Synthesis and characterization of Pillared Metal Sulfates (Diamine)MeSO4, (Me = Zn, Cd)

Article abstract of DOI:10.1002/zaac.201300171

Hybrid organic-inorganic materials of the type (diamine)- MeSO₄ (Me = Cd, Zn) [diamine = p-xylylenediamine (PXDA) or mxylylenediamine (MXDA)] have not been described in the literature to date. Four compounds of this type, namely, (MXDA)ZnSO₄ (1), (MXDA)CdSO₄ (2), (PXDA)ZnSO ₄ (3), and (PXDA)CdSO₄ (4), were synthesized by solvothermal methods. Since all compounds crystallized as very fine powders, crystal structure studies were performed using powder diffraction methods. All compounds crystallize in the orthorhombic crystal system and the cell parameters are: a = 9.8004(4) ?, b = 10.7829(3) ?, c = 4.88473(19) ? for 1; 9.8824(10), 11.0907(7), 4.9663(5) ? for 2; 9.8496(3), 21.2419(5), 4.89556(17) ? for 3; and 10.1136(4), 21.6625(3), 4.9562(2) ? for 4. The compounds with MXDA as a linker, crystallize in the space group P21ma, those with PXDA in Pnma. These hybrid materials are built of inorganic monolayers [-Me-(SO₄)^-] joined by organic linkers created by diamines (PXDA or MXDA). Me metal ions and SO₄^2- anions form layers with a honeycomb structure. In addition tos crystal structure, chemical analyses and SEM investigations were performed. Thermal stability of the compounds was also investigated using TG-DSC methods and XRD as a function of temperature.

Full text of DOI:10.1002/zaac.201300171

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:15:59
Pages: 8
ARTICLE
DOI: 10.1002/zaac.201300171
Synthesis and Characterization of Pillared Metal Sulfates (Diamine)MeSO4,
(Me = Zn, Cd)
Katarzyna Luberda-Durnas´,[a] Dariusz Mucha,[a] Paula Sanz-Camacho,[b] and
Wiesław Łasocha*[a,b]
Keywords: Layered compounds; X-ray diffraction; Electron microscopy; Organic-inorganic hybrid composites
Abstract. Hybrid organic-inorganic materials of the type (diamine)- 11.0907(7), 4.9663(5) Å for 2; 9.8496(3), 21.2419(5), 4.89556(17) Å
MeSO4 (Me = Cd, Zn) [diamine = p-xylylenediamine (PXDA) or m- for 3; and 10.1136(4), 21.6625(3), 4.9562(2) Å for 4. The compounds
xylylenediamine (MXDA)] have not been described in the literature to with MXDA as a linker, crystallize in the space group P21ma, those
date. Four compounds of this type, namely, (MXDA)ZnSO4 (1), with PXDA in Pnma. These hybrid materials are built of inorganic
(MXDA)CdSO4 (2), (PXDA)ZnSO4 (3), and (PXDA)CdSO4 (4), were monolayers [–Me–(SO4)–] joined by organic linkers created by di-
2–
synthesized by solvothermal methods. Since all compounds crys-
amines (PXDA or MXDA). Me metal ions and SO4 anions form
tallized as very fine powders, crystal structure studies were performed layers with a honeycomb structure. In addition to crystal structure,
using powder diffraction methods. All compounds crystallize in the
orthorhombic crystal system and the cell parameters are: a =
chemical analyses and SEM investigations were performed. Thermal
stability of the compounds was also investigated using TG-DSC meth-
9.8004(4) Å, b = 10.7829(3) Å, c = 4.88473(19) Å for 1; 9.8824(10), ods and XRD as a function of temperature.
The obtained materials were the subject of wide-range re-
search aimed at their full structural characterization based on
Introduction
As has been recently found, even simple inorganic salts (e.g. powder diffraction data. Their morphology and thermal sta-
sulfates) create interesting layered or linear structures under bility were also investigated.
solvothermal conditions in the presence of amines. A number
of compounds, which belong to this class, have been described
in the literature.[1–4] These materials are interesting because
of their potential applications in catalysis, as sorption or ion
exchange materials, etc.
Results and Discussion
X-ray Powder Diffraction
While studying the MeSO4-diamine system (Me = Zn or
Cd), a new group of compounds was obtained. These materials
with the formula (diamine)MeSO4 formed using solvothermal
methods. Their diffraction patterns and unit cell parameters are
similar to typical MeQ(amine)1/2 compounds (Q = S, Se,
Te).[5–10] Because these new materials crystallize as very fine,
greasy powders, the formation of a novel type of complexes
was proved by X-ray powder diffraction data analysis.
