Ba6P12N17O9Br3- A column-type phosphate structure solved from single-nanocrystal data obtained by automated electron diffraction tomography

Article abstract of DOI:10.1002/ejic.201101149

Oxonitridophosphate Ba₆P₁₂N₁₇O ₉Br₃ was synthesized by heating a multicomponent mixture of BaBr₂, BaS, phosphoryl triamide and thiophosphoryl triamide in an evacuated and sealed silica-glass ampoule to 750 °C. Ba₆P ₁₂N₁₇O₉Br₃ was obtained as the main product as a nanocrystalline powder. The crystal structure was determined ab initio on the basis of electron diffraction data acquired from a single needle-shaped nanocrystal by automated diffraction tomography. Ba ₆P₁₂N₁₇O₉Br₃ crystallizes in the hexagonal space group P6₃/m (no. 176) with unit cell parameters a = 14.654(19), c = 8.255(9) A and Z = 2. Its structure includes triangular, column-shaped anions of _∞ ¹{(P₁₂N₁₇O₉)^9-}, which are built from vertex-sharing P(O,N)₄ tetrahedra with 3-rings and three-coordinate nitrogen atoms. The 1D anions are separated by Ba²⁺ and Br^- ions, which are arranged in channels parallel to the phosphate anions along [001]. The Ba²⁺ ions are eight- and nine-coordinated by Br^- and O/N atoms, respectively.

Full text of DOI:10.1002/ejic.201101149

FULL PAPER
DOI: 10.1002/ejic.201101149
Ba P N O Br – A Column-Type Phosphate Structure Solved from Single-
6
12 17
9
3
Nanocrystal Data Obtained by Automated Electron Diffraction Tomography
[a]
[b]
[b]
[a]
Enrico Mugnaioli, Stefan J. Sedlmaier, Oliver Oeckler, Ute Kolb, and
Wolfgang Schnick*[
b]
Keywords: Solid-state reactions / Barium / Structure elucidation / Automated electron diffraction tomography / Silicate
analog / Phosphates / Oxonitrides
Oxonitridophosphate Ba
heating a multicomponent mixture of BaBr
triamide and thiophosphoryl triamide in an evacuated and
sealed silica-glass ampoule to 750 °C. Ba Br was
obtained as the main product as a nanocrystalline powder.
The crystal structure was determined ab initio on the basis
of electron diffraction data acquired from a single needle-
shaped nanocrystal by automated diffraction tomography.
6
P
12
N
17
O
9
Br
3
was synthesized by
P6
3
/m (no. 176) with unit cell parameters a = 14.654(19), c =
2
, BaS, phosphoryl
8.255(9) Å and Z = 2. Its structure includes triangular, col-
umn-shaped anions of 1
vertex-sharing P(O,N) tetrahedra with 3-rings and three-co-
ordinate nitrogen atoms. The 1D anions are separated by
9–
ϱ
17 9
{(P12N O ) }, which are built from
6
P
12
N
17
O
9
3
4
2
+
–
Ba and Br ions, which are arranged in channels parallel to
the phosphate anions along [001]. The Ba ions are eight-
and nine-coordinated by Br and O/N atoms, respectively.
2+
–
6 12 17 9 3
Ba P N O Br crystallizes in the hexagonal space group
Introduction
cantly higher degree of condensation than the maximum
Oxonitridophosphates represent
a silicate-analogous value possible in oxosilicates. The introduction of a more
class of compounds as the valence electron concentration covalent bond character may improve properties such as
of SiO equals that of P/O/N, i.e. valence electron count chemical, thermal and mechanical stability, which is advan-
2
=
16/3. Consequently, for P/O/N compounds a structural tageous for the potential applications of oxonitridophosph-
[
3]
chemistry as complex as that of silicates is expected. The ate networks (e.g. new zeolites). At present, only a compa-
tetrahedron-based structures of (oxo)silicates are classified rably small number of P/O/N compounds is known; how-
as orthosilicates with isolated Q -type [SiO ] tetrahedra, ever, the individual representatives are different, which
disilicates with Q -type tetrahedra, chain- and ring-type makes further research exciting.
