Syntheses and structural characterization of Cu(II) and Mn(II) coordination polymers with the neutral flexible bidentate N-donor ligands

Article abstract of DOI:10.1016/j.ica.2016.12.021

Four new coordination polymers of [Cu(μ-bip)₂(N₃)₂·2H₂O]_n(1), [Cu(μ-bbd)₂(μ₄-N₃)₄]_n(2), [Mn(μ-bip)₂(NCS)₂]_n(3) and [Mn(μ-bip)₂(N₃)₂]_n(4) were prepared by using the neutral N-donor ligands 1,3-bis(imidazolyl)propane (bip) and 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd), mono-anionic NCS^?or N₃^?ligands and appropriate metal salts of Cu(II) and Mn(II) ions. The results of the X-ray measurements demonstrate that in the crystal structure of 1, 3 and 4 the metal ions adopts MN₆(M = Cu, Mn) an octahedral geometry while, in the structure of 2, the copper(II) ion forms CuN₅trigonal bipyramides. In the polymer 1, 3 and 4 the N₃^?or NCS^?groups are terminally bonded to the metal center and each bip ligand with anti-gauche conformation acts as bridging ligand connecting two metal ions to form a one-dimensional zig-zag chain. Whereas in the polymer 2, the N₃groups adopt so called End-on mode of connection with metal center and the each bbd with anti-anti-anti conformation acts as bridging connecting two copper(II) ions to form a two-dimensional network with a hcb [point symbol (3⁶)] topology. Compounds 1, 3 and 4 are isostructural with each other.

Full text of DOI:10.1016/j.ica.2016.12.021

Accepted Manuscript
Syntheses and structural characterization of Cu(II) and Mn(II) coordination
polymers with the neutral flexible bidentate N-donor ligands
Arash Lalegani, Mohammad Khaledi Sardashti, Mehdi Khalaj, Roman Gajda,
Krzysztof Woźniak
PII:
S0020-1693(16)30640-5
http://dx.doi.org/10.1016/j.ica.2016.12.021
ICA 17383
DOI:
Reference:
Inorganica Chimica Acta
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Received Date:
Revised Date:
Accepted Date:
7 October 2016
15 December 2016
18 December 2016
Please cite this article as: A. Lalegani, M. Khaledi Sardashti, M. Khalaj, R. Gajda, K. Woźniak, Syntheses and
structural characterization of Cu(II) and Mn(II) coordination polymers with the neutral flexible bidentate N-donor
ligands, Inorganica Chimica Acta (2016), doi: http://dx.doi.org/10.1016/j.ica.2016.12.021
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Syntheses and structural characterization of Cu(II) and Mn(II) coordination
polymers with the neutral flexible bidentate N-donor ligands
Arash Lalegani*a, Mohammad Khaledi Sardashtib, Mehdi Khalaja, Roman
Gajdac and Krzysztof Woźniakc
aYoung Researchers and Elite Club, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran
bDepartment of Chemistry, Faculty of Sciences, Shahrekord Branch, Islamic Azad University
Shahrekord, Iran
cBiological and Chemical Research Centre, Chemistry Department, University of Warsaw,
ŻwirkiiWigury 101, 02-089 Warszawa, Poland.
*
E-mail: arashlalegani@yahoo.com
Tel.: +98 2834220838; Fax: +98 2834226118
Abstract
Four new coordination polymers of [Cu(µ-bip)2(N3)2.2H2O]n (1), [Cu(µ-bbd)2(µ4-N3)4]n (2),
[Mn(µ-bip)2(NCS)2]n (3) and [Mn(µ-bip)2(N3)2]n (4) were prepared by using the neutral N-donor
ligands 1,3-bis(imidazolyl)propane (bip) and 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd), mono-
-
anionic NCS- or N3 ligands and appropriate metal salts of Cu(II) and Mn(II) ions. The results of
the X-ray measurements demonstrate that in the crystal structure of 1, 3 and 4 the metal ions
adopts MN6 (M= Cu, Mn) an octahedral geometry while, in the structure of 2, the copper(II) ion
-
forms CuN5 trigonal bipyramides. In the polymer 1, 3 and 4 the N3 or NCS- groups are
terminally bonded to the metal center and each bip ligand with anti-gauche conformation acts as
bridging ligand connecting two metal ions to form a one-dimensional zig-zag chain. Whereas in
the polymer 2, the N3 groups adopt so called End-on mode of connection with metal center and
the each bbd with anti-anti-anti conformation acts as bridging connecting two copper(II) ions to
form a two-dimensional network with a hcb [point symbol (36)] topology. Compounds 1, 3 and 4
are isostructural with each other.
Keywords: Copper; Manganese; N ligands; Coordination polymers; bidentate ligands.
1. Introduction
The design, synthesis and structural characterization of new coordination polymers have received
considerable attention in recent years. The current interest is not only due to a wide variety of

