LETTERS

A microdiffraction set-up for nanoporous

metal–organic-framework-type solids
CHRISTOPHE VOLKRINGER1 , DIMITRY POPOV2 , THIERRY LOISEAU1 *, NATHALIE GUILLOU1 ,
GERARD FEREY1 , MOHAMED HAOUAS1 , FRANCIS TAULELLE1 , CAROLINE MELLOT-DRAZNIEKS1,3 ,
MANFRED BURGHAMMER2 AND CHRISTIAN RIEKEL2
1
Institut Lavoisier—UMR CNRS 8180, Institut Universitaire de France, Université de Versailles Saint Quentin en Yvelines, 45, avenue des Etats-Unis,
78035 Versailles, France
2
ESRF, B.P. 220, 38043, Grenoble Cedex, France
3
Royal Institution of Great Britain, 24 Albemarle Street, London, W1S 4BS, UK
* e-mail: loiseau@chimie.uvsq.fr

Published online: 16 September 2007; doi:10.1038/nmat1991

For the past decade, the emerging class of porous metal–organic

frameworks1–3 has been becoming one of the most promising
materials for the construction of extralarge pore networks in
view of potential applications in catalysis, separation and gas
storage. The knowledge of the atomic arrangements in these
crystalline compounds is a key point for the understanding of
the chemical and physical properties. Their crystal size limits
the use of single-crystal diffraction analysis, and synchrotron
radiation facilities4 may allow for the analysis of tiny crystals.
We present here a microdiffraction set-up for the collection
of Bragg intensities, which pushes down the limit to the
micrometre scale by using a microfocused X-ray beam of 1 µm.
We report the structure determination of a new porous metal–
5 µm
organic-framework-type aluminium trimesate (MIL-110) from a
single crystal of a few micrometres length, showing very weak
scattering factors owing to the composition of the framework
(light elements) and very low density. Its structure is built up Figure 1 Scanning electron micrograph of hexagonal needle-like single
from a honeycomb-like network with hexagonal 16 Å channels, crystals of MIL-110. A crystal of 3 × 3 × 10 µm size was used for
involving the connection of octahedrally coordinated aluminium synchrotron-radiation microdiffraction.
octameric motifs with the trimesate ligands. Solid-state NMR
(27 Al, 13 C, 1 H) and molecular modelling are finally considered for
the structural characterization.
In solid-state sciences, the development of knowledge is from ab initio methods. In the case of MOF compounds, it required
strongly dependent on the determination of the crystal structure the development of new methods that combine targeted chemistry
of solids. The latter is easily accessible as soon as single crystals and computer modelling to reach the solution6 and explain the
of reasonable size (≥10 µm) are available. If not, ab initio unprecedented properties for these solids. This applies in particular
structure determination from powder diffraction data becomes to new aluminium-based MOF materials, rarely reported7–9 despite
necessary, with its difficulties and its limitations, particularly in their real interest for industrial applications owing to their relatively
terms of cell volume. It can therefore be anticipated that, in the low cost at the manufacturing scale10 .
years to come, more and more new solids will be isolated in A possibility to maintain single-crystal diffraction and its
powdered form, and beyond a certain degree of complexity their related accuracy up to the largest cells of MOFs is to develop
structure, despite continuous technological improvements, will synchrotron-radiation-diffraction techniques related to protein
remain unknown, and this will prevent possible applications for the crystallography4 , for data collection from very small microcrystals
corresponding solids. (about 1−2 µm). This paper presents a new trend in this direction,
The future of the exploding domain of porous metal–organic which is applied to the determination of a new three-dimensional
frameworks (MOFs)1,2 is particularly affected by the above remarks topology in the family of aluminium carboxylates, hardly accessible
because the new solids, more and more in powdered form, show from powder diffraction. The microdiffraction set-up developed at
larger and larger cells3,5 , which can reach more than 700,000 Å3 in the European Synchrotron Radiation Facility (ESRF) in Grenoble
MIL-101 for instance. For such volumes, without single crystals, it enables for the first time single-crystal diffraction with a spot of
becomes difficult or even impossible to reach a structural solution about 1 × 1 µm2 .

