Construction of diverse dimensionality in eight coordination polymers of bivalent metal ions using 5-nitroisophthalate and different linear N,N′-donor linkers

Article abstract of DOI:10.1016/j.poly.2015.10.052

Assembly of 5-nitroisophthalate (nip^2-) with first row transition metal salts [Mn(II), Fe(II), Co(II), Zn(II)] in combination with the various neutral auxiliary N,N′-donor linkers, e.g., 2,5-bis-(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh), 1,3

Full text of DOI:10.1016/j.poly.2015.10.052

Polyhedron 102 (2015) 634–642
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Polyhedron
journal homepage: www.elsevier.com/locate/poly
Construction of diverse dimensionality in eight coordination polymers
of bivalent metal ions using 5-nitroisophthalate and different linear
N,N0-donor linkers
⇑
Dilip Kumar Maity, Biswajit Bhattacharya, Arijit Halder, Anamika Das, Debajyoti Ghoshal
Department of Chemistry, Jadavpur University, Jadavpur, Kolkata 700 032, India
a r t i c l e i n f o
a b s t r a c t
Assembly of 5-nitroisophthalate (nip2ꢀ) with first row transition metal salts [Mn(II), Fe(II), Co(II), Zn(II)]
in combination with the various neutral auxiliary N,N0-donor linkers, e.g., 2,5-bis-(4-pyridyl)-3,4-diaza-
2,4-hexadiene (4-bpdh), 1,3-bis(4-pyridyl)propane (bpp) and 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene
(4-bpdb), yielded eight new coordination polymers (CPs), namely {[Mn(4-bpdh)(nip)(H2O)2]ꢁH2O}n (1),
{[Fe(4-bpdh)(nip)(H2O)2]ꢁH2O}n (2), {[Co(4-bpdh)(nip)(H2O)2]ꢁH2O}n (3), {[Mn2(bpp)2(nip)2(H2O)2]ꢁ
Article history:
Received 22 July 2015
Accepted 4 October 2015
Available online 03 November 2015
Keywords:
H2O}n (4), {[Fe(bpp)(nip)(H2O)]ꢁH2O}n (5), [Zn(bpp)(nip)(H2O)]n (6), {[Fe(4-bpdh)1.5(nip)]ꢁ(4-bpdh)0.5
}
n
Coordination polymers
Single crystal X-ray structures
PXRD and TGA study
Solid state UV–Vis spectra
Photoluminescence study
(7) and {[Fe(4-bpdb)(nip)]ꢁ(4-bpdb)0.5(H2O)}n (8) using the slow diffusion technique at room tempera-
ture. The complexes 1–8 were characterized by single crystal X-ray diffraction analysis and were further
characterized by elemental analysis, infrared spectroscopy (IR) and powder X-ray diffraction (PXRD).
Complexes 1–3 are isostructural and exhibit a one-dimensional (1D) metal-carboxylate chain with pen-
dant 4-bpdh ligands, which is further extended into a three-dimensional supramolecular structure by
means of H-bonding and p–p interactions. Complexes 4–6 are also isomorphous, but distinctly different
from the first three complexes. They exhibit a similar 2-fold interpenetrated three-dimensional (3D) net
with 66 dia net topology. Compound 7 displays a two-dimensional (2D) grid-like structure, having 4-bpdh
ligands in the crystal void, and this is further extended by means of intermolecular p–p interactions into
a 3D supramolecular structure, whereas compound 8 possesses a different 2D grid structure containing
free 4-bpdb ligands in the void spaces. The thermal stabilities and UV–Vis spectra of all the complexes
and the luminescent properties of complex 6 were also studied.
Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction
is needless to mention the importance of crystal structures in dis-
cussions on CPs and it is a very common phenomena in the design
The strategic design of metal organic frameworks (MOFs), also
known as coordination polymers (CPs), has received immense
interest due to their well controllable network structures [1–5],
topological aspects [6,7] and their promising widespread applica-
tions as functional materials for the purpose of gas storage and
separation [8–11], catalysis [12–14], magnetism [15–17], lumines-
cence [18–21] etc. It has been well established that the design of
coordination polymers depends on many factors, such as the nat-
ure of the organic ligands and the presence of functional groups
[22,23], coordination number of the metal ions [24,25], solvent
systems [26–28], pH of the medium [29–31], reaction temperature
[32,33], and so on. A precise correlation of the aforesaid factors,
however, is yet to be achieved during the crystallization of CPs. It
of CPs, that despite of having all the prerequisites for the reaction,
crystals are not afforded at all, or crystals of undesired product are
obtained. This indicates that not only the chemical binding but also
the ease of crystallization is very crucial in the design of CPs to get
a meaningful outcome. Sometimes steric and electronic factors
individually or additively facilitate the process of crystallization
of CPs and that could also be a very important precondition for
the design of CPs.
Based on that, we have picked up a popular isophthalate func-
tionalized ligand with a reasonably bulky and electron withdraw-
ing –NO2 group at the 5 position. Here, 5-nitroisophthalate
(nip2ꢀ) possesses the same aromatic skeleton as that of isophtha-
late (ip2ꢀ), along with the uncoordinated 5-position substituent
which can exerts a steric effect. That additional steric effect may
result in close packing of the structure of CPs and hence facilitate
the process of crystallization, offering a new opportunity for the
⇑
Corresponding author.
E-mail address: dghoshal@chemistry.jdvu.ac.in (D. Ghoshal).
http://dx.doi.org/10.1016/j.poly.2015.10.052
0277-5387/Ó 2015 Elsevier Ltd. All rights reserved.

