Structural Analysis and Controllable Fabrication of Two Pentazolate-Based 3D Topological Networks

Article abstract of DOI:10.1021/acs.inorgchem.1c00627

Two novel sodium-pentazolate frameworks (namely, MPF-3 and MPF-4) were achieved by adding simple additives. MPF-3 exhibits an aesthetic three-dimensional (3D) framework with the zeolitic MTN topology, featuring Na28N80 and Na20N60 nanocages. In MPF-4, two left-handed helical chains construct enclosed homochiral channels filled with dimethyl sulfone molecules, which constitute a zeolite-like UNJ topology. Importantly, the preparation of these two compounds provides an effective experimental means to explore the unique symmetrical structure and multiple coordination modes of pentazolium anion and demonstrates that it is possible to regulate the crystal structure through appropriate additives.

Full text of DOI:10.1021/acs.inorgchem.1c00627

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Structural Analysis and Controllable Fabrication of Two Pentazolate-
Based 3D Topological Networks
Yuteng Cao, Honglei Xia, Kangcai Wang, Qinghua Zhang,* and Wenquan Zhang*
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ABSTRACT: Two novel sodium-pentazolate frameworks (namely, MPF-3 and MPF-4) were achieved by adding simple additives.
MPF-3 exhibits an aesthetic three-dimensional (3D) framework with the zeolitic MTN topology, featuring Na28N80 and Na20N60
nanocages. In MPF-4, two left-handed helical chains construct enclosed homochiral channels filled with dimethyl sulfone molecules,
which constitute a zeolite-like UNJ topology. Importantly, the preparation of these two compounds provides an effective
experimental means to explore the unique symmetrical structure and multiple coordination modes of pentazolium anion and
demonstrates that it is possible to regulate the crystal structure through appropriate additives.
he azolate derived frameworks present simple geometry,
T
yet a rich diversity of topologies, such ZIFs, Co3(BTP)2,
and FMOF-1.1−7 The cyclopentazolate (cyclo-N5 ) anion, as a
−
novel type of full-nitrogen-donor ligand among the azole
family, has attracted wide attention because of its potential in
high-energy-density materials (HEDMs).8−13 Different from
−
traditional unidentate or multidentate ligands, the cyclo-N5
anion has multiple fascinating properties, such as five nitrogen
atoms and five lone pairs of electrons. This indicates the
−
importance of the cyclo-N5 anion in preparing multidimen-
sional intricate target networks, providing infinite possibilities
for the development of crystal chemistry. For instance, the
−
pentacoordinated N5 ring with bonded metal ions could be
regarded as an expanded pentagon building unit,14 which is
optimally favorable for the directed self-assembly of pentasil-
zeolite topology architectures. This means topology networks
could be systematically tailored through suitable metal nodes
and pentazolate anion linkers themselves.
In 2017, Lu et al. reported the first sodium-N5 hydrate
9
−
([Na(H2O)(N5)]·2H2O), in which N5 anions were stabi-
lized well through interactions with surrounding Na(I) ions
and H2O molecules (Figure 1a). In 2018, we constructed the
first pentazolate-based zeolitic framework (Na48(N5)48·xH2O),
denoted as MPF-1 (Figure 1b).14 This compound features a
zeolitic MEP topology (MEP = melanophlogite), with two
types of Na20N60 and Na24N60 nanocages. Noticeably, MPF-1
Figure 1. (a) The first NaN5 hydrate, [Na(H2O)(N5)]·2H2O.9 (b)
Na20N60 and Na24N60 nanocages of MPF-1.14 (c, d) The 3D networks
of MPF-3 and MPF-4.
of 3D crystal structures due to the multiple coordination
−
−
capacity of the cyclo-N5 anion.