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 LETTERS
a b

AI(1)
AI(2)

b a

c d

Figure 2 Representation of the structure of MIL-110. a, View along the c axis showing the channels delimited by the discrete Al8 clusters and the trimesate group. b, View
of the Al8 cluster showing the three bioctahedral edge-shared units Al(2)–Al(2) capped by two Al(1) octahedra. The Al8 moiety is connected to nine carboxylate functions of
the trimesate molecules. In the ordered crystal structure (P63 22), only one site Al(2) is observed for the dimeric edge-shared bioctahedral units whereas the Al(2) sites are
split between two positions Al(2) and Al(3) in P-62c. c, View along the c axis showing the connection mode of the Al8 clusters with the trimesate species parallel to the walls
of the channels. d, The two types of connection of the two different aluminium octahedral units Al(1) and Al(2), Al(3) of the bioctahedral units. This shows the two possibilities
of Al(1)–Al(2,3) linkages resulting in the disordering situation. In the ordering structure (described in P63 22), only one (left) of the connection mode is observed. In the
disordered structure, the positions of the carboxylate groups are identical in the two different possibilities of connection of octahedra (orange, Al(1) octahedron; purple,
Al(2,3) octahedron).

The beam from an undulator is monochromated and focused This new set-up enabled the study of porous aluminium
on the sample by a pair of mirrors, which enables us to reach a flux trimesates (1,3,5-benzene tricarboxylate or btc). In this system,
density at the sample of up to 3 × 1010 photons s−1 µm−2 at about several phases exist, but with narrow ranges of stability, which
0.97 Å wavelength. A set of micro-apertures is used for background prevent the growth of large crystals. This study is devoted
reduction11 . In order to reach the necessary rotational accuracy, to the solid Al8 (OH)12 {(OH)3 (H2 O)3 }[btc]3 ·nH2 O, hereafter
a new microgoniometer (see the Supplementary Information) labelled MIL-110 (MIL standing for Materials of Institut
combining a low-wobble air-bearing spindle and a piezo- Lavoisier). It is obtained (see the Methods section) after a
micromanipulator carrying a magnetic-base sample support was hydrothermal treatment of a mixture of aluminium nitrate,
developed. The optical alignment precision was about 1 µm using trimethyl 1,3,5-benzenetricarboxylate, nitric acid and water, which
an integrated optical microscope with a low-vibration sample stage. leads to the formation of well-defined hexagonal rod-shaped
The crystal was rotated around a direction close to the six-fold axis crystals of 5−30 µm and 0.5−3 µm section (Fig. 1). After collection
coinciding with the crystal elongation. It must be noted that our of the data using the new set-up, the structure was solved by a direct
previous attempts to collect correct Bragg-diffraction data using method with SHELXS-86 (ref. 12) and refined with SHELXL-97
other synchrotron stations were unsuccessful. (ref. 13) software within the WinGX suite14 .

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LETTERS
a a
AI1 AI2/AI3 5.4
2.3
δ iso = 5.1 p.p.m. δ iso = 5.6 p.p.m. 7.3
3.1
CQ = 1.81 MHz CQ = 3.51 MHz
8.2
ηQ = 0.55 ηQ = 0.63
Area = 26% Area = 74%
9.3

b c

20 15 10 5 0 –5 –10
δ iso = 4.6 p.p.m. δ iso = 5.4 p.p.m.
(p.p.m.)
CQ = 1.97 MHz CQ = 3.69 MHz
ηQ = 0.51 ηQ = 0.60

20 10 0 –10 –20
b
(p.p.m.) 135.3

Figure 3 Solid-state 27 Al NMR spectroscopy of MIL-110. a, 1D 27 Al{1 H} MAS

spectrum. b, 2D 27 Al MQMAS spectrum. c, Isotropic projection of 27 Al MQMAS 171.6
spectrum. The individual simulations of the two components are in purple and 170.6
173.8
green, the sum of these simulations are in blue, and the experimental spectra in red.

