Supporting Information
Wiley-VCH 2010
69451 Weinheim, Germany
AgIISO4 : A Genuine Sulfate of Divalent Silver with Anomalously
Strong One-Dimensional Antiferromagnetic Interactions**
Przemysław J. Malinowski, Mariana Derzsi, Zoran Mazej, Zvonko Jagličić, Bartłomiej Gaweł,
Wiesław Łasocha, and Wojciech Grochala*
anie_200906863_sm_miscellaneous_information.pdf
Contents
1. Figure S1. Rietveld structural fit utilizing the powder XRDP of AgSO4 obtained from reaction (1b)
between AgF2 and H2SO4. The unindexed reflexes are very weak, and can be assigned to traces of
AgSO3F and AgHSO4.
2. Figure S2. Powder XRDP for AgSO4 obtained from reaction (1a) between Ag(SbF6)2 and K2SO4 in
anhydrous HF; reflexes corresponding to impurity phases have been marked with arrows (AgHSO4)
and blue rhombuses (AgSO3F).
3. Figure S3. Powder XRDP of a product of thermal decomposition at 150 oC of AgSO4 obtained from
reaction (1b) (A), reaction (1a) (B) and Ag 2S2O7 obtained via thermal decomposition of AgHSO4 in
230 ºC (C); reflexes corresponding to KSbF6 have been marked with arrows.
4. Figure S4. Raman spectra of (A) AgSO4 obtained from reaction (1b) collected from various spots at
the surface (A1, A2), as well as for (B) AgSO4 obtained from reaction (1a) and (C) Ag2SO4 and (D)
Ag2S2O7.
5. Table S1. Bands seen in Raman and IR spectra of AgSO4 obtained from reaction (1b) and in the IR
spectrum of Ag 2S2O7.
6. Figure S5. FTIR spectrum (top) for gases evolved during thermal decomposition of AgSO4 obtained
from reaction (1b) at temperature corresponding to maximum IR absorbance, and profile of intensity of
the strongest IR band vs. T (bottom).
7. Figure S6. Profile of intensity of the strongest MS peaks vs. T for gases evolved during thermal
decomposition of AgSO4 obtained from reaction (1b).
8. Figure S7. TGA & DSC profiles of AgSO4 obtained from reaction (1a).
9. Figure S8. IR spectra of (A) product of thermal decomposition at 150 oC of AgSO4 obtained from
reaction (1b); (B) product of thermal decomposition of AgHSO4 at 230ºC; (C) K2S2O7 as a reference.
10. Figure S9. ESR spectrum of AgSO4 at 2.4 K.
11. Figure S10. Plot of parameters of the ESR signal (bandwidth, integrated intensity) vs. T.
12. Table S2. The GGA- and LDA-preoptimized fractional coordinates of Ag, S and O atoms in the
unit cell of AgSO4 constrained at experimental values of uni cell vectors and angles.
13. Table S3. Results of the GGA and GGA+U calculations for AgSO4 in AFM, FM and metallic state
using magnetic cells equivalent to the unit cell (energy in kJ/mol AgSO4).
14. Table S4. The calculated atomic magnetic moments for AgSO4 and CuSO4 (GGA+U).
15. Figure S11. Partial atomic DOS calculated for AgSO4 with the LSDA+U method.
16. Synthesis of AgHSO4 and Ag 2S2O7.
17. Extended view of crystal structure of AgSO4.
18. Details of Rietveld refinement.
19. Lattice parameters of AgSO4 at 85 K.
20. Bonner-Fischer fit.
21. Electronic band structure of CuSO4 as obtained with the LSDA+U method (UCu(d) = 8 eV, UO(p)
= 4 eV, US(p) = 2 eV, Jall_atoms= 1 eV)
22. Literature.
S1
1. Figure S1. Rietveld structural fit utilizing the powder XRDP of AgSO4 obtained from reaction
(1b) between AgF2 and H2SO4.