D.K. Maity et al. / Polyhedron 102 (2015) 634–642
635
discovery of intriguing topologies [34–36]. On the other hand,
although the nitro group (–NO2) in carboxylate ligands does not
take part in coordination to transition metal ions, it has a marked
impact on the electron density of the whole ligand due to the pull-
ing of electrons by the nitro group from the –COOꢀ group present
in the 5-nitroisophthalate (nip2ꢀ) ring. This reduced electron den-
sity may restrict the very common bis-chelating coordination
mode of this ligand, making this much more useful for creating
structural diversity in comparison to the unsubstituted isophtha-
late ligand.
4-acetyl pyridine, 4-pyridine carboxaldehyde and hydrazine hydrate
for the above synthesis were purchased from Sigma–Aldrich Chem-
ical Co. Inc. and used as received. Highly pure 1,3-bis-(4-pyridyl)
propane (bpp), manganese(II) chloride tetrahydrate, iron(II)
perchlorate hydrate, cobalt(II) nitrate hexahydrate, zinc(II) nitrate
hexahydrate and 5-nitroisophthalic acid (H2nip) were purchased
from Sigma–Aldrich Chemical Co. Inc. and used as received. The
sodium salt of 5-nitroisophthalic acid (Na2nip) was synthesized by
the gradual addition of Na2CO3 to a H2nip water suspension in a
1:1 ratio. The neutralization was checked by measuring the pH of
the solution and then it was allowed to stand for 8 h. Finally the
solvent was evaporated using a water bath until dry. All other
chemicals and solvents were AR grade and were used as received.
As one of the crucial exoteric factors, N,N0-donor auxiliary linkers
are widely used along with polycarboxylate ligands for the design of
CPs and careful choice of the N,N0-donor linker is one of thesignificant
aspects in such synthesis [37–39]. This is basically due to the fact that
the conformational rigidness, configurations and substituents on the
N,N0-donor linkers have important roles in controlling the structural
assemblies, which further affect the overall network, dimensionality
and even the properties of the CPs. In order to investigate the
influence of N,N0-donor co-ligands on the variation of entangled
networks and to achieve unusual topologies or physical properties,
three different N,N0-donor linkers with rationally tuned length
and rigidity, namely 2,5-bis-(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-
bpdh), 1,3-bis-(4-pyridyl)propane (bpp) and 1,4-bis(4-pyridyl)-2,
3-diaza-1,3-butadiene (4-bpdb), were introduced into the M(nip)
system (Scheme 1). In this paper, we report the syntheses and struc-
tures of eight coordination polymers, namely {[Mn(4-bpdh)(nip)
(H2O)2]ꢁH2O}n (1), {[Fe(4-bpdh)(nip)(H2O)2]ꢁH2O}n (2), {[Co(4-bpdh)
(nip)(H2O)2]ꢁH2O}n (3), {[Mn2(bpp)2(nip)2(H2O)2]ꢁH2O}n (4), {[Fe
(bpp)(nip)(H2O)]ꢁH2O}n (5), [Zn(bpp)(nip)(H2O)]n (6), {[Fe(4-bpdh)1.5
2.2. Physical measurements
Elemental analyses (carbon, hydrogen and nitrogen) were
performed using
a Heraeus CHNS analyzer. Infrared spectra
(4000–400 cmꢀ1) were taken on KBr pellets, using a PerkinElmer
Spectrum BX-II IR spectrometer. X-ray powder diffraction (PXRD)
patterns of the bulk samples were recorded in a Bruker D8 Discover
instrument using Cu Ka radiation. Thermal analysis (TGA) was car-
ried out on a METTLER TOLEDO TGA 850 thermal analyzer under a
nitrogen atmosphere (flow rate: 50 cm3 minꢀ1), in the temperature
range 30–600 °C with a heating rate of 2 °C minꢀ1. UV–Vis spectra
were recorded on a Perkin Elmer Lambda 35 UV–Vis spectropho-
tometer. Emission spectra were recorded on a HORIBA Jobin Yvon
(Fluoromax-3) fluorescence spectrophotometer.
(nip)]ꢁ(4-bpdh)0.5
}
(7) and {[Fe(4-bpdb)(nip)]ꢁ(4-bpdb)0.5(H2O)}n
n
(8). All the complexes were characterized by single crystal X-ray
crystallography, IR spectroscopy, powder X-ray diffraction (PXRD),
elemental analysis, thermogravimetric (TG) analysis and solid
state UV–Vis spectroscopy. Moreover, luminescent properties of
compound 6 and the bpp ligand were also investigated in detail.
2.3. Syntheses
2.3.1. {[Mn(4-bpdh)(nip)(H2O)2]ꢁH2O}n (1)
An aqueous solution (20 mL) of Na2nip (1 mmol, 0.255 g) was
mixed with a methanolic solution (20 mL) of 2,5-bis-(4-pyridyl)-
3,4-diaza-2,4-hexadiene (4-bpdh) (1 mmol, 0.238 g) and stirred
for 30 min to mix it well. MnCl2ꢁ4H2O (1 mmol, 0.198 g) was dis-
solved in 20 mL of water in a separate beaker. In a crystal tube,
3 ml of the Mn(II) solution was then slowly and carefully layered
with 6 ml of above mentioned mixed-ligand solution using 3 ml
of buffer solution (1:1 of H2O and MeOH) between the two solu-
tions. The tube was sealed and kept undisturbed at room temper-
ature and after seven days colorless block shaped single crystals
suitable for X-ray diffraction analysis were obtained at the wall
2. Experimental
2.1. Materials
2,5-Bis-(4-pyridyl)-3,4-diaza-2,4-hexadiene
(4-bpdh)
and
1,4-bis-(4-pyridyl)-2,3-diaza-1,3-butadiene (4-bpdb) were prepared
according to literature procedures [40]. The starting materials
Scheme 1. Synthetic outline for complexes 1–8.

