Substituent dependent layer topologies in copper isophthalate coordination polymers containing long-spanning dipyridylamide ligands

Article abstract of DOI:10.1016/j.molstruc.2017.01.049

Hydrothermal reaction of copper nitrate, a 5-position substituted isophthalic acid, and the long-spanning dipyridylamide ligand 1,6-hexanediaminebis(nicotinamide) (hbn) resulted in two new coordination polymers whose layer topologies and interpenetration mechanisms depend critically on the nature of the substituent. The new phases were structurally characterized by single crystal X-ray diffraction. {[Cu(meoip)(hbn)]·H₂O}_n (1, meoip?=?5-methoxyisophthalate) exhibits [Cu(meoip)]_n chain motifs with embedded {Cu₂(OCO)₂} dinuclear units, pillared by pairs of hbn ligands into a decorated (4,4) grid topology. {[Cu₃(sip)₂(hbn)₃(H₂O)₄]·11.5H₂O}_n (2, sip?=?5-sulfoisophthalate) displays neutral [Cu₃(sip)₂(H₂O)₄] fragments connected by hbn ligands into 3,4-connected layer motifs with a {4.6²}₂{4²6²8²} topology, derived from the standard (4,4) grid with regular removal of some pillars. The layer motifs in 2 engage in 2D?+?2D?→?3D parallel interpenetration, with entrained co-crystallized water molecule tapes. Thermal decomposition behavior of the new phases is also discussed.

Full text of DOI:10.1016/j.molstruc.2017.01.049

Journal of Molecular Structure 1135 (2017) 67e74
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Substituent dependent layer topologies in copper isophthalate
coordination polymers containing long-spanning dipyridylamide
ligands
Renee K. Randolph, 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:
Hydrothermal reaction of copper nitrate, a 5-position substituted isophthalic acid, and the long-spanning
dipyridylamide ligand 1,6-hexanediaminebis(nicotinamide) (hbn) resulted in two new coordination
polymers whose layer topologies and interpenetration mechanisms depend critically on the nature of the
substituent. The new phases were structurally characterized by single crystal X-ray diffraction.
{[Cu(meoip)(hbn)]$H2O}n (1, meoip ¼ 5-methoxyisophthalate) exhibits [Cu(meoip)]n chain motifs with
embedded {Cu2(OCO)2} dinuclear units, pillared by pairs of hbn ligands into a decorated (4,4) grid to-
Received 15 November 2016
Received in revised form
14 January 2017
Accepted 18 January 2017
Available online 19 January 2017
pology. {[Cu3(sip)2(hbn)3(H2O)4]$11.5H2O}n (2, sip
¼
5-sulfoisophthalate) displays neutral [Cu3(si-
Keywords:
p)2(H2O)4] fragments connected by hbn ligands into 3,4-connected layer motifs with a {4.62}2{426282}
topology, derived from the standard (4,4) grid with regular removal of some pillars. The layer motifs in 2
engage in 2D þ 2D / 3D parallel interpenetration, with entrained co-crystallized water molecule tapes.
Thermal decomposition behavior of the new phases is also discussed.
Crystal structure
Coordination polymer
Copper
Layer
Interpenetration
Dipyridylamide
© 2017 Elsevier B.V. All rights reserved.
1. Introduction
workers prepared a series of substituted isophthalate zinc coordi-
nation polymers with pyridine capping ligands [10]; sterically
Exploratory research into the synthesis and property charac-
terization of divalent metal coordination polymers has remained
active for over two decades. This genre of materials has shown
multifunctional properties such as gas storage [1], selective mo-
lecular adsorbing [2], drug-delivery [3], and heterogeneous catal-
ysis [4]. The aesthetic appeal of their underlying molecular
structures and topologies has also spurred continued study [5], in
addition to the general infrequency of a priori structure design [6].
