Journal of Solid State Chemistry 190 (2012) 221–225

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Journal of Solid State Chemistry

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Structure of a new form of silicon phosphate (SiP2O7) synthesized

at high pressures and temperatures
Kurt Leinenweber n, Linda A. Stearns 1, Jacob M. Nite, Péter Németh 2, Thomas L. Groy
Department of Chemistry, Arizona State University, Tempe, AZ 85287-1604, USA

a r t i c l e i n f o abstract

Article history: A new high-pressure phase of SiP2O7 has been found and its crystal structure solved and refined from
Received 18 August 2011 a single crystal grown at a condition of 16 GPa and 2000 1C and recovered to ambient conditions.
Received in revised form The material is monoclinic, with the space group P21/c and lattice parameters a ¼ 4.3042(7) Å,
4 February 2012
b ¼ 7.1505(12) Å, c ¼ 6.2897(11) Å, b ¼103.805(2). The structure contains SiO6 octahedra in a corner-
Accepted 12 February 2012
Available online 21 February 2012
sharing arrangement with P2O7 dimers, the same structural elements and vertex-sharing present in all
the low-pressure forms of SiP2O7. However, the network is more condensed: the topology of the
Keywords: packing of SiO6 octahedra and P2O7 dimers (represented by Si and the bridging oxygen that both lie on
Phosphates centers of symmetry) is that of the CsCl structure, with some distortion. The resulting phase is 11.2% to
Silicon phosphate
22.3% denser than the various low-pressure forms of SiP2O7. The structural data indicates that the P2O7
High pressure
dimers are linear (P–O–P angle ¼ 1801), an unusual feature for phosphates.
Crystal structur
& 2012 Elsevier Inc. All rights reserved.

1. Introduction polyhedra are linked (by corners, edges or faces) or through

SiP2O7 is interesting from a crystal chemical point of view,
because it is one of the few oxides stable at ambient pressure that
has silicon in six coordination, and is used in a variety of
applications such as as a component in fuel cells and as source
wafers for N-type (phosphorus) diffusion into silicon wafers.
SiP2O7 has a variety of modifications crystallizing at one atmo-
sphere [1–8] (Table 1). Not all of the modifications are fully
characterized in terms of structure; in particular only four of
them have had structures reported from powder or single-crystal
x-ray diffraction. These structures are all based on SiO6 octahedral
units that share corners with P2O7 groups, groups which are in
turn composed of two PO4 tetrahedra sharing one corner. It is
likely that the other polymorphs are also composed of such
groups.
Additional polymorphism is often found at high pressure for
many materials, with the thermodynamic requirement that the
stable high pressure phases are denser than the low-pressure
ones. In crystalline materials that can be represented by a
polyhedral model, this densification can occur through changes
in the packing of a polyhedral network, changes in how the
n
Corresponding author. Fax: þ1 480 965 2747.
E-mail address: kurtl@asu.edu (K. Leinenweber).
1
Current address: The Biodesign Institute, Evolutionary Medicine and
Informatics, Arizona State University, Tempe, AZ 85287-5001, USA.
2
Current address: Chemical Research Center of the Hungarian Academy of
Sciences, 1025 Budapest, Pusztaszeri út 59-67, Hungary.
increases in the coordination numbers of the atoms. It is inter-
esting to ask the question of what are the densification mechan-
isms in phosphates. In this study it was undertaken to look for
dense high pressure polymorphs of SiP2O7. The structural chem-
istry of phosphates is still relatively less understood than that of
silicates, another group that is based on a high-valency tetrahe-
dral cation and in which there is a great deal of polymorphism. In
the silicates, the coordination of the silicon eventually changes
from four to six. SiP2O7 is often noted for having six-coordinated
silicon even at ambient pressure. Sixfold coordination of phos-
phorus, on the other hand, is very rare, although it is expected to
occur at some pressure, possibly very high, in any phosphate, and
has been seen in two recent examples [9,10]; likewise, seven-
coordination of silicon, another option for coordination increase,
is only indicated in one example, a monoclinic zirconia-type
polymorph from a meteorite [11]. However, it is also possible
for the packing to become denser even when the coordinations
remain the same. Several recent papers have found this type of
behavior, packing changes with pressure, for other tetravalent-
cation phosphates [12,13].
In this study, samples of silicon phosphate were subjected to
high pressures and temperatures. At a pressure of 8 GPa and
temperature of 1000 1C, the low pressure form (SiP2O7–AIV) was
still stable, but at pressures of 16 GPa to 21 GPa and temperatures
ranging from 1300 1C to 2000 1C, a new high pressure form was
found. This new form may be designated SiP2O7-hp. The structure
of this new material has been solved from single-crystal x-ray
diffraction and is found to be a unique structure with very dense

0022-4596/$ - see front matter & 2012 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2012.02.031
222 K. Leinenweber et al. / Journal of Solid State Chemistry 190 (2012) 221–225

Table 1
List of several previously reported phases of SiP2O7, along with the new phase described here.

