Structural study of hydrated/dehydrated manganese thiophene-2,5- diphosphonate metal organic frameworks, Mn(Od3P-C4H 2S-POd3)·2H2O

Article abstract of DOI:10.1021/ic301187y

Synthesis of thiophene-2,5-diphosphonic acid 2 is reported, and its use for synthesis of the original pristine materials Mn(Od₃P-CHS-POd ₃)·2HO 3 is reported. The structure of material 3 has been fully resolved from single-crystal X-ray diffraction. Mn(Od₃P-CHS- POd₃)·2HO 3 crystallizes in a monoclinic cell (space group P2) with the following parameters: a = 11.60(1) A, b = 4.943(5) A, c = 19.614(13) A, β = 107.22°. A noticeable feature of the structure of compound 3 is the orientation of the thiophene heterocycles that adopt two different orientations in two successive layers (along c). Thermal analysis of compound 3 indicates that the water molecules are easily removed from 160 to 230 °C while the dehydrated structure is stable up to 500 °C. The dehydrated compound obtained from 3 can be rehydrated to give the polymorphic compound Mn(Od₃P-CHS-POd₃)·2HO 4, which crystallizes in an orthorhombic cell (space group Pnam) with the following parameters: a = 7.5359(3) A, b = 7.5524(3) A, c = 18.3050(9) A. The main difference between the structures of 3 and 4 arises from both the orientation of the thiophene rings (herringbone-type organization in 4) and the structure of the inorganic layers. The thiophene-2,5-diphosphonic acid moieties engaged in materials 3 and 4 adopt a different orientation likely due to rotation around the P-C bonds and via the dehydrated state 5, which is likely more flexible than the hydrated states. Study of the magnetic properties performed on compound 3 and 4 and on the dehydrated compounds Mn(Od ₃P-CHS-POd₃) 5 complemented by the structural study has permitted us to characterize the antiferromagnetic ground state of sample 3, a weak ferromagnetic component in sample 4, and complete paramagnetic behavior in sample 5.

Full text of DOI:10.1021/ic301187y

Article
pubs.acs.org/IC
Structural Study of Hydrated/Dehydrated Manganese Thiophene-
2,5-diphosphonate Metal Organic Frameworks, Mn2(O3P−C4H2S−
PO3)·2H2O
Jean-Michel Rueff,*,† Olivier Perez,† Alain Pautrat,† Nicolas Barrier,† Gary B. Hix,‡ Sylvie Hernot,§
Helene Couthon-Gourves,§ and Paul-Alain Jaffres*,§
́
̀
̀
̀
†CRISMAT, UMR CNRS 6508, ENSICAEN, Universite
France
́ ́
de Caen Basse-Normandie, 6 Boulevard du Marechal Juin, 14050 Caen,
‡School of Science and Technology, Nottingham Trent University, Nottingham NG11 8NS, United Kingdom
§Universite
́ ́ ́
de Brest and Universite Europeenne de Bretagne, CNRS UMR 6521, CEMCA, IFR 148 ScInBios, 6 Avenue Victor Le
Gorgeu, 29238 Brest, France
S
* Supporting Information
ABSTRACT: Synthesis of thiophene-2,5-diphosphonic acid 2 is
reported, and its use for synthesis of the original pristine materials
Mn2(O3P−C4H2S−PO3)·2H2O 3 is reported. The structure of
material 3 has been fully resolved from single-crystal X-ray
diffraction. Mn2(O3P−C4H2S−PO3)·2H2O 3 crystallizes in a
monoclinic cell (space group P2) with the following parameters: a
= 11.60(1) Å, b = 4.943(5) Å, c = 19.614(13) Å, β = 107.22°. A
noticeable feature of the structure of compound 3 is the orientation
of the thiophene heterocycles that adopt two different orientations in
two successive layers (along c). Thermal analysis of compound 3
indicates that the water molecules are easily removed from 160 to
230 °C while the dehydrated structure is stable up to 500 °C. The dehydrated compound obtained from 3 can be rehydrated to
give the polymorphic compound Mn2(O3P−C4H2S−PO3)·2H2O 4, which crystallizes in an orthorhombic cell (space group
Pnam) with the following parameters: a = 7.5359(3) Å, b = 7.5524(3) Å, c = 18.3050(9) Å. The main difference between the
structures of 3 and 4 arises from both the orientation of the thiophene rings (herringbone-type organization in 4) and the
structure of the inorganic layers. The thiophene-2,5-diphosphonic acid moieties engaged in materials 3 and 4 adopt a different
orientation likely due to rotation around the P−C bonds and via the dehydrated state 5, which is likely more flexible than the
hydrated states. Study of the magnetic properties performed on compound 3 and 4 and on the dehydrated compounds
Mn2(O3P−C4H2S−PO3) 5 complemented by the structural study has permitted us to characterize the antiferromagnetic ground
state of sample 3, a weak ferromagnetic component in sample 4, and complete paramagnetic behavior in sample 5.
ylate derivatives are commercially available and others were
specifically designed.11
INTRODUCTION
■
Over the last decades, metal organic frameworks (MOF) have
been extensively studied with the aim of identifying new
families of molecular materials that could be used for new
applications.1 A key question regards the rules that, at an
atomic scale, govern the assembly of the primary building units
(organic and inorganic building blocks) to form successively
the secondary building units (SBU) and the final materials.2
Rigid,3 flexible,4 or semiflexible5 organic building blocks have
been engaged in the synthesis of MOF with the aim of
evaluating the consequences of their intrinsic flexibility on the
topology of the resulting materials. It noticeable that the use of
rigid polyfunctional organic precursors has produced a wide
variety of hybrid materials that have been studied for their
properties in diverse fields including magnetism,6 lumines-
cence,7 catalysis,8 gas storage,9 or drug release.10 For the design
of such materials, the carboxylic acid functional group has
played a central role since many carboxylate and polycarbox-
Besides the use of carboxylic acid derivatives to design MOF,
other functional groups including phosphonic acids12 or
sulfonic acids13 have been used to produce original structures
that exhibit interesting properties. In particular, the presence of
two different functional groups (heteropolyfunctional organic
precursors) has proved to be a valuable strategy to produce
materials with singular properties. Indeed, Morris et al.
synthesized a material with two carboxylic acid and one
sulfonic acid functional groups linked to a rigid motif (e.g., a
benzene ring). This material exhibits at the solid state a
reversible bond breaking that involves connection of organic
molecules with the inorganic network.14 Synthesis of
phosphonic acid, polyphosphonic,15 or phosphonic−carboxylic
Received: June 5, 2012
© XXXX American Chemical Society
A
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abbreviations were used: s singlet, d doublet, t triplet, m multiplet.