Most reported crystalline coordination polymer solids are based on
aromatic dicarboxylate ligands such as isophthalate (ip) [7] or
terephthalate [8]. Specific coordination environment preferences at
the divalent metal atom, variable carboxylate binding modes, and
the inclusion of dipyridyl-type coligands act synergistically during
self-assembly to influence the final dimensionality and topology of
the final material [9]. One possible means of altering the structural
features of an isophthalate-based coordination polymer is to
employ derivatives with non-ligating or potentially ligating sub-
stituents in the 5-position of the aromatic ring. Yang and co-
bulkier substituents appeared to result in lower coordination
polymer dimensionality. Our group observed a similar trend in
some substituted isophthalate zinc coordination polymers with the
longer-spanning coligand bis(4-pyridylmethyl)piperazine (bpmp)
[11,12]. [Zn(ip)(bpmp)]n showed
a system of five-fold inter-
penetrated diamondoid nets [11], while {[Zn(meoip)(bpmp)]$
8H2O}n (meoip ¼ 5-methoxyisophthalate, Scheme 1) adopted an
undulating (4,4) grid topology [12]. Inclusion of a ligating sulfonate
moiety in the 5-position resulted in {[Zn(sip)(Hbpmp)]$4H2O}n
(sip ¼ 5-sulfoisophthalate, Scheme 1) which displayed a three-fold
interpenetrated binodal lattice with (426)(426583) topology.
Therefore no reduction in dimensionality with respect to the
unsubstituted isophthalate derivative was observed in this case,
although there was a decrease in interpenetration level. A fasci-
nating self-penetrated structure with a 3,5-connected (63)(6783)
topology was observed in {[Co(amip)(4-bpmp)]$3H2O}n (amip ¼ 5-
aminoisophthalate, Scheme 1) [13], showing the versatility of the
amip ligand to serve as an exotridentate donor ligand using both of
its carboxylate termini as well as its amine group. {[Co(nip)(3-
pina)]n
(nip
¼
5-nitroisophthalate,
3-pina
¼
3-
* Corresponding author.
E-mail address: laduca@msu.edu (R.L. LaDuca).
pyridylisonicotinamide) and {[Co(meoip)(3-pina)]n both manifest
http://dx.doi.org/10.1016/j.molstruc.2017.01.049
0022-2860/© 2017 Elsevier B.V. All rights reserved.

68
R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
Scheme 1. Ligands discussed in this study.
a non-interpenetrated dimer-based 3-D pcu network, showing an
invariance to the nature of the substituent in the 5-position of the
isophthalate ring [14]. Utilizing more flexible dipyridyl coligands
has resulted in some intriguing pseudo-rotaxane topologies, for
instance in [Co2(mip)2(dpp)2(H2O)]n (mip ¼ 5-methylisophthalate,
dpp ¼ 1,3-di(4-pyridyl)propane) [15]. We thus attempted to pre-
pare a series of divalent copper coordination polymers containing
5-substituted isophthalate ligands and the even longer spanning
2.2. Preparation of {[Cu(meoip)(hbn)]·H2O}n (1)
Cu(NO3)2$2.5H2O (65 mg, 0.28 mmol), 5-methoxyisophthalic
acid (55 mg, 0.28 mmol), and hbn (91 mg, 0.28 mmol) were
mixed with 0.55 mL of 1.0 M NaOH solution and 10 mL of distilled
H2O in a 23 mL Teflon-lined acid digestion bomb. The bomb was
sealed and heated in an oven at 120 ꢀC for 22 h, and then was cooled
slowly to 25 ꢀC. Blue crystals of 1 (115 mg, 68% yield based on Cu)
were isolated after washing with distilled water, ethanol, and
acetone and drying in air. Anal. Calc. for C27H30CuN4O8 1: C, 53.86;
H, 5.02; N, 9.31% Found: C, 53.41; H, 4.98; N, 9.22%. IR (cmꢁ1): 3334
(w), 3100 (w), 1664 (m), 1648 (m), 1618 (m), 1589 (s), 1573 (s), 1541
(m), 1450 (m), 1417 (m), 1396 (s), 1335 (s), 1193 (m), 1129 (m), 1102
(m), 1055 (m), 919 (m), 881 (m), 835 (m), 788 (m), 779 (s), 724 (s),
698 (s), 656 (s).
and
more
flexible
dipyridylamide
coligand
1,6-
hexanediaminebis(nicotinamide) (hbn). This ligand has infre-
quently been employed in coordination polymer chemistry outside
of some work by Wang and colleagues, who reported the synthesis
of the 3,4-connected layered phase {[Cu(amip)(hbn)(H2O)]$2H2O}n
in 2013 [16], along with a series of cobalt/hbn coordination poly-
mers with substituted isophthalate ligands [17]. In this contribution
we present the single-crystal structures, divergent topological
features, and thermal properties of two new layered copper coor-
dination polymers with hbn and substituted isophthalate ligands:
{[Cu(meoip)(hbn)]$H2O}n (1) and {[Cu3(sip)2(hbn)3(H2O)4]$
11.5H2O}n (2).