interesting structures, but also because of versatile applications as functional materials. The final
structure of coordination polymer depends on a variety of factors such as: coordination geometry
of the metal ions, the length of a spacer which usually is a rigid or flexible linking ligand, choice
of crystallization solvent, steric hindrance or electronic effects. Apart from these, the choice of a
suitable co-ligand is also important for design of the coordination polymer structures [1]. Among
many types of linking ligands, the N-donor ligands could be used to build both simple and
complex structures of coordination polymers [2]. Many of them reveal interesting luminescent
properties [3]. To form more complex structures, molecules with many N-donor atoms are used
[4]. However, the total number of donor atoms in a ligand does not determine its linking
character. Depending on the distribution of donor atoms within particular molecule and its
conformation, ligands with more than one donor atom can still play a chelating role [5]. In this
paper we are going to focus on coordination polymers which consist of some bidentate N-donor
ligands. In the field of our interest are especially two types of such ligands, namely those
containing imidazole [6] or pyrazole moieties [7]. They are recently successfully used in design
of novel coordination polymers. Such ligands play an important role in coordination chemistry,
and they can coordinate with a variety of transition metals to form 1D, 2D and 3D coordination
polymers. Besides, some weak interactions, such as aromatic π-π stacking, classical hydrogen
bonds (N-H···O and N-H···N) and non-classical hydrogen bonds (C-H···X, X = O, N, F, Cl, Br,
and I) often affect the structures of complexes, and they can further link discrete subunits, or
low-dimensional entities, into high-dimensional supramolecular networks [8]. Apart from bip
and bbd, which play a role of the main linking ligands in the structures of polymers described in
-
this paper, also two other different ligands are used, the azide and thiocyanate ligands. The N3
anion is known to coordinate to metals in both terminal and bridging modes. As bridging ligand,
the azide ligand can link a pair of metal centers in either an End-to-End or End-on coordination
mode (Scheme 1). It is not easy to predict which coordination mode will be adopted by the azide
ligand coordinating to a metal. Coordination polymers of copper(II) azide are of a great research
interest due to their diverse and fascinating structures and potential applications in molecular
magnetism [9]. A similar situation is also with thiocyanate ligands. There are known many
-
structures of coordination polymers in which presence of a N3 ligand enables to form complex
path of connections thanks to its linking role [10]. In this work, we would like to study the

design, synthesis and structural characteristics of new copper(II) and manganese(II) polymers
with two neutral flexible pyrazole and imidazole based ligands (Scheme 2).
Scheme 1. Possible coordination modes for azido ligands.
Scheme 2. Structures of the flexible ligands;bbd [1,4-bis(3,5-dimethypyrazol-1-yl)butane] and
bip [1,3-bis(imidazolyl)propane].
2. Experimental
2.1. Materials and general methods
All experiments were carried out in air. Starting materials were purchased from commercial
sources and used without further purification. The ligand bbd was prepared according to the
published method [7a]. Infrared spectra (4000-400 cm-1) were recorded from KBr disks with a
BOMEN MB102FT-IR spectrometer. Elemental analyses for C, H and N were performed on a
Thermo Finigan Flash EA 1120 CHN analyzer. X-ray powder diffraction patterns were recorded
on a Philips X’Pert Pro diffractometer (Cu Ka radiation, k = 1.54184 Å) in the 2h range 5-50˚.
Thermal analyses were performed on Bahr-STA 503 TG/DTA thermal analyzers under dynamic
nitrogen. A ramp rate of 10 ˚Cmin-1 in the range of 25-900°C was used.