The new compounds feature a unique structural architecture.
They are built of parallel monolayers consisted of Zn2+ or Cd2+
and sulfate anions. Amines, MXDA, or PXDA, are connecting
adjacent layers, by the covalent bonds with metal atoms from
the 2D inorganic slabs –Me–SO4–, forming a 3D network.
Since all compounds crystallize as very fine powders, struc-
tural investigations were performed using X-ray powder dif-
fraction (XRPD). Firstly, XRPD data were recorded using a
diffractometer working in Bragg-Brentano geometry, if further
studies indicate the presence of texture, for purpose of struc-
tural studies, additional measurements were performed in DSH
geometry (samples loaded into capillaries).
XRPD patterns for (MXDA)ZnSO4 (1) and (MXDA)CdSO4
(2) were recorded with a diffractometer working in Debye-
Scherrer geometry (capillary size 2r = 0.7 mm). Cell param-
eters were found using the WinPLOTR program package.[11]
The space group was obtained with the program
EXPO2009,[12] which calculates normalized structure factors,
prepares intensity statistics; subsequently the program suggests
space groups ranked in the order of their probability. Positions
of heavy atoms and atoms of organic parts were found using
direct methods and global optimization techniques. Calcula-
tions were performed using the EXPO2009 and FOX[12,13] pro-
grams. The structure models were refined with the Rietveld
method (JANA2006 program[14]). Using LeBail fitting, the
background, zero shift, unit cell, and profile parameters, in-
cluding asymmetry, were refined one by one. Afterwards, the
* Prof. W. Łasocha
Fax: +48-124251923
E-Mail: nclasoch@cyf-kr.edu.pl
[a] Jerzy Haber Insitute of Catalysis and Surface Chemistry PAS
Niezapominajek 8
30–239 Krakow, Poland
[b] Faculty of Chemistry
Jagiellonian University
Ingardena 3
30–060 Krakow, Poland
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:15:59
Pages: 8
W. Łasocha
ARTICLE
positions of atoms were fitted. For all atoms isotropic thermal Table 2. Selected interatomic distances of compound 1.
displacement parameters were applied. The absorption correc-
Atom 1
Atom 2 (symm. code)
d /Å
tion was introduced, assuming a cylindrical sample shape.
Geometric restraints on bond lengths and angles and con-
straints on atomic displacement parameters were used to im-
prove the stability of the refinement. Figure 1 and Figure 2
show the Rietveld plots of compounds 1 and 2.
Zn1
Zn1
Zn1
Zn1
Zn1
Zn1
O1
O2
N1
2.111(16)
2.199(15)
2.203(12)
2.203(12)
2.427(9)
2.427(9)
N1 (x, –y+2, z)
O3
O3 (x, –y+2, z)
Table 3. Selected interatomic distances of compound 2.
Atom 1
Atom 2 (symm. code)
d /Å
Cd1
Cd1
Cd1
Cd1
Cd1
Cd1
O1
O2
N1
2.400(9)
2.400(5)
2.275(2)
2.275(2)
2.400(1)
2.400(1)
N1 (x, –y+2, z)
O3(x, y, z+1)
O3 (x, –y+2, z+1)
Diffraction patterns of (PXDA)ZnSO4 (3) and (PXDA)-
CdSO4 (4) were recorded using a diffractometer working in
Bragg-Brentano geometry. The diffraction patterns of 3 and 4
were indexed as in cases 1 and 2 using the WinPLOTR pro-
gram package. The compounds with PXDA as ligand crys-
tallize in the space group Pnma. All steps in the refining pro-
cedure were essentially the same as in the case of compounds
1 and 2. In these cases, only small preferred orientation was
detected and taken into account in Rietveld refinement (March-
Dollase texture function, direction [010]). The Rietveld plots
for (PXDA)ZnSO4 and (PXDA)CdSO4 are shown in Figure 3
and Figure 4, respectively.
Figure 1. Rietveld refinement plots for (MXDA)ZnSO4 (1).
Figure 2. Rietveld refinement plots for (MXDA)CdSO4 (2).
