Hydrothermal synthesis of two Zinc coordination Polymers with 1-(1H-Tetrazol-5-ylmethyl)-1H-benzotriazole Ligands

Article abstract of DOI:10.1002/zaac.201300206

The direct reaction of ZnBr2 with H-1-mbtz [1-mbtz = 1- (1H-tetrazol-5-ylmethyl)-1H-benzotriazole] gives the two-dimensional complex [Zn(Br)(1-mbtz)] (1), whereas the reaction of benzotriazol-1- yl-acetonitrile with NaN3 in the presence of water and a Lewis acid (ZnBr2) affords the 2D coordination polymer [Zn₂(OH)(1-mbtz)3H₂O] (2). The central zinc atom in 1 is bonded to one terminal bromine atom and three different nitrogen atoms from two tetrazole ligands and one BTA group (BTA = benzotriazole), and each 1-mbtz ligand is coordi- nated to three zinc atoms forming a 2D framework. The coordination polyhedron around the metal atom in 2 is a slightly distorted trigonal bipyramid made up by one zinc atom, four nitrogen atoms as well as one oxygen atom, two of the 1-mbtz ligands coordinated to three zinc atoms and the third 1-mbtz ligand acts in a bidentate fashion, which leads to the formation of a complicated 2D network. The syntheses and solid-state structures of the two coordination polymers are reported.

Full text of DOI:10.1002/zaac.201300206

ARTICLE
DOI: 10.1002/zaac.201300206
Hydrothermal Synthesis of Two Zinc Coordination Polymers with
1-(1H-Tetrazol-5-ylmethyl)-1H-benzotriazole Ligands
Su-Wen Sun,[a] Lei Jin,[a] Ping-Ping Shi,[a] Ming-Liang Liu,[a] Li-Hui Kong,[a] and
Qiong Ye*[a]
Keywords: In situ synthesis; Tetrazole; Zinc; Hydrothermal condition; Crystal structure
Abstract. The direct reaction of ZnBr2 with H-1-mbtz [1-mbtz = 1- nated to three zinc atoms forming a 2D framework. The coordination
(1H-tetrazol-5-ylmethyl)-1H-benzotriazole] gives the two-dimensional polyhedron around the metal atom in 2 is a slightly distorted trigonal
complex [Zn(Br)(1-mbtz)] (1), whereas the reaction of benzotriazol-1-
bipyramid made up by one zinc atom, four nitrogen atoms as well as
yl-acetonitrile with NaN3 in the presence of water and a Lewis acid one oxygen atom, two of the 1-mbtz ligands coordinated to three zinc
(ZnBr2) affords the 2D coordination polymer [Zn2(OH)(1-mbtz)3H2O] atoms and the third 1-mbtz ligand acts in a bidentate fashion, which
(2). The central zinc atom in 1 is bonded to one terminal bromine atom
leads to the formation of a complicated 2D network. The syntheses and
and three different nitrogen atoms from two tetrazole ligands and one solid-state structures of the two coordination polymers are reported.
BTA group (BTA = benzotriazole), and each 1-mbtz ligand is coordi-
thesis through [2+3] cycloaddition reactions between organic
Introduction
cyano compounds and NaN3 in the presence of Zn2+ ions as
In recent years, the design of metal-organic frameworks
Lewis acid catalyst (Scheme 1). Hydrothermal or solvothermal
(MOFs) containing central metal atoms and multi-functional
syntheses acting as powerful methods to construct novel coor-
ligands have triggered tremendous interests and attention ow-
dination polymers have been extensively developed. Xiong and
ing to their fascinating structural diversities[1–6] and potential
co-workers[32,33] have found that single crystals of coordina-
applications in numerous fields such as catalysis, nonlinear op-
tion polymers can often be produced under hydrothermal con-
tics, electrical conductivity, gas storage, magnetism, fluores-
ditions. As a result, combining the in situ tetrazole ligands
cence, and ferroelectricity.[7–12] In order to acquire designed
syntheses and the utilization of hydrothermal techniques, a
frameworks and predictable properties, a wide range of re-
number of novel coordination polymers have been
search and studies are being focused on constructing novel
reported.[34–36] In comparison with the direct tetrazole-synthe-
MOFs by selecting versatile organic ligands and functional
sis method using tetrazole precursor derivatives (usually a cy-
metal ions. Accordingly, heterocyclic carboxylic acids such as
ano group), the in situ hydrothermal synthesis was shown to
benzotriazoly-, tetrazoly-, pyridine-, and pyrazole- as building
initiate [2+3] cycloaddition of azides with nitriles and has ab-
blocks have attracted much attention.[13–20] Among these het-
solute advantages. Firstly, the benefit of the in situ method is
erocyclic rings, especially, ligands based on tetrazolate have
making all the reactions occur just in one step, being able to
been one of the most attractive themes because they possess
assemble the desired product in one step, whereas the direct
multiple coordination modes and have the ability to produce
method maybe require more than one step. Secondly, the in
various types of MOFs that display abundant marvelous archi-
situ method is highly efficient as there is no need for ligand
tectures.[21–29] In 2001, Sharpless and co-workers described a
synthesis and thus being environmental friendly.[37] Lastly, it
safe, convenient and environmentally friendly approach for the
is easier to get more complicated structures through the in situ
synthesis of 5-substituted 1H-tetrazoles, which can be ac-
method.