2.2. Preparation of 1,3-bis(imidazolyl)propane (bip)
This ligand was prepared according to the reported method [11] with some modification.
Typically a mixture of imidazole (3.4 g, 50 mmol) and KOH (2.8 g, 50 mmol) in THF (50 mL)
was stirred at 66 °C for 1 h, and the 1-bromo-3-chloropropane (2.4 g, 25 mmol) was added. The
mixture was cooled to room temperature after being stirred at 60 °C for 24 h. The THF was then
removed and extracted with ethyl acetate (100 × 3 mL). The extracted solution was put in a water
bath (90 °C) for 3 h, and the colorless oil bip was obtained in 70% yield (6.2 g). Anal. Calc. for
C9H12N4: C, 61.34; H, 6.86; N, 31.79; found: C, 61.28; H, 6.80; N, 31.71%. Selected IR (KBr,
cm-1):3369 (w), 3127 (m), 2939 (w), 1513 (s), 1451 (m), 1289 (w), 1232 (s), 1109 (s),1088 (s),
936 (m), 830 (m), 751 (m), 662 (s), 623 (s), 468 (w).
2.3. Preparation of [Cu(µ-bip)2(N3)2.2H2O]n(1)
A mixture of EtOH and water (1:1, 5 mL) was gently layered on the top of an aqueous solution
(5 mL) CuCl2·2H2O (0.017 g, 0.10 mmol) in a test tube. A solution of bip (0.035g, 0.2 mmol)
and NaN3 (0.019 g, 0.2 mmol) in EtOH/H2O (2:1, 6 mL) was added carefully as a third layer.
Blue crystals suitable for single crystal X-ray measurements were obtained after a few days (0.41
g, 76% based on Cu). Anal. Calc. for C18H28N14O2Cu: C, 40.33; H, 5.26; N, 36.58; found: C,
40.28; H, 5.19; N, 36.51%. Selected IR (KBr, cm-1): 3394(w), 3130 (m), 2020 (s), 1635 (m),
1517 (m), 1404 (w), 1364 (w), 1272 (w), 1104 (m), 832 (w), 726 (w), 660 (w), 627 (w), 469 (w).
2.4. Preparation of [Cu(µ-bbd)2(µ4-N3)4]n (2)
A mixture of MeOH and water (1:1, 5 mL) was gently layered on the top of an aqueous solution
(5 mL) CuCl2·2H2O (0.017 g, 0.10 mmol) in a test tube. A solution of bbd (0.049g, 0.2 mmol)
and NaN3 (0.019 g, 0.2 mmol) in MeOH/H2O (2:1, 6 mL) was added carefully as a third layer.
Needle transparent crystals were obtained after 6 days. Red crystals suitable for X-ray
crystallography were obtained after a few days (0.45 g, 83% based on Cu). Anal. Calc. for
C14H22Cu2N16: C, 31.05; H, 4.09; N, 41.38; found: C, 40.33; H, 5.26; N, 36.58%. Selected IR
(KBr, cm-1): 3345 (w), 2929 (w), 2859 (w), 2357 (m), 2328 (m), 2082 (s), 2035 (m), 1562 (m),
1364 (w), 1287 (w), 1114 (m), 852 (w), 736 (w), 658 (w).
2.5. Preparation of [Mn(µ-bip)2(NCS)2]n (3)