Elemental analyses were recorded with an automatic apparatus CHNS-
O Thermo-Quest. Infrared (IR) spectroscopy spectra were recorded
on a FTIR Thermo Nicolet FT-IR Nexus spectrometer working in
absorbance mode in the 400−4000 cm−1 range at 4 cm−1 optical
resolution. A powder sample was diluted by mixing KBr (2 wt %).
Mass spectroscopy analyses were performed on a Bruker Autoflex
MALDI TOF-TOF III LRF200 CID. Thermogravimetric analyses
(TGA) were recorded at a rate of 3 °C/min from 30 to 800 °C under
air or nitrogen gas flow using a SETARAM TGA 92 apparatus.
Differential scanning calorimetry (DSC) was performed at a rate of 10
°C/min from 10 to 280 °C under nitrogen gas flow using a Perkin
Elmer DSC 4000 apparatus equipped with an Intracooler.
derivatives has also produced materials exhibiting interesting
properties (e.g., microporosity16). We previously synthesized
and used rigid polyfunctional organic precursors in which a
benzene ring acts as a rigid platform.17 According to this
strategy the use of 4-carboxyphenylphosphonic acid A (Scheme
1) when reacted with an europium salt produced a luminescent
Scheme 1. Chemical Structure of Compounds A−C and 2
The magnetic susceptibility and magnetic moment of the different
samples were measured in a SQUID MPMS (Quantum design).
Magnetic suceptibilities were recorded as a function of temperature
using a zero-field-cooling procedure or a field-cooling−zero-field-
cooling procedure (B = 0.1 T).
Scanning electron microscopy (SEM) and energy-dispersive
spectroscopy (EDS) have been performed using a Zeiss Supra 55
electron microscope.
material characterized by its high thermal stability.18 Reaction
of the carboxylic−phosphonic derivative B with copper salts
gives rise to a homochiral helical structure.19 The same organic
precursor B reacted with zinc nitrate has produced a 2D or 3D
hybrid material depending on the pH of the reaction media,
illustrating the possibility with some experimental conditions to
observe chemoselectivity in the course of hybrid material
construction.20 Finally, compound C when combined with a
copper salt produced a complex 3D structure21made of
inorganic columns connected by organic parts.
On the basis of these results, which clearly indicate the
relevance of studying further the use of rigid phosphonic or
polyphosphonic derivatives for construction of hybrid materials,
functionalization of thiophene has come to our attention.
Indeed, in the literature, several materials based on the use of
thiophene−carboxylate or thiophene−dicarboxylate as organic
building blocks are reported; these materials are interesting for
both their structures and their properties. Indeed, thiophene-
2,5-dicarboxylate (TDC) gives rise to several kinds of
connections between the carboxylate function and the
inorganic network,22 and diverse properties (luminescence,23
chiral material,24 magnetism25,29) have been reported.
To the best of our knowledge, use of the phosphonic acid
equivalent of thiophen−carboxylate for design of hybrid
structure has been only seldom investigated. One study reports
the use of thiophene-2-phosphonic or thiophene-3-phosphonic
acids for construction of a hybrid structure following an
organometallic route of synthesis that makes use of
dimethylzinc (ZnMe2) as the inorganic source.26 In that
study, the layered structure of the zinc−phosphonate hybrid
material was confirmed by powder X-ray diffraction and the
structure was further investigated by solid state NMR. A second
study reports the use of thiophene-2-phosphonic acid for
modification of TiO2 surfaces.27 In that instance, the organic
compound acts as an interface modifier for design of
photovoltaic devices. We aim to report herein the first use of
thiophene-2,5-diphosphonic acid 2 (Scheme 1) for construc-
tion of hybrid materials. Materials produced were obtained as
single crystals, allowing unambiguous description of the
structure. Complementary characterization, including the
thermal stability and magnetic properties of these compounds,
is reported.
Tetraethyl Thiophene-2,5-diphosphonate 1. NiBr2 (0.48 g ;
2.2 mmol), 2,5-dibromothiophene (3.6 g, 14.8 mmol), and mesitylene
(10 mL) were placed under a nitrogen atmosphere in a two-neck
round-bottom flask fitted with a reflux condenser and an addition
funnel. The suspension was heated at 180 °C, and triethylphosphite
(7.4 g, 44.5 mmol) was carefully added dropwise for 30 min. At the
end of the addition, the solution was heated further at 180 °C for 6 h.
After cooling to room temperature, the volatiles, including the solvent,
were removed in vacuo. Dichloromethane (50 mL) was added, and the
solution was washed with water (3 × 50 mL). The organic phase was
dried over MgSO4, filtered, and concentrated in vacuo to produce an
oil. After purification by column chromatography on silica gel
(CH2Cl2/MeOH: v/v 100/2) compound 1 was isolated in 85%
yield (4.5 g) as a pale yellow oil.
1H NMR (300.13 MHz, CDCl3): 1.34 (m, O−CH2-CH3), 4.17 (m,
3
3
O−CH2-CH3), 7.63 (d, JHH = 5.5 Hz, CH), 7.65 (d, JHH = 5.6 Hz,
CH). 31P NMR (121.49 MHz, CDCl3): 9.98 (s). 13C NMR (75.47
MHz, CDCl3): 16.1 (s, O−CH2-CH3), 62.9 (s, O-CH2−CH3), 136.1
1
3
2
(dd, JCP = 203.7 Hz, JCP = 5.7 Hz, C-P), 136.2 (d, JCP = 15.2 Hz,
2
CC−P), 136.4 (d, JCP = 15.3 Hz, CC−P). MS (MALDI-TOF):
m/z calcd for C12H23O6P2S (M + H) 357.069; found 357.057.
