N-donor ligands-directed coordination of Zn- azido complexes

Article abstract of DOI:10.1016/j.ica.2017.09.064

Two zinc (II) pseudo-halide complexes [Zn(L₁)(N₃)₂]_n (1 L₁: 1,2-diaminocyclohexane) and Zn(L₂)₂(N₃)₂ (2 L₂: 4,5-dimethy-2-(pyridine-2-yl) imidazo

Full text of DOI:10.1016/j.ica.2017.09.064

Accepted Manuscript
Research paper
N-donor ligands-directed coordination of Zn- azido complexes
Jing-Wen Wang, Chen Chen, Yao-Ja Li, Yang-Hui Luo, Bai-Wang Sun
PII:
S0020-1693(17)31006-X
https://doi.org/10.1016/j.ica.2017.09.064
ICA 17923
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
28 June 2017
19 August 2017
29 September 2017
Please cite this article as: J-W. Wang, C. Chen, Y-J. Li, Y-H. Luo, B-W. Sun, N-donor ligands-directed coordination
of Zn- azido complexes, Inorganica Chimica Acta (2017), doi: https://doi.org/10.1016/j.ica.2017.09.064
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N-donor ligands-directed coordination of Zn-azido
complexes
Jing-Wen Wang, Chen Chen, Yao-Ja Li, Yang-Hui Luo*, Bai-Wang Sun*
School of Chemistry and Chemical Engineering, Southeast University, Nanjing
2
11189, P. R. China
*E-mail: peluoyh@sina.com (Luo); chmsunbw@seu.edu.cn (Sun); Fax:
+86-25-52090614; Tel：+86-25-52090614.

Abstract two zinc (II) pseudo-halide complexes [Zn(L
1
)(N
3
)
2
]
n
(1
1
L :
1
,2-diaminocyclohexane) and Zn(L (N (2 L : 4,5-dimethy-2-(pyridine-2-yl)
2
)
2
3
)
2
2
imidazole) have been synthesized and characterized. Single-crystal X-ray structural
II
analysis revealed that the central Zn atoms in 1 displays distorted trigonal
–
bipyramidal arrangement with a 1D chain structure bridged by N
3
anions, while in 2,
II
the central Zn atoms incorporating with two bidentate L
2
ligands, and adopts an
octahedral geometry and shows a “butterfly” coordination framework. Structural
analysis demonstrated that the organic ligands play an important role in determining
the resultant structure. In addition, both complexes were further characterized by
thermal stability properties and Hirshfeld surface analysis.
Keywords Crystal structure; Coordination polymer; N-donor ligands; azido.
1
Introduction
Over the past years, coordination polymers (CPs) and metal-organic frameworks
MOFs) are the subjects of great interest due to their intriguing variety of topologies
(
and structures as well as their enormous potential in many fields, such as magnets,
ion-exchange, heterogeneous catalysts, chemical sensing, luminescence and gas
storage [1-7]. Despite the remarkable achievements reached in this aspect so far, the
rational control in the construction of coordination frameworks remains a
considerable challenge at this stage and much more work is required to extend the
knowledge in this field [8-11]. To a certain degree, the final structures of coordination
polymers and metal-organic frameworks can be reasonably controlled and directed by
combination of various forces such as metal-ligand coordination bond and much

weaker interactions [12-14].
In addition, several factors including metals atoms, temperature, the organic
anions and N-donor ligands can affect the final structures of coordination polymers
and metal-organic frameworks [15-18]. Taking into account the various factors, the
choice of the organic ligand is a key factor that affects the construction of
coordination compounds with interesting structures [19, 20]. Besides, the skillful
introduction of co-ligands into the self-assembly process can also result in completely
different structural motifs [10, 21]. Organic N-heterocycle ligands are good building
blocks for the construction of coordination polymers or metal-organic frameworks,
beacuse amino groups and multidentate chelating aromatic nitrogen atoms have an
excellent coordination capability and versatile coordination modes [22-24]. Among
them, imidazole derivatives are regarded as interesting ligands, because they can
adopt different conformations according to the geometric needs of the different metal
3
ions [24]. On the other hand, cleavage of the sp C-N bond in cyclohexylamine (87.6
-1 2
kcal mol ) is relatively facile [23], so it can be used as an excellent multi-functional
ligand for the construction of coordination polymers [25-27]. Additionally, in our
-
-
previous work, the effect of pseudohalide anions (SCN and SeCN ) on the
spin-crossover of SCO systems was proof and the multidendate 4,5-dimethy-2
-
(pyridine-2-yl)imidazole was selected as organic ligand to react with Fe(ClO
4
2
) [ 28,
29].
Taking inspiration from the points mentioned above, we explored organic
aromatic ligand 4,5-dimethy-2-(pyridine-2-yl)imidazole as organic ligand (L ),
2