complished with water as solvent and zinc salts as cata-
lysts.[30,31] Ever since, there have been tremendous research
interests aimed at investigation of in situ tetrazole ligand syn-
* Dr. Q. Ye
Fax: +86-25-52090626
E-Mail: yeqiong@seu.edu.cn
Scheme 1.
[a] Ordered Matter Science Research Center
College of Chemistry and Chemical Engineering
Herein we have repeated the Demko-Sharpless reaction un-
der hydrothermal conditions in an effort to generate crystals
that may follow the structural regular patterns of the solid in-
termediates. Therefore, we report the syntheses and crystal
Southeast University
Nanjing 211189, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300206 or from the au-
thor.
Z. Anorg. Allg. Chem. 2013, 639, (12-13), 2317–2323
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Q. Ye et al.
ARTICLE
structures of two 2D zinc tetrazole coordination polymers, compound 1 adopts a two-dimensional coordination network
where BTA (BTA = benzotriazole) and tetrazole ligands exist and the asymmetric unit contains one 1-mbtz ligand and one
together. The direct reaction of ZnBr2 with H-1-mbtz under zinc atom as well as one bromine atom. The local coordination
hydrothermal reaction conditions was completed. Surprisingly, environment around the central zinc ions can be best described
the reaction products obtained in the in situ synthesis and the as a slightly distorted tetrahedral arrangement (Figure 1),
direct synthesis have quite different framework structures.
where each zinc ion is bonded to one terminal bromine atom
(Br1) and three different nitrogen atoms [N1i, N4ii, N6; sym-
metry code: (i) –x, 2–y, 2–z; (ii) x, 1.5–y, 0.5+z], which belong
to the tetrazole ligand (N1i, N4ii) and the BTA group (N6).
The bond lengths of Zn–N range narrowly from 2.014(2) to
2.024(2) Å and the bond length of Zn1–Br1 is 2.3286 Å, show-
ing the weaker binding force with the zinc ion. The Zn–N bond
lengths are slightly shorter than those in Zn(OH)(3-ptz)
Results and Discussion
[ZnBr(1-mbtz)] (1) is obtained by the treatment of H-1-
mbtz, ZnBr2, and H2O under hydrothermal conditions, whereas
the reaction of benzotriazol-1-yl-acetonitrile with NaN3 in the
presence of water and a Lewis acid (ZnBr2) under similar con-
ditions yields [Zn2(OH)(1-mbtz)3H2O] (2). For each reaction
the IR spectrum indicates the absence of the cyano group,
which is consistent with [2+3] cycloaddition between the cy-
ano group and the azide anion, suggesting that cyano has
changed to the tetrazole with several typical tetrazolyl group
peaks at 1453, 1475, and 1343 cm–1. Bands at 1555, 1483,
1155, 789, and 705 cm–1 are attributed to the benzotriazole
aromatic ring. Disappearance of the N–H vibrations of the li-
gand suggests that the nitrogen atoms of the tetrazole ligand
were ionized to balance the charge of the metal ion. In the IR
spectrum of 2, strong peaks and wide band over 3400 cm–1
suggests that the hydroxyl group and coordinated water mole-
cules are present.