structures in different conformations with Q -type tetra-
0
4–
4
1
2
The potential of the structural versatility of oxonitrido-
phosphate chemistry has not been properly exploited to
date because most P/O/N compounds elude identification
and structural characterization. Typical reaction products
are either amorphous or contain very small crystals, which
often consist of various phases with different unknown
compositions and cell parameters. As single crystals usually
occur in the micro- or nanosize, structure characterization
by single-crystal X-ray diffraction is not possible and has
been substituted by combinations of different analytical
methods such as powder (P)XRD and solid-state NMR
3
hedra, ribbon- and layer-type structures with Q -type tetra-
hedra and 3D frameworks, in which Q -type tetrahedra are
4
[
1]
all-side vertex-connected to build diverse topologies. Al-
though there is a huge number of examples for each cat-
egory of oxosilicates, such abundance has not been reported
for oxonitridophosphates; however, due to the presence of
nitrogen within the tetrahedron-based networks the struc-
tural variability should be even larger. N atoms may, more
[3]
frequently than O atoms, interconnect three (N ) or even
[
4]
four (N ) tetrahedral centres and the corresponding bond
lengths and angles are much more flexible.[ The presence
of nitrogen atoms can lead to 3D frameworks with a signifi-
2]
[4]
spectroscopy. Such an approach, however, cannot be used
as a standard route for the structural investigation of oxoni-
tridophosphate, because the assignment of different phases
to contributions of PXRD or NMR signals is difficult and
not always successful. High-resolution TEM can visualize
single nanoparticles, but gathering 3D structural infor-
mation by this technique is not straightforward when the
cell parameters exceed 1 nm or when the high electron dose
rate required results in fast deterioration and amorphi-
[
[
a] Institut für Physikalische Chemie, Johannes-Gutenberg-
Universität,
Welderweg 11, 55099 Mainz, Germany
b] Department Chemie, Ludwig-Maximilians-Universität,
Butenandtstraße 5–13 (D), 81377 München, Germany
Fax: +49-89-2180-77440
E-mail: wolfgang.schnick@uni-muenchen.de
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201101149.
[
5]
zation.
Eur. J. Inorg. Chem. 2012, 121–125
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
121

E. Mugnaioli, S. J. Sedlmaier, O. Oeckler, U. Kolb, W. Schnick
FULL PAPER
Electron diffraction can deliver structural information Crystal Structure Analysis
from single nanocrystals with sub-Angstrom resolution and
A rod-shaped crystal of around 500ϫ80ϫ80 nm was se-
significantly milder illumination but is traditionally biased
by data incompleteness and dynamic effects.[6] However, the
recently-developed automated diffraction tomography
lected for ADT. An ADT tilt series of Ϯ60° was acquired
in steady steps of 1°. The acquisition was coupled with pre-
cession of the electronic beam in order to improve reflection
(
ADT) method for electron diffraction data acquisition and
[
9,17]
intensity integration.
After the 3D diffraction space was
[
7–10]
analysis
has proved to be a straightforward, fast and
[
8]
reconstructed, a metrically hexagonal cell with param-
eters a ≈ 14.7 Å and c ≈ 8.3 Å was determined. The long di-
rection of growth of the rod was parallel to c. On the basis
of this cell, an intensity data set was integrated and treated
according to the kinematical approximation.
efficient method for structure solution of nanocrystalline
materials, even if highly beam sensitive.[
11–13]
In conven-
tional electron diffraction data acquisition, the crystal is
manually oriented along low-index crystallographic zones,
which is a time-consuming process and requires experience.
In contrast, during ADT acquisition, the crystal is tilted
along an arbitrary axis by steady steps, which exploits the
full range of the TEM goniometer. ADT is able to deliver
electron diffraction data with a higher completeness (up to
The Laue symmetry was 6/m (internal residual Rsym
2%) but not 6/mmm (Rsym = 32%). The extinction condi-
=
2
tion 00l with l = 2n leads to space groups P6 (no. 173)
3
and P6 /m (no. 176), and ab initio structure solution was
3
achieved with the latter. The correct solution was the one
with the best residual (R) and the best figure of merit. All
atom positions were determined at the first run and cor-
rectly identified using the default parameters. The structure
model is in good agreement with the atomic ratio Ba/P/Br
of 28:58:14 obtained by EDX spectroscopy (from the same
crystal from which ADT data were acquired).