demonstrates the simplicity and feasibility of the cyclo-N5
Different attempts have been conducted to explore
anion in assembling pentasil-zeolite topologies. Actually, the
molecular design of topology networks heavily depends on
coordination geometry and steric configuration of nodes and
linkers.15−20 However, the self-assembly process of linkers as
well as metal nodes may not strictly follow angles and
directions, which is bound to reduce the possibility of
preparing the target structures.21−27 This further implies that
−
characteristic N5 -derived frameworks. In our continuous
efforts, we detected that the slight alterations of external
Received: March 2, 2021
−
a cyclo-N5 anion with definite angles and shapes is an ideal
ligand to use in preparing pentasil frameworks. The
pentazolium salts of the same composition may form a variety
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−
Figure 2. (a) The coordination environment of the cyclo-N5 anion and Na(I) ion in MPF-3. (b) Na28N80 and Na20N60 nanocages and the
simplified topology structures. (c) The connection modes of the 64·512 and 512 cages. (d) The further assembly of the 512 nanocage with six
−
surrounding 64·512 cages and the 64·512 cage with four identical ones. (e) The cyclo-N5 anion with bonded Na(I) ions and the pentagon and
hexagon topology units. (f) The zeolitic MTN topology network of MPF-3 viewing along the [100] direction.
conditions might induce various pentazolate assemblies with
varying topologies.28 The introduction of appropriate solvents
or additives could observably regulate the crystallization
behaviors of NaN5 salts and thus influence the crystal
structures. Herein, we have presented two new sodium-
pentazolate frameworks, namely, MPF-3 and MPF-4 (Figure
1c,d), which are obtained by adjusting the exterior conditions.
NaN5 hydrate and dimethyl sulfone (MSM) at a specific ratio
were added into the corresponding amine aqueous solution,
and two disparate compounds were isolated by solvent
evaporation. MPF-3 (CCDC 2065205) features an MTN-
type (MTN = ZSM-39) zeolite network.29,30 To our
knowledge, pentazolate-based MTN topology is unprece-
dented. Meanwhile, MPF-4 (CCDC 2065206) possesses a
homochiral framework, with two left-handed helical inter-
penetrating chains showing UNJ topology.31 The two
unit (Figure 2e).14 In this way, Na28N80 nanocages are
constituted of 12 pentagons and four hexagons, like that of a
soccer ball. And the other Na20N60 nanocage consists of 12
pentagons. From the topological viewpoint, the Na28N80 and
Na20N60 cages can be simplified as 64·512 and 512 cages,
respectively (Figure 2b). Figure 2c shows that the two kinds of
nanocages are adjacent to each other by sharing the same
pentagonal unit. In MPF-3, each 64·512 cage shares all its
hexagonal faces to four adjacent 64·512 cages, and the
remaining pentagons are shared to 12 512 cages (Figures 2d,
S1a), which indicates that each Na28N80 nanocage is
surrounded by 16 nanocages, while each small 512 cage shares
12 pentagonal faces with six adjacent 512 cages and six 64·512
cages (Figures S1b, 2d). Further assembly in this manner, wih
these 64·512 and 512 cages, with a ratio of 2:1, give rise to the
MTN topology. Figure 2f shows the topology network of
MPF-3 viewing along the [100] direction, and the same
topology projection also exists along the [010] direction
(Figures S2, S3a).30
−
complexes further demonstrate the feasibility of the N5
anion in constructing topology materials as a bridging group.
Single-crystal X-ray diffraction revealed that MPF-3
crystallizes in the tetragonal I41/amd space group (Table
S1). Remarkably, the cell volume of MPF-3 is gigantic, up to
9.1 nm3, which is rare among metal-pentazolate frameworks
(MPFs) and even inorganic compounds. As shown in Figure
In addition, MPF-3 exhibits a negatively charged framework.