Thiophene-2,5-diphosphonic Acid 2. A 9 mL (67.3 mmol)
amount of trimethylsilylbromide was added to a solution of tetraethyl
thiophene-2,5-diphosphonate 1 (4 g, 11.2 mmol) in dry methylene
chloride (80 mL). The mixture was stirred at room temperature for 12
h and concentrated in vaccuo. The residue was recovered in 150 mL of
methanol and stirred at room temperature for 1 h. Following
evaporation of methanol, diphosphonic acid 2 was quantitatively
obtained (2.7 g) as a white crystalline solid (See Supporting
Information, Figure SI1, for X-ray powder diffraction).
3
1H NMR (300.13 MHz, D2O): 4.33 (s large, OH), 7.36 (d, JHH
=
3
5.5 Hz, CH), 7.37 (d, JHH = 5.6 Hz, CH). 31P NMR (121.49 MHz,
D2O): 7.25 (s). 13C NMR (75.47 MHz, CDCl3): 135.1 (d, 2JCP = 15.5
Hz, CC−P), 135.3 (d, 2JCP = 15.5 Hz, CC−P), 137.7 (dd, 1JCP
=
3
203.0 Hz, JCP = 6.3 Hz, C-P). Anal. Calcd for C4H6O6P2S (244.10):
C, 19.68; H, 2.48; S, 13.14. Found: C, 19.10; H, 2.40; S, 12.72.
Hydrothermal Synthesis of Mn2(O3P−C4H2S−PO3)·2H2O 3.
Thiophene-2,5-diphosphonic acid 2 (0.05 g, 0.2 mmol), urea (0.024 g,
0.4 mmol), and Mn(NO3)2·6H2O (0.118 g, 0.4 mmol) were dissolved
in distilled water (15 mL). The resulting solution was placed in a
PTFE insert of 50 mL. After stirring 15 min the pH of the mother
solution (pHinitial) was 1.66. The insert was then transferred in a
Berghof pressure digestion vessel and heated from room temperature
to 140 °C in 20 h, heated 40 h at 140 °C, and cooled to room
temperature in 40 h. At the opening of the PTFE insert the pH of the
solution (pHfinal) was 4.13, and the final material, obtained as light
brown crystals with suitable size for structure resolution on a single
crystal, was isolated by filtration, washed with water rinsed with
absolute ethanol, and dried in air.
EXPERIMENTAL SECTION
■
1
General. All compounds were fully characterized by H, 13C, and
31P NMR spectroscopy (Bruker AC 300 spectrometer). The following
B
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A pattern matching of the whole preparation realized from the
single-crystal data permitted us to confirm that compound 3 was
obtained as a single phase (see Supporting Information, Figure SI2, for
pattern matching from single-crystal data).
Mn2(O3P−C4H2S−PO3)·2H2O (3): yield 0.06 g (78%). Anal.
Calcd: C, 12.45; H, 1.57. Found: C, 12.57; H, 1.86. IR (KBr): 3517,
3457.7, 3107.8, 1604.9, 1504.8, 1428.2, 1299.7, 1287.9, 1222.9, 1207.3,
1099.9, 1070.6, 1043.7, 1003.3, 972.8, 841.6, 816.4, 755.9, 749.3,
611.6, 591.7.
RESULTS AND DISCUSSION
■
Synthesis and Characterization of the Materials.
Thiophene-2,5-diphosphonic acid 2 was synthesized in a two-
step sequence that makes use of 2,5-dibromothiophene as a
starting material (Scheme 2). In a first step substitution of the
Scheme 2. Synthesis of Thiophene-2,5-diphosphonic Acid,
a
2
Figure 1. Representative crystal of Mn2(O3P−C4H2S−PO3)·2H2O 3
with a platelet shape observed by SEM.
the characteristic band of the water bending vibration (δ H2O).
Spectra reveal also in the 3000 cm−1 wavenumber region the
symmetric (υs H2O) and at higher wavenumber the asymmetric
(υas H2O) stretching bands of lattice water molecules: 3461 and
3528 cm−1. Finally, the stretching vibration band of the
aromatic C−H bond29 is observed at 3108 cm−1.
a
(i) NiBr2, triethylphosphite, mesitylene, 180 °C. (ii) Me3SiBr,
CH2Cl2. (iii) MeOH.
two bromide atoms using a nickel-assisted Arbuzov reaction
(Tavs’s method28) produced tetraethyl thiophene-2,5-di-
phosphonate 1 in 85% yield. In this reaction the use of nickel
bromine, NiBr2, which gives rise to more reproducible results, is
preferred compared to NiCl2, which is generally used for
synthesis of arylphosphonates from arylbromides. Direct
hydrolysis of the diphosphonate 1 with concentrated HCl
proved to be unsuccessful. Indeed, the expected product was
contaminated by side products attributed to breaking of one
P−C bond as confirmed by 31P NMR, which indicated the
presence of phosphate at 0.3 ppm (D2O). Therefore, use of
milder conditions, previously used for synthesis of thiophene-2-
phosphonic acid by Gerbier et al.,26 were tested. Hydrolysis of
the phosphonate function was achieved in a two-step sequence
that starts by silylation of the diphosphonate 1 with
bromotrimethylsilane. Then the silylated intermediate was
quantitatively converted into the expected diphosphonic acid 2
by reaction with methanol. With this mild method of
hydrolysis, the thiophene−diphosphonic acid 2 was isolated
without any trace of the degradation product as revealed by
NMR data and elemental analysis.
Thermogravimetric curves recorded in air (Figure 2) exhibit
a first mass loss between 150 and 250 °C, which is ascribed to
Figure 2. TGA curves of Mn2(O3P−C4H2S−PO3)·2H2O 3 recorded
in air or N2 from room temperature to 750 °C.
Compound 2 was used in hydrothermal syntheses along with
manganese salt (Mn(NO3)2.6H2O), water, and urea (see
Experimental Section). The pH of the initial solution, measured
15 min after stirring the substrates in water, was 1.66, and the
final pH (measured at the opening of the pressure vessel) was
4.13. From this reproducible hydrothermal synthesis (140 °C,
40 h) single crystals from the compound Mn2(O3P−C4H2S−
PO3)·2H2O 3 with suitable size that allowed characterization by
X-ray diffraction were produced. Pictures recorded by scanning
electron microscopy (SEM) permitted us to confirm the
homogeneity of platelet shape of the crystals in the synthesis
batch and their average size of 200 × 200 × 4 μm (Figure 1).