100% for orthorhombic or more symmetric crystal families)
and a significant reduction of dynamic effects as the diffrac-
tion is collected off-zone.
A recent example of oxonitridophosphate structure de-
[14]
termination by ADT is SrP N O.
There, the structural
3
5
investigation was facilitated by the synthesis of a single-
phase material. Nevertheless, the ADT approach is as ef-
ficient for multiphase systems, where bulk methods, such as
Table 1. Crystallographic data of Ba
parentheses) and details of ADT data collection, structure solution
6 12 17 9 3
P N O Br (esd values in
PXRD, are limited by peak overlap.[
15,16]
The procedure is
relatively straightforward when the compound of interest and refinement.
forms small crystals with well-defined morphologies and
compositions so that recognition and isolation by low-reso-
lution TEM imaging and energy-dispersive X-ray (EDX) Crystal system
spectroscopy can be performed. As this is the case for many
P/O/N compounds, a systematic investigation of oxonitri-
dophosphates has become possible.
Formula
Formula mass [gmol ]
Ba
1817.49
hexagonal
P6 /m (no. 176)
a = 14.654(19)
c = 8.255(9)
V = 1535(3)
2
6 12 17 9 3
P N O Br
–1
Space group
Cell parameters [Å]
3
(from X-ray powder diffraction)
3
Cell volume [Å ]
Here, we report the synthesis and structure determi-
nation of a new oxonitridophosphate, Ba P N O Br ,
Z
ρ
c
–
3
[gcm ]
3.932
column, colourless
0.50ϫ0.08ϫ0.08
6
12 17
9
3
Crystal shape, colour
Crystal size [μm]
Data collection
which has a rare column structure built of vertex-sharing
P(O,N)4 tetrahedra. Although Ba P N O Br was the
6
12 17
9
3
main synthetic product, its yield was limited by the presence
of other phases.
Diffractometer/radiation
Tecnai F30 S-TWIN TEM, λ =
0.01970 Å
295(2)
–60/+60
–19ՅhՅ19, –18ՅkՅ19,
Temperature [K]
Tilt range [°]
h, k, l
Results and Discussion
–10ՅlՅ10
Measured reflections
Completeness [%]
Resolution [Å]
8520
99
0.77
0.22
Synthesis
Ba P N O Br was obtained by the reaction of a multi-
6
12 17
9
3
R
sym
component system of BaBr , BaS, PO(NH ) and PS-
2
2 3
Structure Solution and Refinement
Structure solution method
(
NH ) in silica glass ampoules at 750 °C. Not all of the
[18]
2
3
direct methods
[19]
reaction parameters could be controlled independently in Structure refinement method
least-squares refinement on F2
Independent reflections
1343
1121
35
2/21
such a synthetic system (e.g. NH3 partial pressure and
Independent reflections (Ͼ 4σ)
amount of oxygen) so the optimal conditions for obtaining
Refined parameters
phase-pure products could not be determined. However, the
Constraints/restraints
procedure given in the Experimental Section yields Ba P - R indices [Fo2 Ն2σ (F ) ]
2
6
12
o
R1 = 0.276
wR2 = 0.649
R1 = 0.290
wR2 = 0.642
2.192
N O Br as the main product with at least two side phases.
1
7
9
3
R indices (all data)
This can be concluded from the PXRD pattern as the
strongest reflections can be assigned to the main reflections
GoF
Weighting scheme
of Ba P N O Br (Supporting Information, Figure S3)
–1
= σ2F 2
2
6
12 17
9
3
w
o
+ (0.2000P)
+ 2F )/3
o c
2
2
and the remaining reflections cannot be jointly indexed.
Ba P N O Br was obtained as a nanocrystalline powder
with P = (F
Max./min. residual
electron density [eÅ ]
6
12 17
9
3
–
3
0.588/–0.516
with rod-shaped crystallites.
122
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 121–125

6 12 17 9 3
Ba P N O Br – A Column-Type Phosphate Structure
Accurate lattice parameters were determined from the coordinate nitrogen atoms. The formal building block for
eleven strongest peaks in the PXRD pattern, which were the complex anion corresponds to the chlorophosphazene
[
22]
unambiguously assigned to the phase and uniquely indexed. P N Cl
(Figure 3), which is composed of three con-
The refinement of the structure of Ba P N O Br was ex- densed 3-rings. The columns are generated by the formal
6
7
9
6
12 17
9
3
clusively performed based on the ADT data, which provide substitution of all chlorine atoms by oxygen and nitrogen
a reliable and stable result as shown by the refinement of atoms and the infinite interconnection of the resulting
[
14]
SrP N O.