Compounds 1 and 2 with MXDA as ligand crystallize in the
space group P21ma. Selected crystallographic data of
(MXDA)MeSO4 are summarized in Table 1, selected in-
teratomic distances in Table 2 and Table 3, respectively.
Table 1. Crystallographic data for (MXDA)ZnSO4 (1) and
(MXDA)CdSO4 (2).
Figure 3. Rietveld refinement plots for (PXDA)ZnSO4 (3).
Empirical formula
ZnSO4·C8H12N2 (1) CdSO4·C8H12N2 (2)
Basic crystallographic data of (PXDA)MeSO4 are summa-
rized in Table 4, selected interatomic distances in Table 5 and
Table 6.
Formula weight /g·mol–1 297.65
344.57
orthorhombic
P21ma
9.8645(9)
11.0854(6)
4.9572(4)
542.08(7)
7.2
Crystal system
Space group
a /Å
orthorhombic
P21ma
9.8004(4)
10.7829(3)
4.88473(2)
516.21(3)
6.9
b /Å
Structure Description
c /Å
V /Å3
Rp
Compounds 1–4 crystallize in the orthorhombic crystal sys-
tem. They have three-dimensional structures built of
–Me–(SO4)– layers, connected by diamines (MXDA or
PXDA) through covalent bonds with the metal atoms (Me)
Rwp
RF
Color
9.2
9.2
6.1
6.8
white
white
2
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:15:59
Pages: 8
Pillared Metal Sulfates (Diamine)MeSO4, (Me = Zn, Cd)
Figure 4. Rietveld refinement plots for (PXDA)CdSO4 (4).
Table 4. Crystallographic data for (PXDA)ZnSO4 (3) and
(PXDA)CdSO4 (4).
Empirical formula
ZnSO4·C8H12N2 (3) CdSO4·C8H12N2 (4)
Formula weight /g·mol–1 297.65
344.57
Crystal system
Space group
a /Å
orthorhombic
Pnma
orthorhombi
Pnma
Figure 5. Basic fragments of structure: (A) (MXDA)MeSO4 (1, 2),
(B) (PXDA)MeSO4 (3, 4).
9.8496(3)
21.2419(5)
4.8956(2)
1024.27(5)
6.8
9.1
5.1
white
10.1136(4)
21.6625(3)
4.9562(2)
1086.83(7)
9.6
12.3
6.5
white
b /Å
In each compound, the atoms Me (Zn, Cd) are surrounded
by six ligands, two nitrogen atoms (in cis position to each
other) and four oxygen atoms, forming a distorted octahedron.
The sulfur atoms are tetrahedrally coordinated by oxygen
atoms.
c /Å
V /Å3
Rp
Rwp
RF
Color
The –Me–SO4– layers in all compounds are essentially sim-
ilar; they are flat as being located exactly on the crystallo-
graphic mirror plane. A –Cd–SO4– layer is shown in Fig-
ure 6A. Interestingly, from the viewpoint of topology, the lay-
ers –Me–SO4– are similar to the layers in MeQ(amine)1/2 com-
pounds.[5] In both cases, there exist fused six-membered rings,
their vertices are alternately occupied by the three Me atoms
and by three anions (SO42– in our studies). Each vertex is com-
mon to three rings. Inorganic layers can be described by topo-
logical index 63. However, in the presented cases, each Me
atom is coordinated by two amine groups; this results in dif-
ferent stoichiometry, octahedrally coordinated central metal
atoms can be more easily accommodated in flat Me–SO4 lay-
ers, whereas in MeQ(amine)1/2 such layers are puckered.
The use of different amines determines the space group, in
which these type of compounds [(amine)MeSO4] crystallize.
All compounds with MXDA as an organic linker crystallize
in the space group P21ma, whereas compounds with PXDA
crystallize in Pnma. This could be related to the arrangement
of the linking fragment and the preference of terminal –CH2–
NH2 groups to adopt cis or trans conformation (mutual orien-
Table 5. Selected interatomic distances of compound 3.
Atom 1
Atom 2 (symm. code)
d /Å
Zn1
Zn1
Zn1
Zn1
Zn1
Zn1
O1
O2
2.250(8)
2.399(4)
2.399(4)
2.112(6)
2.112(6)
2.263(9)
O2 (x–1/2, y, –z–1/2)
N1
N1 (x, –y+1/2, z)
O3
Table 6. Selected interatomic distances of compound 4.