2.3. Preparation of {[Cu3(sip)2(hbn)3(H2O)4]·11.5H2O}n (2)
Cu(NO3)2$2.5H2O (65 mg, 0.28 mmol), sodium 5-
sulfoisophthalate (75 mg, 0.28 mmol), and hbn (91 mg,
0.28 mmol) were mixed with 0.55 mL of 1.0 M NaOH solution and
10 mL of distilled H2O in a 23 mL Teflon-lined acid digestion bomb.
The bomb was sealed and heated in an oven at 120 ꢀC for 22 h, and
then was cooled slowly to 25 ꢀC. Blue crystals of 2 (128 mg, 71%
yield based on Cu) were isolated after washing with distilled water,
2. Experimental section
2.1. General considerations
ethanol, and acetone and drying in air. Anal. Calc. for C70H103Cu3
-
N12O35S2 2: C, 43.62; H, 5.39; N, 8.72% Found: C, 43.43; H, 5.09; N,
8.58%. IR (cmꢁ1): 3286 (w), 2923 (w), 1658 (m), 1604 (m), 1541 (s),
1488 (m),1433 (m),1358 (s),1235 (m),1204 (m),1165 (m),1103 (m),
1060 (m), 1034 (s), 997 (m), 837 (m), 774 (m), 738 (s), 696 (s), 681
(s), 658 (s).
Copper nitrate hydrate and 5-methoxyisophthalic acid were
commercially obtained from Sigma Aldrich. Sodium 5-
sulfoisophthalate was purchased from TCI America. 1,6-
hexanediaminebis(nicotinamide) (hbn) was prepared by conden-
sation of 1,6-hexanediamine and two molar equivalents of nic-
otinoyl chloride hydrochloride in dry pyridine. The reaction
mixture was quenched with water, and then the product was iso-
lated via CH2Cl2 extraction and removal of solvent in vacuo [18].
3. X-ray crystallography
Water was deionized above 3M
U
ecm in-house. IR spectra were
Diffraction data for 1 and 2 were collected on a Bruker-AXS
recorded on powdered samples using a Perkin Elmer Spectrum One
DRIFT instrument. Thermogravimetric analysis was performed on a
TA Instruments Q-50 Thermogravimetric Analyzer with a heating
rate of 10 ꢀC/min up to 600 ꢀC. Elemental Analysis was carried out
using a Perkin Elmer 2400 Series II CHNS/O Analyzer.
SMART-CCD X-ray diffractometer using graphite-monochromated
Mo-K
a
radiation (
l
¼ 0.71073 Å) at 173 K. The data were pro-
cessed via SAINT [19], and corrected for both Lorentz and polari-
zation effects and absorption effects using SADABS [20]. The
structures were solved using direct methods with SHELXTL [21]

R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
69
Table 1
4. Results and discussion
Crystal and structure refinement data for 1e2.
4.1. Synthesis and spectra
Data
1
2
Empirical formula
Formula weight
Crystal system
Space group
C27H30CuN4O8
602.09
triclinic
C70H103Cu3N12O35S2
1935.38
triclinic
A crystalline sample of 1 was produced by the hydrothermal
reaction of copper nitrate, the 5-methoxyisophthalic acid, and hbn
in the presence of aqueous base. Compound 2 was prepared by
hydrothermal reaction of copper nitrate, sodium 5-
sulfoisophthalate, and hbn. The infrared spectra of 1 and 2 were
consistent with their structural components as determined by
single-crystal X-ray diffraction. Intense, broad asymmetric and
symmetric CeO stretching bands within the carboxylate ligands
were obsꢁe1rved at 1573 and 1335 cmꢁ1 for 1, and at 1541 and
~1600 cmꢁ1 to ~1300 cmꢁ1 are attributed to the stretching modes
of the pyridyl rings of the hbn ligands [23]. Features corresponding
to CeH bending and ring puckering within the pyridyl moieties
exist in the region between ~900 and ~650 cmꢁ1. Broad, weak
spectral bands in the vicinity of ~3000e3400 cmꢁ1 indicate the
presence of bound and unbound water molecules in the spectrum
of 2. The carbonyl stretching bands the hbn ligands appeared at
1648 cmꢁ1, and 1658 cmꢁ1 respectively for 1 and 2.
