Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎

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Solid State Nuclear Magnetic Resonance

journal homepage: www.elsevier.com/locate/ssnmr

Trends

NMR crystallography: Applications to inorganic materials

Charlotte Martineau
Tectospin, Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles St-Quentin en Yvelines, 45, avenue des Etats-Unis,
78035 Versailles cedex, France

art ic l e i nf o a b s t r a c t

Article history: Current developments of NMR crystallography as well as some recent applications to diamagnetic
Received 5 June 2014 inorganic solids are presented. First, we illustrate how solid-state NMR data can be used in combination
Received in revised form with diffraction data for the determination of the periodic part of the crystal structures, from the space
3 July 2014
group selection, to the structure determination over the refinement and validation processes. As ss-NMR,
contrary to diffraction (powder and single-crystal), is not restricted to periodic boundary conditions, ss-
Keywords: NMR data can be used to further complete the structural description of materials, including studies of
NMR crystallography local order/disorder, etc. This illustrated through examples, which are shown and discussed in the second
Inorganic compounds part of this review.
Powder diffraction
& 2014 Elsevier Inc. All rights reserved.
Structure solution
Structure refinement
Local order

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Periodic model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Determination of the unit cell dimensions and space group. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Building a structural model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.1. From NMR data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.2. From powder diffraction and NMR data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Structure refinement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Beyond periodicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Cation distribution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. Anion distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3. Linker distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.4. Correlated disorder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.5. Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.6. Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction to the study of molecular and crystalline structure and properties,

According to the International Union of Crystallography (IUCr),
crystallography [from Greek κρυσταλλος (krustallos) ice, crys-
tal þ γραφειν (graphein) to write] “is the branch of science devoted
E-mail address: charlotte.martineau@uvsq.fr
with far-reaching applications in mineralogy, chemistry, physics,
mathematics, biology and materials science.” [1]. 2014 is the Inter-
national Year of Crystallography, which celebrates “the 100th
anniversary of X-ray diffraction as well as the 400th anniversary
of Kepler's observation in 1611 of the symmetrical form of ice
crystals, which began the wider study of the role of symmetry in
matter”. If X-ray diffraction is by far the most powerful and widely