There might be charge-balancing cations in the whole
structure, which cannot be directly located. Worthy of mention
is the hexagonal units of MPF-3 (Figure 2e). Unlike that of
2a, each central Na(I) interacts with six adjacent cyclo-N5
MPF-1,14 the six-membered unit seems like a cyclo-N5 anion
−
−
anions, and five N atoms of the full-nitrogen ring are
connected to neighboring five Na(I) ions, forming an infinite
3D structure. The N−N and Na−N bond lengths are in the
range of 1.304(7)−1.341(8) Å and 2.407(5)−2.599(4) Å,
respectively (Table S2). It is intriguing that MPF-3 features
two types of ball-like nanocages, Na28N80 and Na20N60 (Figure
2b). The larger Na28N80 nanocages are comprised of 28 Na(I)
ions as nodes and 16 N5 rings as linkers. From the van der
Waals surfaces, the inner diameter is ∼8 Å and the calculated
volume is ∼268.1 Å3.29 Correspondingly, Na20N60 nanocages
contain 20 Na(I) nodes and 12 cyclo-N5− anion linkers, whose
inner diameter and calculated volume are ∼5.8 Å and ∼102.2
Å3, respectively.
interacting with six Na(I) ions. Essentially, this is a disordered
tetracoordinated pentazolate ligand. The phenomenon is
caused by synergistic effects yielded by the excellent
−
coordination ability of the N5 anion as well as spatial
arrangement, which was first discovered in MPFs. The
construction of MPF-3 proves that the pentazolate anion
ring is capable of interacting with more metal ions during
crystal growth.
The preparation of MPF-1 creates a new approach to zeolitic
topologies by making use of pentazolate-based pentagonal and
hexagonal building units.14 By simply adjusting external
conditions, another MTN-type MPF-3 was achieved, which
proves the effectiveness of this synthetic strategy. It is
promising that more pentasil MPFs, such as DDR (deca-
dodecasil 3R) and DOH (dodecasil 1H) may be exper-
−
As we have reported, pentacoordinated cyclo-N5 as well as
bonded Na(I) ions could be regarded as a regular pentagonal
B
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Figure 3. (a) The asymmetric unit of MPF-4 and the coordination environment of the Na(I) ions and cyclo-N5− anions. (b) The tubular channel
−
structures composed of Na(I) ions and cyclo-N5 anions. (c) Topological representation of the UNJ network. (d) Schematic drawing of the
channels. (e) Single left-handed helix chain and the schematic drawing along the [100] direction. (f) Double helical chains and the schematic
drawing along the [100] direction.
imentally obtainable by following a relatively precise
templating effect. More importantly, the successful manufac-
ture of the two topological networks will provide a judicious
reference for the choice of nodes and linkers in designing
increasingly complicated pentasil topologies.
channel is enclosed by six identical ones, indicating that the
adjacent nanotubes are fused together by Na(I)−N5 edge
sharing (Figure 3d).
−
Another prominent structural feature of the MPF-4
framework is the double helical chains that makes up channels.
Helicity is a special form of one-dimensional chirality,33−35 and
MPF-4 possesses two interpenetrating left-handed topology
chains simultaneously (Figure 3e,f). In general, the MOF
homochirality is transmitted from the building units to the
whole framework,31 while the fabrication of MPF-4 is
The introduction of auxiliary ligands will bring about the
formation of MPFs with diverse topologies. Single crystal
structural analysis showed that MPF-4 crystallizes in the
orthorhombic P212121 space group (Table S4). The asym-
−
metric unit includes three Na(I) ions, three cyclo-N5 anions,
−
and one dimethyl sulfone (MSM) molecule (Figure 3a). In
MPF-4, Na8 adopts a distorted pyramid geometry, which
interacts with five adjacent N atoms from five full-nitrogen
rings, while Na6 and Na7 are bonded to five N atoms of five
pentazolate anions and two O atoms of an MSM ligand,
featuring a slightly distorted octahedral configuration. As an η5-
introduced from achiral cyclo-N5 anion precursors based on
auxiliary MSM ligands. And the two left-handed helix chains
further assemble enclosed helical channels. Therefore, MPF-4
exhibits a left-handed framework with intrinsic homochir-
ality.31
−
From a topological analysis perspective, Na(I) ions and N5
−
linker, each cyclo-N5 bridges five Na(I) ions to form an
ligands of MPF-4 can be regarded as five-connected nodes and
five-connected annular linkers, repectively. This simplification
leads to the formation of the enlarged pentagonal building
units, which are further assembled to generate a six-periodic
framework with helical channels along the [100] direction
(Figure 3e,f).31,36 From this, the MPF-4 framework possesses
the zeolite-like UNJ topology network.31,37 On the basis of the
enlarged regular pentagon (Figure 3a). The Na−N bond
lengths are in the range of 2.405(5)−2.594(5) Å, and the
lengths of Na−O bonds are 2.497(6) and 2.633(6) Å (Table
S5). All five N atoms of each cyclo-N5− anion ring are coplanar,
with the N−N bonds ∼ 1.31 Å and the torsion angle between
0.0(6)° and 1.3(6)° (Tables S6, S7).