P1
P1
a (Å)
b (Å)
c (Å)
10.0276 (10)
10.1545 (10)
14.0842 (14)
90.3293 (13)
90.6441 (12)
109.5318 (11)
1351.4 (2)
2
1.480
0.865
0.9030
ꢁ12 ꢂ h ꢂ 12,
ꢁ12 ꢂ k ꢂ 12,
ꢁ16 ꢂ l ꢂ 16
21818
4937
0.0386
11.3632 (8)
12.6658 (9)
15.9665 (12)
97.7157 (8)
90.9055 (8)
108.7680 (8)
2151.8 (3)
1
1.494
0.877
0.9471
ꢁ13 ꢂ h ꢂ 13,
ꢁ15 ꢂ k ꢂ 15,
ꢁ19 ꢂ l ꢂ 19,
35739
7901
0.0352
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
V (Å3)
Z
D (g cmꢁ3
m
)
1358 cm
for 2. Moderate intensity bands in the range of
(mmꢁ1
)
Min./max. transmission
hkl ranges
Total reflections
Unique reflections
R(int)
Parameters
R1 (all data)
327
0.0627
582
0.0547
R1 (I > 2
s(I))
0.0539
0.0456
4.2. Structural description of {[Cu(meoip)(hbn)]·H2O}n (1)
wR2 (all data)
0.1466
0.1411
0.981/e1.028
1.057
0.1305
0.1222
1.179/e0.521
1.056
wR2 (I > 2
s(I))
Max/min residual (ee/Å3)
G.O.F.
The asymmetric unit of compound 1 contains a divalent copper
atom, a fully deprotonated meoip ligand, an hbn ligand whose
central aliphatic chain is disordered over two positions in a 75:25
ratio, and one water molecule of crystallization. A very distorted
{CuN2O3} trigonal bipyramidal coordination environment is
within the OLEX2 crystallographic software suite [22]. All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms
were placed in calculated positions and refined isotropically with a
riding model. Crystallographic details for 1 and 2 are given in
Table 1.
observed at copper (Fig. 1a), with a
t value of 0.55 [24]. Pyridyl
nitrogen donor atoms from two hbn ligands are located in the
nominal axial positions of the trigonal bipyramid. Equatorial posi-
tions are taken up by single carboxylate oxygen atom donors from
Fig. 1. a) Coordination environment in 1. Thermal ellipsoids are depicted at 50% probability. Symmetry codes are as in Table 2. b) [Cu(meoip)]n chain motif in 1, showing syn-skew
bridged {Cu2(OCO)2} dinuclear units.

70
R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
Table 2
three different meoip ligands. Bond lengths and angles within the
coordination sphere are listed in Table 1.
Selected bond distance (Å) and angle (ꢀ) data for 1.
Exotridentate meoip ligands with a m3-
k3-O:O00:O000 binding
Cu1eO1
1.964 (3)
2.226 (3)
2.077 (2)
2.002 (3)
2.010 (3)
124.48 (10)
146.20 (10)
89.13 (12)
O1eCu1eN4#3
O3#2eCu1eO2#1
N1eCu1eO2#1
N1eCu1eO3#2
N1eCu1eN4#3
N4#3eCu1eO2#1
N4#3eCu1eO3#2
90.56 (12)
89.31 (10)
92.34 (12)
88.24 (11)
179.36 (12)
88.29 (12)
91.70 (11)
Cu1eO2#1
Cu1eO3#2
Cu1eN1
mode connect copper ions into [Cu(meoip)]n neutral coordination
polymer ribbon motifs (Fig. 1b), with the bridging carboxylate
termini constructing {Cu2(OCO)2} dimeric units with a Cu/Cu
internuclear distance of 4.158(2) Å. The full span of the meoip li-
gands thereby connects the dimeric units to form the [Cu(meoip)]n
neutral chains, at an interdimer Cu/Cu distance of 7.654(4) Å. The
[Cu(meoip)]n chain motifs are oriented parallel to the a crystal di-
rection, and are pillared into [Cu(meoip)(hbn)]n coordination
polymer layers by the long-spanning hbn ligands (Fig. 2). The
dipyridylamide ligands span an internuclear Cu/Cu distance of
18.41(1) Å; the central six-carbon aliphatic chain in the major
disorder component has a gauche-anti-anti conformation (four-
atom torsion angles ¼ 69.4, 175.8, and 172.7ꢀ). If the {Cu2(OCO)2}
dimeric units are considered to be 4-connected nodes, the under-
lying topology of the [Cu(meoip)(hbn)]n layers is that of a (4,4)
rectangular grid. Isolated water molecules of crystallization are
held within the layer motifs by engaging in hydrogen bonding
donation to ligated meoip carboxylate oxygen atoms, and hydrogen
bonding acceptance from hbn amide groups (Table 2). Adjacent
[Cu(meoip)(hbn)]n layers are oriented parallel to the (0 1 1) crystal
planes, stacking by means of non-classical CeH/O interactions
between hbn pyridyl nitrogen atoms and hbn carbonyl groups in
neighboring layers (Fig. S1).