Name Space group Unit cell parameters Synthesis Structural description Density

SiP2O7-AI Pa-3 A ¼22.42 Å [1] [1,2] 3.21

SiP2O7-AII Tetragonal A ¼22.36, c ¼14.91 [1] [1]
SiP2O7-AIII P21/c A ¼4.73 Å, b¼ 6.33 Å, c¼ 14.71 Å, b ¼ 90.1 [1,3] [4] 3.05
SiP2O7-AIV P21/n A ¼4.71 Å, b¼ 11.98 Å, c¼ 7.62 Å, b ¼ 91.2 [1,3] [4–6] 3.11
SiP2O7-BI Hexagonal A ¼8.18, c¼ 11.85 [1]
SiP2O7 Form I P63 A ¼4.72, c ¼11.82 [7] [8] 2.92
SiP2O7 Form II Same as AIV (acc. to Poojary table) [7]
SiP2O7 Form III Tetragonal A ¼14.20, c¼ 7.39 [7]
Form IV Cubic (same as AI?) A ¼7.47 [7]
SiP2O7-hp (current study) P21/c a¼ 4.30, b ¼7.15, c ¼6.29, b ¼ 103.8 This study This study 3.57

Table 2
List of high pressure experiments and run products relevant to this study.

Run Number Pressure (GPa) Temperature (1C) Duration (h) Capsule Run products

R-430a 8 1000 5.75 Welded Pt SiP2O7-AIV þSiPO4(OH)

R-434b 8 1000 50 Welded Pt SiP2O7-AIV þSiPO4(OH) (xtals) þSiO2 (coesite)
R-439c 8 1000 9 Welded Pt SiPO4(OH)
BB-278a 21 1500 2 Graphite SiP2O7 (hp) þSiO2 (stishovite)
BB-357a 17.5 1300 2 Welded Au SiP2O7 (hp) þSiPO4(OH)
BB-695a 16.5 1525 1.5 Welded Pt SiP2O7 (hp) þSiPO4(OH)
BB-711a 16 2000 1 Welded Pt SiP2O7 (hp, xtals) þmelt
T1072d 18.8 1500 0.4 BN SiP2O7 (hp) þSiO2 (stishovite)

a
Starting material Si5O(PO4)6 with 4–5% naturally adsorbed H2O.
b
Starting material SiO2 þ Si5O(PO4)6 with 4–5% naturally adsorbed H2O.
c
Starting material Si5O(PO4)6 with 4–5% naturally adsorbed H2O plus additional added H2O for better mineralization.
d
In-situ experiment in the large-volume press at GSECARS, Argonne National Laboratories.