The three-dimensional framework of MIL-110 is built up from

the connection of inorganic aluminium octamers through btc
ligands delimiting large hexagonal channels (Fig. 2a). The real
structure determined from the XRD single-crystal analysis shows
atomic disorder in some parts of the octamer and necessitates
refining the structure using the space group P -62c and three Al
sites, two of them being occupied at half occupancy. This disorder
will be discussed later, but the crystal chemistry of MIL-110 210 200 190 180 170 160 150 140 130 120 110 100
(p.p.m.)
structure is described more easily considering the ideal ordered
structure, estimated by using further computer modelling (starting
from the refined atomic coordinates found by XRD analysis) and Figure 4 Solid-state 1 H and 13 C NMR spectroscopy of MIL-110. a, 1 H MAS and
corresponding to space group P 63 22 with two aluminium sites b, 13 C{1 H} CPMAS NMR spectra. A simulation and decomposition of the 1 H spectrum
Al(1) and Al(2) in a ratio 1:3 (see the Supplementary Information are given.
for more details). The ideal octamer (Fig. 2b) is formed of eight
octahedrally coordinated aluminium cations. The octamer contains
three edge-sharing bioctahedral dimers Al(2)–Al(2) and two
octahedra Al(1) each sharing three of their vertices with the triplet noticing that along [001] each hexagon of the apparent honeycomb
of dimers. Nine carboxylate functions cap the octamer, linking lattice must be decomposed into two triangles (defined by three Al8
Al(1) to the Al(2) octahedra and the two Al(2) of the dimer. The clusters) rotated away from each other by a 60◦ angle and shifted
nature of the ligands surrounding each aluminium, oxo, hydroxo by c/2 along [001]. The estimated free pore diameter is about
and aquoligands with Al–O distances in the range 1.83–2.15 Å in 16 Å (on the basis of the ionic radius of 1.35 Å for oxygen), which
the real structure, is consistent with bond-valence calculations15 . is in agreement with the quite high thermal parameters of atoms
The Al(1) octahedra can be formulated as AlO3 (OH)3 . Their delimiting the pores. The longest axes of thermal ellipsoids are
oxygens originate from the carboxylates and each hydroxyl is oriented towards the direction of the channels (see the figure in
shared with one Al(2) octahedron. In the latter, the aluminium Supplementary Information). The structure is nanoporous. From
atoms are AlO2 (OH)3 (H2 O) or AlO2 (OH)4 , depending on the the N2 adsorption isotherm at 77 K, a Brunauer–Emmett–Teller
nature of the terminal group (hydroxo or aquo). The water or (BET) specific surface of 1,400 m2 g−1 (Langmuir: 1,790 m2 g−1 ) is
hydroxyl group is terminal and, among the three OH groups, two deduced. These values are slightly greater than to those observed in
form the common edge of the dimer. In the disordered structure the MCM-41 type mesoporous materials17 with pore diameters up
(space group P -62c ), the Al(2) sites are split into two half-occupied to 100 Å.
ones (Al(2) and Al(3)). This corresponds to two chiral orientations The 27 Al magic-angle spinning (MAS) nuclear magnetic
of the Al8 cluster (Fig. 2d). This octamer is new and differs from resonance (NMR) spectrum of MIL-110 shows in the chemical
that described previously16 . We exclude twinning domains, which shift range of −15 to 10 p.p.m. a pattern of two overlapping
could induce a disordering situation, as indicated in the Methods lines, specifying a sixfold coordination for aluminium sites.
27
section. The three-dimensional linkage between octamers and btc Al{1 H} cross-polarized with high-power decoupling or just
is seen in Fig. 2c. To the best of our knowledge, this represents a straightforward 27 Al{1 H} high-power decoupled measurements
new structure type in the crystal chemistry of MOFs. It is worth result in significantly narrowed spectra compared to 27 Al MAS.