Cu1eN4#3
O1eCu1eO2#1
O1eCu1eO3#2
O1eCu1eN1
Symmetry transformations: #1 ꢁx þ 2, ꢁy þ 1, ꢁz; #2 xꢁ1, y, z; #3 x þ 1, y þ 1, zꢁ1.
4.3. Structural description of {[Cu3(sip)2(hbn)3(H2O)4]·11.5H2O}n
(2)
The asymmetric unit of compound 2 consists of a copper atom
on a crystallographic inversion center (Cu1), a general position
copper atom (Cu2), one trianionic sip ligand, a full hbn ligand (hbn-
A), half of another hbn ligand (hbn-B) whose central CeC
s bond is
located over another crystallographic inversion center, two aqua
ligands, and net five and three-quarters water molecules of crys-
tallization. Two distinct coordination environments are observed in
2 (Fig. 3a). The Cu1 atoms are coordinated in a {CuN2O2} square
planar fashion by trans carboxylate oxygen atom donors from two
sip ligands, and trans pyridyl nitrogen atom donors from two hbn-A
ligands. In contrast the Cu2 atoms adopt a very distorted {CuN2O3}
square pyramidal coordination environment (
t
¼ 0.32). Its basal
Fig. 2. {[Cu(meoip)(hbn)] coordination polymer layer motif in 1. [Cu(meoip)]n chain motifs are drawn in red in the online version of this article. (For interpretation of the ref-
n
erences to colour in this figure legend, the reader is referred to the web version of this article.)

R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
71
Fig. 3. a) Coordination environments in 2. Thermal ellipsoids are depicted at 50% probability. Symmetry codes are as in Table 4. b) [Cu3(sip)2(H2O)4] fragment in 2.
plane contains trans pyridyl nitrogen donor atoms from hbn-A and
hbn-B ligands, along with an sip carboxylate oxygen atom and a
bound water molecule in trans positions. The elongated apical po-
sition is filled by another bound water molecule. The sulfonate
moiety of the sip ligands does not ligate to copper in 2. Bond
lengths and angles within the disparate coordination environments
are listed in Table 3.
The Cu1 atoms on special positions are connected to two Cu2
atoms by pairs of bis(monodentate) sip ligands to construct neutral
[Cu3(sip)2(H2O)4] coordination fragments with a Cu/Cu distance
angles ¼ 76.4, 175.8, 71.7ꢀ) that connect Cu1 atoms to Cu2 atoms
with a Cu/Cu distance of 18.964(8) Å, and by anti-anti-anti
conformation hbn-B ligands (four-atom torsion angles ¼ 177.8, 180,
177.8ꢀ) that connect Cu2 atoms to each other with a Cu/Cu dis-
tance of 17.547(8) Å. Treating the Cu1 atoms as 4-connected nodes
and the Cu2 atoms as 3-connected nodes results in a 3,4-connected
2
2 2 2
€
layer topology with a Schlafli symbol of (4.6 )2(4 6 8 ) (Fig. 5) as
computed by TOPOS [25]; this net can be construed as a (4,4) grid
with regular, ordered removal of some pillaring ligands. When
viewed from the side, the [Cu3(sip)2(hbn)3(H2O)4]n layers show a
sawtooth pattern that permits 2D þ 2D / 3D parallel interpene-
tration (Fig. 6). Multifarious hydrogen bonding pathways involving
the water molecules of crystallization assist in stabilizing the
of 10.451(4)
Å (Fig. 3b). In turn these are linked into
[Cu3(sip)2(hbn)3(H2O)4]n coordination polymer layers (Fig. 4) by
gauche-anti-gauche conformation hbn-A ligands (four-atom torsion
Table 3
Hydrogen Bonding Distance (Å) and Angle (ꢀ) data for 1e2.