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2 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
used technique to unravel the crystalline structure of solids, it is
not the only available tool we have at hand as there are many
other spectroscopic techniques which are complementary with
powder diffraction, like electron microscopy, infra-red (IR), X-ray
absorption near edge structure (XANES), extended X-ray absorp-
tion fine structure (EXAFS) or nuclear magnetic resonance (NMR)
spectroscopy.
The study of the structure of the periodic part of crystalline
solids in fact requires a rather limited amount of information,
which are (i) the unit cell dimensions, (ii) the space group, (iii) the
nature of the atoms and (iv) their relative position in the unit cell.
One way of accessing these pieces of information is to submit the
solids to a beam of X-ray. The Bragg's law and structure factors
indeed relate the diffraction peak positions and intensity to the
electron density and the atomic coordinates. These principles are
nowadays easily and widely applied to single-crystals, for which
the diffraction peaks can be measured in the three directions of
space, and the structure reconstructed from these data. Single-
crystal diffraction has therefore provided a huge number of
successes, in a wide range of solids, including inorganic solids.
There is however one critical limitation of this technique, as it
requires that crystals of large enough size, stability and quality are
grown. Although recent development of microdiffraction [2] setup
has considerably reduced the minimum required size of the crystal
down to less than a few cubic microns, there is still an incredibly
large number of materials for which it is not possible to grow such
single-crystals. In this case, the structure determination has to be
carried out from X-ray diffraction data collected on polycrystalline
powders. This poses a serious problem, as crucial information, in
particular the phases of the diffraction peaks, is lost when going
from a 3D measure on a single-crystal to a 2D projection over a
powder, an ensemble of tiny single-crystals, each having its own
orientation. For this purpose, a series of methods and algorithms
(direct methods [3], Patterson method [4], charge-flipping [5], real
space methods [6] with simulated annealing [7] and its derivative
parallel tempering [8] algorithms, etc) and associated softwares
have been developed – and are still being developed – to try to
retrieve the missing information from powder diffraction patterns.
However, for ab initio structure determination, i.e., when there is
no prior knowledge about the structure, this process can become
highly time-consuming, and even often unsuccessful at all for very
complex systems.
It turns out that solid-state NMR (ssNMR) spectra contain
relevant data for structure determination and, these pieces of
information are, interestingly, highly complementary to the dif-
fraction data. NMR spectroscopy is indeed sensitive to the nature
of the atom through the Larmor frequency, and to the local
environment of each atom, while diffraction is based on periodi-
city and relies on electron density to distinguish the atoms.
Moreover, the progress in NMR methods and techniques (high
field, fast magic-angle spinning (MAS), pulse sequences for high-
resolution, sensitivity enhancement techniques for faster acquisi-
tion etc) has given access to the resolution and visibility of
structural features, even for complex materials. More recently,
the developments of first-principles calculations to periodic com-
pounds have offered another opportunity to link the structural
data to NMR observables. The term NMR Crystallography [9] has
been proposed a decade ago, with the initial idea to perform
structure determination from NMR data only, but now it encom-
passes all studies in which the NMR data are used along with the
diffraction, first-principles calculations of other spectroscopic
techniques to perform the structure determination, and go beyond
what diffraction proposes, i.e., beyond strict periodicity. The
description of both the periodic and non-periodic parts of solids
has been defined by Mackay [10] as Generalized Crystallography,
and this is what the combination of NMR and diffraction has to
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offer. It is also particularly important for fully disordered systems
like glasses for which the information available on powder
diffraction patterns are very limited.
The major difference between using powder diffraction and
ss-NMR – in particular for inorganic solids which may contain a
large number of different elements - comes from the fact that
diffraction requires a rather limited number of experimental data
(usually a single X-ray powder diffraction measurement), while an
almost infinite number of NMR measurements can be imagined,
designed and performed, each of them yielding different structural
data. This probably explains why there is not yet a very general
strategy for NMR Crystallography (as there exists in diffraction),
but rather there are many different trends explored, which are
very solid- (or class or solid) dependant. NMR Crystallography is
an active field of research, as attested by the special issue on the
subject published last year [11,12]. A few of the strategies devel-
oped recently for inorganic materials are covered and discussed
here. This review is by no mean exhaustive, but reports some
examples in the fields of oxides [13–26], fluorides [27–33], porous
solids like Al- [34–40], Ti- [41,42], Ga- [43,44], or V- [45,46] based
phosphates or oxonitrophosphate [47], zeolites, metal-organic
frameworks (MOFs) based on metals like 27Al [48–53], Ga [54],
45
Sc [55], 43Ca [56,57], 25Mg, 67Zn [58], Zr [59,60], 17O [61] etc. One
goal of this article is to show how the strengths of ss-NMR data are
really decupled when they are combined with powder diffraction,
electron diffraction, as well as other spectroscopic techniques and
calculations of NMR observables.
2. Periodic model
As mentioned earlier, there are four mains step to determine
the periodic structure of a compound [62] (Fig. 1) (i) finding the
unit cell dimensions, and the space group, (ii) finding the nature of
the atoms and their approximate relative positions, that is, build-
ing a structural ‘model’, (iii) refining this model, i.e., finding atomic
coordinates that match the best an experimental function (usually
the powder diffractogram). If all these steps can be performed, in
principle, from powder diffraction data only, there are numerous
cases where, due to peak overlap or other ambiguities on the
diagram, (i) the solution might not be unique, (ii) no solution is
found because the solution space to be searched is too vast or its
landscape contains too many local minima, preventing conver-
gence of the calculations in a reasonable amount of time.
As illustrated in Fig. 1, ss-NMR data can be used along with the
diffraction data to increase the chances of success of each of these
steps, and sometimes reduce the time necessary to perform these
steps. If initially the NMR data were used only as a validation tool
for a structure independently determined from powder diffraction
data, it was recently shown that NMR data could be used prior to
the structure search, to guide and make more efficient the process.
Some of the most recent examples illustrating each stage are
reported and discussed in the next paragraphs.
2.1. Determination of the unit cell dimensions and space group
Determination of the unit cell dimension and space group is
traditionally done by indexing the powder diffraction pattern.
Determination of the unit cell dimensions is still very difficult – if
not possible – to perform from ss-NMR data, and this is the major
item that is left to diffraction (X-ray or electrons) only. It can seem
a rather trivial step, but this is in fact the most important one, as
without a unit cell, the next steps of structure determination could
not be achieved, as they all somehow involved calculations within
a ‘box’. The space group can be found by searching for systematic
extinctions of (hkl) reflections. However, (i) only 120 extinction
 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3

Fig. 1. Schematic representation of the main steps for ab initio structure resolution. In blue and red the information or methods used with powder diffraction and ss-NMR
data, respectively. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

symbols are univocally related to one space group [63], (ii) strong
peak overlap may generate ambiguities. Therefore, if the Laue class
can usually be determined, it is very often that line indexing does
not lead to a unique solution.
The role of ss-NMR at this stage is thus to provide comple-
mentary data to select the proper space group among the list of
space groups provided by the diffraction data. NMR data can give
access to the ‘crystallochemical formula’. This formula gathers the
nature, number and relative intensity of all the atoms of the
asymmetric unit, the asymmetric unit being the smallest unit that
will be repeated through symmetry operations to create the 3D
structure. A space group, to be compatible with a structure, must
contain enough ‘Wyckoff positions’ to accommodate all the
measured atoms. The principles of space group selection by NMR
were exposed by Taulelle some ten years ago [64]. In short, it
makes sure that the space group contains Wyckoff positions with
appropriate relative multiplicity, and that if there are atoms
located on special positions with no degree of freedom, there are
enough of these positions in the chosen space group to accom-
modate all these atoms. In principle it is a useful concept for
inorganic solids, as virtually all the space groups can be considered
(contrary to organic solids or proteins, most of which crystallize in
monoclinic space groups). However, in practice, this method – i.e.,
space group selection by NMR only – mostly works for compounds
with highly symmetrical space groups, and containing atoms
sitting on special positions with no degree of freedom. Therefore,
the most efficient use of ss-NMR is, through the determination of
the number of inequivalent sites, to sort out among the space
groups provided by the diffraction data [15,29,43,58,65–69].
In particular, it can ascertain or dismiss the presence of a center
of symmetry, which sometimes is ambiguous from diffraction
data only.
2.2. Building a structural model.
That is indisputably the most difficult and hazardous step in
the whole process, where failure is very (very) often encountered.
This is therefore the step where ss-NMR has probably the most
impact. At this stage, the goal is to build an approximate structural
model (number, nature and connectivity of the cation polyhedra,
presence of organic moieties, guest molecules, etc.). When no iso-
structural compounds or compounds with a closely related struc-
ture exist, this has to be done ab initio, i.e. blindly. A number of
methods have been developed over the years to perform this
ab initio structure determination, as already mentioned in the
introduction section. Although these algorithms have been
improved and are now more and more efficient, there are many
reasons that can make the structure determination difficult from
PXRD data only, among which the problem of peak overlaps
leading to unreliable extracted line intensities, the size of the unit
cell (too large), the ratio between the number of atomic para-
meters and the number of observed reflections (which has to be
low enough), extreme atomic contrast (either too large or too low),
possible disorder, poor crystallinity, computation time, etc.
The role of ss-NMR can be of two types: (i) construct an initial
model from the NMR data only, (ii) provide constraints (distances,
topology), so as to drive more efficiently the search for the
structural model from the powder diffraction data. Both are
detailed below.
2.2.1. From NMR data
It is well known that homonuclear and heteronuclear inter-
nuclear distances can be measured from ss-NMR data, by measur-
ing e.g. diffusion rates, build-up curves (DQ, REDOR, etc.), or