A mixture of methanol and water (1:1, 5 mL) was gently layered on the top of an aqueous
solution (5 mL) of MnCl2.4H2O (0.0197 g, 0.10 mmol) in a test tube. A solution of bip (0.035 g,
0.2 mmol) and KNCS (0.019 g, 0.2 mmol) in MeOH/H2O (2:1, 6 mL) was added carefully as a
third layer. Transparent crystals were obtained after 4 days (0.39 g, 74% based on Mn). Anal. Cal.
for C20H24MnN10S2: C, 45.88; H, 4.62; N, 26.75; found: C, 45.79; H, 4.53; N, 26.68%. Selected
IR (KBr, cm-1): 3442 (w), 2930 (m), 2050 (vs), 1523 (s), 1236 (m), 1110 (m), 1086 (m), 934 (w),
832 (w).
2.6. Preparation of [Mn(µ-bip)2(N3)2]n (4)
A mixture of methanol and water (1:1, 5 mL) was gently layered on the top of an aqueous
solution (5 mL) of MnCl2.4H2O (0.0197 g, 0.10 mmol) in a test tube. A solution of bip (0.035 g,
0.2 mmol) and NaN3 (0.013 g, 0.2 mmol) in MeOH/H2O (2:1, 6 mL) was added carefully as a
third layer. Transparent crystals were obtained after 4 days (0.41 g, 83% based on Mn). Anal.
Calc. for C18H24MnN14: C, 43.99; H, 4.92; N, 39.90; found: C, 43.21; H, 4.85; N, 39.82%.
Selected IR (KBr, cm-1): 3338 (w), 3116 (m), 2036 (vs), 1620 (w), 1518 (s), 1462 (w), 1440 (w),
1450 (w), 1395 (w), 1328 (m), 1236 (m), 1101 (s), 1087 (s), 932 (s), 822 (m), 760 (m), 663 (s).
Caution: Azide compounds are potentially explosive and should be handled with care.
2.5. X-ray crystallography
The single-crystal X-ray diffraction experiments were carried out using an Agilent SuperNova
diffractometer equipped with Mo radiation source. Collection of the X-ray data as well as unit
cell refinement and initial data reduction were performed by using the CrysAlis Pro software
[12]. The structures were solved by direct methods using the SHELXS program and refined with
SHELXL [13]. Basic parameters describing the measurement procedure as well as the
refinement results are collected in Table 1.
3. Results and discussion
3.1. Synthesis
Coordination polymers 1-4 were prepared by the reactions (1) - (4) in a methanol or ethanol and
water solution.

CuCl2.2H2O + 2NaN3 + 2bip Cu(µ-bip)2(N3)2.2H2O+ 2NaCl+2H2O
CuCl2.2H2O+ 2NaN3 + 2bbd Cu(µ-bbd)2(µ4-N3)4+ 2NaCl +2H2O
MnCl2.4H2O+ 2KNCS + 2bip Mn(µ-bip)2(NCS)2+ 2KCl +4H2O
MnCl2.4H2O + 2NaN3 + 2bip Mn(µ-bip)2(N3)2+ 2NaCl+4H2O
(1)
(2)
(3)
(4)
Polymers 1-4 are relatively stable and can be stored in a desiccator because these complexes
slowly decompose in the ambient air. Both are insoluble in common organic solvents such as
DMF, MeCN, DMSO. The direct mixing of the reactants is not a general method for the
preparation of these polymers because it leads to the formation of precipitate or undesirable
products. In order to get suitable crystals for single crystal X-ray measurements a three-layer
diffusion method was used. In this method a buffer band (methanol or ethanol-water) is utilized
to separate the two solutions, one of them is an aqueous solution of the metal salt and the other is
methanol or ethanol solution of the ligand. When these two solutions diffuse into the buffer band
and meet with each other, the product slowly forms and crystallizes in the buffer band.
3.2. Description of crystal structures
Coordination polymers investigated in this paper consists of three main building blocks: metallic
-
centers (Cu or Mn), linking ligands (bip or bbd) and N3 or NCS- ligands. Herein, we will
describe four of such structures for which single-crystals suitable for X-ray measurements have
been obtained. In general, as a result of mixing of such building blocks two groups of structures
are formed: either one-dimensional coordination polymers or two-dimensional coordination
networks.
3.2.1. One-dimensional coordination polymers
Three out of four synthesized compounds form one-dimensional coordination polymers. These
are: [Cu(µ-bip)2(N3)2.2H2O]n (1), [Mn(µ-bip)2(NCS)2]n (3) and [Mn(µ-bip)2(N3)2]n (4). Because
of a great deal of similarity between these structures, they will be discussed together. In the case
of the structures 1, 3 and 4, where the coordination number of the metallic center is six, all the
polymers are isostructural. They crystallize in the P space group of the triclinic crystal system
with one molecule in the unit cell (Table 1). This means that only half of the molecules are
present in the asymmetric parts of the unit cells. The transition metal atoms are placed at the