The infrared spectrum of Mn2(O3P−C4H2S−PO3)·2H2O 3
is shown in Figure SI3 (see Supporting Information). The
infrared spectra have at low wavenumbers, between 700 and
1300 cm−1, the typical bands of the phosphonate functional
group. At higher wavenumbers, spectra exhibit at 1608 cm−1
loss of two molecules of coordination water present around the
transition metal: 9.12% for Mn2(O3P−C4H2S−PO3)·2H2O
(theoretical loss 9.3%). After 500 °C, a second mass loss is
observed and attributed to transformation of the dehydrated
materials into the corresponding transition metal phosphate
clearly identified by powder X-ray diffraction and for which
formation is in good agreement with the total mass loss
recorded: Mn2P2O7 for Mn2(O3P−C4H2S−PO3)·2H2O (obs
25.4%; calcd 26.4%). Mass gain observed just before final
decomposition of the material has been attributed to an
oxidation process, which was confirmed by thermogravimetric
analysis performed under nitrogen to not exhibit such mass
gain. It is interesting to observe that the temperature of
degradation of the dehydrated structure that likely occurs
according to a combustion reaction is observed above 450 °C,
which is a slightly higher temperature than that observed for the
C
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compound {Co(thiophene-2,5-dicarboxylate)(H2O)1.5]n.29 The
presence of a phosphorus atom is one parameter that can
explain this gain of thermal stability.
Data Collection and Structure Determination. Crystals
with regular platelet shapes and shining faces were extracted
from batch synthesis. The preliminary X-ray diffraction
investigation was performed at room temperature using Mo
Kα radiation on a Kappa CCD (Bruker Nonius) diffractometer.
Large ω and χ scans were used to control the crystalline quality
of the different samples and determine cell parameters. All
tested specimens lead to the following cell: a1 = 4.9684(4) Å, b1
= 5.8105(6) Å, c1 = 18.793(3) Å, α1 = β1 = γ1 ≈ 90°. A first data
collection was performed using a middle-sized single crystal
(150 × 80 × 5 μm3). A scanning angle of 0.8°/frame and a Dx
(detector−sample distance) value of 34 mm have been chosen;
ϕ and ω scans were used. The observed condition limiting the
possible reflections, hkl: h + k + l = 2n, is consistent with an I
centering vector, and the following space groups can be
considered: Immm, Im2m, I2mm, Imm2, I212121, and I222.
EvalCCD software30 was used to extract reflections from the
collected frames. Empirical absorption correction was applied
using the SADABS software.31 Symmetry determination
following structure solution in P1 was performed using the
“charge flipping” method32 implemented in SUPERFLIP;33,34 it
leads to space group I2mm. A structural model considering the
I2mm space group was then built up with SUPERFLIP33 using
the charge flipping method. Manganese, phosphorus, sulfur,
oxygen, and 2 carbon atoms were located; at this stage the
carbons, not implied in the coordination sphere of the
phosphorus, are missing. This first model is introduced in the
refinement program Jana2006;35 all atomic positions were
refined, and then anisotropic displacement parameters (ADP)
are considered for all atoms. Fourier difference synthesis does
not allow location of the final expected carbon atoms.
Moreover, a huge value is observed along the b axis for ADP
of the sulfur atom S (u22 ≈ 0.39 Å2), 10 times those observed
along the a or c axis. Final refinement based on the F(obs)
procedure leads to R(obs) = 0.095 and wR(obs) = 0.131. The
absence of two carbons in this structural analysis could be
related to a disorder due to possible rotation of the thiophene
cycle around the axis defined by the two phosphorus−carbon
bonds.
Figure 3. Mn2(O3P−C4H2S−PO3)·2H2O 3 section of the reciprocal
space ((0kl) for the (a1, b1, c1) setting) calculated from the
experimental frames (left) and the corresponding drawing (right).
Cells ① and ② are reported. Intense reflections allowing definition of
cell ① are depicted using black disks, while weak reflections are
represented using gray dots.
using the SADABS software.31 Details of data collection are
reported in Table 1.
a
Table 1. Details of Data Collection for Compounds 3 and 4
hydrated 3
rehydrated 4
chemical formula
Mn2(O3P−C4H2S−
PO3)·2H2O
Mn2(O3P−C4H2S−
PO3)·2H2O
symmetry
monoclinic
primitive
11.60(1)
4.943 (5)
19.614 (13)
107.22 (6)
P2
orthorhombic
primitive
7.5359(3)
7.5524(3)
18.3050(9)
90
lattice centring
a, Å
b, Å
c, Å
β (deg)
space group
wavelength (Å)
scan strategy
scan angle (deg)/Dx (mm)
(sin θ/λ)max
reflns index limit
Pnam
0.71073
0.71073
φ /ω
φ /ω
0.8/34
0.8/34
0.86
0.94
−20 ≤ h ≤ 13
−5 ≤ k ≤ 8
−35 ≤ l ≤ 35
16 622
−14 ≤ h ≤ 12
−14 ≤ l ≤ 8
−34 ≤ k ≤ 34
22 606
measd reflns
unique reflns
8028
3701
unique refls with I ≥ 3σ(I) 3213
abs corr
2560
To confirm previous results, data collection was performed
using the same experimental conditions but a larger crystal (300
× 150 × 6 μm3). The (0kl) section of reciprocal space
calculated from the series of experimental frames shows rows of
weak additional reflections located at k = n/2; this (0kl) plane is
indicated in Figure 3. On the basis of this observation, a new
cell can be defined to index the whole diffraction pattern: a2 =
SADABS31
SADABS31
0.031/0.041
internal R value after
correction (obs/all)
0.026/0.037
refinement program
JANA200635
226
JANA200635
119
number of refinement
parameters
weighting method
σ
σ
3
11.621(1) Å, b2 = 4.9684(4) Å, c2 = 19.670(3) Å, β2
=
ρmin/ρmax (e/Å )
2.43/−4.56
618
−0.6/0.5
760
107.181(3)°. The relationship with the previous cell is as
follows
F(000)
reliability factors (R/Rw)
0.039/0.039
1.60/1.55
0.043/0.071
1.45/1.34
goodness of fit
a2 = 2b1; b2 = −a1; c2 = −b1 + c1
a
Reliability factors are based on F.