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4 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Fig. 2. (a) 23Na 2D NMR experiment recorded under DOR conditions. (b) Spin diffusion curves constructed from a series of 2D 23
Na NMR measurements in a sodium
diphosphate compound [72]. Reproduced by permission of the Royal Society of Chemistry.

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 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 5

through the measurement of some NMR parameters (chemical

shift, quadrupolar parameters, etc). This property has initially been
developed for NMR Crystallography of small organic molecules,
with the measurement of 1H–1H spin diffusion rates [70].
It provides a distance matrix, from which the relative positions
of the molecules in the unit cell can be worked out.
Recently, Bryce et al. showed the possibility to extend the
method to quadrupolar nuclei for inorganic materials, thanks to
the use of double rotation (DOR) techniques, which provides the
necessary high-resolution in the 23Na (nuclear spin equals to 3/2)
2D NMR spectra (Fig. 2) [71]. Applied to sodium diphosphates
Na4P2O7 and Na3HP2O7  H2O, spin diffusion curves were mea-
sured, modeled and the dipolar coupling values – thus distances –
were extracted. These values were then used to validate the
assignment of the NMR resonances.
For pure-silica zeolites, Brouwer et al. proposed a method to
build a structural model starting with initial knowledge of (i) the
unit cell dimension and space group as determined from powder
diffraction and (ii) a homonuclear distance matrix [72–78]. Zeo-
lites have a structures based on the assembly of corner-sharing
SiO4 tetrahedra (T-sites), forming porous framework, in which are Mcorr Pa {Pb, Pc}* Pd Pe {Pf, Pg}*
located the templating agents before calcination (cations or
organic moieties). They are notoriously difficult to obtain as {Ala, 0 1 1 0 1 1 1
single-crystal, and the structure determination of these com-
pounds is still a challenge by powder X-ray diffraction only. Great Alb} 0 1 1 0 1 1 1
success was obtained with the additional use of electron micro-
scopy with the charge-flipping algorithm [79–81]. NMR provides Alc 1 1 1 1 1 0 0
another source of information.
The homonuclear distance matrix can indeed be constructed Ald 1 1 1 1 0 1 1
through the measurement of 29Si double-quanta (DQ) build-up
curves [82–84]. The low natural abundance of 29Si nucleus Ale 1 1 1 0 1 1 1
(nuclear spin equals to 1/2, natural abundance of 4%) is favorable
to this method as the assumption that DQ curves are obtained for Alf 0 1 1 1 0 1 1
isolated 29Si–29Si spin pair is valid, a requisite to go from the
measured build-up curves to the actual Si–Si internuclear dis-
Fig. 3. Top: 27Al–31P 2D correlation NMR spectrum of an aluminophosphate and
tances with analytical expression. Depending on the recoupling
bottom: corresponding graph matrix [88].
method, the 29Si–29Si DQ-build-up curve provide access to Si–Si
distances up to about 8 Å between pairs of atoms.
As mentioned above, with the knowledge of the unit cell be abstracted as the nodes of the graph, while the bridging oxygen
dimension and possibly space group (previously extracted from atoms (or the organic linkers for MOFs) represent the edges of this
powder diffraction data), an algorithm was developed which graph. In NMR, the resonances represent the number of nodes
allows a step-by-step construction of a candidate structure [74], (independent of the nature of the atom and of its coordination
which is in a later stage optimized (by energy minimization and/or number), while the correlation peaks on a 2D NMR spectrum
refinement from the XRD data, when the materials are crystalline indicate the number of the graph edges, and which nodes are
enough). Recent improvements of this method have been pro- connected through these vertices. Brouwer et al. recently showed
posed, which can yield a structure model even when the crystal- how such graph theory could be used to reconstruct a silicate
lographic space group is unknown (i.e., only unit cell dimensions network from a limited number of experimental data [88]: one
are known a priori). The principles were illustrated for a hypothe- powder diffraction pattern, that provides the unit cell dimensions
tical 2D zeolite structure, and have then been successfully applied (this is still a requirement for all the structure determination
to the structural determination of molecularly ordered but non- strategies), and a single 2D 29Si–29Si NMR spectrum (assuming all
crystalline silicate framework [85]. NMR lines are resolved), that provides the number of inequivalent
Si sites along with their relative multiplicity, the number of
equivalent positions in the unit cell (Z) as well as the Si–Si
2.2.1.1. Graph theory. For compounds which form extended 2- or connectivities. Knowledge about the space group is not manda-
3D frameworks (as is the case for most zeolites, aluminophosphates tory. One strong limitation is that the graph generation is sub-
or metal-organic frameworks (MOFs)), the concept of graph theory mitted to combinatorial explosion of computation time, and at
(no consideration of distance, one only considers the link between present can only be applied, in a reasonable amount of time, to
the atoms) can be used to build a structural model. A graph is made simple frameworks (i.e., below 4 vertices). They mention that the
of nodes (also called vertices) connected to each other through approach can be extended to heteronuclear systems like
linkers. The use of graph to describe the structure of solids is not new aluminophosphates.
and for example the software TOPOS [86] is a very handy tool to
identify isomorphic compounds (i.e., compounds having different
structures but similar topology). 2.2.2. From powder diffraction and NMR data
It turns out that both the frameworks of porous solids and Real space methods are the most recent and efficient methods
ss-NMR correlation spectra can be defined as graphs (Fig. 3 [87]). for structure solution from powder diffraction, and probably the
The cation polyhedra (or inorganic clusters for MOFs) can indeed methods for which NMR can have the most beneficial impact. Real