inversion centers and are surrounded by six nitrogen atoms, which resemble the axially
compressed octahedral coordination geometry. The equatorial plane is formed by four imine
nitrogen atoms from the imidazole rings of the four symmetry related µ2-bip ligands. The axial
positions are occupied by two azide nitrogen atoms (thiocyanate nitrogen atoms in the case of 3).
In this type of structure, two neighboring metal ions are interconnected by two bridging µ2-bip
ligands (see Fig. 1). As a result; a 20-membered macrocyclic dimeric unit is formed. The dimeric
units are linked together and form infinite one-dimensional chains. Crystal structures of 1, 3 and
4 built of layers formed by such chains (Fig. 2). Each of the linking ligands adopts an anti-
gauche conformation with the dihedral angle between the two imidazole rings are 71.65˚ for 1,
71.25˚ for 3 and 73.57˚ for 4, and links two metal ions through the imines nitrogen atoms. In the
structure of 1, there are two additional water molecules. Each of them is involved into two O-
H···N hydrogen bonds with the azide anions. The H···N hydrogen bond length varies between
2.18 and 2.03 Å. In the presence of such interactions, the neighboring chains are further extended
into a 2D framework structure (Fig. 3).
It is not surprising that even small changes in the structure of linking ligands as, for example a
change of the position of the donor atoms or different spacer lengths can cause significant
changes of the topology of whole structures. Inserting the molecule of bpp (see Scheme 3) to the
structure of 1 instead of bip leads to the formation of a dinuclear complex instead of a
coordination polymer [8d]. There are also known coordination polymers of Mn(II) where the
azido ligands play the role of the bridging ligands. In one of them, where bip is replaced by bipy
(see Scheme 3), three-dimensional coordination network of [Mn(4,4'-bipy)(N3)2]n is formed [14].
In the others, where 2-ampy or 4-azpy is usedinstead of the bip ligand (see Scheme 3), the
coordination polimers built of the 1D chains are also formed [15].
Coordination polymers similar to the compound 3 can also be found in the literature, where
instead of the bip ligand either bpe or bbbt are used (see Scheme 3) [16]. In these cases,some
two-dimensional coordination polymers are formed. However, it must be underlined that in the
case of Mn(NCS)2(bpe), a 2D motif exists only when hydrogen bonds to water molecules
embedded into the structure are included.

Scheme 3. Structures of the ligands: bpp [1,3-bis(3,5-dimethylpyrazolyl)propane]; bipy
(bipyridine); 2-ampy (2-aminopyridine); 4-azpy (4-azidopyridine); bpe (1,2-bis(4-pyridyl)-
ethane); bbbt [1,1'-(1,4-butanediyl)bis-1H-benzotriazole].
3.2.1. Two-dimensional coordination network
The compound 2 crystallizes in the P21/c space group of the monoclinic crystal system with two
molecules in the unit cell (Table 1). Again, this means that only half of the molecule is present in
the asymmetric part of the unit cell. Selected bond lengths and bond angles are given in Table 2.
As shown in Fig. 4, the copper ion in this structure is five-coordinated in a distorted CuN5
trigonal bipyramidal geometry (= 0.78) based on the Addison analysis where = 0.00 describes
a perfect square pyramid and = 1.00 a trigonal bipyramidal geometry [17]. The equatorial
positions of the trigonal bipyramid are defined by one N atom from bbd ligand and two N atoms
from the azide anions. The two axial positions are occupied by N atoms from the other two azide
ligands. The coordination angles around the copper atom are in the range from 79.17(5) to
169.01(6)˚. The particular polyhedra of CuN5 are connected by edges and form ribbons directed
along the b axis (Fig. 5).
The bbd ligand is located at the center of inversion, thus forming the Cu(µ-bbd)(µ4-N3)4 moiety.
The copper atoms are bridged via the nitrogen atoms which belong to the azide ions. In such a
way, the copper and nitrogen atoms form specific four-membered rings. The Cu···Cu distances
within the four-membered ring are 3.185Å and 3.187Å. These moieties are connected by the