(3-ptz
=
3-pyridyltetrazole) [2.042(4)–2.464(4) Å] and
ZnCl(4-ptz) (4-ptz = 4-pyridyltetrazole) [2.026(4), 2.031(3),
and 2.036(4) Å].[38] Meanwhile, the N–Zn–N angles range
from 103.75 (10)° to 114. 22(1)° and the N–Zn–Br angles from
108.07(7)° to 114.72(7)°, which obviously have a large
deviation from the ideal angle (109.47°) and thus creating dis-
torted tetrahedra. Besides, each 1-mbtz ligand is coordinated
to three central zinc atoms leading to the formation of the 2D
layered network. As shown in Figure 2, two zinc atoms link
the two 1-mbtz ligands resulting in the formation of a 16-
Compound 1 crystallizes in the monoclinic system, space
group P21/c. Crystallographic data of 1 (Table 1) reveals that
Table 1. Crystal and refinement data of 1 and 2.
1
2
Empirical formula
Formula weight
Temperature /K
Radiation, Wavelength /Å
Crystal system
Space group
Unit cell parameters
a /Å
b /Å
c /Å
α /°
β /°
C8H6BrN7Zn
345.48
293(2)
Mo-Kα; 0.71073
monoclinic
P21/c
C48H40N42O3Zn4
1514.70
293(2)
Mo-Kα; 0.71073
triclinic
¯
P1
Figure 1. Coordination environments of the central ZnII atoms in com-
pound 1 (30% probability thermal ellipsoids). Hydrogen atoms are
omitted for clarity. The label (i), (ii), and (iii) were generated by sym-
metry code: (i) –x, 2–y, 2–z; (ii) x, 1.5–y, 0.5+z; (iii) x, 1.5–y, –0.5+z;
respectively.
7.3032(14)
8.521(2)
17.015(3)
90
93.194(11)
90
1057.2(4), 4
2.171
0.2ϫ0.2ϫ0.2
8.4270(17)
9.5626(19)
18.648(4)
80.83(3)
79.79(3)
73.56(3)
1408.9(5),1
1.785
0.2ϫ0.2ϫ0.2
3.14–27.48
γ /°
Volume /Å3, Z
Calculated density /g·cm–3
Crystal size /mm3
θ Range for data collection 3.39–27.47
/°
Color
Crystal shape
colorless
block
colorless
block
Reflections collected
Independent reflections
10210
14497
2398 [R(int)
0.0523]
154
1.042
R1 = 0.0340,
=
6401 [R(int)
0.1286]
442
1.039
R1 = 0.0852,
=
Parameters refined
Goodness-of-fit on F2
Final R indices [I Ͼ[2θ(I)]
wR2 = 0.0762
R1 = 0.0387,
wR2 = 0.1630
R1 = 0.1422,
R indices (all data)
wR2 = 0.0791
0.494 and –0.879
wR2 = 0.1814
1.537 and –1.123
Largest diff. peak and hole
Figure 2. 2D sheet structure of compound 1 paralled to bc plane. Hy-
drogen atoms and some ligands are omitted for clarity.
/e·Å–3
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Hydrothermal Synthesis of Zinc Coordination Polymers
membered ring (Ra) composed of two zinc atoms, ten
nitrogen
atoms,
and
four
carbon
atoms
(Zn1N1N3C1C8N5N7N6Zn1N1N3C1C8N5N7N6), causing
the BTA ring and tetrazole ring to have a dihedral angle of
65.635(8)°. The planes that the two BTA ligands occupy are
nearly parallel with the dihedral angle of 0.00(8)°. Notably, the
coordination bases are N1 atoms from tetrazole rings and N6
atoms from BTA rings. When the N4 atoms from tetrazole
rings are included, an another much larger ring (Rb) is formed,
which is constructed by two BTA groups, four tetrazoles rings
as well as four zinc ions (Figure 2). The two kinds of rings are
adjacent and extend to the 2D network in RaRbRaRb se-
quence. Furthermore, the two BTA ligands in the Rb ring are
nearly parallel too, with the dihedral angle of 0.00(9)° and the
distance of 3.4986 Å. Viewed along the a axis, the neighboring
two kinds of rings extend infinitely to outspread layers leading
to the formation of the 2D plane (Figure 2). To get better in-
sight into the intricate framework structure of 1, its topological
analysis was carried out. As discussed above, each central zinc
atom links three nitrogen atoms and one vertex bromine atom,
and thus can be defined as 4-connecting node, and the 1-mbtz
ligand coordinated with three zinc atoms can be defined as a
3-connector, according to the simplification principle of the
TOPOS software.[39,40] The overall network topology of 1 can
be described as an unprecedented (4,3)-connected framework
(Figure 3) with Schläfli symbol of {3.122}{3.6.7}2{6.122}.