636
D.K. Maity et al. / Polyhedron 102 (2015) 634–642
of the tube. The crystals were separated and washed with a
methanol–water (1:1) mixture and dried under air (Yield: 63%).
Anal. Calc. for C22H23N5O9 Mn: C, 47.49; H, 4.17; N, 12.59. Found:
suitable for X-ray diffraction analyses were obtained after 10 days.
The crystals were separated and washed with a methanol–water
(1:1) mixture and dried under air (Yield 55%). Anal. Calc. for
C, 47.51; H, 4.22; N, 12.55%. IR spectra (cmꢀ1):
m(H2O) 3403;
C
21H19N3O7Zn: C, 51.39; H, 3.9; N, 8.56. Found: C, 51.41; H, 3.14;
N, 8.51%. IR spectra (cmꢀ1):
(H2O) 3437; (C@N) 1640; (N@O)
1526(as), 1360(s); (C–O) 1226; (CH–Ar) 3104; (C@C) 1530.
m
(C@N) 1602;
m
m
(N@O) 1543(as), 1376(s);
(C@C) 1606–1422.
m(C–O) 1293–1221;
m
m
m
m(CH–Ar) 3097;
m
m
m
2.3.2. {[Fe(4-bpdh)(nip)(H2O)2]ꢁH2O}n (2) and {[Fe(4-bpdh)1.5(nip)]ꢁ
(4-bpdh)0.5 (7)
2.3.7. {[Fe(4-bpdb)(nip)]ꢁ(4-bpdb)0.5(H2O)}n (8)
}
n
This product was synthesized by the same procedure as that
used for 2, but with 4-bpdb (1 mmol, 0.210 g) instead of 4-bpdh
(1 mmol, 0.238 g). Deep red colored block shaped crystals suitable
for X-ray diffraction analysis were obtained after ten days. The
crystals were separated and washed with a methanol–water
(1:1) mixture and dried under air (Yield 70%). Anal. Calc. for
These two compounds were identified simultaneously by fol-
lowing the same procedure as that for 1, but using Fe(ClO4)2ꢁxH2O
(1 mmol, 0.255 g) instead of MnCl2ꢁ4H2O in the single layer
reaction. The yield of yellowish block shaped single crystals of
compound 2 was greater than the reddish block shaped crystals
of compound 7. Both the single crystals of 2 and 7, suitable for
X-ray diffraction analysis, were obtained after 15 days. The crystals
were separated manually and washed with a methanol–water
(1:1) mixture and dried under air. For 2 (Yield: 45%) Anal. Calc.
for C22H23N5O9Fe: C, 47.41; H, 4.16; N, 12.57. Found: C, 47.48; H,
C
26H20N7O7Fe: C, 52.19; H, 3.37; N, 16.39. Found: C, 52.24; H,
3.34; N, 16.44%. IR spectra (cmꢀ1):
(H2O) 3461; (C@N) 1632;
(N@O) 1528(as), 1383(s); (C–O) 1237; (CH–Ar) 3086; (C@C)
1538.
m
m
m
m
m
m
The bulk compounds of six complexes, except 2 and 7, were
synthesized in the powder form by the direct mixing of the corre-
sponding ligand solutions and the M(II) salt solution in water in an
equal-molar ratio. In the case of 2 and 7, the bulk products were
prepared as crystals, following the procedure mentioned in Sec-
tion 2.3.2. The purity of the complexes was verified by PXRD,
which gave a good correspondence between the simulated PXRD
patterns. The purity of the bulk sample was further confirmed by
the results of elemental analysis and IR spectra as well, which were
also found to be in accordance with the data obtained for the single
crystals.
4.2; N, 12.53%. IR spectra (cmꢀ1):
(N@O) 1554(as), 1378(s); (C–O) 1298–1211;
3101–3041;
C36H31N9O6Fe: C, 58.31; H, 4.21; N, 17. Found: C, 58.39; H, 4.25;
N, 17.4%. IR spectra (cmꢀ1):
(C@N) 1610; (N@O) 1528(as),
1362(s); (C–O) 1289–1216; (CH–Ar) 3076; (C@C) 1528–1413.
m(H2O) 3395;
m
(C@N) 1607;
m
m
m(CH–Ar)
m
(C@C) 1604–1416. For 7 (Yield 22%) Anal. Calc. for
m
m
m
m
m
2.3.3. {[Co(4-bpdh)(nip)(H2O)2]ꢁH2O}n (3)
This compound was synthesized by following the same proce-
dure as that used for 1, but with Co(NO3)2ꢁ6H2O (1 mmol,
0.297 g) instead of MnCl2ꢁ4H2O. Pink colored block shaped single
crystals suitable for X-ray diffraction analysis were obtained after
two weeks. The crystals were separated and washed with a metha-
nol–water (1:1) mixture and dried under air (yield: 62%). Anal.