bidentate bridging bbd ligand. Thus, a two-dimensional framework with an hcb [point symbol
(63)] topology (Fig. 6) is formed [18]. The topology of this coordination polymer was determined
with the use of the ToposProprogram [19]. In the structure of 2, the µ-bbd ligands show anti-
anti-anti conformation with the shortest N···N and Cu···Cu distances of 7.567 Å and 8.549 Å,
respectively. The dihedral angle between the two 3,5-dimethylpyrazole rings is equal to 0˚. In
addition, the formation of an intermolecular C-H···N hydrogen bond between the azide nitrogen
atom and the C-H bonds of imidazole and phenyl rings of the bbd ligands takes place in this
structure with the distances of 2.46Å, which plays the key role in the formation of the final 3D
structure.
However, a simple substitution of the N3 terminal ligands by NCS leads to the formation of the
[Cu(µ-bbd)(NCS)2]n coordination polymer which is characterized by a distorted square-planar
surrounding of the N-donor atoms around the copper center and a one-dimensional chain
structure similar to that observed in the case of the compound 3 [8g]. Accordingly, the co-ligands
-
(N3 and SCN-) are responsible for directing the dimensionality of these polymers.
3.3. Spectroscopic characterization
The IR spectra of compounds 1-4 exhibit strong bands corresponding to the stretching vibration
of the C=N bonds of the imidazole and 3,5-dimethylpyrazolyl rings of the bip and bbd ligands in
the range from 1517 to 1562 cm-1, respectively. The medium bands in the range from 3345 to
2859 cm-1can be assigned to the C-H stretching vibrations of the methylene group [-(CH2)-] of
the spacer unit. The as(N3) stretching mode of the azido ion, located at approximately 2000 cm-1,
is very useful for determination of the nature of the coordination modes of this group. The
presence of the s(N3) vibration mode is related to the existence of terminal or End-on azido
groups and it does not appear for the End-to-End bridging mode. This fact, together with the
presence of a weak band at about 1297 cm-1 corresponding to the s (N3) vibration mode, support
the presence of both End-on bridging and terminal azido ligands. Intense absorption band at
2020 cm-1 for 1, is attributed to the as(N3) of the terminal azide ligand and the absorption bands
at 2082 cm-1 for 2 attributed to the as(N3) of EO bridged azides [20]. Intense absorption bands at
2050 cm-1 and 2036 cm-1for 3 and 4 are attributed to the (CN) and (NN) of the terminal N-
coordinated thiocyanate and azide ligand, respectively. This is in agreement with the crystal
structures of 3 and 4. The purity of the synthesized compounds was checked by performing X-

ray powder diffraction (XRPD) in which the experimental spectra were consistent with their
simulated spectrum (Fig. S1).
3.4. Thermal analysis properties
In order to examine the thermal stability of the compounds, thermal gravimetric analysis (TGA)
was carried out for polymers 1 – 4 with the heating rate of 10 ˚C min-1 in the temperature range
from 25 to 900 ˚C under the nitrogen atmosphere. As shown in Fig. 7 and Fig. 8 the TGA curves
of 2, 3 and 4 exhibit one main step of weight loss in the ranges from 180 to 250˚C, from 300 to
400˚C and from 210 to 290˚C, respectively corresponding to the combustion of the organic bbd
and bip ligands. Thermal gravimetric analysis of 1 shows that this compound is stable up to ca.
100˚C (Figure 7). The first step started at 100 ˚C and was completed at 180 ˚C, which
corresponds to the release of lattice water molecules. The second step, covering temperature
from 200˚Cup to 410˚C, corresponds to the decomposition of the organic µ2-bip ligands and the
azide groups.
Conclusion
We have successfully synthesized and determined the crystal structure of four new coordination
polymers. All of them were synthesized according to the similar procedure so any differences in
their crystal structure are depended on the building blocks they are formed from. As a result of
mixing these blocks either one dimensional infinite polymeric chains or two-dimensional
coordination network were obtained. Structures containing atom of manganese as a coordination
centre form only one-dimensional polymers but structures with copper as metallic centre is able
to form two-dimensional coordination network. In the case of polymer which is built around
copper, such a network is possible when bbd as linking and N3 ligand are used. The comparison
of the structures of polymers with other structures containing similar building blocks shows that
very subtle changes of the used ligands lead to significantly different structures characterized by
higher or lower level of complexity. Despite the fact that it is too early to make some
generalizations about likely topology of the coordination polymers formed with the use of bbd as
building blocks, the next step towards better understanding of the role of these ligands has to be
taken.
Acknowledgement