-
3
pseudohalide (N ) were selected as co-ligands, beside, saturated N-heterocyclic
ligand 1, 2-cyclohexanediamine, which can adopt various coordination modes to bind
metal centers of specific coordination geometry, is employed as another comparative
organic ligand, to react with Zn(NO
different types of organic ligands on the structures and properties of coordination
compounds. As expected, two new complexes have been obtained [Zn (L )(N (1)
and Zn(L (N ) (2) (Scheme 1). Single-crystal X-ray diffraction results revealed that
3
2
) , aiming to further investigate the influence of
1
3 2 n
) ]
2
)
2
3
the 1 displays a 1D chain polymer with five-coordinated trigonal bipyramidal
arrangement while 2 is in six-coordinated octahedral geometry. TGA, PXRD and
Hirshfeld Surface also were performed.
2
Results and discussion
2.1.1 Crystal Structure of Complex 1
II
The asymmetric coordination unit of complex 1 composed of one central Zn ion, one
-
II
L
1
ligand and two N ions. As can be seen in Figure 1b, the each central Zn ion is
3
five-coordinated in a distorted trigonal bipyramidal environment with five N atoms,
-
two from L ligands [Zn1-N2: 2.078(2) and Zn1-N1 2.019(3) Å] and three from N
3
1
ligands [Zn1-N6: 2.237(3) Å, Zn1-N8= 2.306(3) Å, Zn1-N3: 1.974(3) Å]. Where, the
axial positions are occupied by N1, N2 and N3 with the N1-Zn1-N3 bond angle of
137.14 (2), N2-Zn1-N3 bond angle of 136.21 (3) and the equatorial mean plane is
slightly distorted with N6-Zn1-N8 bond angle of 175.34 (19). The L ligand behaves
1
-
as the bidentate ligand via two amino groups, and N
3
co-ligands bridge the adjacent
II
central Zn ions affording a 1D chain structure with the Zn···Zn distance of

-
6
.310(1)Å (Figure 1b). The N anions use two different types of bridging modes. One
3
-
N
3
behaves as the terminal ligand, adopting the EO-bridged azide pairs binding mode;
-
the other N
3
behaves as the EE-bridged azides with N6-Zn-N8 into an infinited 1D
chains forming a coordination polymer, additionally, these adjacent 1D chains are
…
further connected via N-H N hydrogen bonding interaction between coordinated
-
amino group of L
1
ligand and the uncoordinated N atoms of N
3
ions as well as
…
C-H C weak interaction to resulting in 3D layered structure (Fig. 1c).
Figure 1 (a) The asymmetric unit of compounds 1. (b) 1D chain diagram of
compound 1. (c) The crystal packing of compound 1 viewed along the b-axis and the
intermolecular hydrogen bond interactions have been marked. Hydrogen atoms are
omitted for clarity.

Table 2 Selected bond lengths (Ǻ) and angles (°) for complexes 1 and 2
1
1
2
2
Zn1-N1
Zn1-N2
Zn1-N3
Zn1-N6
N1-H-N5
2.038
2.089
1.971
2.248
3.350
Zn1-N1
Zn1-N2
Zn1-N4
Zn1-N5
Zn1-N7
Zn1-N9
1.964
1.951
2.004
1.970
1.941
1.969
1.9665
83.15
88.75
170.03
173.84
88.37
177.30
Mean
2.0865
86.15
138.33
92.69
90.81
N1-Zn1-N2
N1-Zn1-N3
N2-Zn1-N6
N3-Zn1-N6
N1-Zn1-N2
N7-Zn1-N4
N7-Zn1-N5
N2-Zn1-N9
N5-Zn1-N9
N1-Zn1-N4
2.1.2 Crystal Structure of Complex 2
Complex 2 crystallizes as colorless block crystals in the orthorhombic Pbcn space
II
-
group, the asymmetric unit (ASU) consisting of a Zn ion, two N
3
ions, and two
II
ligands L
2
(Figure 2a) displays a ‘‘batterfly-like” motif. In the crystal, each Zn ion
adopts a distorted six-coordinated in an octahedral geometry surrounded by four N
-
atoms originating from ligands L
2
liking two wings and two N atoms from N
3
ions
which just similar to two antennae. Every ‘‘batterfly” motif packed into 1D chains
…
through N3 N6 solitary electrons contacts (Fig. 1b), and the 1D chains then stacked
…
...
into 3D motif (Fig. 1c) by C-H π and π π weaker interactions. For the ‘‘batterfly-like”
unit, the average Zn-N distance is 1.9665 Ǻ (Table 2) which is significantly shorter
-
than which has been reported complexes [10, 30]. Besides, the N
3
ion is almost linear
[
[
N7-N8-N20, 177.47(7)], whereas the Zn-N-N (N) linkages are slightly bent
Zn1-N7-N8, 119.23(5)]. In addition, the selected bond distances and angles of
complexes 1, 2 are tabulated in Table 2 and geometrical parameters for hydrogen