2. Figure S2. Powder XRDP for AgSO4 obtained from reaction (1a) between Ag(SbF6)2 and
K2SO4 in anhydrous HF; reflexes corresponding to impurity phases have been marked with
arrows (AgHSO4) and blue rhombuses (AgSO3F).
S2
3. Figure S3. Powder XRDP of Ag2S2O7 obtained via thermal decomposition of AgHSO4 at 230
ºC (A), and of a product of thermal decomposition at 150 oC of AgSO4 obtained from reaction
(1a) (B); reflexes corresponding to KSbF6 have been marked.
4. Figure S4. Raman spectra of (A) AgSO4 obtained from reaction (1b) collected from various
spots at the surface (A1, A2), as well as for (B) AgSO4 obtained from reaction (1a) and (C)
Ag2SO4 and (D) Ag 2S2O7 obtained by thermal decomposition of AgSO4.
S3
5. Table S1. Bands seen in Raman and IR spectra of AgSO4 obtained from reaction (1b) and in
the IR spectrum of Ag2S2O7. (obtained by thermal decomposition of AgSO4).***
AgSO4 (synth. 1b) AgSO4 (synth. 1b)
IR
Raman
Ag2 S2O7 (A1 set)
IR
Ag2S2O7
Raman
1156 sh
1116 w
1306 sh
1081 s
1142 sh
1077 m-s*
1265 vs
767 w
1084 vs
967 vs
1238 vs
730 m
1055 s
760 w
1198 s
620 w
1050 vs
725 m*
1167 vw, sh
591 w
1002 sh
615 m-s
1076 m
545 w
993 sh
586 w
1058 w
501 m
985 sh
494 m
1027 s
474 vw**
960 sh
469 m
883 w
930 sh
448 w
850 w
887 vw
419 m
801 s
670 m
337 sh
770 sh
660 sh
325 m-s*
726 m
610 m
641 w
600 sh
580 s
578 m
547 sh
575 m
510 w
523 w
358 m
318 m
237 m
222 sh
167 m
* Some amount of silver (I) pyrosulfate is present due to inevitable thermal decomposition of the
strongly–absorbing black AgSO4 sample in the laser beam, as testified by presence of 1077 cm- 1,
725 cm- 1 and 325 cm- 1 Raman bands [A].
** Spectrum below 400 cm–1 not measured because of notch filter.
*** All wavenumbers ±2 cm–1.
S4
6. Figure S5. FTIR spectrum (top) for gases evolved during thermal decomposition of AgSO4
obtained from reaction (1b) at temperature corresponding to maximum IR absorbance, and
profile of intensity of the strongest IR band vs. T (bottom).
7. Figure S6. Profile of intensity of the strongest MS peaks vs. T for gases evolved during thermal
decomposition of AgSO4 obtained from reaction (1b).
S5
8. Figure S7. TGA & DSC profiles of AgSO4 obtained from reaction (1a).
9. Figure S8. IR spectra of (A) product of thermal decomposition at 150 oC of AgSO4 obtained
from reaction (1b); (B) product of thermal decomposition of AgHSO4 at 230ºC; (C) K2S2O7 as a
reference.
10. Figure S9. ESR spectrum of AgSO4 at 2.4 K.
S6
11. Figure S10. Plot of parameters of the ESR signal (bandwidth, integrated intensity) vs. T.
Note unusual behaviour of both parameters in function of temperature.
12. Table S2. The GGA- and LDA-preoptimized fractional coordinates of Ag, S and O atoms in
the unit cell of AgSO4 constrained at experimental values of unit cell vectors and angles.
GGA*:
S1
O1
O3
O5
O7
Ag1
Ag2
0.1721
0.9042
0.4830
0.2502
0.0600
0.0000
0.5000
0.6256
0.2891
0.6145
0.8064
0.7745
0.0000
0.5000
0.2511
0.2236
0.2545
0.1055
0.4190
0.0000
0.5000
LDA*:
S1
0.1515 0.6230 0.2553
O1
0.8988 0.2867 0.2160
O3
0.4639 0.6289 0.2710
O5
0.2392 0.8191 0.1166
O7
0.0150 0.7515 0.4232
Ag1
0.0000 0.0000 0.0000
Ag2
0.5000 0.5000 0.5000
*The remaining atoms are symmetry-related.