The final residuals are high when compared P O N(O,N) entities along [001]. These domed building
3
5
6 3 12
with those of standard X-ray refinement but are in the nor- units face concave/concave and convex/convex and are in-
mal range for structure refinement based on electron dif- terconnected by six bridging O or N atoms. The linkage of
fraction data. The P–(O,N) distances were restrained to be these entities (on one side with three O/N atoms of their
equal within a certain standard deviation, and overall dis- inner three tetrahedra and on the other side with three
placement parameters were used for chemically equivalent, O/N atoms of their outer three tetrahedral) results in 4-
light atoms. Crystallographic data and further details con- and 6-rings, respectively (Figure 2). The O(6) atom does not
cerning the structure refinement are summarized in Table 1. interconnect the tetrahedra within a column and is ter-
Table 2 shows the positional and displacement parameters minally bound.
for all atoms.
Table 2. Atomic coordinates, Wyckoff symbols and isotropic dis-
2
placement parameters (Uiso) [Å ] for the atoms in Ba
6
P
12
N
17
O
9
Br
3
3
(space group P6 /m, esd values in parentheses); c.n. = coordination
number; occupancy of N(2)–N(5) and O(2)–O(5) is 5/6 and 1/6,
respectively.
Atom[c.n.]
Wyckoff
symbol
x
y
z
Uiso/Ueq
[
10]
Ba(1)
6h
6h
6h
12i
12i
4f
12i
12i
6h
0.5791(4) 0.9657(4)
0.9230(10) 0.1973(10)
0.1410(13) 0.1925(13)
0.7843(6) 0.3428(6) 0.4218(9) 0.045(2)
0.8569(7) 0.5453(7) 0.5649(10) 0.050(2)
¼
¼
¼
0.0549(16)
0.121(4)
0.104(4)
[10]
Ba(2)
Br(1)
P(1)[
4]
4]
3]
P(2)[
[
N(1)
N/O(2)
2/3
1/3
0.420(3)
0.054(6)
[2]
[a]
0.8715(8) 0.4604(8) 0.4610(15) 0.055(3)
0.7828(9) 0.2627(7) 0.5595(14)
0.8053(14) 0.3065(14)
0.1091(15) 0.4586(16)
[2]
N/O(3)
N/O(4)
N/O(5)
[2]
¼
¼
6 9 3
Figure 1. Crystal structure of Ba P N O Br viewed along [001].
12 17
9–
[2]
1
6h
12i
12 17 9
Triangular columns of ϱ{(P N O ) } are built from vertex-shar-
[
1]
2+
–
O(6)
0.9355(12) 0.6616(11) 0.493(2)
0.079(5)
ing P(O,N)4 tetrahedra separated by Ba ions (black) and Br
gray) ions to form channels along [001].
(
[a] The value applies to all atoms N/O(2) to N/O(5).
Structure Description and Discussion
Ba P N O Br exhibits a structure characterized by
6
12 17
9
3
isolated columnar anions. The columns themselves, how-
ever, are highly condensed so that the overall degree of con-
densation (ratio of tetrahedral centres and bridging atoms),
κ = 0.46, is rather high. Classification into the conventional
categories of tetrahedral networks (see introduction) is not
possible for Ba P N O Br . A comparably complex 1D
Figure 2. Structure of a single triangular column in Ba
Br viewed along [100] (P black, O/N gray, O white); three-coor-
dinate N(1) is indicated.
6 12 17
P N -
O
9
3
6
12 17
9
3
[20]
anion has been observed in Ce Si N O .
2
9
14 43
7
The structure of Ba P N O Br can be derived from
6
12 17
9
3
[
21]
that of rare-earth metaborates RE(BO ) (RE = Tb–Lu)
and isotypic oxonitridophosphate SrP N O, respectively.