Calc. for C22H23N5O9Co: C, 47.15; H, 4.14; N, 12.5. Found: C,
2.4. Crystallographic data collection and refinement
Suitable single crystals of compounds 1–8 were mounted on the
tip of thin glass fibers with commercially available super glue. X-
ray single crystal data collection of all eight crystals were per-
formed at room temperature using a Bruker APEX II diffractometer,
equipped with a normal focus, sealed tube X-ray source with gra-
47.23; H, 4.19; N, 12.54%. IR spectra (cmꢀ1):
(C@N) 1607; (N@O) 1535–1556(as), 1350(s);
1219; (CH–Ar) 3102; (C@C) 1610–1416.
m
(H2O) 3420;
m
m
m(C–O) 1292–
m
m
phite monochromated Mo K
a radiation (k = 0.71073 Å). The data
2.3.4. {[Mn2(bpp)2(nip)2(H2O)2]ꢁH2O}n (4)
were integrated using the SAINT [41] program and the absorption
corrections were made with SADABS [42]. All the structures were
solved by SHELXS 97 [43] using the Patterson method and followed
by successive Fourier and difference Fourier synthesis. Full matrix
least-squares refinements were performed on F2 using SHELXL-97
[43] with anisotropic displacement parameters for all non-hydro-
gen atoms. All the hydrogen atoms were fixed geometrically by
the HFIX command and placed in ideal positions in the case of all
structures except 3, where the hydrogen atoms of water molecules
were located from the Fourier map. The thermal parameter of the O
atom of the lattice water is quite high for 4 and 5, thus the H-atom
of the said O atom could not be located properly. Additionally in
case of 4, one of the H atoms of the coordinated water molecule
O1W has been found with a two fold disorder and thus has been
fixed with occupancies at 0.5. All calculations were carried out
using SHELXS 97, SHELXL 97, PLATON v1.15 [44], ORTEP-3v2 [45] and WINGX
system Ver-1.80 [46] and TOPOS [47,48]. Data collection and struc-
ture refinement parameters and crystallographic data for all the
complexes are given in Table 1.
This was synthesized by the same procedure as that used for 1,
but with 1,3-bis-(4-pyridyl)propane (bpp) (1 mmol, 0.198 g)
instead of 2,5-bis-(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh)
(1 mmol, 0.238 g). Colorless block shaped crystals suitable for
X-ray diffraction analysis were obtained after seven days. The
crystals were separated and washed with a methanol–water
(1:1) mixture and dried under air (Yield 70%). Anal. Calc. for
C
42H40N6O15Mn2: C, 51.55; H, 4.12; N, 8.59. Found: C, 51.59; H,
4.16; N, 8.54%. IR spectra (in cmꢀ1):
(H2O) 3399; (C@N) 1622;
(N@O) 1530(as), 1359(s); (C–O) 1222; (CH–Ar) 3102; (C@C)
1530–1426.
m
m
m
m
m
m
2.3.5. {[Fe(bpp)(nip)(H2O)]ꢁH2O}n (5)
This has been synthesized by the same procedure as that used
for 4, but with Fe(ClO4)2ꢁxH2O (1 mmol, 0.255 g) instead of
MnCl2ꢁ6H2O. Reddish block shaped crystals suitable for X-ray
diffraction analysis were obtained after seven days. The crystals
were separated and washed with a methanol–water (1:1) mixture
and dried under air (Yield 65%). Anal. Calc. for C21H21N3O8Fe: C,
50.52; H, 4.24; N, 8.42. Found: C, 50.55; H, 4.28; N, 8.4%. IR spectra
(cmꢀ1):
(C–O) 1221;
m
(H2O) 3398;
m
(C@N) 1633;
m
(N@O) 1535(as), 1367(s);
3. Results and discussion
m
m
(CH–Ar) 3099; m
(C@C) 1539–1425.
3.1. Crystal structure descriptions of the CPs
2.3.6. [Zn(bpp)(nip)(H2O)]n (6)
This has been synthesized by the same procedure as that used
for 4, but with Zn(NO3)2ꢁ6H2O (1 mmol, 0.297 g) instead of
MnCl2ꢁ4H2O (1 mmol, 0.198 g). Colorless block shaped crystals
The structural diversity of the eight CPs are depicted in
Scheme 1, exhibiting various coordination modes of the nip2- dian-
ion (Scheme 2) and structural differences of the linear dipyridyl

D.K. Maity et al. / Polyhedron 102 (2015) 634–642
637
Table 1
Crystallographic and structural refinement parameters of complexes 1–8.