bonds are shown in Table 3.
Figure 2. (a) The asymmetric unit of compounds 2. (b) 1D chain diagram of
compound 2 (c) The crystals packing of compound 2 viewed along the b-axis.
Hydrogen atoms are omitted for clarity.
2
.1.3 Structural Discussion of Complexes 1 and 2
Complexes 1 and 2 were obtained via the assembly of Zn(NO
the presence of ligand L , L respectively, affording different coordination modes and
-
3 2 3
) and azido (N ) with
1
2
supramolecular lattices, coordination polymers (CPs) and metal-organic frameworks
II
(
MOFs), respectively. In complexes, the central Zn ion adopts five- and
six-coordinated forming two different distorted arrangement, trigonal bipyramidal and
octahedral geometry, for compounds 1, 2, resulting from the different N-heterocycles
donor organic ligands which L
1
belongs to saturated, whereas L is a part of aromatic
2
compounds. It implies the saturation of N-donor ligands can influence coordination
-
modes of compounds. Besides, it should be noted that the N
3
anions represent two

kinds of binding modes (EO and EE bridged model) in 1 and only adopts EO bridged
model forming the monodentate coordination fashions in 2. As a result, compound 1
shows an infinite 1D coordination polymer and 2 displays mononuclear metal-organic
framework compound. These structural distinguish may be ascribed to the distinct
coordination ability and steric bulk of the N-heterocyclic ligands (L
1
and L ).
2
Table 3 Geometrical parameters for the hydrogen bonds in compounds 1 and 2.
.
..
…
...
...
D-H A
D A(Å) H A(Å) ∠D-H A(°)
Symmetry operation
Compound 1
.
..
N1-H1A N5
3.411
3.084
3.141
3.171
3.448
2.622
2.422
2.310
2.298
2.597
148.29
131.44
155.47
167.06
160.26
3/2-x, -1/2+y, -1/2+z
3/2-x, -1/2+y, -1/2+z
3/2-x, 1/2+y, -1/2+z
3/2-x, 1/2+y, 1/2+z
3/2-x, -1/2+y, 1/2+z
...
N1-H1A N6
...
N1-H1B N3
...
N2-H2A N3
...
N2-H2B N5
Compound 2
…
C1-H1 N20
3.376
3.534
2.735
2.634
126.82
156.29
…
C10-H10A N11
2.2 Hirshfeld Surface
Hirshfeld surface is a powerful tool for the identification of intermolecular
interactions. The 3D dnorm values are mapped onto a red-blue-white color Hirshfeld
surface and red regions represent closer contacts, blue regions represent longer
contacts and white regions represent the distance of contacts which is exactly the vdW
separation. What is more, the 3D dnorm can be converted into 2D fingerprint plots,
which we can analysis the intermolecular contacts and get a quantitative summary of
the nature and type of intermolecular contacts [31, 32].
The 3D Hirshfeld surface (dnorm) and 2D fingerprint plots of complex 1 and 2 are
shown in Figure 3. In complex 1, the red regions on the dnorm surface represent the
…
significant N-H N hydrogen bonding interactions, which represent the closest