packing of the SiO6 and P2O7 units. The structural data and the
structural features of the new phase are reported here.
2. Experimental methods
X-ray peaks from an unidentified phase were first found in
experimental run products recovered from a pressure of 21 GPa
and a temperature of 1500 1C. Lower pressures and higher
temperatures were then attempted in order to isolate single
crystals of the phase. The record of all the high pressure experi-
ments in the system SiO2–P2O5–H2O for this study and the study
of Stearns et al. [14] are shown in Table 2. These experiments
used a multi-anvil high pressure device first introduced by Kawai
and Endo [15]; our specific modification of the design was
introduced by Walker et al. [16], and details of the multi-anvil
cell assemblies used in this study are described in Leinenweber
et al. [17]; we used the 14/8, 10/5 and 8/3 assemblies from that
paper. The phosphorus source for all experiments was Si5O(PO4)6
with a certain amount of physisorbed water, the same material
used in [14]. The water content (4–5 wt%) was determined by a
weight loss test on the starting material weighed, heated to
800 1C in a Pt crucible, recovered, and re-weighed. For the single
crystal synthesis attempts, a welded platinum capsule was used,
and the naturally physisorbed water in the starting material acted
as a mineralizer for the growth of single crystals. Despite the
presence of water in the charge, crystals large enough for single-
crystal structure analysis were not obtained in runs at 1300 1C
and 1525 1C; finally, a run at 16 GPa and 2000 1C produced
crystals, coexisting with a melt, that were suitable for single-
crystal x-ray diffraction.
The sample was checked by electron probe microanalysis to
verify its stoichiometry and purity. Within the sealed platinum
capsule, no elements other than Si, P and O were visible in the
EDS spectra of the crystals or the associated melt. Using
wavelength dispersive analysis on all three elements, the compo-
sition of the crystals was close to the ideal stoichiometry SiP2O7.
Also, a probe total close to 100% on an oxide basis indicated that
hydrogen (from the H2O mineralizer) did not occupy the phase in
significant quantities. The probe results for three points in the
sample were: Si 11.170.4%, P 19.1 70.4%, O 69.84 70.06%,
compared to the theoretical values of 10 atom percent for Si, 20
atom percent for P, and 70 atom percent for O.
The single crystal data collection was performed on a Bruker
SMART APEX single crystal diffractometer. Details of the data
collection and refinement are shown in Table 3.
Once the structure of the new phase was determined, full
powder diffraction experiments combined with Rietveld refine-
ment using GSAS were performed on the six experiments R-430
to BB-695 in Table 2, in order to ascertain the phase assemblages
in each run and to check for consistency with the single-crystal
results. The resulting phase assemblages are listed in Table 2, and
the powder patterns for the new phase were verified to be
consistent with the single-crystal structure. Because of the desire
to preserve the high-quality single crystals, the sample from
BB-711 was not ground up for powder diffraction, but the
microprobe and single-crystal data are indicative of a sample
with a single phase of SiP2O7 plus a melt and it is so indicated in
the run table.
3. Results and discussion
The refined structure parameters for the new high pressure
form of SiP2O7 are shown in Table 4, and the aniosotropic thermal
parameters are listed in Table 5. First-neighbor interatomic
distances are given in Table 6, and bond angles are listed in
Table 7. This structure, shown in Fig. 1, appears to be unique.
It has the same basic structural units as the low-pressure phases:
SiO6 groups (octahedra) and P2O7 groups (dimers of two tetrahedra
 K. Leinenweber et al. / Journal of Solid State Chemistry 190 (2012) 221–225 223