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 LETTERS
Figure 5 shows the scattering power, S = (F000 /Vcell )2 l3 Vcryst (F000 ,
106 zero-order structure factor; Vcell , unit-cell volume; l, wavelength;
Vcryst , crystal volume), of the current structure compared with
9 other high-resolution microdiffraction studies4 . Radiation-damage
104 10
effects, which limit in particular protein microcrystallography, do
8
not apply here. The small beam size used in the present study, which
Vcryst (µm3)

4
7 could be extended to nanobeams, even suggests the possibility of
102
studying single crystals within aggregates.
6 This breakthrough enabled characterization of the cationic
5 3 disorder on two possible orientations of the Al–OH–Al
1 MIL bonding. Surprisingly, it affects only slightly the assembly
100 2
of trimesate moieties, because the carboxylate positions are
1
identical whatever the orientation of the Al–OH–Al linkage in
the Al8 building block. Such a detailed description could hardly
10 –2
1010 1012 1014 1016 have been found from powder diffraction data. Single-crystal
S information on micrometre-sized crystals efficiently provides, with
additional further data from modelling and NMR, very accurate
Figure 5 Irradiated crystal volume—V cryst —scaled against scattering structure determinations.
power—S—for a selected high-resolution single-crystal microdiffraction
experiment; adapted from refs 4,18. The scattering power has been scaled to an METHODS
average electron density S = (F 000 /V cell ) 2 l3 V cryst (ref. 20); for experiments with a
beam size smaller than the crystal size, V cryst corresponds to the irradiated volume SYNTHESIS
MIL-110 was hydrothermally synthesized from a mixture containing
during a single exposure. Filled circle, MIL-110; open squares, inorganic structures:
aluminium nitrate (Al(NO3 )3 9H2 O, Aldrich, 98%), trimethyl
1, CaF2 (ref. 21); 2, kaolinite (ref. 20); 3, birnessite (ref. 22); filled diamond, protein
1,3,5-benzenetricarboxylate (C6 H3 (CO2 CH3 )3 , 98%, Aldrich, denoted
crystals: 4 (ref. 23); 5 (ref. 24); 6 (refs 25,26); 7 (ref. 26); 8 (ref. 27); 9 (ref. 28); Me3 btc), concentrated nitric acid (HNO3 ) 4 M and deionized water. The molar
10 (ref. 29). composition was 1.5 Al (0.6659 g, 1.8 mmol), 1 Me3 btc (0.3025 g mg,
1.2 mmol), 3.3 HNO3 (1 ml, 4.0 mmol) and 226 H2 O (5 ml, 277.8 mmol). The
MIL-110 phase is obtained in very acidic conditions (pH ≈ 0) by adding
This is consistent with Al sites with Al–H dipole–dipole couplings concentrated nitric acid. The starting mixture was placed in a Teflon cell, which
as we would expect from Al–OH and Al−OH2 groups. A two- was heated in a steel Parr autoclave for 72 h at 210 ◦ C. The resulting powdered
dimensional 27 Al multiple-quantum MAS (MQMAS) spectrum pale yellow product was filtered off, washed with deionized water and dried in
(Fig. 3a) shows two overlapping isotropic resonances with air at room temperature. Optical microscope analysis indicated that the sample
contrasting anisotropic lineshapes owing to the difference in is composed of elongated needle-like crystals 5−30 µm long. The scanning
quadrupolar coupling. The two aluminium sites show very close electron micrographs show hexagonal shapes (0.5−2 µm diameter) of the
chemical shift parameters but different quadrupolar coupling rodlike crystals.
constants CQ . After an iterative process of refinement between the
SINGLE-CRYSTAL X-RAY DIFFRACTION
one- and two-dimensional spectra, the 27 Al{1 H} one-dimensional
MIL-110 crystallizes with a hexagonal cell, a = b = 21.520(5) Å,
spectrum (Fig. 3b) leads to two components with a relative 3
c = 13.021(1) Å, V = 5222.3(1) Å . The structure was solved in the
population ratio of 1:3 assigned to Al(1) (4f ) and Al(2 or 3) space group P -62c by direct methods, developed by successive difference
(12i) sites, respectively. The larger quadrupolar CQ observed for Fourier syntheses, and refined by full-matrix least squares on all F 2 data