Figure 4. View of the extended zigzag-shape 3D supramolecular net-
work in 1 along the c axis. The dashed line represents the C–Br short
contact interactions.
Quite different from that found in compound 1, the 2D struc-
ture of 2 is much more complicated, which was revealed by
X-ray single-crystal diffraction investigation. Crystallographic
¯
data of 2 (Table 1) indicates that 2 is triclinic, space group P1.
The asymmetric unit contains two zinc atoms, three 1-mbtz
ligands, one hydroxyl group as well as a water molecule,
where the occupancy of the water molecule is one half. The
BTA groups and tetrazole ligands have dihedral angles of
47.76(2)°, 68.85(3)°, and 82.71(2)° respectively. There are two
crystallographically independent central zinc atoms. The Zn1
atom is coordinated by four nitrogen atoms (N19, N12, N8iv,
N1v; symmetry code: (iv) 1+x, –1+y, z; (v) 3–x, 1–y, –z), in
which the N19 atom is from the BTA ligand and the others
from the tetrazole group, and one oxygen atom O1. The Zn2
ion has a same coordination environment as the Zn1 ion, each
Zn2 atom is bonded to four nitrogen atoms (N18, N15, N4vi,
N6viii; symmetry code: (vi) –1+x, 1+y, z;(viii) x, –1+y, z) and
one oxygen atom O1, which means the O1 is a bridge linking
Figure 3. Topological representation of the 2D framework for 1.
More interestingly, in the ab plane, the complicated two- the two different central zinc atoms. Besides, the two zinc
dimensional polymer structure of compound 1 looks like a zig- atoms are also linked by the C10–N15 tetrazole ligand. Un-
zag chain (Figure 4). The tetrazole ligand acts as μ2-tetrazolyl commonly, the zinc atoms are pentacoordinate instead of quad-
mode with two nitrogen atoms (1,3 position) bridging two zinc ridentate or sexadentate, as shown in Figure 5. The coordina-
atoms to form a zigzag chain, owing to the nearly parallel tion polyhedron of the metal atom is a slightly distorted trigo-
arrangement of the BTA ligands on both sides of the chain. nal bipyramid performed through one zinc atom in a center,
There are some weak non-classical hydrogen bonds (Table 3) two nitrogen atoms (N8, N19 for Zn1; N6, N18 for Zn2) and
found in the structure. Intermolecular C5–H5A···N3 (x, –1+y, one O1 atom in the equatorial plane with the deviation of the
z) hydrogen bonds between the BTA ring and the tetrazole ring plane 1 and 2 being 0.1171 Å and 0.2137 Å and two nitrogen
and C8–H8A···Br1 (x, 3/2–y, –1/2+z) hydrogen bonds play a atoms (N1, N12 for Zn1; N4, N15 for Zn2) in the axis plane
very important role in the stability of the two-dimensional net- with the N1–Zn1–N12 equaling to 162.7(3)° and the N4–Zn2–
work. Relatively short contacts C8–Br1 = 3.493 Å and C1– N15 equaling to 173.4(3)°. It is interesting to note that the
Br1 = 3.297 Å between the adjacent 2D supramolecular planes adjacent two zinc ions (Zn1 and Zn2) together with the bridged
together with other noncovalent interaction-static attractive O1 atom and one tetrazole ring result in a formation of a
forces, like Coulomb and van der Waals forces, link the 2D five-membered ring (R1) composed of two zinc atoms
network packing together by AAA sequence type along the a and two nitrogen atoms as well as one oxygen atom
axis to a 3D framework.
(Zn1N12N15Zn2O1). Two R1 rings are separated by two
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Q. Ye et al.