Table 3 Because the higher density is not caused by an increase in

Selected parameters from the measurement and refinement of the structure of first-neighbor coordination, it must be found in the coordinations
high pressure SiP2O7.
of higher neighbors, or (equivalently) in the way the structural
Crystal description Prismatic units are arranged. One way to look at this is through ring sizes:
in high pressure SiP2O7, the smallest are P–Si–P–Si, and the next
Crystal color Clear pale colorless smallest are P–Si–Si–P–Si. A smaller average ring size is one
Crystal size max (mm) 0.072 possible feature of a more condensed phase. Many of the low-
Crystal size mid (mm) 0.048
Crystal size min (mm) 0.034
pressure forms contain only 5-gons as the basic ring; the
Dx (mg m  3) 3.569 hexagonal form (Form I of Makart [7]) has the four-membered
Absorption coefficient m (mm  1) 1.444 ring but the layers are connected by larger rings (6-membered)
Data collection temperature (1K) 296.(2) and there are cavities in the structure that lead to the lowest
Data collection wavelength (Å) 0.71073
density of all the polymorphs.
Radiation type Mo Ka
Another viewpoint is to look at the morphology of the packing.
Radiation source Fine focus sealed tube
Radiation monochromator type Graphite This does not work well in all the polymorphs, but in the case of
Measurement device Bruker smart APEX the cubic low-pressure phase, SiP2O7-I, this has been done in two
Measurement method o and j scans useful ways [8]. One is to look at only the positions of Si and of the
Area detector mean resolution 8.3330
bridging P–O–P oxygen, thus treating the SiO6 groups and P2O7
Number of measured reflections 2192
Rint 0.0262
groups as simple units, or points. In this view, it is found that the
[S9s(I)9]/[9net(I)9] 0.0261 Si atoms and bridging O atoms form an NaCl-like packing. The
hmin 6 second view is to look at the Si atoms and P atoms; in this view,
hmax 6 the arrangement is that of pyrite (FeS2).
kmin  10
Looking at the new high pressure phase from the first of these
kmax 10
lmin 8 two viewpoints turns out to be a useful device: the Si and
lmax 8 bridging O atoms (O4 in this structure) form an arrangement
ymin 4.39 not far from a CsCl arrangement. The subcell defined by these
ymax 30.51 atoms has the three edges 4.76 Å, 4.30 Å, 4.76 Å, and associated
Number of independent reflections 572
Number of observed reflections 502
angles are 80.91, 97.31, 80.91. Although obviously distorted by the
Observed criterion 42s(I) presence of the linear P2O7 groups, this still has an obvious
Absorption correction type Multi-scan resemblance to a CsCl arrangement, with the Si atoms at the
Minimum transmission Tmin 0.82 corners of the pseudocubic cell and the O(4) atoms at the center
Maximum transmission Tmax 0.95
(or vice-versa); this may be seen by plotting the positions of these
Structure factors for least-squares Fsqd
Least-squares derivatives matrix Full atoms in projection, as is done along (0 1 0) in Fig. 2. These two
Primary structure solution Direct atoms are the only atoms in the structure to lie on centers of
Secondary structure solution Difmap symmetry, as is true in the classic CsCl arrangment–i.e., the
Extinction correction method SHELXL O(4) atoms lie at the true center defined by eight Si atoms and
Extinction coefficient (k) 0.038(8)
vice-versa.
Reflections used in L.S. derivatives 572
Parameters refined 50 We may use this construction to compare the transition from
Rall 0.0307 the high-temperature ambient pressure cubic phase, SiP2O7–AI, to
Robs 0.0257 the high pressure phase, SiP2O7-hp, and make the general state-
wRall 0.0694
ment that the basic packing is going from an NaCl-like to a CsCl-
wRobs 0.0671
Goodness of fit (S) 1.154 like packing, thus it may be broadly described by referring to the
Max e  /Å3 in final diff. map 0.480 classic B1 to B2 transition in binary structures. The density
Min e  /Å3 in final diff. map  0.414 change due to a typical B1–B2 transition is in the 10 to 20%
range; in KCl, for example, the zero-pressure densities for the
unquenchable B2 (KCl-type) structure has been estimated from
its equation of state by Walker et al. [18] and compared to the
Table 4
Fractional atomic coordinates, isotropic thermal parameters, and site occupancies measured zero-pressure density of the B1 structure, giving a
for the high-pressure phase of SiP2O7. density increase of 16.5% for the B1 to B2 transition. In SiP2O7-
AI to hp transition the density change is 11.2%. This density
Atom Site x y z Ueq (Å2) Occ.
increase is in the low part of the range, possibly because P–O–P
angles in SiP2O7-AI are bent while those in SiP2O7-hp are straight.
P1 4e 0.88708(13) 0.61169(8) 0.18287(9) 0.00449(18) 1
Si1 2b 0.5 0.5 0.5 0.0049(2) 1 Finally, a point should be made about the straight P–O–P
O1 4e 0.6495(4) 0.4887(2) 0.2626(3) 0.0062(3) 1 angle. In the pyrophosphate structures, earlier reported straight
O2 4e 0.7359(4) 0.7930(2) 0.0911(2) 0.0068(3) 1 P–O–P angles have often turned out to be artifacts of refinements
O3 4e 0.1901(4) 0.6434(2) 0.3610(2) 0.0060(3) 1 in too high-symmetry space groups (cf. Tillmanns et al. [2]), and
O4 2c 0.0 0.5 0.0 0.0074(4) 1
angles of 1401 are more typical. Because of this, the structure was
S.G. P21/c; a ¼4.3042(7) Å, b¼ 7.1505(12) Å, c ¼ 6.2987(11) Å, b ¼103.805(2)1. refined in two lower-symmetry subgroups that do not have
centers of symmetry at the bridging oxygen location, allowing
the angle to deviate from 1801. In both cases, angles close to 1801
linked at a corner). In addition, the units link by sharing corners just were obtained, and the r-values were slightly worse than in the
as in the low-pressure polymorphs. However, the density is sig- higher symmetry space group. In addition, the density distribu-
nificantly higher, with a calculated density of 3.57 g/cm3 compared tion around the bridging oxygen was examined and there are no
to, for example, 3.11 g/cm3 for the monoclinic polymorph SiP2O7– significant residual scattering peaks that might be indicative of
AIV that we find in all our lower-pressure run products. This density off-center positions for O(4). Third, the thermal factors for
increase of 14.8% is surprising considering that the coordination O(4) are not anomalously high or anisotropic (Tables 4 and 5).
polyhedra and linkages are similar in both phases. Finally, the bond lengths are all very reasonable. In the absence of
224 K. Leinenweber et al. / Journal of Solid State Chemistry 190 (2012) 221–225

Table 5
Anisotropic thermal parameters (Å2) for the high-pressure phase of SiP2O7.