2
3
[14]
3
5
In these compounds, triangular columns, such as those in
Ba P N O Br , form corrugated layers. Formally, the
6
12 17
9
3
structure of Ba P N O Br is obtained by cutting col-
6
12 17
9
3
–
umns out of the layers, where the Br ions act as “chemical
scissors”. The triangular columns run along [001] with the
Ba and Br ions located between them (Figure 1). The
(P N O ) } columns (Figure 2) are composed of Q -
and Q -type P(O,N) tetrahedra with a Q /Q molar ratio
2
+
–
1
9–
4
{
ϱ
12 17 9
3
4
3
Figure 3. A single molecule of P N Cl (left)[22] and the corre-
4
6
7
9
of 1:1, which comprise terminally bound oxygen and three- sponding formal building unit in Ba
6
P
12
17 9 3
N O Br (right).
Eur. J. Inorg. Chem. 2012, 121–125
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
123

E. Mugnaioli, S. J. Sedlmaier, O. Oeckler, U. Kolb, W. Schnick
FULL PAPER
The range of bond lengths (158.3–165.8 pm) corresponds values of 316.0 and 323.0 pm. All of the distances (Table 3)
to that usually observed in oxonitridophosphates. The re- agree well with the sum of the respective ionic radii in-
[
24,25]
–
sulting angles range between 107.9 and 111.1°, which is volved.
close to the values of a regular tetrahedron (109.5°). The
The Br ions in Ba P N O Br are arranged to form
P–(O,N)–P angles between 120.1 and 141.8° are also typical channels along [001] (Figure 1). Staggered stacks of Br tri-
for P/O/N networks. More information about bond lengths angles with a separation of 412.8 pm are arranged accord-
6
12 17
9
3
–
and angles is given in Table 3.
ing to the 6 screw axis (Figure S2). The Br–Br distance
3
within the triangles is 438.1 pm.
Table 3. Selected interatomic distances [pm] and angles [°] in
Ba
6
P
12
N
17
O
9
Br
3
(esd values in parentheses).
Conclusions
Ba(1)–(O,N)
Ba(2)–(O,N)
Ba(1)–Br
Ba(2)–Br
P–(O,N)
P–N(1) –P
P–(O,N)–P
276.4(16)–320.3(12)
288.0(31)–369.3(19)
348.0(24)
316.0(22), 323.0(28)
158.3(12)–165.8(10)
120.0(4), 120.0(5), 120.0(5)
120.1(8)–141.8(5)
107.9(8)–111.1(9)
9 times
8 times
The ADT method, now routinely operable, opens the
chance to discover new compounds even from inhomogen-
eous and nanocrystalline samples. This chance should be
grasped as the concept of oxonitridophosphates yields ex-
traordinary compounds with open-framework structures,
8 times
[
3]
4 times
12 times
[
26]
(O,N)–P–(O,N)
such as P N (NH) (NH ),
Li H
[P O N24–y]Xz
4
4
4
3
x
12–x–y+z 12
[4]
y
[
27]
(
X = Cl, Br)
and Ba P O6+xN66–xCl8+x
,
and highly
1
9 36
[
28]
The formula
Ba P N O Br involves two- and threefold bridging as ADT structure determination of SrP
of the 1D anion in condensed layer structures, such as Sr
3
[
P
6
O
6
N
8
.
The
has revealed a
well as terminal O/N atoms. As the direct experimental dif- layer structure with a degree of condensation κ = 1/2, and
ferentiation between O and N is impossible owing to their Ba Br represents a further exceptional structure.
similar scattering factors, their reasonable assignment was To the best of our knowledge, such a highly condensed, 1D
based on Pauling’s rules and experience with other oxoni- anion as that seen in Ba Br has not been ob-
tridic compounds, for which solid-state NMR and lattice served in any tetrahedron-based class of compounds so far.
energy calculations have been helpful for proper O/N as- Ba Br can be considered as a variant of SrP
14]
N O
5
6
12 17
9
3
3
P
N
O
6
12
17
9
3
P
N
O
6
12
17
9
3
P
N
O
N O
3 5
6
12
17
9
3
[
3]
–
signment. N was assumed with full nitrogen occupancy as cut into snippets. The “chemical scissors” are Br ions,
it links three tetrahedra. The terminally bound position was which form columns from corrugated layers and stabilize
[1]
assigned to fully occupied O . For the twofold bridging the channels in Ba
P
N
O
Br
. Starting from this channel
6
12
17
9
3
[
2]
positions, an N occupancy with a statistical admixture of arrangement, it would be interesting to see if further cat-
[
2]
+
1
/6 O was assumed. Other ordered or disordered models ions, e.g. Li , can be incorporated. With an enlargement of
may also be possible, however, one has to stick to the the structure in the Ͻ100Ͼ directions and a simultaneous
atomic ratio N/O = 17:9 as long as the Br positions are adaptation of the O/N ratio for charge equalization, this
fully occupied (as suggested by the refinement) and no hy- could lead to future lithium ion conductors.