the Al(2 or 3) signals of the dimers, reflects the lower site point (obtained from intensity values after correction for polarization of the X-ray
symmetry for Al(2 or 3) than for Al(1). The 1 H MAS spectrum beam) using SHELXTL. Owing to the small crystal size, no absorption
(Fig. 4a) shows two signals at 2.3 and 3.1 p.p.m. with a 1:1 ratio correction was required. Structure solution indicated the positions of three
attributed to the corner- or edge-sharing bridging µ2 -OH within unique aluminium atoms (Al1, Al2 and Al3), but a disorder of two aluminium
the Al8 cluster. The signal at 5.4 p.p.m. corresponds to terminal sites (Al2 and Al3) is observed and the corresponding Al cations together with
water molecules η-H2 O and/or η-OH bonded to Al. 1 H resonating oxygen atoms attached have been refined with an occupancy factor of 50%.
at 7–9 p.p.m. are the aromatic protons of btc. The absence of the The final refinement including anisotropic thermal parameters of all
non-hydrogen atoms converged to R1 = 0.155. R1 = 6kFo | − |Fc k/6|Fo |,
low field signal above 10 p.p.m. reflects the complete deprotonation
where Fo and Fc are observed and calculated structure factors respectively,
of carboxylic functions. In the 13 C{1 H} cross-polarization MAS
larger than 4σ(Fo ). A twin refinement was done in order to check for the two
(CPMAS) spectrum (Fig. 4b), the signals at about 135 p.p.m. are possible twinning possibilities: (1) a plane of symmetry perpendicular to the
assigned to the aromatic carbons and the three resonances at 171, six-fold axis and (2) a plane of symmetry perpendicular to the [110] vector. In
172 and 174 p.p.m. to the three inequivalent carboxylate groups. both cases the accepted space group of twin domains was P 31c (number 159).
These three inequivalent carboxylic carbon atoms indicate that a The twin refinement showed, however, unreasonable anisotropic thermal
further ordering can be proposed, with a strict alternation of right- parameters and interatomic distances and Rfree values higher than 0.3
and left-handed Al8 units. However, as several solutions may be (R1 values calculated from a ‘test’ set of reflections, which are not included in
given to this issue, we did not further our attempts to describe the the refinement), and was therefore discarded. All the calculations were
structure as precisely. carried out using the SHELX-TL program on the basis of F 2 . The crystal data
In conclusion, this paper describes an advanced technique in are given in the Supplementary Information. The chemical formula for
MIL-110 deduced from the X-ray diffraction analysis is the following:
microdiffraction using synchrotron radiation for solving from very
Al8 (OH)12 {(OH)3 ,(H2 O)3 }[btc]3 ·nH2 O. Crystallographic data and
tiny single crystals the structure of a previously unknown phase. parameters of experiments are gathered in the Supplementary Information.
Even though previous experiments with larger microbeams on the
known structures of CaF2 and kaolinite18 have shown that it is SURFACE AREA STUDY
possible to reach still smaller crystal sizes and scattering powers, For the study of the BET surface area, the solid was activated with the following
MIL-110 interestingly corresponds to the smallest crystal volumes procedure to remove the encapsulated species: 0.2 g of a MIL-110 sample was
and scattering powers used until now for a high-resolution study4 . placed in 60 ml methanol (high-performance liquid chromatography grade,

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LETTERS
99.9%, Aldrich) for 6 h in a Teflon-lined steel Parr autoclave heated at 100 ◦ C. 9. Loiseau, T. et al. MIL-96, a porous aluminum trimesate 3D structure constructed from a hexagonal
The powdered product was then filtered off, mixed with water for 5 h and network of 18-membered rings and mu3-oxo-centered trinuclear units. J. Am. Chem. Soc. 128,
10223–10230 (2006).
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