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6 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
space methods use algorithms like simulated annealing, parallel
tempering or charge flipping and require as a priori knowledge a
unit cell, if possible a space group (not mandatory, e.g., the charge
flipping algorithm can work in P1), and the approximate number
and nature of atoms in the unit cell. They then randomly generate
candidate structures until convergence to a given cost function
(total energy, powder diffraction diagram) is reached. In these
Monte-Carlo based methods, computation time quickly becomes a
strong limitation, even for efficient (parallel) computers we have
nowadays. For a unit cell containing a number N of inequivalent
sites, the convergence rate indeed grows as exp(N2). Therefore,
one limitation is the number of independent parameters (atomic
coordinates for each ‘object’ in the unit cell), as often mentioned
by the authors of the programs: the limit of ESPOIR [89] seems to
be close to 15–30 independent atoms maximum or 6 independent
objects, the FOX [90] and PSSP [91] software capabilities have been
tested for only 6–20 degrees of freedom. Finally, the software
FOCUS [92], specifically designed to perform structure search on
materials like zeolite or aluminophosphate requires time to expect
relevant structural models ranging from a few days to several
months.
The major role of NMR combined with these methods is
therefore to lower this critical number of parameters down to a
level that becomes computable again.
2.2.2.1. Knowledge about the unit cell content. The first obvious
constraint to extract from NMR data are the exact number of
inequivalent atoms in the asymmetric unit, as well as the
coordination number of the atoms, which can usually be
straightforwardly determined from NMR parameters like
chemical shifts or quadrupolar parameters. This latter allows
considering the full polyhedron (or molecule when organic
moieties are present) as an ‘object’, rather than considering the
cations and linker atoms each as isolated species. The number of
40 35 30 25 20 15 10 100 80 60 40 20 0 -20 -40 -60 -80-100
43
13 Ca chemical shift (ppm)
C chemical shift (ppm)
Fig. 4. Schematic representation of combining diffraction data (determination of unit cell dimension and space group) and solid-state NMR (determination of the number
and nature of the species). The structure search is then performed with a direct space software (FOX in that case), with the powder diffraction diagram as experimental cost
function. The example shows the data for Ca(BuPO3).
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independent parameters is then reduced from three times N
coordinates for each of the N atoms down to three atomic
coordinate and three angles for the ‘object’. In addition to having
the exact number of species in the unit cell, knowledge about the
coordination number already represents a great step towards
success.
Using these pieces of information, structural model can be
determined, even for compounds that show difficult powder
diffractogram (poor crystallinity, strong absorption), as illustrated,
for example, for the structures of a few phosphonates that were
recently reported by Laurencin et al.. The synchrotron powder
diffraction showed strong profile anisotropy due to the layered
character of these compounds, as well as strong baseline distor-
tion. Nonetheless, the unit cell and space groups could be
determined by indexation. 1H, 13C, 31P and 43Ca NMR solid-state
NMR data further provided the number of inequivalent Ca sites,
phosphonate groups and their protonation states, as well as the
number of water molecules in the unit cell (Fig. 4). These species
were used as input independent ‘objects’ in the software FOX [92],
which converged to a sensible solution for all four layered samples
studied Ca(C6H5–PO3H)2, Ca(C6H5–PO3)  2H2O, Ca(C4H9–PO3H)2
and Ca(C4H9–PO3)  H2O. As discussed in their paper, the structural
models were then refined at the DFT level and validated by first-
principles calculations of the NMR parameters, which were in very
good agreement with the experimental data [93].
2.2.2.2. Adjacency matrix. A second way to reduce the number of
independent parameters is to use larger units of connected
polyhedra (instead of using the polyhedra as isolated species).
This concept was recently proposed for aluminophosphates
(AlPOs) [98]. Under hydrothermal synthesis conditions, the struc-
ture of these solids is made from strict alternation of aluminum
polyhedra and phosphorus tetrahedra connected through bridging
oxygen atoms. Compared to zeolites, AlPOs present a much larger
 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
variety of topologies because of the ability of the metal cations (in
particular Al3 þ , Ga3 þ …) to adopt various coordination states
within the lattice: from tetrahedral to octahedral through penta-
coordination.
For these heteronuclear compounds, building an independent
model from the homonuclear DQ build-up approach is indeed not
ideal as (i) the cations (Al and P) have high natural abundance (i.e.,
the isolated spin pair hypothesis is not valid), (ii) most of them are
quadrupolar and therefore one would require the use of the DOR
technique mentioned above. The a priori knowledge about Al–P
connectivity scheme however proved to be the useful information
for structure determination, actually more important than the
distances themselves [98]. The connectivity between the Al poly-
hedra and the P tetrahedra can be obtained from ‘standard’ 2D
27
Al–31P heteronuclear NMR spectra, either J-based or dipolar-
based (CP, INEPT or HMQC-type). The only requirement is, for
compounds with numerous overlapping 27Al resonances, to use a
multiple-quantum (MQ) filter so as to obtain an isotropic – thus
resolved – 27Al dimension [94].
From the 2D 27Al–31P NMR spectrum, large building units can
be constructed ‘by hand’, by looking at the cross-correlation peaks,
assuming only the first Al–P neighbors give signals, and consider-