drogen is present in the compound, which can be assumed
by comparison with similar, hydrogen-free SrP N O Ba
One of our aims was the synthesis of phase-pure
Br . Currently, at least two side phases are
present in typical samples. These phases might be related to
The electrostatic plausibility for the structure model, also both SrP O and Ba Br . It can be imagined
P
N
O
3
5
6
12
17
9
3
(proved by elemental analysis).
N
P
N
O
3
5
6
12
17
9
3
in respect of the atomic O/N ratio and their distribution, that structural cut-outs of (e.g. two or three) interlinked
was verified with lattice energy calculations according to (double or triple) columns might be present as single-phase
[
23]
the Madelung part of lattice energy (MAPLE) concept.
The calculations were carried out for two differently O/N- pounds could exhibit crystal structures built up of finite
ordered structural models using the formal ionic charges of pieces of a column (prism-like). As for SrP O and
the atoms (Table S1). The total MAPLE value averaged Ba Br , the systematic investigation of other
nanocrystals or nanodomains. Other intermediate com-
N
5
3
P
N
O
6
12
17
9
3
–
1
over the two models (319181 kJmol ) is close to the sum oxonitridophosphate structures could benefit from single-
of the total MAPLE values of the hypothetical starting ma- crystal electron diffraction data collected by ADT.
–
1
terials 3BaBr + 9BaO + 9PON + 5P N (323053 kJmol ;
2
3
5
Δ = 1.2%).
The columnar anions in Ba P N O Br are separated
by Ba ions. Both crystallographically independent Ba
Experimental Section
6
12 17
9
3
2
+
2+
Synthesis: Phosphoryl triamide and thiophosphoryl triamide were
synthesized according to literature methods.[
29–31]
Freshly distilled
sites exhibit a coordination number of ten (Figure S1).
–
3 3
POCl (99%) or PSCl (98%; both from Acros Organics, Geel, Bel-
gium; 10–20 mL) were added directly and slowly to liquid ammonia
in a flame-dried three-necked 1 L flask. Subsequently, the elimi-
Ba(1) is surrounded by nine O/N atoms and one Br ion.
The O/N atoms, including two terminal O atoms, are lo-
cated at distances between 276.4 and 320.3 pm. The Ba(1)–
Br distance is 348.0 pm. Ba(2) is surrounded by eight O/N
atoms, four of which are terminal O atoms, and two Br–
nation of NH
extraction with distilled Et
2 3
in vacuo, OP(NH and SP(NH )
4
Cl from the products was carried out by a Soxhlet
NH in dry CH Cl for 3 d. After drying
were available as starting mate-
2
2
2
2
)
3
anions. The Ba(2)–(O,N) distances range from 288.0– rials in form of colourless, water sensitive powders. Their purity
69.3 pm (Figure S1), whereas the Ba(2)–Br distances have was verified by PXRD.
3
124
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 121–125

Ba
6
6
P
12
12
N
17
17
O
9
9
Br
Br
3
3
– A Column-Type Phosphate Structure
Ba
P
N
O
was synthesized by a multicomponent system. In
[3] R. Marchand, W. Schnick, N. Stock, Adv. Inorg. Chem. 2000,
0, 193–233.
5
a typical procedure, BaBr
2
(35.7 mg, 0.120 mmol; Sigma–Aldrich,
[
4] S. J. Sedlmaier, M. Döblinger, O. Oeckler, J. Weber, J.
99.999%), BaS (40.7 mg, 0.240 mmol; Sigma–Aldrich, 99.9%),
Schmedt auf der Günne, W. Schnick, J. Am. Chem. Soc. 2011,
OP(NH
2
)
3
(27.4 mg, 0.288 mmol) and SP(NH
2
)
3
(48.0 mg,
133, 12069–12078.