1
2
3
4
Formula
C
22H23N5O9Mn
C22H23N5O9Fe
557.30
monoclinic
P21/c
16.419(5)
7.505(5)
19.650(5)
90
C22H23N5O9Co
560.38
monoclinic
P21/c
16.3446(2)
7.5226(1)
19.5825(3)
90
C42H40N6O15Mn2
978.68
orthorhombic
Pnna
17.2254(4)
14.0118(3)
18.2207(5)
90
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
556.39
monoclinic
P21/c
16.4823(3)
7.5363(2)
19.7751(4)
90
a
(°)
b (°)
91.101(1)
90
2455.92(9)
4
1.505
0.599
91.254(5)
90
2420.8(19)
4
1.529
0.685
90.976(1)
90
2407.40(6)
4
1.546
0.776
90
90
c
(°)
V (Å3)
4397.73(18)
4
1.475
Z
Dc (g cmꢀ3
)
l
(mmꢀ1
)
0.651
F(000)
1148
1152
1156
2008
h range (°)
Reflections collected
Unique reflections
1.2–27.5
38368
5640
1.2–27.6
39541
5558
2.1–27.5
37267
5517
1.6–27.5
68034
5076
Reflections I > 2
r(I)
4655
4351
4478
3749
Rint
0.030
1.07
0.0344
0.1131
ꢀ0.41, 0.45
0.037
1.01
0.0369
0.1126
ꢀ0.42, 0.33
0.040
1.03
0.0313
0.0848
ꢀ0.34, 0.35
0.035
1.03
0.0446
0.1406
ꢀ0.44, 0.72
Goodness–of–fit (F2)
R1 (I > 2
wR2(I > 2
min/max (e Å3)
r
r
(I))a
(I))a
D
q
5
6
7
8
Formula
C
21H21N3O8Fe
C21H19N3O7Zn
490.78
monoclinic
C2/c
C36H31N9O6 Fe
741.55
C26H20N7O7Fe
598.34
triclinic
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
499.26
orthorhombic
Pnna
triclinic
ꢀ
ꢀ
P1
P1
17.1017(5)
14.0287(4)
18.1303(5)
90
90
90
4349.7(2)
8
1.519
14.322(5)
18.378(5)
16.194(5)
90
100.945(5)
90
4185(2)
8
1.558
10.072(5)
12.349(5)
15.655(5)
108.615(5)
95.044(5)
108.650(5)
1708.8(12)
2
10.0749(6)
10.1223(5)
14.1708(9)
85.611(4)
78.733(4)
74.380(4)
1364.52(14)
2
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dc (g cmꢀ3
)
1.441
0.503
1.456
0.611
l
(mmꢀ1
)
0.747
1.223
F(000)
2048
2016
768
614
h range (°)
Reflections collected
Unique reflections
1.6–27.5
68693
5024
1.8–27.6
33489
4836
1.4–27.6
27850
7765
1.5–27.6
38470
6052
Reflections I > 2
r(I)
3843
2561
4781
3046
Rint
0.033
1.03
0.0366
0.1136
ꢀ0.41 0.45
0.126
0.99
0.0619
0.1682
ꢀ0.61, 0.46
0.049
1.02
0.0671
0.1957
ꢀ0.40, 0.93
0.094
1.10
0.1291
0.2807
Goodness–of–fit (F2)
R1 (I > 2
wR2(I > 2
min/max (e Å3)
r
r
(I))a
(I))a
D
q
ꢀ0.75, 0.81
a
R1
=
R
||Fo| ꢀ |Fc||/
R
|Fo|, wR2 = [
R
(w(F2o ꢀ F2c)2)/
R .
w(F2o)2]1/2
linkers in complexes 1–8. Moreover, structural details for all the
complexes are discussed below.
atoms (O1, O5a and O6a) of two different nip2ꢀ ligands, two coor-
dinated water molecules (O1W and O2W) and one pyridyl nitrogen
atom (N1) of a 4-bpdh linker. In compounds 1–3, the M(II)–O bond
lengths vary from 2.1092(14) to 2.2697(12) Å (Mn–O for 1), 2.038
(3) to 2.259(2) Å (Fe–O for 2) and 2.0329(12) to 2.1554(13) Å
(Co–O for 3), and the corresponding M(II)–N bond lengths for
1–3 are 2.3177(15) Å (Mn–N for 1), 2.392(2) Å (Fe–N for 2) and
2.1886(14) Å (Co–N for 3) (Tables S1–S3). Here, one end of the
3.1.1. {[M(4-bpdh)(nip)(H2O)2]ꢁH2O}n [M = Mn for 1, Fe for 2 and Co
for 3]
Single-crystal X-ray structural analysis revealed that com-
pounds 1–3 are isostructural, having the monoclinic P21/c space
group with a Z value of 4. All the compounds show the formation
of a one-dimensional (1D) structure of M(II) [M = Mn for 1, Fe for
2 and Co for 3] ions linked by the 5-nitroisophthalate dianion
(nip2ꢀ) in a bridging chelate-monodentate fashion, where the
4-bpdh ligand is pendent. The asymmetric unit of all three
compounds contains one M(II) ion, one 4-bpdh ligand, one
5-nitroisophthalate ligand, two coordinated water and one lattice
water molecule. The M(II) ion shows a distorted octahedral geom-
etry with MO5N coordination environment (Fig. 1a for 1, S1a for 2
and S2a for 3). Here, each metal center is ligated to three oxygen
5-nitroisophthalate ligand binds in
a bridging monodentate
fashion and the other end binds in a chelating fashion between
two metal centers, resulting in the formation of a 1D metal
carboxylate chain (Fig. 1b for 1, S1b for 2 and S2b for 3) along the
c-axis. In the crystal packing, the coordinated water molecules and
the lattice water molecule are attached to each other, along with
the carboxylate oxygen atoms of the 5-nitroisophthalate ligand,
and one coordinated water molecule is also attached to the pyridyl
N-atom by means of H-bonding forming a 2D sheet in the

638
D.K. Maity et al. / Polyhedron 102 (2015) 634–642
Scheme 2. Different bridging modes of 5-nitroisophthalate (nip2ꢀ); (a) chelating- monodendate in 1–7 and (b) chelating-bidentate in 8.
Fig. 1. (a) Coordination environment around the Mn(II) ions in 1; Mn (green), N (blue), O (red), C (black). (b) 1D metal carboxylate chain with pendant 4-bpdh ligands in 1. (c)
Supramolecular 3D structures in 1 by locking 1D chains through
p–p interactions and H-bonding (p–p interactions: cyan dotted lines and H-bonding: pink dotted lines).