Figure. 3 3D molecular Hirshfeld dnorm surfaces and 2D fingerprint plots of
complexes 1 and 2.
intermolecular interactions in the crystal. The small red points on the dnorm surfaces
are corresponding to the significant N4-Zn interaction, which due to the close
II
approach of an N atom of azide anion to the central Zn ion. And the blue regions
…
represent the H H interactions. Obviously, the blue regions occupy the most of
Hirshfeld surface about 35.8% to the total Hirshfeld surfaces. Actually, the proportion
…
…
of N-H N and N Zn interaction calculated by two-dimensional (2D) fingerprint plot

are found to be 47.3%, and 1.8% to the total Hirshfeld surfaces of complex 1, which is
consistent with the analysis of the crystal structure. In complex 2, the larger red
regions on the upper right and bottom right of the dnorm surfaces are corresponding
…
…
to the C-H N weak hydrogen bonding and N N interactions which have a great
significant contribution to the total Hirshfeld surfaces with comprise of 36.4%, 2.2%,
…
respectively, to the total Hirshfeld surfaces. Interestingly, N Zn interactions are found
…
only in compound 1, and C H intermolecular interactions exist only in compound 2.
These differences of the interaction in the crystal structures of compounds 1, 2 also
…
are clearly shown in Fig. 1 and Fig. 2. Apart from those above, the presence of H H,
…
…
N N and C N intermolecular interactions are observed, and the percentages of them
are summarized in Fig. 4.
Figure. 4 Percentage contributions from individual intermolecular interactions to the
Hirshfeld surfaces of complexes 1 and 2.
2.3 Thermal Study
The thermal behaviors of complexes L
1
and L are investigated on a Proteus Thermal
2

analyse system (from NETZSCH TG 2009 F3) and the heating rate is around 20 K
-1
min with the temperature range of 30-600℃. Figure 5 shows the TGA traces of them.
For complex 1, the complex keeps stable up to 292 °C and then suffers a sharp weight
loss until heating to 330 °C, which is due to the decomposition of the ligands with
mass loss of 38.52% (the calculated ratio is 42.48%) to give the Zn(N
3
2
) residue. With
regard to complex 2, the thermal profile of 2 is different from the 1, the abrupt weight
loss of the main framework occurs from 359 °C, by the mass decomposition of two
ligands about 70.38% (the calculated ratio is 69.83%). In addition, the phase purities
of the complexes are also identified by PXRD patterns, which show the essential
II
difference to diverse central Zn ion distorted arrangement (Figure. 6).
Figure. 5 TGA profiles of compounds 1, 2 in the temperature range of 30-600℃.
Fig. 6 Experimental and simulated PXRD patterns for both complexes

3
Conclusions
In summary, two new zinc (II) coordination complexes, [Zn(L
1
3 2 n
)(N ) ] (1) and
Zn(L (N (2), have been successfully synthesized and structurally characterized.
2
)
2
)
3 2
Single-crystal X-ray analysis show structural diversity in both complexes essentially
II
arising from the usage of different ligands resulting in different central Zn ion
distorted arrangement, trigonal bipyramidal and octahedral geometry, respectively. In
…
addition, complex 1 exhibits the characteristic Zn N interaction. Systematic
exploration of the significant ligands effect with other metal atoms as well as
pseudo-halide ions is currently underway and this work will contribute to further
insights in the rational design of coordination complexes.
4
Experimental
4.1 Materials and physical measurements
All reagents were obtained commercially, and used without further purification.
thermogravimetric analysis (TGA) was performed using a NETZSCH TG 2009 F3
-
1
system at a heating rate of 20 K min under an atmosphere of dry nitrogen flowing at
3
-1
2
0 cm min over the range from 50 to 600℃. Elemental analyses for carbon,
hydrogen and nitrogen were performed using a Vario-EL III elemental analyzer. X-ray
powder diffraction was recorded on a D8 ADVANCE XRD (Bruker, Germany) with
Cu Kα radiation (λ = 1.54056 Å) at 40 mA and 45 kV. The sample was packed into a
glass holder and diffraction patterns were collected over a 2θ range of 5-50, at a scan
-1
rate of 3° min .