ARTICLE
tetrazole rings and thus causing another plane atoms (N19 and N18) of the BTA groups. Ligand B, the C20–
(Zn1O1Zn2N4N2N1Zn1O1Zn2N4N2N1) (R2) with the mean N21 1-mbtz ligand, due to the particularity of N9 atom failed
deviation being 0.4028 Å. Furthermore, the bonds Zn1–N19 to coordinate, acts as in a bidentate fashion and coordinates to
and Zn2–N18,which are from the two BTA parts, are approxi- two zinc atoms (one Zn1 and one Zn2 atoms) leading to the
mately perpendicular to the plane of this large ring with dihe- formation of the complicated 2D network (Figure 6). The C3–
dral angles between the BTA ring and the R2 being 83.27(1)° N6 tetrazole ligand acts as a μ2-tetrazolyl mode through N6,
and 78.27(1)°, separately. All the Zn–N [2.176(7) Å, N8 atoms (1,3 position) bridging Zn1 and Zn2 atoms, likewise,
2.062(7) Å, and 2.072(6) Å as well as 2.273(7) Å in the Zn1 the C1–N3 tetrazole ligand adopts the μ2-tetrazolyl mode
atom, and 2.082(6) Å, 2.180(7) Å, and 2.091(7) Å as well as through N1, N4 atoms (1,3 position), however the C10–N15
2.197(7) Å in the Zn2 atom] bond lengths are normal, it is tetrazole ligand adopts another kind of μ2-tetrazolyl mode (1,2
worth noting that the bond lengths of Zn–N are much longer position).
than those found in compound 1. The angles in the equatorial
plane around each zinc atom range from 109.4(3)° to 139.6(2)°
for Zn1 and 107.7 (3)° to 126.7(3)° for Zn2, whereas the
angles between axis atoms and the equatorial atoms for Zn1
being from 81.1(2)° to 100.5(3)° and for Zn2 range from
85.7(2)° to 93.3(2)°, which significantly deviate from those
expected for an ideal trigonal bipyramid. The difference of the
Zn–N bond lengths and the direction of the 1-mbtz ligands
around each zinc atom must be primary factor to result in the
formation of two different central zinc atoms.
Figure 6. 2D sheet structure of compound 2. Hydrogen atoms and
benzene rings are omitted for clarity.
Moreover, each zinc atom is connected with four 1-mbtz
ligands and one oxygen atom. There are many interesting hy-
drogen bonds, including C13–H13A···N5, C15–H15A···N12
weak intramolecular hydrogen bonds and C2–H2A···N7 (1+x,
–2+y, z), C19–H19A···N3 (2–x, 1–y, –z), C20–H20A···N5 (x,
–1+y, z), and C22–H22B···N20 (–1+x, 1+y, z) weak intermo-
lecular hydrogen bonds (Table 3), and there are also some C–
H···π interactions (Figure 7), which is evidence for a edge-to-
face C–H···π interactions between the C(14) hydrogen atom of
the BTA rings in one sheet to N(14) tetrazole rings in the next
[C14···Cg1 distance: 3.499(0) Å, C14–H14A···Cg1 angle:
160.01(5)°] (Cg1 is the centroid of the tetrazole ring), and π–
π stacking interactions (Figure 7) found in the 2D network. It
needs to note that this π–π stacking interaction between the
neighboring BTA rings is a novel three-layer interaction,
where the middle ring shows the different orientation from
those of the up and low layers, thus forming a interesting sand-
Figure 5. Coordination environments of the central zinc atoms in com-
pound 2 (30% probability thermal ellipsoids). Hydrogen atoms and
benzene rings are omitted for clarity. The labels iv, v, vi, vii, and viii
were generated by symmetry code: (iv) 1+x, –1+y, z; (v) 3–x, 1–y, –z;
(vi) –1+x, 1+y, z; (vii) x, 1+y, z; (viii) x, –1+y, z; respectively.
Similarly to compound 1, each Zn1 ion shares two 1-mbtz
ligands with adjacent Zn1 ion to create a 16-membered ring
(R3) composed of two 1-mbtz ligands linked by two Zn1
atoms, in which the two benzotriazole rings are approximately
parallel. The Zn1 ion also shares two 1-mbtz ligands with adja-
cent Zn2 and form a different 14-membered ring (R4) around
Zn2
(Zn2N4C1C2N14N20N19Zn1N8C3C22N17N16N18),
which is nearly vertical with the above 16-membered ring, the
dihedral angle of the two rings equals to 85.860(8)°. In 2, evi-
dently, 1-mbtz ligands have two coordination patterns: ligand
A1, the C2–N14 1-mbtz ligand, and ligand A2, the C22–N17
1-mbtz ligand, are tridentate coordinating to neighboring zinc
atoms (two Zn1 and one Zn2 atoms, one Zn1 and two Zn2
atoms, respectively), through 1 and 3 positions (N1, N4 and
Figure 7. Three kinds of C–H···π and π–π stacking interactions in the
N6, N8, respectively) of the tetrazole ring and the nitrogen compound 2.