To collect a great number of weak reflections, but avoiding
any detector saturation by reflections of strong intensity, two
different exposure times (160 and 32 s/deg) have been used to
collect data. Diffracted intensities were collected up to θ = 40°.
No condition limiting possible reflections is observed, and then
the possible space groups are P2/m, Pm, and P2. EvalCCD
software30 was used to extract reflections from the collected
frames; reflections were merged and rescaled as a function of
the exposure time. Empirical absorption correction was applied
Following the procedure described above a structure solution
was performed in P1 space group using SUPERFLIP.33,34 The
electron density corresponding to the final model is compatible
with the P2 space group; structure determination carried out in
the P2/m or Pm space group does not lead to satisfactory
solution. The structural model in this space group, including 4
Mn, 4 P, and 2 S atoms, is then introduced in the refinement
D
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Figure 4. Diffraction patterns collected of Mn2(O3P−C4H2S−PO3)·2H2O 3 versus temperature.
program Jana2006;35 all atomic positions were refined, and
then ADP are considered for all atoms. Refinement leads to an
agreement factor equal to 14%. Fourier differences were then
calculated, allowing the location of 16 oxygen and 8 carbon
atoms. Then, applying a (sin θ/λ) limit equal to 0.5, regions
where the contribution of the H atoms to the structure factors
is larger, Fourier difference synthesis is used to find the H
atoms. Eight H atoms are found in the coordination sphere of
O atoms; the bond valence calculations36 for the oxygen atoms
are in agreement with introduction of these H atoms. Two
independent Mn2(O3P−C4H2S−PO3)·2H2O motifs are ob-
served. The final refinement procedure leads to R(obs) = 0.039
and wR(obs) = 0.039. The value refined for the Flack
parameter37 (0.510(3)) is compatible with a twinned crystal.
Atomic parameters are summarized in Tables SI1 and SI2 (see
Supporting Information), and interatomic distances are listed in
Table SI3, Supporting Information. Note that use of the very
weak additional reflections greatly contributes to the high noise
level observed on the Fourier difference maps; these data
essential for determining the thiophene cycles are of lower
quality.
As previously discussed, the thermogravimetric analyses
(TGA) show the stabilization of a dehydrated phase above
250 °C, the temperature where the pristine compound loses 2
water molecules, and below 500 °C, final decomposition. A
selection of crystals of the pristine material 3 were weighed and
heated above 250 °C. The experiment was stopped when the
expected loss of weight, corresponding to 2 H2O, was obtained;
the resulting sample (compound 5) will be called “dehydrated”.
To analyze the structure of this dehydrated compound, a single-
crystal X-ray diffraction experiment was placed with the
“heated” crystals. However, a breakdown of the detector of
our KappaCCD diffractometer has delayed this study. After 1
month and fixing the detector problem, single crystals of the
heated sample have been tested using X-ray diffraction. All
tested crystals show the same characteristics. The following cell
parameters are evidenced: a3 = 7.5359(3) Å, b3 = 7.5524(3) Å,
c3 = 18.3050(9) Å, α3 = β3 = γ3 = 90°. A strategy based on ϕ
and ω scans (scan angle of 0.8°/frame with an exposure time of
96s/frame; an extra scan with an exposure time of 9 s/frame
has been considered to avoid the saturation effect expected for
intense reflections) was defined for θmax = 42° and Dx = 34 mm.
The values observed for the internal reliability factor for the
mmm, 4/mmm, and 4/m Laue class (0.085, 0.583, and 0.563,
respectively) are in favor of orthorhombic symmetry.
Structure determination was performed using SUPERFLIP;33
a starting point has been obtained but with misnamed oxygen
and carbon atoms. The model including corrections of the
atoms designation has been introduced in JANA2006;35 the
structure can be described with 1 Mn, 1 P, 1S, 4O, and 2 C
atoms. All atomic positions and ADP were refined. The
reliability factor reaches a value of 0.063. Fourier difference
synthesis shows important residues around the Mn position
(2.3 e·Å−3). Introduction for Mn and S of anharmonic ADP
developed up to the fourth order leads to a significant reduction
of the agreement factor (RFobs = 0.049). Fourier difference
synthesis calculated for sin θ/λ ≤0.5 evidences residues
compatible with 1 H atom in the neighborhood of 1 C and 2
H in the vicinity of 1 O atom. Introduction of these two H
atoms in the environment of this oxygen reveals an improve-
ment of bond valence calculation36 (0.48 without the two H
and 1.9 with). The final stage of the refinement leads to the
same chemical formula, Mn2(O3P−C4H2S−PO3)·2H2O, as for
the pristine compound 3; it is incompatible with a dehydrated
compound. TGA performed on the remaining part of the
“dehydrated” sample evidences a rehydration process in
agreement with the refinement result. Actually, the studied
structure does not correspond to a dehydrated but to a
rehydrated form identified as compound 4. Atomic parameters
are summarized in Tables SI4 and SI5 (see Supporting
Information), and a selection of distances and angles are listed
in Table SI6, Supporting Information.
X-ray Powder Diffraction versus Temperature. To follow
the structural evolution of the compound Mn2(O3P−C4H2S−
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PO3)·2H2O 3 as a function of temperature, X-ray powder
diffraction patterns were collected on a Bruker D8 diffrac-
tometer in Bragg−Brentano geometry using Cu Kα1 radiation
(1.54056 Å), selected by an incident germanium monochro-
mator, and equipped with a Lynx-Eye detector and an Anton
Paar HTK1200N high-temperature chamber. Diagrams were
collected using a step scan of ∼0.014°/2θ ranging from 6° to
60°/2θ, recorded every 30 °C between 30 and 300 °C, and
summarized in Figure 4. This study shows that the monoclinic
structure corresponding to the hydrated form is stable until 150
°C and in the range of temperature corresponding to the
dehydratation process (see TGA analysis part Figure 2).