…
…
DeH
A
d(H … A)
:DHA
d(D A)
symmetry transformation for A
1
O1WeH1WA$$$O3
O1WeH1WB$$$O3
N2eH2/O1W
N3eH3/O6
N3eH3/O6A
1.98 (2)
2.12 (2)
2.08 (2)
2.11 (2)
2.08 (3)
2.849 (4)
2.953 (4)
2.941 (5)
2.918 (9)
2.91 (2)
170 (4)
167 (4)
174 (4)
166 (5)
174 (5)
ꢁx þ 2, ꢁy þ 1, ꢁz
xꢁ1, yꢁ1, z
xꢁ1, yꢁ1, z
xꢁ1, yꢁ1, z
2
O5WeH5WA$$$O3W
O5WeH5WB$$$O6
O1WeH1WA$$$O8
O1WeH1WB$$$O4
O2WeH2WA$$$O5W
O2WeH2WB$$$O1W
O3WeH3WA$$$O2W
O3WeH3WB$$$O4W
O4WeH4WA$$$O9
O4WeH4WB$$$O4
O11eH11B/O2
O12eH12B/O10
N2eH2/O2W
1.88
1.97
1.93
1.89
1.89
1.89
2.04
2.07
1.85
1.88
1.87
1.98
2.06
2.07
2.742 (4)
2.812 (3)
2.745 (3)
2.714 (3)
2.753 (4)
2.744 (3)
2.866 (5)
2.886 (5)
2.688 (4)
2.741 (3)
2.698 (3)
2.815 (3)
2.867 (4)
2.930 (4)
173.6
162.0
155.0
158.2
173.7
165.8
158.7
156.7
159.8
172.7
155.4
158.8
152.6
165.2
ꢁx, ꢁy þ 1, ꢁz þ 2
xꢁ1, yꢁ1, z
ꢁxꢁ1, ꢁy þ 1, ꢁz þ 3
ꢁxꢁ1, ꢁy þ 1, ꢁz þ 3
ꢁx, ꢁy þ 1, ꢁz þ 2
x, y, zꢁ1
ꢁx, ꢁy þ 1, ꢁz þ 2
ꢁx, ꢁy þ 1, ꢁz þ 2
ꢁx þ 1, ꢁy þ 1, ꢁz þ 2
N3eH3/O6
ꢁx, ꢁy þ 1, ꢁz þ 3

72
R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
Table 4
coordination polymer, the hbn ligands bind to six copper atoms,
Selected bond distance (Å) and angle (ꢀ) data for 2.
two via their terminal pyridyl ligands, and two at each carbonyl
oxygen atom. In compound 2, the hbn ligands serve only as dipodal
tethers.
Cu1eO3
1.964 (2)
1.964 (2)
2.013 (3)
2.013 (3)
1.984 (2)
2.024 (2)
2.207 (2)
1.999 (2)
1.996 (2)
180.0
O3#1eCu1eN1
O3#1eCu1eN1#1
N1#1eCu1eN1
O1eCu2eO11
O1eCu2eO12
O1eCu2eN4#2
O1eCu2eN5
O11eCu2eO12
N4#2eCu2eO11
N4#2eCu2eO12
N5eCu2eO11
N5eCu2eO12
N5eCu2eN4#2
88.63 (10)
91.37 (9)
180.0
Cu1eO3#1
Cu1eN1
Cu1eN1#1
Cu2eO1
151.40 (9)
121.21 (8)
85.81 (9)
86.59 (9)
87.31 (9)
91.24 (10)
92.51 (9)
97.84 (9)
87.11 (9)
170.88 (10)
4.4. Thermal properties
Cu2eO11
Cu2eO12
Cu2eN4#2
Cu2eN5
Compound 1 underwent dehydration and partial decarboxyl-
ation between 20 and 250 ꢀC, with a mass loss of 5.3% higher than
that expected for elimination of one molar equivalent of water
(3.3% calc'd). Ligand combustion occurred above 250 ꢀC, with a final
mass remnant of 21.7% at 600 ꢀC corresponding roughly to a
deposition of CuCO3 (20.5% calc'd). Compound 2 underwent elim-
ination of its co-crystallized water molecules between 25 and 75 ꢀC,
with an observed mass loss of 9.7% corresponding roughly to the
expected 10.7% value for loss of 11.5 molar equivalents of water. Its
bound water molecules were eliminated between 75 and 140 ꢀC,
with a mass loss of 3.3% matching well with the expected value of
3.7% for four molar equivalents of water. Ligand combustion again
occurred above 250 ꢀC. The final mass remnant of 25.0% at 600 ꢀC is
higher than that expected for deposition of CuCO3 (19.2% calc'd)
indicating the likely presence of uncombusted organic char. The
TGA traces for 1 and 2 are shown in Figs. S2eS3, respectively.