Atom 1
Atom 2 (symm. code)
d /Å
Cd1
Cd1
Cd1
Cd1
Cd1
Cd1
O1
O2
2.432(15)
2.469(10)
2.469(10)
2.368(14)
2.368(14)
2.414(17)
O2 (x–1/2, y, –z–1/2)
N1
N1 (x, –y+1/2, z)
O3
tation). Such a phenomenon was observed in the case of
[5]
MeQ(diamine)1/2
,
where two different space groups accord-
ing to an even or odd number of carbon atoms in aliphatic
from the layer. Compounds 1, 2 and 3, 4 are isostructural, and diamine NH2–(CH2)n–NH2 were found. Figure 6B and C show
all compounds show significant similarities. This is demon- layered structures, the alignment of the diamines, and linking
strated clearly in Figure 5A and B, where basic structures’ fragments in the structures of (MXDA)ZnSO4 and
fragments are presented.
(PXDA)ZnSO4.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
3

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:16:00
Pages: 8
W. Łasocha
ARTICLE
Figure 7. The orthogonal alignment of MXDA molecules (black bars
represent aromatic rings) seen through –Me–SO4– layers.
Figure 6. Structure of (amine)MeSO4, (A) layer of –Zn–SO4–. View
along layers: (B) (MXDA)ZnSO4, (C) (PXDA)ZnSO4.
Figure 8. The alignment of amines between inorganic layers in
(A) (1, 2) (amine – MXDA), (B) (3, 4) (amine – PXDA).
In all structures the diamine rings are perpendicular to each
other. The arrangement of amines is shown in Figure 7. More-
over, in compounds 1 and 2 the MXDA molecules are arranged
The materials obtained are similar to reported recently re-
orthogonally to –Me–SO4– layers (lying exactly on the plane ported open-framework sulfates.[1–4] Nevertheless, some dif-
of symmetry m), in contrast to compounds 3 and 4 (Figure 8). ferences can be observed. The most important is the way of
In these compounds the LS planes of diamines are perpendicu- connection of the organic components. In case of the new com-
lar, but their long axes are arranged obliquely to the –Me– pounds, the amine molecules are linked directly by covalent
SO4– layers. This is the result of the different mutual positions of bonds to the metal atoms, whereas in the open-framework
–CH2–NH2 groups in both amines (p-xylylenediamine and m- compounds[1–4] ammonium fragments are connected by ionic
xylylenediamine).
forces and hydrogen bonds. Also, only the new compounds
4
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:16:00
Pages: 8
Pillared Metal Sulfates (Diamine)MeSO4, (Me = Zn, Cd)
were obtained as three-dimensional hybrid inorganic-organic
materials. An interesting representative of such a kind of
open-framework compound is [H3N(CH2)3NH3][Cd2(H2O)2-
(SO4)3].[4] It is a lamellar material with a 44 topology of the
Cd–SO4– layer. In this case fused rings in the layer are built of
two octahedrally coordinated cadmium atoms and two sulfate
groups, whereas in our compounds three metal atoms and three
sulfate groups are involved.
Chemical Analyses
The obtained compounds provided good diffraction images,
but they were greasy materials, difficult to properly wash and
drain. The chemical analyses are in general agreement with the
results of the structure solution, but indicate also that samples
(particularly MXDA complexes) are significantly contami-
nated by amorphous or liquid admixtures.
(PXDA)ZnSO4: ZnSO4C8H12N2 (297.65 g·mol–1): C 33.92 Figure 9. SEM images of compounds (amine)MeSO4: (A) (MXDA)-
ZnSO4 (B) (MXDA)CdSO4 (C) (PXDA)ZnSO4 (D) (PXDA)CdSO4.
(calcd. 32.28), H 4.22 (4.06), N 9.61 (9.41), S 9.79 (10.77)%.
This result indicates a small excess of amine.
(MXDA)ZnSO4: ZnSO4C8H12N2 (297.65 g·mol–1): C 38.95
(calcd. 32.28), H 4.16 (4.06), N 9.63 (9.41), S 10.70 (10.77)%.
In this case the chemical analysis also indicates an excess of
amine, but in larger quantities.
(MXDA)ZnSO4: Three weight loss steps, 21.04%, 14.79%,
and 22.81% (in the range 210 °C to 520 °C), correspond to
releases of amine. It is also possible that in the last mass loss
(22.81%), two combined effects occur: the release of amine
and the first step of decomposition of ZnSO4 to ZnO. Total
loss of weight is 81.64% and the product is ZnO. TG-DSC
results of (MXDA)ZnSO4 are shown in Figure 10.