ing typical Al–P distances. This approach was applied to layered
aluminophosphates AlPO-(Al5P7)–DAE and AlPO–(Al5P7)–DAP
[95,98]. When strait usage of diffraction-based algorithms was
difficult, a 100% rate of convergence was obtained when connected
polyhedra – instead of isolated polyhedra – were used as input
objects in FOX. The choice of the initial set of structural subunits is
important as the more documented the knowledge about the Al–P
adjacency matrix is, the more efficient and fast the structural
search will be. This is illustrated in Fig. 5 for AlPO–(Al5P7)–DAP: by
increasing the connectivity between the identified polyhedra
(which can be done by a careful analysis of the correlations on
the 2D NMR spectrum), the number of degrees of freedom is
reduced which in turn reduces the number of independent
parameters to be determined from the powder diffraction data.
The immediate impacts are –(i) to bring the system below the
threshold of the computability limit, i.e., allowing convergence to
be reached, and –(ii) to greatly diminish the calculation time
needed to converge [96,97]. It also pushes further the limits of the
complexity of the systems that can be solved.
Fig. 5. Left: Time required to get convergence to a structural model for AlPO4–
(Al5P7)–DAP by using the FOX software versus the number of degrees of freedom (n)
The various SBUs, constructed from the 27Al–31P 2D NMR correlation spectrum and
used for the structure search are shown [88].
Please cite this article as: C. Martineau, Solid State Nucl. Magn. Reson. (2014), http://dx.doi.org/10.1016/j.ssnmr.2014.07.001i
7
It must be noted that, for this step, the methods reported above
mostly (only) makes use of the NMR information regarding the
cation(s), rarely regarding the linker atoms (in particular oxygen or
fluorine). These atoms are usually difficult to locate on the powder
diffraction data because of their low atomic density (in particular
when they are located close to a heavy atom). As will be shown
in the next step, the 17O and 19F NMR data are mostly interesting in
the refinement step, rather than for the structure determination
itself.
2.3. Structure refinement
Structure refinement consists of performing small variations of
the atomic coordinates, starting from the previously determined
structural model, in order to provide the best match to one or
several given cost functions (total energy or experimental data,
usually diffraction). For powders, the most used procedure is the
so-called Rietveld method, with powder diffraction pattern(s) as
cost function.
The recent progresses in advances in calculation of the ab initio
NMR parameters (full tensors of chemical shift and electric field
gradients, as well as their relative orientation in the unit cell) for
extended periodic systems with codes like NMR-CASTEP [98],
WIEN2K [99], ABINIT [100], Quantum-Espresso [101], etc, renders
possible – in theory – the use of NMR parameters as cost function
for a refinement (or for a structure search).
The proofs of such a refinement have been given on simple
solids, i.e., solids containing atoms sitting on positions with small
number of variable atomic coordinates [102,103]. For example, in the
case study solid MgBr2, the position of the bromine atom along the
c-axis of the unit cell was refined by minimizing the difference
between experimental 81Br (nuclear spin of 3/2) quadrupolar
coupling constant (CQ) value and those calculated for different
positions of the bromine atom along the c axis. A good agreement
with the diffraction data was obtained, validating the method.
In ITQ-4 zeolite (four T-sites), such procedure has also been carried
out using both Gaussian and CASTEP codes, yielding refined struc-
tures close to that obtained from single-crystal X-ray data [104].
In principle, these calculations could also be used in the
previous step of structure solution search, with the NMR para-
meters as an additional cost function to the powder diffraction
pattern and total energy. Unfortunately, contrary to a theoretical
powder diffraction pattern, which takes less than a millisecond to
compute (as there is an analytical relationship between the atomic
coordinates and the powder diffraction diagram through the
structure factor), the time necessary for the calculation of the
NMR parameters for one candidate structure for inorganic systems
at the DFT-level takes minutes to hours, depending on the code
and on the complexity of the solid. Therefore, it is still impossible,
at the moment, to implement these calculations within the
diffraction softwares (direct space or charge flipping) working
with a Monte-Carlo approach, that generates billions of trial
structures to be evaluated.
Even if the NMR parameters are not used as cost function for
the refinement procedure, comparison of experimental and calcu-
lated NMR parameters can provide an assessment of the proposed
structural model. In particular, a large discrepancy very likely
indicates a problem in the position of one or more atoms, in
particular if the structure was solved from laboratory X-ray
powder diffraction data (as shown in Fig. 6 for an inorganic
fluoride). Numerous examples have shown that these discrepan-
cies can usually be corrected after a geometry optimization at the
DFT level. For details, I refer to the recent review by Bonhomme
et al. and all the references herein [105], as well as improvement of
the calculations reported this year for aluminophosphates and
inorganic fluorides [106,107]. This step of structure optimization at
8 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
Fig. 6. Experimental 19F MAS NMR spectrum of Ba5Al3F19 (top) The NMR spectra
calculated with the NMR-CASTEP code starting with the atomic coordinates from
(a) Rietveld refinement of the synchrotron powder diffraction data (SPD) and
(b) geometry optimization (DFT) are shown below. The agreement with the
experimental data is better for the DFT-optimized structure.
the DFT level was shown to be particularly relevant for compounds
containing atoms with very close or at the other extreme very