O3eCu1eO3#1
O3eCu1eN1
O3eCu1eN1#1
91.37 (9)
88.63 (10)
Symmetry transformations: #1 ꢁx, ꢁy þ 2, ꢁz þ 3; #2 x þ 1, y þ 1, z.
interpenetrated crystal structure (Table 2). The water molecules
form “infinite” tapes with TR(6)A(2)C(2) classification [26] built
from flat six-membered circuits with two “para” associated water
molecules, linked by short two-molecule chains (Fig. 7). The water
tape aggregations are situated in incipient channels parallel to the b
crystal direction, comprising 16.2% of the unit cell volume accord-
ing to PLATON [27].
The topology of compound 2 contrasts with a previously re-
ported copper sulfoisophthalate coordination polymer containing
the hbn ligand [28]. This phase has
5. Conclusions
a
formula of
{[Cu4(sip)2(OH)2(H2O)2]$4H2O}n, with tetranuclear {Cu4(m3
-
Divalent copper coordination polymers containing the long-
spanning dipyridylamide ligand hbn show a marked structural
difference upon altering the 5-position substituent of the anionic
OH)2(H2O)2(O2C)4} clusters connected into a binodal (4,8)-con-
nected (4462)(41461084) topology. In this previously reported
Fig. 4. [Cu3(sip)2(hbn)3(H2O)4] coordination polymer layer motif in 2.
n

R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
73
Fig. 5. Schematic representation of the 3,4-connected {4.62}2{426282} topology layer in 2.
Fig. 6. 2D þ 2D / 3D parallel interpenetration of sawtooth layer motifs in 2.
dicarboxylate ligand. A previously reported 5-aminoisophthalate
(amip) derivative [16] shows binding of the amino group to cop-
per, resulting in the amip ligand serving as a 3-connected node in a
layer structure with a 3,4-connected binodal (42638)(426) topology.
The 5-position methoxy groups in the meoip ligands in compound
1 in this study are unable to bind to copper, resulting in a
{Cu2(OCO)2} dinuclear dimer-based decorated (4,4) grid topology.
The anionic 5-sulfonate group in the sip ligands in compound 2 in
this study also do not bind to copper, but alter the metal to ligand
ratio necessary for a neutral coordination polymer. While com-
pound 2 displays a 3,4-connected binodal net with 4-, 6-, and 8-
membered circuits as seen in the amip derivative, it possesses a
different (4.62)2(426282) topology. Compound 2 differs markedly in
topology from a previously reported related phase that possessed
tetranuclear cluster units. The sawtooth undulations in the layer
motifs in the sip derivative 2 promote uncommonly encountered
2D þ 2D / 3D parallel interpenetration and the encapsulation of
an intriguing water tape morphology. The topologies of both 1 and

74
R.K. Randolph, R.L. LaDuca / Journal of Molecular Structure 1135 (2017) 67e74
Fig. 7. Co-crystallized water molecule tape in 2, showing decorated six-membered circuits linked by short two-molecule chains.
[8] a) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O'Keeffe, O.M. Yaghi,
Science 295 (2002) 469;
2 differ dramatically from the previously reported parent copper
isophthalate phase, which manifests a 2D layer structure with a
(3,5)-connected (426)(42678) topology [28]. Incorporation of
different 5-position substituents on isophthalate ligands continues
to diversity the structural topologies possible in divalent metal dual
ligand coordination polymers.
b) X.-N. Cheng, W.-X. Zhang, Y.-Y. Lin, Y.-Z. Zheng, X.-M. Chen, Adv. Mater. 19
(2007) 1494.
