Neutron and high-pressure X-ray diffraction study of hydrogen-bonded ferroelectric rubidium hydrogen sulfate

The pressure- and temperature-dependent phase transitions in the ferroelectric material rubidium hydrogen sulfate (RbHSO₄) are investigated by a combination of neutron Laue diffraction and high-pressure X-ray diffraction. The observation of disordered O-atom positions in the hydrogen sulfate anions is in agreement with previous spectroscopic measurements in the literature. Contrary to the mechanism observed in other hydrogen-bonded ferroelectric materials, H-atom positions are well defined and ordered in the paraelectric phase. Under applied pressure RbHSO₄ undergoes a ferroelectric transition before transforming to a third, high-pressure phase. The symmetry of this phase is revised to the centrosymmetric space group P2₁/c, resulting in the suppression of ferroelectricity at high pressure.

Computing details

Data collection: MAATEL/ANSTO control program for rhs_150, rhs_300, rhs_300_dis; SMART (Siemens, 1993) for (1); Apex2 (Bruker AXS, 2006) for JB0003_ord, JB0005, JB0006, jb0009; USER DEFINED DATA COLLECTION for JB0008. Cell refinement: LaueG (Piltz, 2011) for rhs_150, rhs_300, rhs_300_dis; SAINT (Siemens ,1995) for (1); Apex2 (Bruker AXS, 2006) for JB0003_ord, JB0005, JB0006, jb0009; USER DEFINED CELL REFINEMENT for JB0008. Data reduction: argonne_boxes (Wilkinson et al., 1988) & LaueG for rhs_150; argonne_boxes (Wilkinson et al., 1988) & LaueG (Piltz, 2011) for rhs_300, rhs_300_dis; Apex2 (Bruker AXS, 2006) for (1), JB0003_ord, JB0005, JB0006, JB0008, jb0009. Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for rhs_150, rhs_300, rhs_300_dis, JB0003_ord, JB0005, JB0006, JB0008, jb0009; Superflip (Palatinus & Chapuis, 2007) for (1). For all compounds, program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003). Molecular graphics: CAMERON (Watkin et al., 1996) for rhs_300, rhs_300_dis, (1), JB0003_ord, JB0005, JB0006, JB0008, jb0009. Software used to prepare material for publication: CRYSTALS for rhs_150; CRYSTALS (Betteridge et al., 2003) for rhs_300, rhs_300_dis, (1), JB0003_ord, JB0005, JB0006, JB0008, jb0009.

(rhs_150) rubidium hydrogen sulfate

Crystal data

HO4S·Rb	F(000) = 240
Mr = 182.54	Dx = 2.940 Mg m^−3
Monoclinic, Pn	Neutron radiation, λ = 0.85 Å
Hall symbol: P -2yac	Cell parameters from 13194 reflections
a = 14.2651 (5) Å	θ = 0–0°
b = 4.5853 (2) Å	µ = 0.0 mm^−1
c = 14.2789 (5) Å	T = 150 K
β = 117.999 (2)°	Block, colourless
V = 824.66 (6) Å^3	1.20 × 1.10 × 0.80 mm
Z = 8

Data collection

KOALA diffractometer	Rint = 0.097
Laue scans	θmax = 71.2°
13194 measured reflections	h = 0→21
2365 independent reflections	k = 0→6
1909 reflections with I > 2.0σ(I)	l = −21→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	All H-atom parameters refined
wR(F^2) = 0.112	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 63.1 86.0 56.8 22.3 9.13
S = 0.96	(Δ/σ)max = 0.0001068
1909 reflections	Δρmax = 0.64 e Å^−3
253 parameters	Δρmin = −0.63 e Å^−3
2 restraints

Special details

Experimental. The crystal was placed in a cryofurnace on the KOALA instrument at 150 K. The crystal was held on an Al pin with silicone grease.