(Color online.)
crystallographic ac plane in all three cases (Table S4). These 2D
sheets are further stitched through intermolecular interac-
tions (Table S5) with the help of pendent 4-bpdh ligands, resulting
in a supramolecular three-dimensional (3D) structure (Fig. 1c for 1,
S1c for 2 and S2c for 3).
ligand, one 5-nitroisophthalate ligand, one coordinated water and
one lattice water molecule, exhibiting a distorted octahedral
geometry with MO4N2 coordination environment (Fig. 2a for 4
and S4a for 5). Each metal ion is connected to three oxygen atoms
(O1, O5b and O6b) of two different bridging nip2- ligands, one coor-
dinated water molecule (O1W) and two pyridyl nitrogen atoms (N1
and N2a) of 4-bpp linkers. In compounds 4 and 5, the M(II)–O bond
length varies from 2.0970(18) to 2.3519(16) Å (Mn–O for 4) and
2.0305(15) to 2.3769(16) Å (Fe–O for 5), respectively, and the corre-
sponding M(II)–N bond lengths for 4 and 5 are 2.2317(18) to 2.287
(2) Å (Mn–N for 4) and 2.1624(16) to 2.2173(18) Å (Fe–N for 5)
(Tables S6 and S7). The bridging nip2ꢀ ligand is bonded to two metal
ions in a chelate-monodented fashion and extends the structure
along the a-axis (Fig. S3a for 4 and S5a for 5), whereas the bridging
bpp ligand also connects two metal centers. Here six nip2ꢀ and six
bpp ligands linked with the M(II) centres form an adamantoid cage
structure (Fig. 2b and c, S3b for 4 and S4b, S4c, S5b for 5). These
adamantoid cages are interlinked to form a three dimensional
diamondoid structure (Fig. 2d, S3c for 4 and S4d, S5c for 5). The
Mꢁ ꢁ ꢁM separation through the nip2ꢀ and bpp ligands are 8.998
p–p
3.1.2. {[Mn2(bpp)2(nip)2(H2O)2]ꢁH2O}n (4), {[Fe(bpp)(nip)(H2O)]ꢁ
H2O}n (5) and [Zn(bpp)(nip)(H2O)]n (6)
Single-crystal structural analysis revealed that 4 and 5 are
isostructural, whereas in 6 the coordination structure is similar
to that of 4/5, but with a minor difference with respect to the lat-
tice water molecule. Compounds 4 and 5 crystallize in the
orthorhombic Pnna space group with Z = 4 and 8, respectively,
whereas compound 6 crystallizes in the monoclinic C2/c space
group with a Z value of 8.
Structural analysis of compounds 4 and 5 reveal the formation of
a three-dimensional (3D) structure of M(II) [M = Mn for 4 and Fe for
5] ions linked by 5-nitroisophthalate dianions (nip2ꢀ) in the bridg-
ing chelate-monodentate fashion and a bridging bpp ligand. The
asymmetric unit of both 4 and 5 contains one M(II) ion, one bpp

D.K. Maity et al. / Polyhedron 102 (2015) 634–642
639
Fig. 2. (a) Coordination environment around the Mn(II) ions in 4; Mn (green), N (blue), O (red), C (black). (b,c) Wire frame model and polyhedral presentation of a single
adamantoid cage constructed through six bpp and six 5-nitroisophthalate ligands bridging with the Mn(II) centers in 4, respectively. (d) A single 4-connected 3D-diamondoid
network in 4. (e) Topological representation of the 2-fold interpenetrating diamondoid networks in 4. (Color online.)
and 11.350 Å (Mnꢁ ꢁ ꢁMn for 4) and 8.936 and 11.302 Å (Feꢁ ꢁ ꢁFe for
5), respectively. Due to this spacious nature of the diamondoid
cavities, in both the structures, two equivalent complementary
diamondoid networks interpenetrate each other to exhibit an over-
all 2-fold interpenetrated diamondoid network (Fig. 2e for 4 and
and N4b) from three different 4-bpdh ligands (Fig. 3a). The Fe–O
bond lengths lie in the range 2.007(3)–2.416(3) Å, whereas the
Fe–N bond lengths are 2.209(3)–2.241(3) Å (Table S9). Here, the
nip2ꢀ ligand binds in a bridging monodentate-chelate fashion, as
found in 1–6, and forms 1D chains along the a-axis; two such
parallel chains are connected by 4-bpdh ligands to form a 1D
ladder extended along the a-axis (Fig. 3b). These 1D ladders are
connected through another set of bridging 4-bpdh ligands
S4e for 5). Moreover, notable
p–p stacking further stabilizes the
interpenetrating diamondoid networks (Table S5). Topological
analysis of 4 and 5 with TOPOS [47,48] suggests that each M(II) center
acts as a 4-connecting uninodal node (Figs. 2d and S4d), and the
overall structure has a 66-dia net topology. The interpenetration
analysis also [47,48] suggests the presence of Class IIa interpenetra-
tion with Zt = 1 and Zn = 2.
and extend the structure into
a 2D sheet (Fig. 3c and d).
There are uncoordinated lattice 4-bpdh ligands situated in the
voids of the crystal framework. The overall structure is also
stabilized by intermolecular
p–p interactions (Fig. S8, Table S10).
[Zn(bpp)(nip)(H2O)]n (6) also had a similar type of diamondoid
structure as that of 4 and 5, only differing with respect to the
lattice water molecule. In 6 the bpp ligand shows more flexibility
than in 4 and 5, as a result the adamentoid cages formed here
are squeezed in comparison to those of 4 and 5. This results in
the squeezing of the diamondoid network and probably the change
of the space group to lower symmetry (orthorhombic Pnna to mon-
oclinic C2/c). This squeezing may also account for the absence of
lattice water molecules in the crystal structure of 6. The relevant
tables and figures related to the structure of 6 are reported in the
ESI (Figs. S6–S7; Table 1, S8 and S5).