(PXDA)CdSO4: CdSO4N2H12C8 (344.57 g·mol–1): C 29.88
(calcd. 27.88), H 3.59 (3.48), N 8.29 (8.12), S 9.02 (9.31)%.
These slight differences can be explained by an excess of
amine.
(MXDA)CdSO4: CdSO4N2H12C8 (344.57 g·mol–1):
C
24.31 (calcd. 27.88), H 3.15 (3.48), N 7.07 (8.12), S 10.03
(9.31)%. That indicates the presence of impurities (synthesis
substrates).
SEM
(MXDA)ZnSO4 (1): SEM images of 1 (Figure 9A) show
that the obtained crystallites share uniform morphology. Domi-
nant are thin plates (thickness from 10 to 50 nm) with very
uneven surfaces. The crystallites are complex aggregates.
(MXDA)CdSO4 (2): SEM images show aggregates of
plate-like crystallites with irregular edges and heterogeneous
surfaces. Their shape and thickness vary greatly (from 0.1 μm
to 1 μm). The crystallites are shown in Figure 9B.
Figure 10. TG-DSC analysis of (MXDA)ZnSO4.
(PXDA)ZnSO4 (3): The crystallites are rectangular and of
different sizes, with a thickness of about 0.1 μm. The edges of
the crystallites are regular and the surfaces are homogeneous
(Figure 9C).
(PXDA)CdSO4 (4): SEM images show that the crystallites
are of different sizes, from 0.1 μm to several μm, and with
thicknesses of about 1 μm or less. The surfaces are quite
homogeneous and the edges are rather regular (Figure 9D).
(MXDA)CdSO4: The weight loss steps (16.55%, 16.96%,
3%) can be explained by the sequential release of two nearly
equal amounts of amines. The total weight loss is 38.72% and
the final product is CdSO4. TG-DSC results of (MXDA)-
CdSO4 are shown in Figure 11.
(PXDA)ZnSO4: The weight loss steps around 300 °C to
510 °C, connected with the first two exothermic peaks, corre-
spond to the loss of amines pertaining to (PXDA)ZnSO4 as a
result of its decomposition 48.96 (calcd. 46%). The last exo-
thermic peak (at 559 °C) is a consequence of zinc sulfate de-
composition with release of SO3 (19.00% loss of mass). The
TG-DSC and XRPD versus Temperature
Using TG-DSC, thermal stability of the compounds was in- total mass loss in is between 72–74% (cal. 73%) and the final
vestigated. For all compounds, the results obtained through product is ZnO. TG-DSC results of (PXDA)ZnSO4 are shown
TG-DSC exhibit multi-step weight losses.
in Figure 12.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
5

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:16:00
Pages: 8
W. Łasocha
ARTICLE
amine is observed. Nearly equal amounts of released amine
suggest the formation of intermediate compounds with the for-
mula (diamine)1/2MeSO4. In the case of zinc compounds 1 and
3, final decomposition leads to formation of ZnO (ca. 670 °C),
whereas CdSO4 is formed (500–550 °C) in the case of cad-
mium-amine sulfates 2 and 4.
The TG-DSC results were verified by temperature-depend-
ent XRPD measurements. (PXDA)ZnSO4 and (PXDA)CdSO4
were investigated in this way (see Figure 14 and Figure 15).
High temperature XRPD data indicate that the samples are
stable until ca. 300 °C and proved the type of final products
of thermal decomposition (ZnO, CdSO4). They also indicate
that the intermediate product formed with one amine per for-
mal molecule (ca. 300–400 °C) is different from the initial
product. The cell parameters of those intermediate products
are: a = b = 10.074(4) Å, c = 21.864(8) Å for (PXDA)CdSO4
and a = b = 9.961(5) Å, c = 21.181(9) Å for (PXDA)ZnSO4.
It seems that the initial orthorhombic structure with formula
(PXDA)Me]SO4 recrystallized to a tetragonal material with the
formula (PXDA)1/2MeSO4. It was tried to isolate and examine
the intermediate phase. However, our efforts have yielded in
complex two-phase mixtures, leading to difficulties in determi-
nation of the space group, which prevented structural studies.
The temperature-dependent XRPD patterns are shown in Fig-
ure 14 and Figure 15.