Refinements of the unit cell parameters versus temperature
reveal that the c axis corresponding to the stacking direction is
constant until 90 °C and then decreased until 150 °C and
confirms that loss of H2O starts above 90 °C. At 180 °C the X-
ray diffraction diagrams correspond to a mixture of the
monoclinic hydrated related phase and the new dehydrated
phase 5. The X-ray diffraction diagrams at higher temperatures
show broad diffraction peaks, which are consistent with a poor
crystalline quality of the dehydrated phase. Nevertheless, this
latter material 5 could be indexed in an orthorhombic unit cell
with the following parameters: a = 18.632 Å; b = 18.354 Å; c =
5.064 Å at 210 °C. In parallel, several “freshly dehydrated”
crystals of compound 5 were tested on the KappaCCD; the
scattering signal is mainly diffuse and thus confirms the
amorphization process observed by powder diffraction.
Scheme 3. Coordination Modes of the Phosphonic Acid
Functions of the Thiophene-2,5-diphosphonic Acid Moiety
(TDP) Included in Mn2(O3P−C4H2S−PO3)·2H2O 3
Structural Description. Hydrated Mn2(O3P−C4H2S−
PO3)·2H2O 3. The hydrated form Mn2(O3P−C4H2S−
PO3)·2H2O 3 can be described by the regular stacking along
the c axis of [MnO6H2]∞ inorganic planes and organic slabs
built up from (O3P−C4H2S−PO3) entities (see Figure 5 and
Figure 6. Mn2(O3P−C4H2S−PO3)·2H2O 3 (a) view of the connexion
between the inorganic layers and the (O3P−C4H2S−PO3) unit, and
(b) projection along the c axis of one inorganic layer (including
phosphonate groups).
are connected to the other via the two phosphonic acid
functional groups present on the thiophenyl heterocycle in
positions 2 and 5; this conformation leads to interplane Mn−
Mn distances ranging from 8.8 to 9.9 Å (Table SI3, Supporting
Information). A description of the (O3P−C4H2S−PO3) organic
planes can be based on the observations of Figure 5a and 5b.
The conformation of the thiophene heterocycles (C4H2S) is
different for levels 1 and 2 identified in Figure 5. In level 1, the
cycles are oriented parallel to the b axis, while in level 2 they are
parallel to the a axis. This arrangement of the (C4H2S) cycles is
reported in Figure 7a, where cycles belonging to two successive
levels are drawn for a projection along [001].
Rehydrated Mn2(O3P−C4H2S−PO3)·2H2O 4. The rehy-
drated Mn2(O3P−C4H2S−PO3)·2H2O 4 adopts a layered
structure; stacking in the direction b, [Mn2O8H4]dimer inorganic
planes alternate regularly with slabs of (O3P−C4H2S−PO3)
entities constituting the organic part of the material (see Figure
8). In the [Mn2O8H4]dimer inorganic planes, displayed in Figure
9c, each Mn atom is surrounded by 5 oxygen atoms; the four
closer oxygen neighbors (with 1.97 Å ≤ dMn−O ≤ 2.00 Å) form
a pseudosquare plane; the fifth O atom assumes a longer Mn−
O distance (dMn−O = 2.41 Å) (see Table SI6, Supporting
Information). Thus, the 5 O atoms define a slightly distorted
square pyramid around the Mn atoms. Two adjacent square
pyramids share an edge; they are arranged in a head-to-tail way
and form a Mn2O8H4 unit shown in Figure 9b. The two O2
edges of these edifices are water molecules; the six remaining O
edges are connected to six P1 atoms (Figure 9c). As a result,
each Mn2O8H4 unit is isolated from the other unit; this feature
Figure 5. Mn2(O3P−C4H2S−PO3)·2H2O 3 projection along the a (a)
and b axes (b). MnO6 and PO3C are represented by gray and light gray
polyhedra. S, C, and H atoms are represented by gray, black, and
crossed disks, respectively.
Scheme 3). In the [MnO6H2]∞ inorganic planes, displayed in
the Figure 6b, each Mn atom is surrounded by 6 oxygen atoms,
assuming six Mn−O distances ranging from 2.09 to 2.44 Å
(Table SI3, Supporting Information). The 6 O atoms define a
distorted octahedron around the Mn atoms. Each MnO6
octahedron shares 5 corners with 5 adjacent octahedra and
one edge with a PO3C tetrahedron of one (O3P−C4H2S−PO3)
entity (see Figure 6a); the last corner is occupied by a water
molecule. Inside the inorganic plane, the shortest Mn−Mn
distances ranged from 3.81 to 3.91 Å (Table SI3, Supporting
Information). Two consecutive [MnO6H2]∞ inorganic planes
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Figure 7. Projections along [001] of the hydrated form 3 (a) and along the b axis for the rehydrated form 4 (b). Only the C4H2S cycles are depicted.
Cycles drawn using gray and black colors belong to levels 1 and 2, respectively (see Figure 5).
Figure 8. Mn2(O3P−C4H2S−PO3)·2H2O 4 projection along the a (a) and b axes (b).
Figure 9. Mn2(O3P−C4H2S−PO3)·2H2O 4 (a) view of the connexion between the inorganic layers and the O3P−C4H2S−PO3 unit (b). Boundary in
a Mn2O8H4 unit (c) projection along the c axis of one inorganic layer (including phosphonate groups).
leads to relatively large interunit Mn−Mn distances (≥4.7 Å)
(see Table SI6, Supporting Information). Two consecutive
[Mn2O8H4]dimer inorganic planes are connected to the other via
the two phosphonic acid functional groups present on the
thiophenyl heterocycle in positions 2 and 5 (Figure 9a). Due to
the position and the geometry of this spacer (O3P−C4H2S−
PO3) the shortest Mn−Mn interlayer distance ranges from 8.59
to 9.72 Å. In the (O3P−C4H2S−PO3) organic planes, shown in
G
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Figure 8a and 8b, the configuration of these planes is different
in levels 1 and 2. The main difference occurs in the orientation
of the thiophenyl ring. However, the arrangement of the
(C4H2S) rings is really revealed in Figure 7b. The (C4H2S)
cycles form an angle of ∼40° with the a direction: the rings
centered at z = 1/2 show a +40° angle, while those centered at
z = 0 show a −40° angle. Inside the same level (1 or 2 in Figure
8) the (C4H2S) cycles are a spaced. The entities of level 1 are
shifted of 1/2 a in comparison to those of level 2. As a
consequence, superposition of the projection along the b axis of
the two levels exhibits a perfect fishbone arrangement.
