Vol.:(0123456789) 1 3
Journal of Materials Science: Materials in Electronics
https://doi.org/10.1007/s10854-018-9388-2
Synthesis, physico-chemical studies and Hirshfeld surface analysis
of a frst 0-D Chlorozincophosphate, (H
2
N(CH
2
)
4
NH(CH
2
)
2
NH
3
Cl)
ZnCl
2
(HPO
4
)
Ali Rayes
1
· Sofan Gatfaoui
2
· Cherif Ben Nasr
2
· Brahim Ayed
3
· Mohamed Rzaigui
2
Received: 3 April 2018 / Accepted: 28 May 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
An original zero-dimensional chloro-substituted zincophosphate monomer, (H
2
N(CH
2
)
4
NH(CH
2
)
2
NH
3
Cl)Zn(HPO
4
)Cl
2
, was
isolated by the reaction of zinc chloride (Zn
2+
, 2Cl
−
) with the amine, 1-(2-aminoethyl)piperazine, H
3
PO
4
and HCl under
ambient conditions. This phase crystallizes in the triclinic space group P-1 (No. 2) with the lattice parameters a = 8.834(2),
b = 8.539(3), c = 11.163(2) Å, α = 93.58(2)°, β = 108.62(2)°, γ = 62.96(2)°, V = 707.3(4) Å
3
, Z = 2, R = 0.027 and Rw = 0.037.
The tri-protonited organic cations are linked to the isolated chloride ions Cl
−
through N–H⋯Cl and C–H⋯Cl hydrogen bonds,
forming corrugated cationic layers extending parallel to (a b) plane. The inorganic framework of the title compound consists
of a network of ZnO
3
Cl and HPO
4
tetrahedral units linked by their oxygen vertices, forming isolated 4-membered rings. These
anionic monomers, (Zn
2
P
2
O
8
Cl
4
H
2
)
4−
, which are held by O–H⋯O hydrogen-bonding interactions, lie between the cationic
layers to maximize the electrostatic interactions and are linked to (H
2
N(CH
2
)
4
NH(CH
2
)
2
NH
3
Cl)
2+
cations via N–H⋯O or
N–H⋯Cl hydrogen bonds, forming a 3-D supra molecular structure. Hirshfeld surface analysis, Solid state NMR, Infrared
spectroscopies and DTA/TGA analysis were also performed to characterize the title compound. Solid state
31
P and
13
C MAS
NMR spectroscopy results were found to be in full agreement with the XRD results.
1 Introduction
Organically template metallophosphate solids are of great
interest in material sciences, as well as in chemistry. Their
anionic framework is generally constructed from corner
sharing MO
n
(n = 4, 5, 6 and M = Al, Ga, Co, Fe, Zn…)
polyhedra and PO
4
tetrahedra, delimiting interconnected
pores or channels in which protonated organic amine
molecules are trapped. This latter interacts generally with
the anionic framework via hydrogen bonds. Thus, the elimi-
nation of the organic amine moieties in these compounds
is possible and could lead to new inorganic microporous
materials, which could not be obtained by other synthesis
method. These microporous compounds are considered
as an important class of solid state materials due to their
widespread applications in heterogeneous catalysis, ion
exchangers, gas separation, molecular sieving [1, 2] and as
hosts for quantum wires and quantum dots [3, 4], photo-
electrochemical, and photophysical processes [5–11]. In this
metal-phosphate family, zinc-phosphates occupy a prime
position but anions substituted zinc-phosphates are less
common and only a few chloro-substituted zincophosphates
are known. These include (H
3
N(CH
2
)
2
NH
3
)
0.5
ZnCl(HPO
4
)
[12] the only one 1-D ladder structure, the other ones
(H
3
N(CH
2
)
6
NH
3
)
0.5
ZnCl(HPO
4
) [ 13 ], (C
5
H
10
NH
2
)
ZnCl(HPO
4
) [14], (C
6
NH
14
)ZnCl(HPO
4
) [15] (C
4
H
10
NO)
ZnCl(HPO
4
) [16] and (C
10
H
10
N
2
)ZnCl(HPO
4
)
2
[17] are 2-D
layer structures with 4.8
2
[7–10] and 6
3
[17] topology. As
F
−
ion in several metal-phosphates, chloride ion acts as a
mineralizer in these compounds.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10854-018-9388-2) contains
supplementary material, which is available to authorized users.
* Brahim Ayed
ayedbrahim@yahoo.com
1
Unité de Recherche Catalyse et Matériaux pour
l′Environnement et les Procédés, Université de Gabès,
Gabès, Tunisia
2
Laboratoire de Chimie des Matériaux, Faculté des Sciences
de Bizerte, Université de Carthage, 7021 Zarzouna, Tunisia
3
Laboratoire de Matériaux et Cristallochimie, Département
de Chimie, Faculté des Sciences Monastir, Monastir 5000,
Tunisia