different electron density. In the former case (e.g., zeolites, sili-
cates, etc.), the electron density map appears as a continuous
cloud. In the latter case, the heavy atoms blow the electron density
map and hinder the location of the light atoms. This is for example
the case of lead or barium fluorides [27,29,108]. It was shown that
an improved agreement between experimental and calculated
NMR parameters was obtained after geometry optimization. EFG
tensors and 19F isotropic chemical shifts are indeed highly sensi-
tive to the distortion of the cationic polyhedron, and to the nature
and number of atoms in the coordination sphere of the fluoride
ions. When the calculations are performed simultaneously on
several nuclei in the solid, this reinforces the validity of the
structural model. The DFT-calculations are also important for line
assignment, and were shown to give assignments consistent with
those independently carried out using 2D correlation experiments
[109].
3. Beyond periodicity
This step concerns all parts of the crystals that cannot be
described by the simple periodic rules of the space groups as
reported in the International Table of Crystallography [65]. Because
of this lack of periodicity, powder diffraction has difficulty to address
these issues. And in fact it has long been neglected, because the ‘low’
resolution the NMR data were generally in good agreement with the
average structures proposed by diffraction methods. However, with
the advances in high-resolution NMR methods, structural details that
go beyond these average structures have been revealed on the NMR
spectra. NMR Crystallography therefore plays a crucial role in this
completion of the structure description, especially now that the
measurements can be associated to DFT-calculations on not fully
periodic system [110].
There are many reasons for which the structure of a compound
can deviate from strict periodicity, ranging from defect, to sub-
stitutions (which leads to chemical or topological distributions),
stacking disorder, presence of guest molecules in porous or layers
Please cite this article as: C. Martineau, Solid State Nucl. Magn. Reson. (2014), http://dx.doi.org/10.1016/j.ssnmr.2014.07.001i
solids, dynamics, etc. This deviation can be straightforwardly
detected when the number of NMR resonances does not match
the number of crystallographic sites in the asymmetric unit cell.
This non-periodicity has to be taken with care, in particular if the
NMR data are used in the search for the periodic model as
reported in the previous sections, as it can provide the wrong
number of inequivalent atoms.
Two types of non-periodic elements can be considered: a
variation of the atoms positions from one asymmetric unit to the
other, that generates topological differences, and a variation of the
nature of the atom occupying a given crystallographic positions
(substitution of atoms, presence of vacancies, defects), that gen-
erates chemical differences without altering the long-range topol-
ogy [111]. The latter is the most common and concern cations, e.g.,
as often encountered in zeolites or silicate (Al/Si, B/Si substitu-
tions), or the anions, e.g., as found in fluorinated metal-phosphates
or MOFs (F/OH distributions). Water molecules in porous frame-
works are usually ‘extra-framework’ species, i.e., they modify
locally the chemical composition but do not substitute a frame-
work atom, thus do not alter the overall topology of the solid. The
case of topological disorder is less usual, but was shown to occur
in borosilicate, with a random distribution of SiO4 tetrahedra and
BO3 units [13]. Information about the distribution on a long-range
scale, i.e., random or correlated order, can be obtained from ss-
NMR data; a few recent examples are detailed below.
3.1. Cation distribution
Two types of cation distributions exist: random or locally
ordered, that give rise to different ss-NMR signatures. Typical
examples are the Al/Si distributions in zeolites, which can be
identified indirectly through the characteristic 29Si isotropic che-
mical shifts, which range is well-defined for SiO4 tetrahedra
having zero to four aluminum as first cation neighbors [112]. This
distribution, highly important as it determines the acidic proper-
ties of the zeolite, is known to be well ordered in a few zeolites, in
particular in the natural zeolite natrolite, and it was very recently
shown that the distribution could be controlled in synthetic
natrolite as well [113]. Other cations can be included in the
framework of silicoaluminophosphate, like zinc atoms in STA-1.
In that case, the 31P nucleus, which isotropic chemical shift is sensitive
to the number of Zn atoms surrounding the phosphorus atoms, is the
perfect spy to identify and quantify the cation distribution [114]. It can
be extended to 29Si/11B distribution, as was illustrated for MCM-70
[115].
Such distributions also exist in dense aluminosilicate, for example
in gehlenite Ca2Al2SiO7 [116], for which Florian et al. reported a fully
disordered arrangement of the tetrahedral pairs in the a–b plane of
the structure. This type of information was obtained by combining a
battery of 1D and 2D NMR experiments, including {29Si}27Al hetero-
nuclear multiple-quantum correlation (HMQC) experiments, along
with DFT-calculations of the NMR parameters.
Other examples reported recently include various pyrochlores
[117,118], in particular Sn/Ti distribution in Y2Ti2  xSnxO7 [119]
investigated by 119Sn (I ¼1/2) NMR spectroscopy though 1D and
2D 119Sn–119Sn INADEQUATE measurements and DFT-calculations,
or LaSrAlO4 [120], in which the La/Sr ordering was observed by
combined analysis of synchrotron and neutron diffraction, pair
distribution function, 27Al 1D and MQMAS NMR and atomistic
calculations.
3.2. Anion distribution
This is the typical case of fluorine/hydroxyl substitutions. These
species are isoelectronic, and therefore they cannot be distin-
guished from X-ray diffraction data (neither single-crystal nor
 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 9