ꢀ
[9] D.J. Tranchemontagne, J.L. Mendoza-Cortes, M. O'Keeffe, O.M. Yaghi, Chem.
Soc. Rev. 38 (2009) 1257 (and references therein).
[10] D.S. Zhou, F.K. Wang, S.Y. Yang, Z.X. Xie, R.B. Huang, CrystEngComm 11 (2009)
2548.
[11] D.P. Martin, M.A. Braverman, R.L. LaDuca, Cryst. Growth Des. 7 (2007) 2609.
[12] A.L. Pochodylo, R.L. LaDuca, CrystEngComm 13 (2011) 2249.
[13] B. Xu, J. Lu, M. Cao, L. Han, R. Cao, Inorg. Chem. Commun. 14 (2011) 1237.
[14] A.D. Sample, M.E. O'Donovan, R.L. LaDuca, Z. Anorg, Allgem. Chem. 642 (2016)
785.
[15] L.F. Ma, L.Y. Wang, M. Du, S.R. Batten, Inorg. Chem. 49 (2010) 365.
[16] X. Wang, J. Luan, H. Lin, Q. Lu, C. Xu, G. Liu, Dalton Trans. 42 (2013) 8375.
[17] X. Wang, J. Luan, H. Lin, G. Liu, M. Le, Polyhedron 71 (2014) 111.
[18] T.S. Gardner, E. Wenis, J.J. Lee, J. Org. Chem. 19 (1954) 753.
[19] SAINT, Software for Data Extraction and Reduction, Version 6.02, Bruker AXS,
Inc., Madison, WI, 2002.
Acknowledgements
Support for this work was provided by the Honors College of
Michigan State University.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.molstruc.2017.01.049.
[20] SADABS, Software for Empirical Absorption Correction. Version 2.03, Bruker
AXS, Inc., Madison, WI, 2002.
[21] G.M. Sheldrick, SHELXTL, Program for Crystal Structure Refinement, Univer-
€
€
sity of Gottingen, Gottingen, Germany, 1997.
References
[22] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl.
Cryst. 42 (2009) 229.
[23] M. Kurmoo, C. Estournes, Y. Oka, H. Kumagai, K. Inoue, Inorg. Chem. 44 (2005)
217.
[24] A.W. Addison, T.N. Rao, J. Reedijk, J. van Rijn, G.C. Verschoor, J. Chem. Soc.
Dalton Trans. (1984) 1349.
[25] 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.
[26] a) L. Infantes, S. Motherwell, CrystEngComm 4 (2002) 454;
b) L. Infantes, J. Chisholm, S. Motherwell, CrystEngComm 5 (2003) 480.
[27] A.L. Spek, PLATON, a Multipurpose Crystallographic Tool, Utrecht University,
Utrecht, The Netherlands, 1998.
[1] L.D. Tran, J.I. Feldblyum, A.G. Wong-Foy, A.J. Matzger, Langmuir 31 (2015)
2211.
[2] M. Foo, R. Matsuda, Y. Hijikata, R. Krishna, H. Sato, S. Horike, A. Hori, J. Duan,
Y. Sato, Y. Kubota, M. Takata, S. Kitagawa, J. Am. Chem. Soc. 138 (2016) 3022.
[3] P.F. Gao, L.L. Zheng, L.J. Liang, X.X. Yang, Y.F. Li, C.Z. Huang, J. Mater. Chem. B 1
(2013) 3202.
[4] F. Wang, F. Li, M. Xu, H. Yu, J. Zhang, H. Xia, J. Lang, J. Mater. Chem. A 3 (2015)
5908.
[5] L. Carlucci, G. Ciani, D.M. Proserpio, Coord. Chem. Rev. 246 (2003) 247 (and
references therein).
[6] T. Fukushima, S. Horike, H. Kobayashi, M. Tsujimoto, S. Isoda, M. Foo,
Y. Kubota, M. Takata, S. Kitagawa, J. Am. Chem. Soc. 134 (2012) 13341.
[7] J. Tao, X.M. Chen, R.B. Huang, L.S. Zheng, J. Solid State Chem. 170 (2003) 130.
[28] X.L. Wang, P. Liu, J. Luan, H. Lin, C. Xu, Z. Naturforsch 67b (2012) 877.