−
The MPF-4 framework features multiple tubular channels
filled with MSM molecules, whose walls are constructed by
multiple coordination capability of the cyclo-N5 anion and
chiral induction strategy of the auxiliary ligand, more
associated pentazolate topologies similar to MPF-4 can be
achieved, which can greatly promote the flourishing of pentasil-
based topologies.
In summary, two novel topologies have been successfully
fabricated through the controllable synthesis strategy of the 3D
sodium-pentazolate framework. MPF-3 is an MTN-type
zeolitic topology with Na28N80 and Na20N60 nanocages.
MPF-4 features homochiral channels comprised of two left-
handed helical chains, with zeolite-like UNJ topology. The two
compounds experimentally demonstrate that the multicoordi-
−
Na(I) ions and N5 anions (Figure 1d). Figure 3b shows that
the channels are running along the [100] direction. In
comparison with the reported (NaN5)2(C2H4N4),32 the cross
section of each channel is an ellipse, due to the steric hindrance
of inner MSM molecules (Figure 3b). Viewing along the [010]
direction, the semimajor axis of channels in the same layer is in
the same direction, and that in adjacent layers are in the
opposite direction (Figure 3c). From the van der Waals
surfaces, the lengths of the major axis and minor axis are ∼8 Å
and ∼5 Å, respectively. The calculated area is ∼31.4 Å2. Each
C
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nated cyclo-N5− anion is a perfect building unit for the induced
fabrication of diverse pentasil-zeolite topologies. The bonding
modes and steric configuration for pentazolates can be
predicted with ease if all five ligating sites are available. This
work not only discovers two novel aesthetic architectures
based on pentacoordinated pentazolate linkers and metal
nodes but also reveals a simple and precise method in the
fabrication of pentasil topologies.
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ASSOCIATED CONTENT
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Accession Codes
CCDC 2065205 and 2065206 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing ata_request@ccdc.cam.ac.uk, or by contacting The
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AUTHOR INFORMATION
Corresponding Authors
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pentazolate salts of NH4 , NH3OH+, N2H5 , C(NH2)3 , and
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Qinghua Zhang − Institute of Chemical Materials, China
Academy of Engineering Physics, Mianyang 621000, China;
orcid.org/0000-0002-4162-7155;
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Email: qinghuazhang@caep.cn
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Wenquan Zhang − Institute of Chemical Materials, China
Academy of Engineering Physics, Mianyang 621000, China;
orcid.org/0000-0002-2766-5040; Email: zhangwq-cn@
caep.cn
Authors
Yuteng Cao − Institute of Chemical Materials, China
Academy of Engineering Physics, Mianyang 621000, China
Honglei Xia − Institute of Chemical Materials, China
Academy of Engineering Physics, Mianyang 621000, China
Kangcai Wang − Institute of Chemical Materials, China
Academy of Engineering Physics, Mianyang 621000, China
Complete contact information is available at:
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Notes
The authors declare no competing financial interest.
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C.; Tong, M. L. A gyroidal MOF with unprecedented interpenetrating
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ACKNOWLEDGMENTS
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