Fig. 7. REDOR results and apportionments. (A) Experimental 13C{15N} REDOR curves (squares) are compared with the molecular dynamics simulations for the different linker
apportionments, large clusters (LC), small clusters (SC), random (Ran), and alternating (Alt). (B) The derived apportionments for the different MTV-MOF-5s [125].

Please cite this article as: C. Martineau, Solid State Nucl. Magn. Reson. (2014), http://dx.doi.org/10.1016/j.ssnmr.2014.07.001i
10 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
powder). Examples were reported for oxifluorides [121] and
fluorinated AlPOs [122,123]. Notably, the nature of the distribution
in AlPOs (random or not) can be evaluated by recording 19F–13P
and/or 19F–27Al 2D NMR spectra. In ULM-3(Al), all bridging
positions between the aluminum polyhedra were found fully
occupied by F  ions while the similar compound ULM-4(Al) a
random distribution of F ions and OH groups has been clearly
identified. The difference in F/OH distribution was ascribed to the
amount of water and the pH of the synthesis medium. When
several positions are available for fluorine, NMR can also provide
information about the location. For example, in the microporous
AlPO4-CLO [124] solid (CLO ¼cloverite-type structure), F can either
be trapped in double-four ring (D4R) cages forming the frame-
work, or be positioned at the terminal positions (Al–F, P–F) that
interrupt the framework. 2D correlation NMR spectra 19F–31P and
19 27
F- Al and the absence of signal in 19F–19F NMR experiments
have indicated the correlated presence between one F ion the D4R
and only hydroxyl groups on the terminal positions of the
aluminum and phosphorus polyhedra.
3.3. Linker distribution
Metal-organic frameworks (MOFs) have structures based on
the assembly of cations forming clusters, linked together though
polycomplexing organic molecules (mostly carboxylates and azo-
lates). One key in the success of these materials is the possibility to
tune its properties by incorporating linkers with functional groups.
To further increase the multi-functional character, MOFs were
prepared with different linkers, with the aim to obtain synergetic
effects. The difficulty is to control the spatial distribution of these
linkers on a mesoscale. Reimer and Yaghi have reported a 13C–15N
(using selectively labeled compounds on the functional group)
REDOR study coupled to simulations of the spin system [125], to
evaluate the distribution of 1,4-benzenedicarboxylate (bdc) linkers
functionalized with different groups (bdc-NH2, bdc-NO2, bdc-
(CH3)2, bdc-(OC3H5)2 and bdc-(OC7H7)2) in MOF-5. The results,
shown in Fig. 7, proves that a control of the distribution of the bdc
linkers, ranging from random, alternating and cluster, could be
obtained by choosing the adequate pair of linkers.
3.4. Correlated disorder
The spatial range of slight structural disorder in partially
ordered solids was investigated in surfactant-templated silicate
layers by analysis of the lineshape of 2D DQ 29Si NMR experiments.
[126]. In such compounds, cross-correlations peaks with shapes
highly elongated along the DQ diagonal of the 2D 29Si–29Si DQ-SQ
INADEQUATE NMR spectrum were indeed observed. This was
related to strong interrelationships between local framework
ordering and disordering and the mobilities of the surfactant
headgroups. Measurement of scalar coupling distributions [127]
can also reveal details about local disorder in solids.
3.5. Defects
Defects in crystal structures are also important features for
understanding the properties of solids, and can benefit from
analysis of NMR spectra, as defects mostly are local-range in
nature.
For example, in the Zircon phase ScVO4  x (0.0rx r 0.1) [128],
oxygen defect concentrations in bulk samples was compared with
the fully oxidized zircon structure ScVO4 using powder X-ray
diffraction, neutron diffraction, and bulk magnetic susceptibility
data as well as 45Sc and 51V solid-state NMR spectroscopy. In the
wurtzite type Zn1  xMgxO (0 rx r0.15) alloys, a combination of
Raman and 67Zn/25Mg NMR spectroscopy and neutron scattering
Please cite this article as: C. Martineau, Solid State Nucl. Magn. Reson. (2014), http://dx.doi.org/10.1016/j.ssnmr.2014.07.001i
was used to identify the local geometry of the Mg and Zn atoms
[129]. In particular, the line broadenings observed on the Raman
and 67Zn/25Mg NMR spectra have shown an increased configura-
tional disorder and crystal defects in the lattice with the increase
of the Mg substitution into a ZnO-rich lattice.
A combination of a wide range of 17O, 29Si, 25Mg, 1H and 2H
NMR data with first-principles calculations (CASTEP), X-ray dif-
fraction and FTIR spectroscopy was used to identify the location of
all the protons and magnesium vacancies in the hydrous form of
wadsleyite β-(Mg,Fe)2SiO4, a mineral is found in the Earth's
mantle. In its fully hydrated state, this mineral was thought to
be ordered from the X-ray diffraction data. In fact, the 1H and 29Si
MAS NMR spectra, supported by all the other data, showed that a
small number of additional protons was also present as Si–OH
groups located in the Mg(3) vacancies [130].
Disorder also becomes important in the case of nanoparticles;
this disorder that can be analyzed by solid-state NMR. For
example, in ZnSe nanoparticle [131], solid-state 77Se and 67Zn
NMR spectra reveal relationship between the distributions of 77Se
and 67Zn environments and the size of the nanoparticle, in
contrast with high degrees of atomic positional order established
by transmission electron microscopy and X-ray diffraction. First-