0.432 mmol) were thoroughly mixed and ground in an Ar-filled
[
[
5] U. Kolb, T. E. Gorelik, E. Mugnaioli, A. Stewart, Polym. Rev.
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glove box (MBraun, Garching, Germany;
O Յ1.0 ppm) and transferred into a silica glass ampoule (wall
2
thickness 2 mm, inner diameter 11 mm). The evacuated and sealed
ampoule (length around 11 cm), was heated in a tube furnace to
H
2
O
Յ0.2 ppm,
2
[7] U. Kolb, T. Gorelik, C. Kübel, M. T. Otten, D. Hubert, Ultra-
microscopy 2007, 107, 507–513.
2
00 and 750 °C with dwell times of 12 and 48 h (heating and cool-
–1
ing rate: 1.0 Kmin ), respectively. The emerging condensation [8] U. Kolb, T. Gorelik, M. T. Otten, Ultramicroscopy 2008, 108,
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6, 542–554.
7
3 2 4 2
products NH and H S were partially deposited as (NH ) S at the
places in the ampoule that cooled first. After breaking the am-
poules, the samples were washed with water and N,N-dimethyl-
4 2 6 12 17 9 3
formamide to remove NH Br, BaBr and BaS. Ba P N O Br was
obtained as a heterogeneous, colourless, water and air resistant,
nanocrystalline powder.
[
[
[
7
4
11] I. Rozhdestvenskaya, E. Mugnaioli, M. Czank, W. Depmeier,
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ADT Data Acquisition and Analysis: For data acquisition, the sam-
ple was suspended in ethanol and sprayed onto a carbon-coated
copper grid using the sonifier described in ref.[9] ADT was per-
formed with a Tecnai F30 S-TWIN TEM equipped with a field
emission gun working at 300 kV. Electron diffraction patterns were
acquired with a CCD camera (14-bit GATAN 794MSC). EDX
spectra were recorded in STEM mode and quantified with Emispec
ESVision software.
ADT data acquisition was performed with a FISCHIONE tom-
[15] C. S. Birkel, E. Mugnaioli, T. Gorelik, U. Kolb, M. Panthöfer,
ography holder, using the acquisition module described in ref.[
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[
STEM images and diffraction patterns were collected using a mild
illumination setting. STEM images were collected by a FISCH-
IONE high angle annular dark field detector. Nano electron dif-
fraction was performed with a 10 μm C2 condenser aperture with
Mugnaioli, U. Kolb, Earth Planet. Sci. Lett. 2011, 310, 422–
4
28.
[
[
17] R. Vincent, P. A. Midgley, Ultramicroscopy 1994, 53, 271–282.
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a 50 nm beam on the sample. ADT was coupled with precession of
the electron beam (precession electron diffraction),[
9,17]
performed
using the NanoMEGAS SpinningStar unit. The precession angle
was kept at 1.2°. The ADT3D[ software was used for data pro-
cessing, which included geometrical parameter optimization, 3D
diffraction volume reconstruction, 3D visualization, automated cell
parameter determination and intensity integration. Ab initio struc-
ture solution was performed by direct methods implemented in
SIR2008, included in the package IL MILIONE.[ Structure re-
finement was performed with the SHELX software.[
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Further details of the crystal structure investigation may be
obtained from the Fachinformationszentrum Karlsruhe,
6
[
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[
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7
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Supporting Information (see footnote on the first page of this article):
Results of MAPLE lattice energy calculations, diagrams of the coor-
dination spheres of the Ba2 ions and arrangement of the Br ions.
+
–
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Acknowledgments
2
We gratefully acknowledge financial support from the Deutsche
Forschungsgemeinschaft (DFG), project B8 in the SFB625, and the
Fonds der Chemischen Industrie (FCI) for a scholarship to S. J. S.
Additionally, we thank C. Minke for SEM measurements.
3552; b) S. Correll, N. Stock, O. Oeckler, J. Senker, T. Nilges,
W. Schnick, Z. Anorg. Allg. Chem. 2004, 630, 2205–2217.
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[
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nich (Germany), 2006.
1
[
Received: October 19, 2011
Published Online: November 21, 2011
7
Eur. J. Inorg. Chem. 2012, 121–125
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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