formation is 424 J/g (163 kJ/mol). The value of the enthalpy
corresponds to those found in the literature for the dehydration
process of hydrated coordination compound,39 and its
importance reflects the significant structural changes that
occur between the well-crystallized compound 3 and the
disordered compound 5. On the time scale of the DSC
experiment, the dehydration process is irreversible since no
peak is observed during the first cooling scan. During the
second heating scan, the DSC curve has between 100 and 150
°C a small broad endothermic peak with an associated enthalpy
of 5.6 J/g. This small value of enthalpy can probably be
associated to a transition involving rotation of the thiophene
rings from a ‘glassy’ state to a more disordered state after 100
°C. Of note, the increase of the “flexiblility” of MOF material
after dehydration was previously observed by Loiseau et al.40
Finally, this transition has been observed during all repeating
heating and cooling scans recorded by DSC but has never been
observed on the PXRD diffractogram recorded during the
different heating and cooling cycles. This result indicates that a
structural change occurs in the organic network.
The nomenclature proposed by Cheetham and co-workers38
has been applied to materials 3 and 4 to classify the
dimensionality of the inorganic and organic subnetworks. In
addition, the inorganic metal oxygen subnetwork corresponds
to a 2D dimensionality (I2), while the organic subnetwork,
independent of the orientation of the thiophenyl heterocycle,
contributes one order (O1) to the dimensionality of the
resulting material. Consequently, materials 3 and 4 are
characterized as having a global dimensionality I2O1.
Dehydrated Form Mn2(O3P−C4H2S−PO3) 5. The X-ray
powder diffraction experiment performed versus temperature
(Figure 4) shows formation above 200 °C of a disordered
material corresponding to the dehydrated form of Mn2(O3P−
C4H2S−PO3)·2H2O and called here Mn2(O3P−C4H2S−PO3)
5. Diffraction patterns collected from 200 to 300 °C for
Mn2(O3P−C4H2S−PO3) present a series of sharp reflections
evidencing a loss of crystallinity of the pristine material
Mn2(O3P−C4H2S−PO3)·2H2O 3. The stacking periodicity of
the inorganic layers deduced from the first peak observed on
the X-ray powder diffraction (XRPD) pattern in the low-angle
region is of 9.3 Å, a value which is in agreement with the
stacking distance d002 ≈ 9.4 Å observed for 3. A differential
scanning calorimetry (DSC) study, performed on crystallite
samples enclosed in an aluminum cap, permitted us to follow
the dehydration process. On the basis of thermogravimetric
analysis (Figure 10), all scans have been recorded between 10
Magnetic Properties. The molar magnetic susceptibility
χmol of the hydrated form hydrated-Mn2(O3P−C4H2S−
PO3)·2H2O 3 is reported in Figure 11a. A maximum of the
magnetic susceptibility χmol is observed at T = 19 K. The
magnetic moment is observed to vary linearly with the field at T
= 4 K up to a field of 5T, with no hysteresis (not shown here).
This indicates antiferromagnetic behavior with a Neel temper-
ature TN = 19 K.
The susceptibility for T > 100 K can be fitted with a Curie−
Weiss law, giving an effective moment μeff = 8.4 μB/fu, i.e., 5.94
μB per manganese ion, and a Weiss constant θ ≈ −20 K (inset
of Figure 11b). It is worth noticing that TN ≈ −θ, i.e., the Weiss
constant is close to the Neel temperature. This is the result of
mean field theory, which implies an unfrustrated magnetic
system with long-range interactions. μeff = 5.94 μB/Mn is in
good agreement with all Mn2+ in the high-spin state (J = S = 5/
2, μeff =5.92 μB). However, for T < 100 K, substantial deviation
from the Curie−Weiss law is observed, as often reported in
low-dimensional magnetic systems. The direction of this
deviation is consistent with antiferromagnetic interactions
which are more apparent when plotting χmol·T versus T
(Figure11b). The latter shows a continuous decrease upon
cooling. A good fit is obtained using a classical spin Heisenberg
model (Fisher model).41 A value of 6 μB per manganese ion and
an antiferromagnetic exchange coupling J/kB= −44 K can be
inferred from the fitting. Taking into account the different bond
lengths between Mn−Mn and Mn−O−Mn described in Table
SI3, Supporting Information, the magnetic exchange mecha-
nism is likely a superexchange between two manganese ions
through the oxygen ion sharing the corners of the octahedron.
The Mn2+−O−Mn2+ bond angle is close to 120°. A robust
antiferromagnetic interaction is then deduced for the transfert
integrals using the Goodenough−Kanamori rules,42,43 in
agreement with our measurements.
Figure 10. Differential scanning calorimetry curves corresponding to
the first heating (line), first cooling (dot), and second heating(dash) of
Mn2(O3P−C4H2S−PO3)·2H2O 3.
The rehydrated Mn2(O3P−C4H2S−PO3)·2H2O 4 has a
layered structure with Mn2O8H4 units. The magnetic properties
of this phase are notably different from the hydrated phase. As
shown in Figure 12a, the antiferromagnetic transition is clearly
suppressed. The susceptibility exhibits a Curie−Weiss form
with only a weak increase for temperatures less than T ≈ 14 K.
Fitting the data with a Curie−Weiss form gives an effective
moment μeff = 8.9 μB/fu, i.e., 6.3 μB per manganese ion, and a
Weiss constant θ ≈ −67 K. This latter value shows that
and 280 °C at a rate of 10 °C/min in order to avoid any
decomposition of the sample. The first heating scan has from
100 to 230 °C an intense broad endothermic peak which
corresponds to dehydration of compound 3 into compound 5.
These temperatures are in good agreement with the temper-
ature of dehydration observed by XRPD as a function of
temperature. The enthalpy associated to this phase trans-
H
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Figure 11. (a) Molar susceptibility of Mn2(O3P−C4H2S−PO3)·2H2O 3 with the antiferromagnetic transition at TN = 19 K. (b) χmol·T as a function
of T. Solid line is the fitting using the Fisher model (classical spin Heisenberg model). (Inset) 1/χmol as a function of T with the high-temperature
Curie−Weiss limit as a dotted line.
