.7% between ꢂ125 and ꢂ150 °C indicates removal of the
bound water molecules (4.2% calc’d). Ligand combustion began to
occur above 250 °C. Thermogravimetric analysis plots for 1–3 are
shown in Figs. S3–S5, respectively.
[
[
[11] M.E. Braun, C.D. Steffek, J. Kim, P.G. Rasmussen, O.M. Yaghi, Chem. Commun.
2001) 2532.
(
[
[
12] D.P. Martin, M.A. Braverman, R.L. LaDuca, Cryst. Growth Des. 7 (2007) 2609.
13] B. Chen, C. Liang, J. Yang, D.S. Contreras, Y.L. Clancy, E.B. Lobkovsky, O.M. Yaghi,
S. Dai, Angew. Chem., Int. Ed. 45 (2006) 1390.
[
14] N.H. Murray, E.M. Low, A.L. Pochodylo, R.L. LaDuca, Inorg. Chim. Acta 428
(
2015) 73.
[
15] R. Sen, D. Mal, P. Brandão, G. Rogez, Z. Lin, CrystEngComm 15 (2013) 2113.
[16] R. Sen, D. Mal, P. Brandão, R.A.S. Ferreira, Z. Lin, Cryst. Growth Des. 13 (2013)
272.
5
[
[
[
17] K. Liu, H. Li, X. Zhang, W. Shi, P. Cheng, Inorg. Chem. 54 (2015) 10224.
18] D. Singh, C.M. Nagaraja, Cryst. Growth Des. 15 (2015) 3356.
19] H. Wang, J. Xu, D. Zhang, Q. Chen, R. Wen, Z. Chang, X. Bu, Angew. Chem., Int.
Ed. 54 (2015) 5966.
20] P.E. Kraft, L.E. Weingartz, R.L. LaDuca, Inorg. Chim. Acta 432 (2015) 283.
21] T.S. Gardner, E. Wenis, J.J. Lee, J. Org. Chem. 19 (1954) 753.
5
. Conclusions
[
[
Divalent metal coordination polymers containing 2,5-furandi-
[22] SAINT, Software for Data Extraction and Reduction, Version 6.02; Bruker AXS
Inc: Madison, WI, 2002.
carboxylate and the conformationally flexible dipyridylamide
ligand 3-pyridylnicotinamide (3-pna) show a marked structural
dependence on the metal coordination environment. A pentagonal
bipyramidal geometry in the cadmium derivative resulted in a 1-D
ladder polymer topology, with the anti-conformation 3-pna ligands
acting as the rungs. Although both the nickel and cobalt congeners
exhibit octahedral coordination environments, the different
arrangement of donors results in a significant alteration in coordi-
nation polymer dimensionality. The pillaring anti-conformation
[
23] SADABS, Software for Empirical Absorption Correction. Version 2.03; Bruker
AXS Inc: Madison, WI, 2002.
[24] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
[
[
[
25] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H.J. Puschmann, Acta
Crystallogr. 42 (2009) 42.
26] (a) L. Infantes, S. Motherwell, CrystEngComm 4 (2002) 454;
(b) L. Infantes, J. Chisholm, S. Motherwell, CrystEngComm 5 (2003) 480.
27] V.A. Blatov, A.P. Shevchenko, D.M. Proserpio, Cryst. Growth Des. 14 (2014)
3576. TOPOS software is available for download at: <http://www.topos.ssu.
samara.ru>.