4
.2 Synthesis of L
The synthetic routes of the ligand L
oxalylchloride (10 mmol) was added dropwise to a CH
2
(4,5-dimethy-2-(pyridine-2-yl)imidazole).
are illustrated in Scheme 1 [28]. 1 ml
Cl solution (100 ml) with 1.5
2
2
2
g N-methylacetamide (20 mmol) at 0℃ under heavy gas evolution. After stirred for
about 30 min, 2-pyridine carboxamide (2.74 g, 10 mmol) was added. The obtained
mixture was stirred for 3h at rt, and the volatiles were removed under reduced
pressure. The residue was dissolved in an aqueous solution of NaHCO
refluxed for a further 2 h at 100 ℃. The water phase was extracted three times with
CHCl . The organic phase was concentrated and re-crystallized from MeOH gave the
ligand L . Yield: 1.14 g, ca. 78%. Elemental analysis (%) for L ): Calc.: C,
9.34; H, 6.40; N, 24.25; found: C, 69.27; H, 6.44; N, 24.19%. IR (KBr, cm1): 3048,
3
(60 ml) and
3
2
2
(C10
H
11
N
3
6
2
9
1
1
980, 2180, 1750, 1560, 1562, 1533, 1482, 1340, 1269, 1235, 1120, 1040, 1015, 987,
1
60, 798, 747, 721. H NMR d: 2.67-2.75 (d, 6H), 7.36 (m, H), 7.85 (m, 1H), 8.38 (d,
1
3
H), 8.59 (d, 1H), 13.00 (s, 1H). C NMR d: 12.6, 43.5, 124.5, 125.6, 131.6, 137.2,
43.4, 149.2, 155.1, 165.9.
Scheme 1. The synthetic route for ligand L .
2
4
.3 Synthesis of complexes 1 and 2.
To a solution of Zn(NO ·6H O (0.4 mmol) in MeOH (10 mL), a solution of ligand
(0.8 mmol) in MeOH (10 mL) was added. The mixture was added into an aqueous
3
)
2
2
L
1

3
solution containing NaN (0.8 mmol) under continuous stirring (Scheme 2). After
stirring for about 30 min, the solution which results from the mixture was filtered off
and allowed to evaporate at room temperature. Crystals suitable for X-ray
single-crystal diffraction or PXRD were obtained within two weeks and collected by
filtration. Yield: ca. 85%. Elemental analysis (%) for 1 (C
H, 0.38; N, 42.51; found: C, 27.43; H, 0.78; N, 42.52%. Complex 2 is synthesized
using a similar method (C20 12Zn): Calc.: C, 48.63; H, 4.08; N, 34.04; found: C,
8.65; H, 4.10; N, 34.24%.
6
H
14
8
N Zn): Calc.: C, 27.33;
20
H N
4
Scheme 2. The synthetic route for complexes 1 and 2.
4.4 X-ray crystallographic study
The single-crystal X-ray diffraction data of complexes 1 and 2 were collected with
graphite-monochromated Mo Ka radiation (λ= 0.071073 nm). A Rigaku SCXmini
diffractometer with the v-scan technique was used [33，34]. The lattice parameters
were integrated using vector analysis and refined from the diffraction matrix, the

absorption correction was carried out by using Bruker SADABS program with the
multi-scan method. The structures were solved by full-matrix least-squares methods
2
on all F data. The SHELXS-2014 and SHELXL-2014 programs [35] were used for
structure solution and structure refinement, respectively. The molecular graphics were
prepared by using the mercury program [36].
Table 1 Crystal data and structure refinement for compounds 1, 2.
Molecular salts
Formula
1
2
C
6
H
14
N
8
Zn
20 20
C H N12Zn
Formula weight
Crystal system
Space group
a/ Å
263.63
orthorhombic
Pna2
493.85
orthorhombic
Pbcn
1
24.882(5)
6.3101(13)
6.9762(14)
1095.3(4)
4
19.000(2)
16.4176(18)
14.5330(16)
4533.5(9)
8
b/ Å
c/ Å
3
V, Å
Z
-3
D calc ( Mg m )
1.586
1.447
T/K
293(2)
293(2)
-
1
µ (mm )
2.225
1.796
Cryst dimensions
0.2×0.25×0.32
0.3×0.25×0.2
3993
No. of reflns collected 2480
No. of unique reflns
No. of params
1863
116
2102
298
2
Goodness-of-fit on F
R1,wR2 (I>2σ(I)
R1,wR2 (all data)
CCDC NO.
1.089
1.050
0.0579, 0.1378 0.1264, 0.3374
0.0812, 0.1505 0.1979, 0.3975
1557016
1557017
Note: due to the poor quality of crystal 2, some of the data collected is not very good but this does
not affect the final structure.
Acknowledgements
This research was based on work supported by the Natural Science Foundation of
China (Grant Nos. 21371031 and 21628101), International S&T Cooperation Program

of China (No. 2015DFG42240) and the Priority Academic Program Development
PAPD) of Jiangsu Higher Education Institutions.
(
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Highlights
ꢀ
ꢀ
The connecting motif of two different organic ligands have been characterized;
-
3
The influence of ligands on the structure of complexes with N anions has been
demonstrated;
-
ꢀ
The connecting types N
3
anions have been classified.

The influences of organic ligands with different binding motifs on the structures and
Ⅱ
-
properties of coordination compounds with Zn and N
3
anions have been
demonstrated.