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Hydrothermal Synthesis of Zinc Coordination Polymers
wich structure with the distance of Cg2–Cg3 and Cg3–Cg4 tance 3.3027 (1) Å, C20–H20B···Cg5 angle 106.529(6)°] and
3.826(1) and 3.940(1) Å, respectively. These hydrogen bonds
together with the C–H···π and π–π interactions obviously have
a crucial impact on the stability of the arrangement of the 2D
architecture. The organic ligands link inorganic zinc nodes to
form 2D net sheets seeing along the c axis (Figure 6), Besides,
seeing from the a axis we can discover these 2D networks
have their thickness shown in Figure 8, which displays those
rings clearly mentioned above.
forming two kinds of parallel interactions with the two BTA
rings nearly paralleling, and the dihedral angle is 0.00(3)°.
There are also some free water molecules found and they con-
nect the 2D network with intermolecular hydrogen bonds C20–
H20B···O1W and O1W–H1WA···N11 (2–x, 1–y, 1–z), which
also have acted as the bridges between adjacent 2D network
and together with the above C20–H20B···π interactions to cre-
ate a 3D network (Figure 10). The presence of water as spacers
between the inorganic anions can alter the distances between
the chains or layers and can also have distinctive hydrogen-
bonding features, which influence the structural packing. Fig-
ure 10 shows the packing view of compound 2, all of these
approximate planes are packed together by AAA type along
the c axis to a dense 3D framework.
Figure 8. View of the thickness of the 2D network in compound 2
along the a axis. Hydrogen atoms and benzene rings are omitted for
clarity.
From a topological perspective view, each central Zn1 and
Zn2 atom may be considered as a five-connecting node and
each O1 bridges to two zinc atoms and it is connection but not
node. 1-mbtz ligands have two coordination patterns men-
tioned above, each ligand A1 and ligand A2 link to three cen-
tral metal atoms and may be defined as three-connecting node,
however, since each ligand B is only coordinated to two zinc
atoms and it is only considered as connection and
not node. Consequently, this results in the formation of
Figure 10. View of 3D framework structure of compound 2 in the ac
plane. Some parts of the 2D network are omitted for clarity. The
dashed line represents the CH–O, OH–N, and C–H···π interactions.
2D
net
with
Schläfli
symbol
of
{3.112}
{3.6.7}4{3.62}{6.8.114}{62.8.9.112} (Figure 9).
Similarly, we found that Xue[34] has also conducted hydro-
thermal reactions through the two different methods and ob-
tained different compounds, based on the 5-(4-pyridyl)tetrazol-
ate ligand, which is consistent with our experiment. In our
group such compounds synthesized through in situ hydrother-
mal methods and based on H-1-mbtz ligands have been re-
ported before, for instance the C32H24Mn5N38O4 com-
pound,[29] which is a 3D coordination polymer, and the ar-
rangement around the three crystallographically independent
metal atoms is different, except the H-1-mbtz ligands, this
novel MnII coordination polymer is also formed by bridging
azide anions and carboxylate ligands. As a result, this polymer
is much complicated than the titled compound 2 in this paper.
Mixed inorganic-organic hybrid coordination polymers were
investigated for fluorescence properties and they may have po-
tential applications as fluorescence-emitted materials. The so-
lid state fluorescent emission spectrum of complex 1 at room
temperature shows that a maximum emission peak occurs at
ca. 404 nm (excitation at 347 nm) (Figure S3). The photolumi-
nescent mechanism may be considered to ligand-to-1igand
transitions, which is in reasonable agreement with other zinc
Figure 9. Topological representation of the 2D framework for com-
pound 2.
Among these 2D networks in 2, another kind of C–H···π
interaction is found, which is from the C20 hydrogen atom
from the BTA ring to the adjacent BTA ring [C20···Cg5 dis- coordination polymers previously reported.[42]
Z. Anorg. Allg. Chem. 2013, 2317–2323
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Q. Ye et al.