We thank Young Researchers and Elite Club, Islamic Azad University Buinzahra Branch and
Warsaw University for the financial support.
Appendix A. Supplementary data
CCDC 1437703, 14337742, 1440534 and 1440537 contains the supplementary crystallographic
data for 1-4, respectively. Crystallographic data can be obtained free of charge from the
Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/datarequest/cif. 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
Table 1. Crystal data and refinement parameters for 1-4.
1
2
3
4
Formula
Formula weight
Crystal system
Space group
a [Å]
C18H24CuN8·2(H2O)·2(N3) C14H22Cu2N16 C20H24MnN10S2 C18H24MnN14
536.08
Triclinic
P
541.55
Monoclinic
P21/c
523.55
Triclinic
P
491.45
Triclinic
P
7.4214(2)
8.3670(3)
10.5154(3)
99.849(3)
100.933(3)
111.815(3)
573.91(3)
1
8.8534(2)
5.8173(1)
20.9816(5)
90
8.8356(4)
8.9643(5)
9.1523(5)
87.336(5)
70.988(5)
63.253(5)
607.72 (6)
1
7.7578(2)
9.0293(3)
9.3674(3)
91.073(3)
104.408(3)
115.427(3)
568.02 (3
1
b [Å]
c [Å]
α [°]
β [°]
90.983(2)
90
 [°]
V [Å3]
1080.45 (4)
2
Z
Dcalcd. [g cm-3]
μ [mm-1]
F(000)
1.551
1.665
1.431
1.437
1.00
2.01
0.75
0.62
279
552
271
255
Rint
0.034
0.056
0.029
0.032
R1[I>2σ(I)]
wR2
0.028
0.038
0.029
0.034
0.071
0.082
0.075
0.094
GOF
1.08
1.13
1.10
1.09
Δ>max, Δ>min (e
0.58, -0.33
0.61, -0.41
0.56, -0.30
1.28, -0.27
Å-3)