Refinement. All atoms refined anisotropically. LAUEG SPECIFIC INFORMATION: HKL generation: wav = 0.850 to 1.700, d-space > 0.670 Image scale factors: refined Wavelength spectra model: 10 point spline + non-param, gamma = 300.0 Efficiency model: Quadratic in Y Extinction correction: off Harmonics (wav/2) correction: on Absorption correction: off Friedel pairs are merged Merge statistics using final weights: R = 7.6 ( 4.2)% wR2 = 9.9 ( 4.8)% GOOF = 2.1 ( 6997 reflns > 4 sig) R = 9.7 ( 5.8)% wR2 =11.7 ( 6.6)% GOOF = 1.8 (all 13194 reflns) Max. harmonic correction = 24.4 esds, 243 hkls corrected by > 1 esd Summary of refineable correction factors: File scale factor min= -3.5% max= 11.3% ave= 2.1% st.dev.= 4.2% Wavelength spectra min= -0.9% max= 1.7% ave= 0.1% st.dev.= 0.4% Refined efficiency min= -2.3% max= 6.9% ave= -0.1% st.dev.= 2.5% Sample absorption min= 0.0% max= 0.0% ave= 0.0% st.dev.= 0.0% Sample extinction min= 0.0% max= 0.0% ave= 0.0% st.dev.= 0.0% ### CheckCIF responses PLAT213_ALERT_2_B Atom S2 has ADP max/min Ratio ···.. 4.6 oblate PLAT090_ALERT_3_C Poor Data / Parameter Ratio (Zmax > 18) ······.. 8.58 Note PLAT213_ALERT_2_C Atom O11 has ADP max/min Ratio ···.. 3.1 oblate PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ···. 2.1 Note - ADPs for S2 and O11 are oblate although the absolute size of the ADP is very small and in line with others in the structure PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 2 Note - No action taken ABSMU01_ALERT_1_G Calculation of _exptl_absorpt_correction_mu not performed for this radiation type. - An absorption correction was not required for this sample PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - No action taken PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check PLAT113_ALERT_2_G ADDSYM Suggests Possible Pseudo/New Space group. Abm2 Check - Structure exhibits pseudo-orthorhombic symmetry, however refinement in Abm2 are not stable. PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 6 Note Rb - No action taken PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT871_ALERT_4_G Laue technique Related ALERTS are Suppressed ··· ! Info PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 369 Note - Completeness is not 100 % for Laue technique PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT956_ALERT_1_G Calculated (ThMax) and Actual (FCF) Hmax Differ 10 Units PLAT957_ALERT_1_G Calculated (ThMax) and Actual (FCF) Kmax Differ 4 Units PLAT958_ALERT_1_G Calculated (ThMax) and Actual (FCF) Lmax Differ 10 Units PLAT960_ALERT_3_G Number of Intensities with I < - 2*sig(I) ··· 11 Check - No action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.2128 (2)	0.6460 (4)	0.08888 (19)	0.0136
Rb2	0.4634 (2)	0.4833 (5)	−0.1610 (2)	0.0137
Rb3	0.29434 (19)	1.0890 (5)	0.41712 (18)	0.0128
Rb4	0.54073 (19)	0.0777 (5)	0.16706 (18)	0.0124
S1	0.0487 (4)	1.0488 (11)	0.1716 (4)	0.0113
S2	0.2954 (4)	1.0388 (10)	−0.0772 (4)	0.0102
S3	0.4514 (5)	0.5225 (10)	0.3258 (5)	0.0110
S4	0.7094 (4)	0.5063 (9)	0.0821 (4)	0.0084
O1	−0.0425 (2)	1.2749 (6)	0.1149 (3)	0.0204
O2	0.0538 (3)	0.9939 (7)	0.2740 (2)	0.0219
O3	0.0137 (2)	0.7969 (6)	0.1020 (2)	0.0178
O4	0.1459 (2)	1.1725 (6)	0.1807 (2)	0.0160
O5	0.2417 (3)	1.2720 (6)	−0.1670 (2)	0.0174
O6	0.3049 (2)	1.1651 (6)	0.0206 (2)	0.0145
O7	0.2211 (2)	0.7951 (6)	−0.1130 (2)	0.0158
O8	0.3963 (3)	0.9703 (6)	−0.0716 (3)	0.0180
O9	0.5442 (2)	0.7018 (7)	0.4165 (2)	0.0187
O10	0.4519 (3)	0.5933 (7)	0.2279 (2)	0.0207
O11	0.4812 (3)	0.2251 (7)	0.3590 (4)	0.0317
O12	0.3543 (2)	0.6075 (7)	0.3269 (3)	0.0188
O13	0.7548 (2)	0.2645 (5)	0.1696 (2)	0.0145
O14	0.6996 (2)	0.3842 (6)	−0.0155 (2)	0.0147
O15	0.7880 (2)	0.7419 (5)	0.1227 (2)	0.0145
O16	0.6084 (2)	0.5904 (6)	0.0756 (2)	0.0152
H1	−0.0162 (5)	1.4791 (11)	0.1141 (5)	0.0243
H2	0.2380 (5)	1.4701 (12)	−0.1404 (5)	0.0245
H3	0.5288 (6)	0.9127 (12)	0.4016 (5)	0.0313
H4	0.7654 (5)	0.0699 (12)	0.1438 (5)	0.0253