Atom U11 U22 U33 U23 U13 U12

P1 0.0049(3) 0.0047(3) 0.0042(3) 0.00010(19) 0.00161(18) 0.00049(18)

Si1 0.0047(4) 0.0052(4) 0.0049(4) 0.0003(3) 0.0013(3)  0.0002(3)
O1 0.0066(7) 0.0063(7) 0.0062(7)  0.0010(5) 0.0026(5)  0.0010(6)
O2 0.0072(7) 0.0053(7) 0.0077(7) 0.0005(6) 0.0014(6) 0.0017(6)
O3 0.0048(7) 0.0062(7) 0.0064(7) 0.0000(6) 0.0001(5) 0.0008(6)
O4 0.0080(10) 0.0081(10) 0.0068(10)  0.0016(8) 0.0034(8) 0.0008(8)

Table 6
Bond distances for the high-pressure phase of SiP2O7.

Atom 1 Atom 2 Distance (Å)

P1 O2 1.5028(15)
P1 O3 1.5199(16)
P1 O1 1.5217(16)
P1 O4 1.5697(6)
Si1 O3 1.7430(15)
Si1 O3 1.7430(15)
Si1 O1 1.7631(16)
Si1 O1 1.7631(16)
Si1 O2 1.8089(15)
Si1 O2 1.8089(15)

Table 7
Bond angles.

Atom 1 Atom 2 Atom 3 Angle

Fig. 1. (1 0 0) plane normal view of the SiP2O7-hp structure. A b–c face of the unit cell
O2 P1 O3 111.80(9)
is shown by the dotted line: the b-axis is to the right, and the c-axis is vertical in the
O2 P1 O1 111.20(9)
plane of the figure. SiO6 octahedra (blue) have darker shading, and the P2O7 groups
O3 P1 O1 111.67(9)
(yellow) are shown as transparent in order to highlight the structural linkage.
O2 P1 O4 109.81(7)
O3 P1 O4 104.75(7)
O1 P1 O4 107.30(7)
O3 Si1 O3 180.0
O3 Si1 O1 90.44(7)
O3 Si1 O1 89.56(7)
O3 Si1 O1 89.56(7)
O3 Si1 O1 90.44(7)
O1 Si1 O1 180.0
O3 Si1 O2 88.98(7)
O3 Si1 O2 91.02(7)
O1 Si1 O2 89.13(7)
O1 Si1 O2 90.87(7)
O3 Si1 O2 91.02(7)
O3 Si1 O2 88.98(7)
O1 Si1 O2 90.87(7)
O1 Si1 O2 89.13(7)
O2 Si1 O2 180.0
P1 O1 Si1 131.47(10)
P1 O2 Si1 170.56(11)
P1 O3 Si1 134.54(10)
P1 O4 P1 180.0

conflicting evidence, we are reporting the higher symmetry space

group and straight P–O–P angle for this phase. Further studies of
this phase, including property measurements such as thermal
expansion, are warranted because of this unusual structural
feature.
Fig. 2. The positions of Si (smaller circles) and O(4) (larger circles) viewed down
the a-axis, with the c-axis horizontal and the b-axis vertical. The dotted line at
upper left shows the projection of the unit cell, while the solid line at lower right
shows the subcell that resembles a CsCl packing. The elevations of the Si and
O(4) atoms in the CsCl-like cell are labeled.

diffraction. The structure is based on a dense (CsCl-like) packing

4. Conclusions of SiO6 octahedra and linear dimeric P2O7 groups.
In terms of the original targets of this study, we did not find an
A new phase of SiP2O7, denoted SiP2O7-hp, has been synthe- increase in either silicon coordination (to seven-fold or higher) or
sized and its structure determined by single-crystal x-ray phosphorus (to five or six-fold) in SiP2O7, up to pressures of
 K. Leinenweber et al. / Journal of Solid State Chemistry 190 (2012) 221–225
21 GPa at high temperatures. Instead, there turned out to be a
structure available with a significantly increased packing density
of the polyhedra, which is the structure that was adopted. It is
still quite possible that this phase will be followed by even denser
phases of SiP2O7 with higher coordinations of silicon and/or
phosphorus, which would be an interesting target for diamond-
anvil cell studies.
Acknowledgments
We acknowledge the COMPRES cell assembly project, though
COMPRES, the Consortium for Materials Property Research in
Earth Sciences under NSF cooperative agreement EAR 01–35554.
We thank Michael O’Keeffe for examining the structure and
verifying that it is unique.
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.jssc.2012.02.031.
225
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