TOPOS [47,48] analysis reveals that the structure can be represented
as a 5-connected uninodal net (Fig. 3e) with a point symbol of
{48ꢁ62}.
3.1.4. {[Fe(4-bpdb)(nip)]ꢁ(4-bpdb)0.5(H2O)}n (8)
ꢀ
Compound 8 crystallizes in the triclinic P1 space group with a Z
value of 2. The structure analysis revealed the formation of two
dimensional (2D) sheets of 8 containing the free 4-bpdb linker in
the network void. Here each asymmetric unit of 8 contains one
Fe(II) ion, one coordinated bridging 4-bpdb linker, one 5-
nitroisophthalate ligand, half a lattice 4-bpdb ligand and one lat-
tice water molecule, forming a distorted octahedral geometry with
FeO4N2 coordination environment (Fig. 4a). There are one water
molecule and half a 4-bpdb molecule in the lattice in each formula
unit. Here each of the Fe(II) ions is linked to four oxygen atoms (O1,
O2, O5b and O6c) of three different nip2ꢀ ligands and two nitrogen
atoms of two different 4-bpdb linkers (N1 and N4a). The Fe1–N and
Fe1–O distances are 2.182(7)–2.183(8) and 2.045(7)–2.321(7) Å,
respectively (Table S11). Here, one end of the nip2ꢀ linkers binds
in a bridging bidentate fashion and the other end binds in chelating
mode linking two metal centers to create one dimensional metal
carboxylate ribbons (Fig. 4b) extended along the b-axis. These 1D
3.1.3. {[Fe(4-bpdh)1.5(nip)]ꢁ(4-bpdh)0.5
} (7)
n
ꢀ
Compound 7 crystallizes in the triclinic P1 space group with a Z
value of 2. Single-crystal X-ray structure analysis reveals the for-
mation of a two dimensional (2D) sheet structure with Fe(II) metal
ions connected by 5-nitroisophthalate and 4-bpdh linkers. The
asymmetric unit of 7 contains one Fe(II) ion, one and half bridging
4-bpdh ligands, one 5-nitroisophthalate ligand and half a lattice 4-
bpdh ligand. The central Fe(II) ion (Fe1) adopts a distorted octahe-
dral geometry surrounded by three oxygen atoms (O1, O2 and O6a)
from two different nip2ꢀ ligands and three nitrogen atoms (N1, N5

640
D.K. Maity et al. / Polyhedron 102 (2015) 634–642
Fig. 3. (a) Coordination environment around the Fe(II) ions in 7; Fe (green), N (blue), O (red), C (black). (b) View of the 1D ladder in 7. (c) 2D sheet in 7 constructed by both
5-nitroisophthalate and 4-bpdh ligands (free 4-bpdh ligands are omitted for clarity). (d) 2D sheet containing a free 4-bpdh ligand in the void space of 7. (e) Topological
representation of the 5-connected 2D sheet of 7. (Color online.)
Fig. 4. (a) Coordination environment around the Fe(II) ions in 8; Fe (green), N (blue), O (red), C (black). (b) 1D metal carboxylate chain in 8 along the b-axis (4-bpdb ligands
are omitted for clarity). (c) 2D sheet containing the free 4-bpdb ligand in the pore in 8 (d) Topological representation of (3,5)-connected binodal 2D sheet in 8; Fe (green) and
Nip2ꢀ (pink). (Color online.)

D.K. Maity et al. / Polyhedron 102 (2015) 634–642
641
ribbons are further extended into a 2D sheet in the ab plane with
the linkage of 4-bpdb ligands (Fig. 4c). The 2D sheet contains an
uncoordinated lattice 4-bpdb ligand and a lattice water molecule
in the cavities of the 2D layer. Network analysis by TOPOS [47,48]
suggests that the structure of 8 can be represented as a (3,5)-
connected binodal net with stoichiometry (3-c)(5-c) (Fig. 4d) and
the corresponding Schläfli symbol is {42ꢁ67ꢁ8}{42ꢁ6}.
3.2. Powder X-ray diffraction (PXRD)
Powder X-ray diffraction (PXRD) analysis was carried out to
confirm the phase purity of the bulk materials for all the com-
pounds at room temperature. The experimental PXRD patterns of
complexes 1–8 are in good agreement with the simulated ones
from their corresponding single crystal structures (Fig. S17–S24),
confirming the phase purity of the complexes.
Fig. 5. Emission spectra of complex 6 and the free N,N0-donor linker bpp.
3.3. Thermogravimetric analysis (TGA)
263 and 332 nm (for 3) and 471 and 612 nm with a shoulder
266 nm (for 7). The absorptions in the range 430–800 nm with
peaks at 538 and 696 nm (for 3) are attributed to visible d–d tran-
sitions. As shown in Fig. S26, bpp demonstrates an intense peak at
To investigate the thermal stabilities of complexes 1–8, their
thermal behaviours were studied by thermogravimetric analysis
(TGA). The TGA experiments were performed on complexes 1–8
in the temperature range 30–600 °C under a N2 atmosphere at a
heating rate of 10 °C minꢀ1. The TGA curves for complexes 1–8
are shown in Fig. S25. The TGA curves of the isostructural com-
plexes 1, 2 and 3 are very similar, with two continuous weight
losses. In each case the first step indicates the loss of a loosely
H-bonded guest water molecule in the temperature range
ꢂ55–60 °C and the second step for the loss of two strongly
H-bonded coordinated water molecules in the temperature range
ꢂ130–160 °C. A sharp weight loss in the temperature range ꢂ55–
160 °C (found 10.7% for 1, 9.65% for 2, 9.5% for 3) was attributed
to the loss of the one lattice and two coordinated water molecules
(calcd 9.7% for 1, 9.7% for 2, 9.6% for 3) and the dehydrated frame-
works are further stable up to the temperature range ꢂ360–370 °C.