principles calculations of NMR parameters were further used to
distinguish between atomic positional and electronic disorder that
propagate from the nanoparticle surfaces.
Another possibility to probe defects in crystal is through the
use of T1 relaxometry, as was shown recently for crystals of fluorite
CaF2 [132,133]. T-1 relaxometry was shown to be sensitive to
inhomogeneity of powders (large defect-free grains versus defec-
tive small ones). In combination with analysis of the diffraction
line profile, these measurements were employed to characterize
the lattice detect in CaF2 after extensive milling. In particular, they
managed to distinguish the different types of defects, surface
defects (related to domain size), line defects (dislocations) and
point (Frenkel) defects, which were found to have a quite different
effect on the powder pattern as well as on the T-1 spin-lattice
relaxation times.
3.6. Glasses
The ultimate lack of periodicity and long-range order is found
in glasses, which makes their structure determination particularly
challenging from the little information available on X-ray diffrac-
tion patterns. The combination of multinuclear solid-state NMR
(17O, 29Si, 11B, 27Al, 19F, etc) data with molecular dynamics (MD)
simulations and calculations of NMR parameters from first-
principles have proven highly efficient to overcome these difficul-
ties and provide accurate descriptions of the local structural
features in oxide or halide glasses. Details about the MD-GIPAW
calculations as well as numerous examples can be found in recent
reviews by Charpentier et al. [134–136] and references within.
Another application of NMR crystallography in glasses is the
detection of polyamorphism, i.e., the simultaneous presence of
different amorphous phases within a glass, which is inaccessible
from powder diffraction. The concept was illustrated in the
molecular glass of triphenyl phosphite with 31P NMR measure-
ments [137].
4. Outlook
In this Trends papers, the various strategies that are currently
being developed for NMR Crystallography have been reported and
illustrated with examples taken in the field of inorganic or hybrid
materials. All throughout the paper is shown the great benefit of
using ssNMR data in combination with powder diffraction data
 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
and first-principles calculations to achieve a more efficient struc-
ture search, and to provide a more accurate structural model than
if those techniques were used independently. If the determination
of the unit cell dimension is still a step that is ‘diffraction specific’
(electron or X-ray), in all the other steps, from space group
determination, to building and refinement of the model, the
inclusion of NMR data and first-principles calculations greatly
increases the efficiency of the structure determination process and
the chance of success. Ss-NMR also allows describing crystal
structures beyond the rules of strict periodicity, by providing
accurate details about chemical, topological disorder, dynamics,
etc. These techniques are also applicable to the fully disordered
compounds that are inorganic glasses. As mentioned in the
introduction, a complete description of a crystal structure requires
both these aspects to be address. This Generalized Crystallography,
a concept introduced by MacKay twenty years ago [10] although
he was not specific about the adequate techniques to use, can be
performed from powder diffraction, ss-NMR data and DFT-
calculations.
The strategies reported here are diverse in their spirit, this can
be explained by the large variety of existing NMR experiments.
The general trend is nonetheless to develop specific approaches of
NMR Crystallography for a given class of samples.
One drawback often mentioned as a barrier for a wider use of
NMR is the ‘slow’ aspect of ss-NMR experiments, which, this is
true, is much more time consuming to perform than the collection
of a single X-ray powder diffraction pattern. However, the recent
advances in NMR signal enhancement techniques (hyperpolariza-
tion methods) as well as other methods of time reduction (non-
uniform sampling, use of parallel receiver, better detection, etc),
have considerably reduced this time. Therefore, the comparison
now is between the time necessary to perform the structure
determination using powder diffraction data only (which can be
infinite) and the time necessary to (i) record the NMR experiments
and (ii) to exploit the results for the structural analysis. The
balance now becomes favorable to NMR, and therefore one can
expect many more of such combined contributions in the field of
inorganic solids.
Acknowledgment
CM is grateful for financial support from the ANR under
contract ANR-12-JS08-0008.
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12 C. Martineau / Solid State Nuclear Magnetic Resonance ∎ (∎∎∎∎) ∎∎∎–∎∎∎
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Charlotte Martineau, b 1983, received her Ph.D. in Chemistry at the Université du
Maine (France) in 2008. After one year as a postdoctoral researcher at the
University of Manitoba (Canada), she became Maitre de Conférence at the
University of Versailles (France) in 2009, and obtained her Habilitation à Diriger
les Recherches (HDR) in 2013. Her research focuses on the development and
application of methods dedicated to solving crystalline structures from solid-state
NMR and powder diffraction data. A particular interest is given to the study of
the non-periodic parts of hybrid and fluorinated materials, accessible by NMR
Crystallography.