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0190 (9)	0.0081 (9)	0.0161 (8)	−0.0002 (6)	0.0102 (7)	0.0005 (6)
Rb2	0.0144 (10)	0.0133 (11)	0.0127 (9)	0.0015 (6)	0.0058 (7)	0.0001 (6)
Rb3	0.0141 (9)	0.0138 (9)	0.0119 (8)	0.0013 (6)	0.0073 (7)	0.0015 (7)
Rb4	0.0125 (8)	0.0119 (9)	0.0126 (8)	0.0000 (6)	0.0059 (7)	0.0006 (7)
S1	0.014 (2)	0.008 (2)	0.012 (2)	0.0024 (15)	0.0067 (18)	0.0038 (16)
S2	0.017 (2)	0.0019 (19)	0.0117 (19)	0.0035 (14)	0.0072 (17)	0.0030 (14)
S3	0.014 (3)	0.008 (2)	0.013 (2)	0.0007 (13)	0.0090 (19)	−0.0001 (14)
S4	0.009 (2)	0.007 (2)	0.0065 (18)	0.0004 (12)	0.0018 (15)	−0.0003 (12)
O1	0.0140 (12)	0.0136 (13)	0.0301 (13)	0.0006 (8)	0.0075 (10)	0.0033 (10)
O2	0.0236 (14)	0.0291 (17)	0.0159 (11)	−0.0028 (9)	0.0115 (10)	0.0032 (9)
O3	0.0215 (12)	0.0094 (11)	0.0215 (11)	−0.0004 (8)	0.0094 (10)	−0.0018 (8)
O4	0.0122 (11)	0.0161 (12)	0.0186 (10)	−0.0011 (8)	0.0065 (8)	0.0021 (9)
O5	0.0279 (14)	0.0106 (13)	0.0117 (10)	0.0041 (8)	0.0076 (10)	0.0020 (8)
O6	0.0189 (11)	0.0140 (12)	0.0093 (9)	0.0022 (8)	0.0055 (8)	−0.0007 (7)
O7	0.0204 (12)	0.0084 (12)	0.0170 (11)	−0.0010 (8)	0.0075 (9)	−0.0004 (8)
O8	0.0183 (13)	0.0177 (14)	0.0218 (12)	0.0027 (8)	0.0125 (10)	−0.0019 (9)
O9	0.0165 (12)	0.0105 (13)	0.0184 (11)	0.0014 (8)	−0.0007 (9)	0.0006 (8)
O10	0.0258 (13)	0.0231 (15)	0.0198 (12)	−0.0056 (10)	0.0161 (10)	−0.0036 (9)
O11	0.045 (2)	0.0059 (13)	0.048 (2)	0.0033 (11)	0.0249 (17)	0.0056 (11)
O12	0.0167 (12)	0.0207 (14)	0.0233 (12)	−0.0001 (8)	0.0130 (10)	−0.0037 (9)
O13	0.0192 (12)	0.0112 (12)	0.0108 (9)	0.0013 (7)	0.0053 (9)	0.0018 (7)
O14	0.0191 (12)	0.0127 (12)	0.0123 (10)	0.0007 (8)	0.0072 (9)	−0.0032 (7)
O15	0.0179 (12)	0.0083 (11)	0.0180 (10)	−0.0009 (7)	0.0090 (9)	−0.0012 (7)
O16	0.0136 (11)	0.0163 (13)	0.0160 (10)	0.0028 (8)	0.0071 (9)	−0.0011 (8)
H1	0.026 (2)	0.013 (3)	0.029 (2)	0.0020 (14)	0.008 (2)	0.0001 (15)
H2	0.030 (3)	0.016 (3)	0.025 (2)	0.0032 (15)	0.011 (2)	0.0012 (15)
H3	0.039 (3)	0.013 (3)	0.034 (3)	0.0032 (19)	0.011 (2)	0.000 (2)
H4	0.032 (3)	0.018 (2)	0.028 (2)	0.0019 (17)	0.0147 (19)	0.0011 (17)

Geometric parameters (Å, º)

