Synthesis and structure of a calcium polyphosphate with a unique
criss-cross arrangement of helical phosphate chains
Lauren E. Jackson1, Benson M. Kariuki1, Mark E. Smith2, Jake E. Barralet3
and Adrian J. Wright1*
1
School of Chemistry, University of Birmingham, Edgbaston. Birmingham B15 2TT, UK.
2
Department of Physics, University of Warwick, Coventry CV4 7AL, UK
3
Faculty of Dentistry, McGill University, Montreal, Quebec, Canada, H3A 2B2
Supplementary Information
Contents
Table 2.
Atomic coordinates and equivalent isotropic displacement parameters (Å2)
for γ-Ca(PO3)2.
Table 3.
Anisotropic displacement parameters for γ-Ca(PO3)2.
Table 4.
Bond lengths (Å) in γ-Ca(PO3)2.
Table 5.
Selected P-O-P angles (°) in γ-Ca(PO3)2.
Table 6.
Atomic coordinates from Rietveld analysis of powder X-ray diffraction
collected on γ-Ca(PO3)2.
Table 7.
FT-IR tabulated data in γ-Ca(PO3)2.
Figure 9.
X-ray powder diffraction profile from the Rietveld analysis of β-Ca(PO3)2,
with observed data as crosses and calculated and difference as continuous
lines. The tick marks indicate the reflection positions.
Figure 10. Extended
bands.
31
P MASNMR spectrum of γ-Ca(PO3)2 showing spinning side
1
Table 2. Atomic coordinates and equivalent isotropic displacement parameters (Å2) for
γ-Ca(PO3)2 from single crystal X-ray diffraction. U(eq) is defined as one third of the trace
of the orthogonalized Uij tensor.
Type
x
O(1)
0.3518(4)
O(2)
y
z
U(eq)
-0.2837(4)
0.7239(3)
0.013(1)
0.5078(4)
-0.2809(4)
0.5444(3)
0.010(1)
O(3)
0.4848(3)
-0.0570(4)
0.6691(3)
0.011(1)
O(4)
0.6853(3)
-0.3793(4)
0.4121(3)
0.010(1)
O(5)
0.5863(3)
-0.1376(4)
0.3582(3)
0.009(1)
O(6)
0.7520(4)
-0.1778(4)
0.5565(3)
0.010(1)
O(7)
0.5935(4)
0.1851(4)
0.5609(3)
0.013(1)
O(8)
0.7179(4)
0.1900(4)
0.3490(3)
0.014(1)
O(9)
0.7900(3)
0.3573(4)
0.5227(3)
0.010(1)
O(10)
0.5616(3)
0.3926(4)
0.4123(3)
0.011(1)
O(11)
0.7050(4)
0.4605(4)
0.2255(3)
0.011(1)
O(12)
0.4691(3)
0.5803(3)
0.2623(3)
0.011(1)
P(1)
0.4086(1)
-0.1878(1)
0.6294(1)
0.007(1)
P(2)
0.6373(1)
-0.2326(1)
0.4659(1)
0.007(1)
P(3)
0.6624(1)
0.2664(1)
0.4600(1)
0.007(1)
P(4)
0.6021(1)
0.5141(1)
0.3133(1)
0.007(1)
Ca(1)
0.7255(1)
0.0081(1)
0.7168(1)
0.008(1)
Ca(2)
0.3981(1)
0.1796(1)
0.6998(1)
0.009(1)
2
Table 3.
Anisotropic displacement parameters for γ-Ca(PO3)2. The anisotropic
displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + .. + 2 h k a* b* U12 ].
U11
U22
U33
U23
U13
U12
O(1)
0.014(2)
0.016(2)
0.007(2)
0.004(1)
0.000(1)
-0.001(2)
O(2)
0.010(2)
0.013(2)
0.009(1)
0.000(1)
0.003(1)
-0.003(1)
O(3)
0.008(2)
0.013(2)
0.010(2)
0.000(1)
-0.003(1)
0.001(2)
O(4)
0.007(2)
0.009(2)
0.012(2)
-0.002(1)
-0.002(1)
-0.001(1)
O(5)
0.011(2)
0.011(2)
0.005(2)
0.005(1)
-0.004(1)
0.000(1)
O(6)
0.010(2)
0.013(2)
0.007(2)
0.000(1)
-0.006(1)
0.000(1)
O(7)
0.009(2)
0.018(2)
0.012(2)
0.005(1)
-0.002(1)
0.000(1)
O(8)
0.014(2)
0.015(2)
0.013(2)
-0.003(2)
-0.001(2)
0.004(1)
O(9)
0.009(2)
0.010(2)
0.009(2)
0.002(1)
-0.006(1)
0.000(1)
O(10)
0.008(2)
0.014(2)
0.009(2)