ARTICLE
Table 3. Non-classic hydrogen bonds /,° of 1 and 2.
Conclusions
D–H···A
H···A
D···A
DHA
Two zinc tetrazole complexes were synthesized under hy-
drothermal conditions. Although they both display 2D planes,
the local coordination arrangements around zinc atoms are dif-
ferent and form different rings, which assemble into two novel
2D structures. The structure of compound 2 obtained by in
situ hydrothermal synthesis is much more complicated. Both
complexes have rich hydrogen bonds, C–H···π, and π–π inter-
actions, which have great impact on the stability of the 2D
network. The fluorescence property of 1 was studied, the re-
sults showed that a maximum emission peak occurred at ca.
404 nm.
1
C8–H8A···Br1iii
C5–H5A···N3viii
2
2.74
2.57
3.658(3)
3.325(4)
159.2
138.3
O1–H1A···N2v
O1–H1A···N2vi
2.51
2.39
2.957(8)
2.963(8)
2.954(17)
3.373(10)
3.384(18)
3.298(11)
3.358(10)
3.449(11)
3.158(10)
3.028(9)
3.499(0)
3.826(1)
3.940(1)
3.303(1)
107.9
117.1
103.6
139.7
146.6
136.3
156.6
149.5
123.0
106.4
160.00(5)
O1W–H1WA···N11ix 2.58
C22–H22B···N20vi
C20–H20B···O1W
C20–H20A···N5viii
C19–H19A···N3x
C15–H15A···N12
C13–H13A···N5
C2–H2A···N7xi
2.57
2.53
2.53
2.48
2.62
2.55
2.61
a)
C14–H14A···Cg1
Cg2···Cg3
Cg3···Cg4
C20–H20B···Cg5
Experimental Section
a)
a)
X-ray Diffraction Studies: Data collection of 1 and 2 were performed
with Mo-Kα radiation (λ = 0.71073 Å) with a Rigaku SCXmini dif-
fractometer by the ω scan technique at room temperature. The structure
was solved by direct methods and refined with full-matrix least-
squares technique using SHELXTL-97 software package.[41] All non-
hydrogen atoms were refined with anisotropic thermal parameters. Hy-
drogen atoms were placed in calculated positions (C–H = 0.96 Å for
Csp2), assigned fixed Uiso values [Uiso = 1.2Ueq (Csp2/N) and
1.5Ueq(Csp3)] and allowed to ride. The crystal data and details con-
cerning data collection and structure refinement are given in Table 1.
Selected bond lengths and angles are listed in Table 2 and the hydrogen
bonds are characterized in Table 3.
a)
106.53(6)
Symmetry code: (iii) x, 1.5–y, z–0.5; (v) 3–x, 1–y, –z; (vi) x–1, y + 1,
z; (viii) x, y–1, z;(ix) 2 –x, 1–y, 1–z; (x) 2–x, 1–y, –z; (xi) 1+x, –2+y,
z.
a) Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroid of the tetrazole or
benzotriazole ring.
gel (eluent: light petroleum-acetic ester 6:1) affording the target prod-
uct benzotriazol-1-yl-acetonitrile (3.74 g, 78%, m.p. 360 K) in the last
order.
Preparation of Compound 1: Direct tetrazole-synthesis method with
Table 2. Selected bond lengths /Å and angles /° for compounds 1 and two-steps was used. That is to get H-1-mbtz as the first step, which
2.
was synthesized by adding benzotriazol-1-yl-acetonitrile (3.48 g,
22 mmol), sodium azide (1.43 g, 22 mmol), ZnBr2 (4.51g, 20 mmol),
and water (40 mL) into a three-necked 250 mL round bottomed flask.
The product was obtained by refluxing the reaction mixture for 24 h.