Figure 12. (a) Molar susceptibility of the rehydrated Mn2(O3P−C4H2S−PO3)·2H2O 4 as a function of temperature. Note the absence of the
antiferromagnetic transition. In the first inset is shown a zoom on the FC-ZFC low-temperature susceptibility. Also shown is 1/χmol as a function of
T . Dotted line is a fit with the high-temperature Curie−Weiss limit. Note the small decrease of susceptibility at low temperature. (b) Molar
susceptibility of the dehydrated form Mn2(O3P−C4H2S−PO3) 5. (Inset) 1/χmol as a function of T. Dotted line is a fit with the high-temperature
Curie−Weiss limit. Note the very small decrease of the inverse of the susceptibility at low temperature.
antiferromagnetic fluctuations are still present, likely via a
superexchange mechanism. The value of the magnetic moment
is slightly larger than the maximum value of the free Mn2+ ion
(5.92 μB), which has no orbital contribution. This may indicate
interacting Mn ions in the dimers. The small increase of the
low-temperature susceptibility (more evident when plotting 1/
χmol as a function of T, see the inset of Figure 12a) and the
small hysteresis observed in the field-cooling−zero-field-cooling
measurements indicate that a very weak ferromagnetism is also
present. A weak quantity of ferromagnetic impurities cannot be
excluded, but the possibility of an intrinsic mechanism could be
addressed. The structure of this sample consists of Mn2+
dimers. Compared to the hydrated form, the octahedra are
now linked by the edges, the Mn ions are closer, and an
examination of the bond lengths indicates that the exchange
mechanism can be a direct exchange between the Mn2+ ions. In
general, there is a critical distance above which ferromagnetic
direct exchange is favored.44 For Mn, the critical distance was
found to be 2.8 Å.45 Here, the main shortest distance between
the manganese ions is 3.1 Å, indicating a possible ferromagnetic
coupling via direct exchange within dimers in this sample.
These dimers are sufficiently isolated to prevent long-range
ordering and a genuine ferromagnetic transition.
Curie−Weiss fit gives similar results: an effective moment μeff =
6.35 μB per manganese ion and a Weiss constant of θ ≈ −61 K.
A small difference is that the excess of magnetic susceptibility
observed at low temperature is lower in Mn2(O3P−C4H2S−
PO3) 5. If intrinsic to the sample, this is consistent with the fact
that the structure is strongly disordered, resulting in an
averaging of the ferromagnetic component.
CONCLUSION
■
The hydrated compound Mn2(O3P−C4H2S−PO3)·2H2O 3 was
synthesized under hydrothermal conditions starting from
thiophene-2,5-diphosphonic acid 2, manganese nitrate, and
urea. Its structure was solved by X-ray diffraction on a single
crystal and can be described as alternating inorganic layers
connected to organic layer via the phosphonate groups. A
remarkable feature of the structure of compound 3 is the
orientation of the thiophene heterocycles that adopts two
different orientations in two successive layers (along c). In one
layer the heterocycles are all oriented in the same direction
parallel to b, while in the second layer the heterocycles are
head-to-tail aligned along a. Dehydration of compound 3
produced the dehydrated material 5 after loss of two water
molecules. Of note, this dehydrated material was stable up to
500 °C, pointing out the great stability of the thiophene-2,5-
diphosphonic acid moiety. Unfortunately, this material was not
crystalline enough for the structure to be solved by X-ray
diffraction. Nevertheless, DSC analysis points out a reprodu-
The magnetic properties of the dehydrated form Mn2(O3P−
C4H2S−PO3) 5 are shown in Figure 12b. Its magnetic
susceptibility is very close to that of the rehydrated form. In
particular, no antiferromagnetic transition is observed, and a
I
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N.; Bein, T.; Fer
́
ey, G. Inorg. Chem. 2004, 43, 3159−3163. (c) Shi, F.
cible low-energy exchange process/transition with an energy
exchange around 120 °C that could arise from the reorientation
of the thiophene heterocycle. The low crystallinity of this
material did not permit validation of this hypothesis by X-ray
diffraction. After leaving this dehydrated material 5 at room
temperature and ambient humidity for 1 month a polymorph
Mn2(O3P−C4H2S−PO3)·2H2O 4 was isolated, and surpris-
ingly, this material exhibited excellent crystallinity. The main
difference between the structures of 3 and 4 arises from both
the orientation of the thiophene rings (herringbone-type
organization in 4) and the structure of the inorganic layers. It
can be concluded that the thiophene-2,5-diphosphonic acid
moieties engaged in materials 3 and 4 adopt different
orientations (rotation around the P−C bonds) and the
dehydrated state 5, which is likely more flexible than the
hydrated states, allows reorganization of the organic and
inorganic network. Finally, the magnetic behavior of com-
pounds 3 and 4 indicates the antiferromagnetic and weak
ferromagnetic behavior, respectively, for these two polymorphs.
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materials. The dehydrated phase 5 presents paramagnetic
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diphosphonic acid as a rigid organic building block to design
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characterized. Moreover, this work exemplifies that very soft
experimental conditions permitted the rehydration step.
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ASSOCIATED CONTENT
* Supporting Information
■
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Hwang, Y. K.; Marsaud, V.; Borie, P. N.; Cynober, L.; Gil, S.; Ferey,
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Crystallographic data (CIFs; CCDC 424643 and 424642 for 3
and 4), positional parameters, and hydrogen-bond lengths and
angle for compounds 3 and 4. This material is available free of
charge via the Internet at http://pubs.acs.org.
M.; Le Gall, T.; Denis, C.; Le Hir, S.; Quentel, F.; Elleo
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AUTHOR INFORMATION
Corresponding Author
*E-mail: jean-michel.rueff@ensicaen.fr (J.-M.R.); pjaffres@
univ-brest.fr (P.-A.J.).
■
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the “Services Communs” of the University of Brest
(RMN-RPE and mass spectrometry) and the technical support
of Sylvie Collin of CRISMAT Laboratory for synthesis.
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