0.002(1)
-0.003(1)
0.001(1)
O(11)
0.013(2)
0.010(2)
0.011(2)
0.000(2)
0.002(1)
0.003(1)
O(12)
0.008(2)
0.010(2)
0.014(2)
0.001(1)
-0.002(1)
0.002(1)
P(1)
0.005(1)
0.008(1)
0.006(1)
0.000(1)
-0.002(1)
0.000(1)
P(2)
0.006(1)
0.008(1)
0.005(1)
0.001(1)
-0.001(1)
0.001(1)
P(3)
0.005(1)
0.007(1)
0.007(1)
0.000(1)
-0.002(1)
-0.001(1)
P(4)
0.005(1)
0.008(1)
0.006(1)
0.001(1)
-0.001(1)
0.000(1)
Ca(1)
0.007(1)
0.008(1)
0.010(1)
0.000(1)
-0.001(1)
0.000(1)
Ca(2)
0.007(1)
0.010(1)
0.009(1)
0.001(1)
-0.002(1)
0.000(1)
3
Table 4. Bond lengths (Å) in γ-Ca(PO3)2
P1-O1
1.46659(2)
Ca1-O1
2.31703(4)
P1-O2
1.60060(2)
Ca1-O3
2.40651(5)
P1-O3
1.48641(3)
Ca1-O5
2.38343(4)
P1-O9
1.59486(3)
Ca1-O6
2.44878(4)
P2-O2
1.59081(3)
Ca1-O7
2.60527(4)
P2-O4
1.58003(3)
Ca1-O8
2.33317(4)
P2-O5
1.49431(3)
Ca1-O12
2.49538(5)
P2-O6
1.49442(3)
Ca2-O3
2.42404(5)
P3-O7
1.48663(2)
Ca2-O5
2.39601(5)
P3-O8
1.48608(3)
Ca2-O6
2.39728(4)
P3-O9
1.60093(3)
Ca2-O7
2.42880(5)
P3-O10
1.59842(3)
Ca2-O8
2.68800(4)
P4-O4
1.61581(3)
Ca2-O11
2.30560(4)
P4-O10
1.60798(3)
Ca2-O12
2.45631(5)
P4-O11
1.47188(3)
P4-O12
1.48759(3)
4
Table 5 Selected P-O-P angles (°) in γ-Ca(PO3)2.
O1-P1-O2
106.304(2)
O7-P3-O8
119.075(2)
O1-P1-O3
121.991(1)
O7-P3-O9
110.740(2)
O1-P1-O9
110.724(1)
O7-P3-O10
108.834(1)
O2-P1-O3
108.513(1
O8-P3-O9
106.190(1)
O2-P1-O9
100.776(2)
O8-P3-O10
111.340(1)
O3-P1-O9
106.492(1)
O9-P3-O10
98.733(2)
O2-P2-O4
100.267(1)
O4-P4-O12
109.772(1)
O2-P2-O5
109.120(1)
O10-P4-O11
110.041(1)
O2-P2-O6
110.100(2)
O10-P4-O12
107.258(1)
O4-P2-O5
110.925(2
O11-P4-O12
121.069(2)
O4-P2-O6
108.146(1)
O5-P2-O6
116.988(1)
5
Table 6. Atomic coordinates from Rietveld analysis of powder X-ray diffraction
collected on γ-Ca(PO3)2.
Atom
x
y
z
Ui/Ue*100
O1
0.346(1)
-0.278(1)
0.723(1)
0.8(1)
O2
0.519(1)
-0.287(1)
0.548(1)
0.8(1)
O3
0.478(1)
-0.067(1)
0.658(1)
0.8(1)
O4
0.680(1)
-0.377(1)
0.413(1)
0.8(1)
O5
0.605(1)
-0.142(1)
0.364(1)
0.8(1)
O6
0.759(1)
-0.168(1)
0.565(1)
0.8(1)
O7
0.596(1)
0.192(1)
0.563(1)
0.8(1)
O8
0.715(1)
0.200(1)
0.350(1)
0.8(1)
O9
0.792(1)
0.360(1)
0.516(1)
0.8(1)
O10
0.564(1)
0.407(1)
0.418(1)
0.8(1)
O11
0.696(1)
0.464(1)
0.223(1)
0.8(1)
O12
0.484(1)
0.577(1)
0.252(1)
0.8(1)
P1
0.405(1)
-0.192(1)
0.629(1)
2.2(1)
P2
0.631(1)
-0.230(1)
0.467(1)
2.2(1)
P3
0.655(1)
0.256(1)
0.461(1)
2.2(1)
P4
0.603(1)
0.514(1)
0.314(1)
2.2(1)
Ca1
0.719(1)
0.008(1)
0.721(1)
1.8(1)
Ca2
0.392(1)
0.179(1)
0.698(1)
1.8(1)
Lattice parameters; a = 9.5820(2)Å, b = 9.5190(2)Å, c = 10.3907(2)Å, β = 93.4782(8)°;
Cell volume = 945.98(3)Å3, Space group = Cc
6
Table 7 FT-IR tabulated data in γ-Ca(PO3)2.
Frequency (cm-1)
Assignment
850-920
υas(POP)
940-1020
υs(PO3)
1080-1110
υs(PO2)
1160-1170
υas(PO3)
1230-1250
υas(PO2)
Figure 9 X-ray powder diffraction profile from the Rietveld analysis of β-Ca(PO3)2, with
observed data as crosses and calculated and difference as continuous lines. The tick
marks indicate the reflection positions.
7
Figure 10 Extended
bands.
31
P MASNMR spectrum of γ-Ca(PO3)2 showing spinning side
8