Table 2. Selected bond distances (Å) and angles (°) for compounds 1 -4.
Compound 1
Cu(1)-N(1)
Cu(1)-N(4)
Cu(1)-N(5)
Compound 2
Cu(1)-N(4)
Cu(1)-N(1)
Cu(1)-N(7)
Cu(1)-N(4)
2.017(9)
2.020(8)
2.531(1)
92.06(4)
88.06(4)
87.94(4)
180.0(4)
91.94(4)
86.64(4)
180.0(4)
87.94(4)
93.36(4)
93.36(4)
91.94(4)
180.0(4)
92.06(4)
86.64(4)
88.06(4)
179.6(1)
2.161(1)
1.984(1)
2.062(1)
1.971(1)
2.114(1)
94.16(5)
120.33(5)
79.17(5)
117.33(5)
94.14(5)
169.01(6)
78.02(6)
99.76(5)
121.88(5)
97.17(6)
N(1)-Cu(1)-N(5)
N(1)-Cu(1)-N(4)
N(1)-Cu(1)-N(5)
N(1)-Cu(1)-N(1)
N(1)-Cu(1)-N(4)
N(5)-Cu(1)-N(4)
N(5)-Cu(1)-N(5)
N(5)-Cu(1)-N(1)
N(5)-Cu(1)-N(1)
N(4)-Cu(1)-N(5)
N(4)-Cu(1)-N(1)
N(4)-Cu(1)-N(4)
N(5)-Cu(1)-N(1)
N(5)-Cu(1)-N(4)
N(1)-Cu(1)-N(4)
N(5)-N(6)-N(7)
Compound 3
Cu(1)-N(1)
N(4)-Cu(1)-N(1)
N(4)-Cu(1)-N(7)
N(4)-Cu(1)-N(4)
N(4)-Cu(1)-N(1)
N(1)-Cu(1)-N(7)
N(1)-Cu(1)-N(4)
N(1)-Cu(1)-N(1)
N(7)-Cu(1)-N(4)
N(7)-Cu(1)-N(1)
N(4)-Cu(1)-N(1)
Compound 4
Mn(1)-N(1)
Mn(1)-N(4)
Mn(1)-N(5)
2.249(8)
2.237(1)
2.257(9)
86.94(3)
91.23(1)
93.06(3)
180.0(3)
87.68(3)
180.0(4)
92.32(3)
91.23(3)
92.32(3)
180.0(3)
93.06(3)
87.68(3)
88.77(3)
86.94(3)
88.77(3)
178.8(1)
Mn(1)-N(1)
Mn(1)-N(4)
Mn(1)-N(7)
2.239(1)
2.266(1)
2.253(1)
91.52(4)
180.0(4)
88.48(4)
91.31(4)
88.69(4)
88.48(4)
180.0(4)
93.35(4)
86.65(4)
91.52(4)
88.69(4)
91.31(4)
86.65(4)
93.35(4)
180.0(4)
178.3(1)
N(1)-Mn(1)-N(4)
N(1)-Mn(1)-N(5)
N(1)-Mn(1)-N(4)
N(1)-Mn(1)-N(1)
N(5)-Mn(1)-N(4)
N(5)-Mn(1)-N(5)
N(5)-Mn(1)-N(4)
N(5)-Mn(1)-N(1)
N(4)-Mn(1)-N(5)
N(4)-Mn(1)-N(4)
N(4)-Mn(1)-N(1)
N(5)-Mn(1)-N(4)
N(5)-Mn(1)-N(1)
N(4)-Mn(1)-N(1)
N(1)-Mn(1)-N(5)
N(1)-C(10)-S(1)
N(1)-Mn(1)-N(4)
N(1)-Mn(1)-N(1)
N(1)-Mn(1)-N(4)
N(1)-Mn(1)-N(7)
N(1)-Mn(1)-N(7)
N(4)-Mn(1)-N(1)
N(4)-Mn(1)-N(4)
N(4)-Mn(1)-N(7)
N(4)-Mn(1)-N(7)
N(1)-Mn(1)-N(4)
N(1)-Mn(1)-N(7)
N(1)-Mn(1)-N(7)
N(4)-Mn(1)-N(7)
N(4)-Mn(1)-N(7)
N(7)-Mn(1)-N(7)
N(1)-N(2)-N(3)

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Fig. 1. Fragments of [Cu(µ-bip)2(N3)2.2H2O]n (above) and [Mn(µ-bip)2(NCS)2]n (below)
coordination polymers.Hydrogen atoms omitted for clarity.
Fig. 2. Layered structures of 1, 3 and 4 formed by 1D chain. Figure created on the basis of 4.
Hydrogen atoms omitted for clarity. Chains belonging to particular layers colored in green, red
and blue.
Fig. 3. O-H···N hydrogen bonds in the structure of 1. Some hydrogen atoms omitted for clarity.
Fig. 4. Fragment of [Cu(µ-bbd)2(µ4-N3)4]n (2) coordination polymer. Cu atom in five
coordination surrounding of 4 N3 terminating ligands and one bbd linking ligand. Hydrogen
atoms omitted for clarity.
Fig. 5. The arrangement of molecules within the unit cell in the crystal structure of 2; view along
c axis. Hydrogen atoms omitted for clarity
Fig. 6. a) View of a portion of the 2D net in 2 with hcb topology. b) Schematic view of the (63)-
hcb network in the structure of 2.
Figure 7. Thermogravimetric curves for 1 and 2.
Figure 8. Thermogravimetric curves for 3 and 4.
Fig. S1. Experimental and simulated X-ray powder diffraction patterns of 1-4 at 293K.

 Highlights
 Structure of the organic ligands play a dominant role in the structural diversity of these
polymers.
 Co-ligand such as azide and thiocyanate also impact on the structure.
 The polymers have been characterized by X-ray diffraction, elemental and thermal
analyses and infrared spectroscopy.