13. Table S3. Results of the GGA, and GGA+U calculations for AgSO4 in AFM, FM and metallic
state using magnetic cells equivalent to the unit cell (energy in kJ/mol AgSO4).
AFM
FM
Metallic
GGA+U (GGA-preoptimized)
-2057.9
-2054.9
-2048.1
GGA (GGA-preoptimized)
-3081.0 (converges essentially to metal)
-3068.0
-3080.2
S7
14. Table S4. The calculated atomic magnetic moments for AgSO4 and CuSO4 (GGA+U).
AgSO4:
Atom s
p
d
total
---------------------------------------S1
0.001 0.003 0.001 0.005
S2
0.001 0.003 0.001 0.005
O1
0.004 0.080 0.000 0.085
O2
0.004 0.080 0.000 0.085
O3
-0.003 -0.085 0.000 -0.088
O4
-0.003 -0.085 0.000 -0.088
O5
0.005 0.024 0.000 0.030
O6
0.005 0.024 0.000 0.030
O7
-0.003 -0.048 0.000 -0.052
O8
-0.003 -0.048 0.000 -0.052
Ag1 0.000 -0.003 0.445 0.443
Ag2 0.003 0.003 -0.396 -0.390
CuSO4:
Atom s
p
d
total
---------------------------------------Cu1
0.001 0.000 0.800 0.801
Cu2
0.001 0.000 0.802 0.804
Cu3
-0.001 0.000 -0.803 -0.804
Cu4
-0.001 0.000 -0.799 -0.801
S1
0.000 0.000 0.000 0.000
S2
0.000 0.000 0.000 0.000
S3
0.000 0.000 0.000 0.000
S4
0.000 0.000 0.000 0.000
O1
0.000 -0.002 0.000 -0.002
O2
0.000 0.004 0.000 0.004
O3
0.000 -0.002 0.000 -0.002
O4
0.000 0.004 0.000 0.004
O5
0.000 0.002 0.000 0.001
O6
0.000 -0.001 0.000 0.000
O7
0.000 0.002 0.000 0.001
O8
0.000 -0.001 0.000 0.000
O9
0.004 0.018 0.000 0.022
O10
0.004 0.021 0.000 0.025
O11
0.004 0.018 0.000 0.022
O12
0.004 0.021 0.000 0.025
O13
-0.004 -0.018 0.000 -0.022
O14
-0.004 -0.021 0.000 -0.025
O15
-0.004 -0.018 0.000 -0.022
O16
-0.004 -0.021 0.000 -0.025
S8
15. Figure S11. Partial atomic DOS calculated for AgSO4 with the GGA+U method.
(i) Note that atomic DOS shown for sulfur atoms (right) has a different vertical scale than those for
Ag1, Ag2 and O atoms (left). Fermi level is represented by a vertical line.
(ii) Note the charge-transfer character of the across-a-bandgap electronic transition with O4predominated states below the Fermi level and the slightly Ag2-predominated states above the Fermi
level.
16. Synthesis of AgHSO4 and Ag2S2O7.
AgHSO4: AgHSO4 was synthesized according to the method by Stiewe and coauthors [B] via reaction:
H2SO4 + Ag2SO4 ? 2 AgHSO4
(Eq. S1)
Remnants of H2SO4 were washed away with trifluoroacetic acid. Dry white crystalline product was
obtained. It’s XRDP shows great similarity to the previously reported one.[C]
Ag2S2O7: Silver (I) pyrosulfate was obtained by thermal decomposition of AgHSO4 at temperatures
above 230°C:
2 AgHSO4 ? Ag2S2O7 + H2O
(Eq. S2)
AgHSO4 heated to ca. 100°C melts and then gets dry again when further heated at 230ºC for few
minutes. The product is a white powder. It’s IR spectrum shows great similarity to that of potassium
pyrosulfate.