After that, they gradually decompose into their corresponding
metal oxides nearly at 600 °C. In the case of compounds 4 and 5,
loss of their lattice water molecule occurs at room temperature
and the thermogravimetric analysis (TGA) also supports this. The
TGA curves of the isostructural compounds 4–6 are also similar,
with a single step weight loss. Complexes 4, 5 and 6 are thermally
stable up to 250 °C, with a weight loss in the temperature range
120–160 °C (found 3.44% for 4, 3.66% for 5, 3.3% for 6), correspond-
ing to the release of one coordinated water molecule (calcd 3.74%
for 4, 3.74% for 5, 3.66% for 6); after that on further heating they
decomposes into their corresponding metal oxides before 600 °C.
For 7, the TGA curve shows no significant weight loss up to
225 °C, due to the absence of any solvent molecules, finally leading
to the formation of ferrous oxide at nearly 600 °C. In the case of 8,
the removal of the guest water molecule is observed within the
temperature range 80–95 °C (found, 3.1%; calcd, 3.0%), and the
decomposition of the compound occurs at 220 °C (Fig. S25) and it
finally collapses into ferrous oxide at nearly 560 °C.
276 nm in the UV range, which also corresponds to the p–
p⁄ or n–
p⁄ transition of the aromatic ring. However, complexes 4 and 5
exhibit UV absorption with maxima at 300 nm (for 4) and 261,
306 and 375 nm (for 5), which are a little bit different from that
of the bpp linker, indicating that they may originate from an
intraligand transition (ILCT) or metal to ligand charge-transfer
transition (MLCT); but complex 6, containing same ligand, shows
a different absorption at 280 nm compared to complexes 4 and 5.
The absorption maximum of complex 6 is similar to the free bpp
ligand, which proves in the d10 Zn system no MLCT is possible.
The free 4-bpdb linker and complex 8 shows absorption maxima
at 318 and 542 nm with a shoulder at 327 nm, respectively.
3.5. Luminescent properties
The luminescent properties of CPs with d10 metal centres have
attracted much attention due to their potential applications as
chemical sensors, in photochemistry and electroluminescence
displays. The luminescence properties of complex 6 as well as
the free bpp in the solid state were investigated at room
temperature. The results are depicted in Fig. 5. Complex 6 and
the bpp linker exhibit similar fluorescence emissions with bimodal
bands at ca. 457/476 nm ((kex = 280 nm) and 468/486 nm
(kex = 280 nm), respectively. The ligand emission peaks may be
attributed to p⁄–n or p⁄
–p transitions. From the luminescence
spectra, it is clear that complex 6 shows a totally N,N0-donor linker
based blue shifted fluorescence compared to the bpp linker. It has
been investigated that for d10 complexes, no emission originates
from metal-centered MLCT/LMCT excited states, since d10 metal
ions are difficult to reduce or oxidize [51,52]. So, it is concluded
that the emission bands of complex 6 are exhibited due to
intra-ligand electron transfer. In general, the enhancement of
luminescent intensity is attributed to coordination of a ligand to
a Zn(II) ion, which effectively increases the rigidity of the ligand
and reduces thermal vibrations, thereby giving a reduction of
energy loss by non-radiative decay [53–55].
3.4. Solid-state absorption spectra
The UV–Vis absorption spectra of complexes 1–8 along with the
free N,N0-donor linkers (4-bpdh, bpp and 4-bpdb) were measured
in the solid state at room temperature. As shown in Fig. S26, 4-
bpdh shows two peaks at 253 and 340 nm in the UV range, which
corresponds to the
p
–
p⁄ or n–p⁄ transition of the aromatic ring
4. Conclusion
[49,50]. However, complex 1 exhibits an intense peak at 309 nm,
which is a different from that of the 4-bpdh linker, indicating that
it may be generated from an intraligand transition (ILCT) or metal
to ligand charge-transfer transition (MLCT) [49,50]. Complexes 2–3
and 7 show UV absorption with maxima at 315 and 415 nm (for 2),
Eight different coordination polymers (CPs) of transition metals
based on 5-nitroisophthalate (nip2ꢀ) with three different linear N,
N0-donor dipyridyl linkers (4-bpdh, bpp and 4-bpdb) have been
successfully synthesized by the slow diffusion technique at room

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D.K. Maity et al. / Polyhedron 102 (2015) 634–642
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1D, 2D and 3D structures. Hydrogen-bonding and stacking
p–p
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Authors gratefully acknowledge the financial assistance given
by SERB and CSIR India (Grant to D.G.). D.K.M. and B.B. acknowl-
edge UGC for the senior research fellowship and A.D. acknowledges
UGC for a Post Doctoral Fellowship for Women. The X-ray diffrac-
tometer facility under the DST-FIST program of Department of
Chemistry (JU) is also gratefully acknowledged. Dr. K.K. Rajak of
JU is gratefully acknowledged for the photoluminescence study.
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Appendix A. Supplementary data
CCDC 1406207–1406214 contain the supplementary crystallo-
graphic data for complexes 1–8. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving. html,
or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/10.
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