After the mixture was cooled to room temperature, the pH was ad-
justed to 1.0 with concentrated HCl (3 m,12 mL) to form a precipitate,
which was filtered, washed with 2ϫ10 mL of HCl (3 m) and dried at
80 °C overnight to get H-1-mbtz as a light yellow solid (3.08 g) in
70% yield. The terminal product 1 was prepared under hydrothermal
conditions: H-1-mbtz (4.0 mmol) and ZnBr2 (2.0 mmol) were placed
in a thick Pyrex tube (ca. 20 cm in length). After addition of water
(3 mL), the tube was frozen with liquid nitrogen, evacuated, and sealed
with a torch. The tube was heated at 120 °C for 4 d and finally slowly
cooled to room temperature (Scheme 2). Colorless prism crystals (pure
phase) suitable for X-ray analysis were formed after two weeks in
60% yield based on ZnBr2 C8H6BrN7Zn: calcd. C 27.81, H 1.75, N
28.38%; found C 27.62, H 1.64, N 28.29%. IR (KBr): ν˜ = 3128 (s),
3030 (s), 2953 (s),1640 (s), 1560 (s), 1476 (m), 1453 (m), 1350 (m),
1050 (s),789 (vs), 705 (s) cm–1.
1
Zn1–N4ii
Zn1–N6
Zn1–N1$3
Zn1–Br1
2.014(2)
2.021(2)
2.024(2)
2.3286(6)
N4ii–Zn1–N6
N4ii–Zn1–N1i
N6–Zn1–N1i
N4ii–Zn1–Br1
N6–Zn1–Br1
N1i–Zn1–Br1
114.22(10)
103.75(10)
104.07(10)
111.88(7)
108.07(7)
114.72(7)
2
Zn1–N19
Zn1–N8iv
Zn1–N1v
Zn1–N12
Zn1–O1
2.062(7)
2.072(6)
2.176(7)
2.273(7)
1.922(5)
1.968(5)
2.082(6)
2.091(7)
2.180(7)
2.197(7)
N19–Zn1–N8iv
N19–Zn1–N1v
N8–Zn1–N1v
N19–Zn1–N12
N1v–Zn1–N12
N18–Zn2–N6viii
N6viii–Zn2–N4vi
N18–Zn2–N15
N6viii–Zn2–N15
N4vi–Zn2–N15
109.4(3)
100.5(3)
91.3(3)
96.0(3)
162.7(3)
126.7(3)
89.3(3)
93.3(3)
88.4(3)
173.4(3)
Zn2–O1
Zn2–N18
Zn2–N6viii
Zn2–N4vi
Zn2–N15
Symmetry code: (i) –x, 2–y, 2–z; (ii) x, 1.5–y, 0.5+z; (iv) x+1, y–1, z;
(v) 3–x, 1–y, –z; (vi) x–1, y+1, z; (viii) x, y–1, z.
Preparation: All reagents were obtained commercially and used as
received without further purification. The initial benzotriazol-1-yl-ace-
tonitrile ligand was synthesized as follows: to a solution of benzotri-
azole (4.8 g, 40 mmol) in acetone (40 mL), K2CO3 (5.0 g, 36 mmol)
was added into it and the mixture was stirred. A solution of bromoace-
tonitrile (10.8 g, 90 mmol) in acetone (15 mL) was dropped slowly
Scheme 2.
Preparation of Compound 2: Compound 2 was prepared under hy-
into the mixture. After stirring at room temperature for 5 h, the mixture drothermal conditions. Benzotriazol-1-yl-acetonitrile (2.0 mmol) with
was filtered. A filtrate was evaporated to dryness under reduced pres- ZnBr2 (1.5 mmol) in the presence of NaN3 (3.5 mmol) were placed in
sure. The solid residue obtained was flash-chromatographed on silica a thick Pyrex tube (ca. 20 cm in length). After addition of water
2322
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© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2317–2323

Hydrothermal Synthesis of Zinc Coordination Polymers
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cooling to room temperature (Scheme 3), colorless prism crystals (pure
phase) suitable for X-ray analysis were formed after two weeks in
65% yield based on ZnBr2 C48H40N42O3Zn4: calcd. C 38.06, H 2.66,
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(w), 3050 (s),2925 (s),1640 (s), 1555 (s), 1483 (m), 1455 (m), 1343
(m), 1155 (m), 789 (vs), 705 (s) cm–1.
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Crystallographic data (excluding structure factors) for the structures in
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Supporting Information (see footnote on the first page of this article):
Details of the powder XRD pattern of 1 and 2 (Figures S1 and S2),
Fluorescence spectrum of 1 in the solid state at room temperature (Fig-
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Received: April 16, 2013
Published Online: July 2, 2013
Z. Anorg. Allg. Chem. 2013, 2317–2323
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2323