Figure 11. TG-DSC analysis of (MXDA)CdSO4.
Figure 12. TG-DSC analysis of (PXDA)ZnSO4.
(PXDA)CdSO4: The two weight loss steps (20.33% and
21.09%) in the range 300 °C to 650 °C correspond to the com-
plete loss of amine belonging to the (PXDA)CdSO4 (calcd.
39.5%). In turn, the two exothermic peaks that appear at 800
and 854 °C may be caused by the melting of some products of
thermal decomposition, such as CdSO4. The final product of
the TG-DSC analysis is cadmium sulfate (CdSO4). TG-DSC
results of (PXDA)CdSO4 are shown in Figure 13.
Figure 14. XRPD pattern vs. temp. for (PXDA)CdSO4.
Figure 15. XRPD pattern vs. temp. for (PXDA)ZnSO4.
Conclusions
Four new hybrid compounds (diamine)MeSO4, (Me = Cd,
Zn) were synthesized under solvothermal conditions (2 d,
Figure 13. TG-DSC analysis of (PXDA)CdSO4.
Summing up the TG-DSC experiments, the obtained com- 160 °C). All materials crystallize in the orthorhombic
pounds are stable to about 300 °C. Next, two-step removal of crystal system: (PXDA)MeSO4 in space group Pnma and
6
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:16:00
Pages: 8
Pillared Metal Sulfates (Diamine)MeSO4, (Me = Zn, Cd)
Methods for Characterization: The simultaneous Thermogravimetry
and Differential Scanning Calorimetry (TG-DSC) studies were per-
formed with a computer-controlled STA 409 PC Luxx system. The
measurements were performed in an air atmosphere. The heating rate
was 10 °C·min–1; the initial temperature was 20 °C, the final 1000 °C.
(MXDA)MeSO4 in P21ma. The cell parameters for compounds
with the same amine but varied metal atoms are slightly dif-
ferent because of the different zinc and cadmium ionic radii.
These three-dimensional hybrid materials are built of infinite
parallel layers –Me–(SO4)–, connected by diamines (MXDA,
PXDA) forming coordination bonds with metal ions. SEM
images showed that the obtained compounds are aggregates of
The morphology of the samples was investigated with a JEOL JSM-
7500F Scanning Electron Microscope. The samples were applied on
plate-shaped crystals. TG-DSC analyses showed that all com- brass stubs and sputter-coated with chrome. The accelerating voltage
was 15 kV.
pounds are stable to about 300 °C, after which a two-step re-
lease of amine is observed. In the case of (MXDA)ZnSO4 and
(PXDA)ZnSO4 the final product is ZnO, whereas for
(PXDA)CdSO4 and (MXDA)CdSO4 the final product is
CdSO4. Although they comprise of more complicated
Chemical analysis was performed with a Euro Vector EA 300 Elemen-
tal Analyzer.
Thermal analysis was performed in air, or helium using an XRK cham-
building blocks, the inorganic layers in MeQ(amine)1/2 and ber produced by Anton Paar. The heat rate was 10 °C·min–1. After
reaching the desired temperature the sample was stabilized for 10 min.
The initial temperature was equal to room temperature; subsequent
temperatures were 100 °C, 200 °C, 300 °C, etc. up to 700 °C.
(amine)MeSO4 are similar from a topological point of view.
Experimental Section
Acknowledgements
Materials: Zinc sulfate hydrate (ZnSO4·7H2O) and cadmium sulfate
hydrate (CdSO4·8H2O) were purchased from Fabryka Odczynników
Chemicznych Gliwice (POCH); p-xylylenediamine and m-xylylenedia-
mine were purchased from Sigma-Aldrich. All chemicals were used as
received without further purification.
This work was supported by the Krakow Interdisciplinary PhD-Project
in Nanoscience and Advanced Nanostructures, operated within the
Foundation for Polish Science MPD Programme co-financed by the
EU European Regional Development Fund. The support of the Polish
Government Program MNiSW, grant NN204546439, is also kindly
acknowledged.
Synthesis of (MXDA)MeSO4 (1, 2): (MXDA)ZnSO4 was obtained by
solvothermal route using ZnSO4·7H2O (0.01 mol) and m-xylylenedi-
amine (MXDA) (0.01 mol). Zinc sulfate hydrate was thoroughly
ground and placed into a 63-mL Teflon-lined stainless steel autoclave
and the amine (MXDA) was added. The mixture was heated at 160 °C
for 2 d and cooled naturally to room temperature. The product 1 was
washed with a mixture of 2-propanol and water (2:1) and finally dried
at room temperature for 24 h. Similar conditions were used for the
synthesis of [(MXDA)Cd]SO4 (2), but in this case the source of Me
atoms was CdSO4·8H2O.