S9
17. Extended view of crystal structure of AgSO4.
S10
18. Details of Rietveld refinement.
Compound obtained according to reaction 1a or 1b created very fine powder, thus suitable for powder
diffraction studies only. Sample was loaded into 0.3 mm quartz capillary (Hilgenberg), diffraction
measurement was performed at room or LN2 temperature using Bruker D8 Discover diffractometer
(Cu Ka radiation, Cu Ka radiation, I(a1) to I(a2) z 2 : 1, VANTEC linear detector).
The powder diffraction pattern was indexed first using Materials Studio package, subsequently the
same lattice parameters were found by the ITO program[D]. The initial crystal structure model was
elaborated by careful localizing O atoms of the C2/m cell with disordered sulphate ions (found at the
initial stages of indexing), and independently for the final P–1 cell by global optimization program
FOX[E].
JANA 2006[F] has been used for Rietveld refinement. Initial profile parameters were obtained by the
LeBail method[G]. Part of diffraction pattern (2? <20o) was excluded from refinement (due to
amorphous humb). Refinement included: scale, zero-point, background (15-terms Legandre
polynomial), lattice parameters, atomic positions and isotropic displacement parameters. Soft restraints
were employed to restrain the geometry of the sulphate group SO42–, d(S-O) = 1.48 Å (s.u.=0.005) and
ang(O-S-O) = 109.47 o (s.u.=0.05). Due to sample absorption, attenuation coefficient was introduced
(µr=3).
For purpose of presenting XRDPs, background has been removed using Crystal Sleuth program[H].
19. Lattice parameters of AgSO4 at 85 K.
a= 4.697 Å, b= 4.741 Å, c= 7.996 Å ; a =103.48°, ß=76.20°, ?=118.15°
1.0
-3
χ (10 emu/mol)
20. Bonner-Fischer fit.
0.5
data
Bonner-Fisher fit
0.0
0
100
200
300
T (K)
S11
400
21. Electronic band structure of CuSO4 as obtained with the LSDA+U method (UCu(d) = 8 eV,
UO(p) = 4 eV, U S(p) = 2 eV, J all_atoms= 1 eV).
22. Literature
[A] R. Fehrmann, N.H. Hansen, N.J. Bjerrum Inorg. Chem. 1983 22, 4009.
[B] A. Stiewe, E. Kemnitz, S. Troyanov, Z. Anorg. Allg. Chem. 1999, 625, 329.
[C] D. B. Dell’Amico, F. Calderazzo, F. Marchetti, S. Merlino, Chem. Mater. 1998, 10, 524.
[D] J. W. Visser, J. Appl. Cryst. 1969, 2, 89.
[E] V. Favre-Nicolin, R. Cerny, J. Appl. Cryst. 2002, 35, 734.
[F] V. Petricek, M. Dusek, L. Palatinus, Jana2006. The crystallographic computing system. Institute of Physics, Praha,
Czech Republic, 2006.
[G] A. LeBail, H. Duroy and J. L. Fourquet, Mater. Res. Bull., 1988, 23, 447.
[H] T. Laetsch and R. T. Downs (2006) Software For Identification and Refinement of Cell Parameters From Powder
Diffraction Data of Minerals Using the RRUFF Project and American Mineralogist Crystal Structure Databases. Abstracts
from the 19th General Meeting of the International Mineralogical Association, Kobe, Japan, 23-28 July 2006.
[I] The central part of the GTOC image was inspired by a popular novel. Costumes were generously supplied by Teatr
Roma, Warsaw, with direction, photography, and image processing by Andrew Churchard and Karol Fijalkowski. The
actors photographed are Przemyslaw Malinowski (Dr Jekyll) and Karol Fijalkowski (Mr Hyde).
[J] Authors are grateful to Dr. A. Wolos for performing ESR measurements and to Prof. Z. Wilamowski for discussing of
the ESR spectra.
S12