References
[1] Y.-P. Yuan, R.-Y. Wang, D.-Y. Kong, J.-G. Mao, A. Clearfield, J.
Solid State Chem. 2005, 178, 2030–2035.
[2] W. Zhou, Q. Chen, D. Zhu, Y. Xu, Z. Anorg. Allg. Chem. 2009,
635, 572–576.
[3] T. Bataille, D. Louër, J. Solid State Chem. 2003, 177, 1235–1243.
[4] G. Paul, A. Choudhury, C. N. R. Rao, J. Chem. Soc. Dalton Trans.
2002, 3859–3867.
[5] X. Huang, J. Li, H. Fu, J. Am. Chem. Soc. 2000, 122, 8789–8790.
[6] X. Huang, H. R. Heulings IV, V. Le, J. Li, Chem. Mater. 2001,
13, 3754–3759.
[7] X. Huang, J. Li, J. Am. Chem. Soc. 2007, 129, 3157–3162.
[8] X. Huang, J. Li, Y. Zhang, A. Mascarenhas, J. Am. Chem. Soc.
2003, 125, 7049–7055.
[9] X. Huang, M. Roushan, T. J. Emge, W. Bi, S. Thiagarajan, J.
Cheng, R. Yang, J. Li, Angew. Chem. Int. Ed. 2009, 48, 7871–
7874.
Synthesis of (PXDA)MeSO4 (3, 4): The synthesis was performed
using ZnSO4·7H2O (0.01 mol) and p-xylylenediamine (PXDA)
(0.0125 mol). Zinc sulfate hydrate and p-xylylenediamine were
ground, mixed, and placed in a 63-mL Teflon-lined stainless steel auto-
clave. The mixture was heated at 160 °C for 2 d and cooled naturally
to room temperature. The product 3 was washed with a mixture of 2-
propanol and water (2:1) and finally dried at room temperature. A
similar method was used to synthesize (PXDA)CdSO4 (4), however
CdSO4·8H2O was used instead of zinc sulfate.
[10] a) K. Luberda-Durnas´, B. Gaweł, M. Łos´, W. Łasocha, Cryst. Res.
Technol. 2011, 46, 1283–1294; b) B. Gaweł, M. Zieba, W. Łaso-
cha, J. Alloys Compds. 2007, 442, 77–79.
[11] Ed. R. Delhez, E. J. Mittenmeijer, Proceedings of the Seventh
European Powder Diffraction Conference (EPDIC 7), 2000, 118–
123.
[12] A. Altomare, C. Caliandro, C. Camalli, C. Cuocci, G. Giacov-
azzo, A. G. G. Moliterni, R. Rizzi, J. Appl. Crystallogr. 2004, 37,
1025–1028.
Crystal Structure Determination: X-ray powder diffraction patterns
(XRPD) of the samples were recorded with a X’PERT PRO MPD
diffractometer, working in Bragg-Brentano or Debye-Scherrer geome-
try; incident and antiscatter slits were 1/4 and 1/2°, respectively (detec-
tor X’CELERATOR, radiation Cu-Kα, X-ray tube working conditions
40 kV and 30 mA). The measurement range was from 4° to 65° 2θ
with interpolated step size 0.02°.
[13] V. Favre-Nicolin, R. Cerny, J. Appl. Crystallogr. 2002, 35, 734–
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-901450 (1), -901449 (2), -9006899 (3), and -900688
(4) (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
743.
[14] V. Petricek, M. Dusek, L. Palatinus, Jana2006 – The Crystallo-
graphic Computing System , Institute of Physics, Prague, Czech
Republic, 2006.
Received: March 25, 2013
Published Online: ᭿
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7

Job/Unit: Z13171
/KAP1
Date: 08-07-13 12:16:00
Pages: 8
W. Łasocha
ARTICLE
K. Luberda-Durnas´, D. Mucha, P. Sanz-Camacho,
W. Łasocha* ...................................................................... 1–8
Synthesis and Characterization of Pillared Metal Sulfates
(Diamine)MeSO4, (Me = Zn, Cd)
8
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0