S1—O1	1.560 (6)	S3—O11	1.441 (6)
S1—O2	1.452 (6)	S3—O12	1.446 (6)
S1—O3	1.451 (6)	S4—O13	1.565 (5)
S1—O4	1.447 (6)	S4—O14	1.445 (5)
S2—O5	1.566 (6)	S4—O15	1.466 (5)
S2—O6	1.457 (6)	S4—O16	1.452 (6)
S2—O7	1.457 (6)	O1—H1	1.010 (6)
S2—O8	1.438 (6)	O5—H2	0.995 (6)
S3—O9	1.580 (6)	O9—H3	0.992 (6)
S3—O10	1.438 (6)	O13—H4	1.003 (6)
O1—S1—O2	105.9 (4)	O10—S3—O11	113.5 (4)
O1—S1—O3	103.8 (4)	O9—S3—O12	106.8 (4)
O2—S1—O3	113.0 (4)	O10—S3—O12	113.0 (4)
O1—S1—O4	108.4 (4)	O11—S3—O12	112.8 (4)
O2—S1—O4	112.7 (4)	O13—S4—O14	108.1 (3)
O3—S1—O4	112.3 (4)	O13—S4—O15	104.7 (3)
O5—S2—O6	107.6 (3)	O14—S4—O15	112.2 (4)
O5—S2—O7	103.9 (4)	O13—S4—O16	105.4 (4)
O6—S2—O7	111.5 (4)	O14—S4—O16	113.4 (4)
O5—S2—O8	106.7 (4)	O15—S4—O16	112.4 (3)
O6—S2—O8	113.1 (4)	S1—O1—H1	113.5 (4)
O7—S2—O8	113.3 (4)	S2—O5—H2	113.9 (4)
O9—S3—O10	107.2 (4)	S3—O9—H3	108.4 (4)
O9—S3—O11	102.6 (4)	S4—O13—H4	114.5 (4)

(rhs_300) rubidium hydrogensulfate

Crystal data

HO4S·Rb	F(000) = 240
Mr = 182.54	Dx = 2.877 Mg m^−3
Monoclinic, P21/n	Neutron radiation, λ = 0.85 Å
Hall symbol: -P 2yn	Cell parameters from 8517 reflections
a = 14.3602 (19) Å	θ = 0–0°
b = 4.6156 (6) Å	µ = 0.0 mm^−1
c = 14.413 (2) Å	T = 293 K
β = 118.069 (8)°	Block, colourless
V = 842.9 (2) Å^3	1.20 × 1.10 × 0.80 mm
Z = 8

Data collection

KOALA diffractometer	Rint = 0.091
Laue scans	θmax = 71.1°
8517 measured reflections	h = −18→16
1612 independent reflections	k = −5→5
1073 reflections with I > 2.0σ(I)	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.055	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 32.8 40.0 29.7 11.0 4.59
wR(F^2) = 0.106	(Δ/σ)max = 0.0002927
S = 1.00	Δρmax = 0.55 e Å^−3
1073 reflections	Δρmin = −0.51 e Å^−3
128 parameters	Extinction correction: Larson (1970), Equation 22
0 restraints	Extinction coefficient: 39 (3)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The crystal was placed on an Al pin with silicone grease.

Refinement. LAUEG SPECIFIC INFORMATION: HKL generation: wav = 0.850 to 1.700, d-space > 0.780 Image scale factors: refined Wavelength spectra model: 10 point spline + non-param, gamma = 300.0 Efficiency model: Quadratic in Y Extinction correction: off Harmonics (wav/2) correction: on Absorption correction: off Friedel pairs are merged Merge statistics using final weights: R = 6.2 ( 3.9)% wR2 = 7.7 ( 4.5)% GOOF = 1.7 ( 3458 reflns > 4 sig) R = 9.1 ( 6.2)% wR2 =10.7 ( 7.1)% GOOF = 1.5 (all 8517 reflns) Max. harmonic correction = 21.2 esds, 122 hkls corrected by > 1 esd Summary of refineable correction factors: File scale factor min= -3.4% max= 5.1% ave= 0.6% st.dev.= 2.1% Wavelength spectra min= -4.1% max= 3.1% ave= -0.1% st.dev.= 1.0% Refined efficiency min= -6.3% max= 2.7% ave= 0.3% st.dev.= 2.3% Sample absorption min= 0.0% max= 0.0% ave= 0.0% st.dev.= 0.0% Sample extinction min= 0.0% max= 0.0% ave= 0.0% st.dev.= 0.0% ### CheckCIF responses PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. S1 Check - The O ADPs of the S(1) HSO4 moiety are discussed in the text. In this ordered refinement they appear anomalously enlarged. ABSMU01_ALERT_1_G Calculation of _exptl_absorpt_correction_mu not performed for this radiation type. - No absorption correction was required for this sample PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - No action taken PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check - Structure is pseudosymmetric PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 Check - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT871_ALERT_4_G Laue technique Related ALERTS are Suppressed ··· ! Info

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.79199 (12)	0.1405 (3)	0.91551 (11)	0.0299
Rb2	0.46093 (14)	0.7021 (4)	0.83619 (14)	0.0320
S1	0.5489 (3)	0.2162 (7)	0.6735 (4)	0.0251
S2	0.7070 (3)	0.7391 (6)	1.0790 (3)	0.0211
O1	0.45770 (18)	0.0155 (5)	0.5980 (2)	0.0486
O5	0.75757 (18)	0.5040 (4)	1.16738 (15)	0.0348
O4	0.64524 (15)	0.1173 (5)	0.67676 (17)	0.0387
O8	0.78116 (16)	0.9791 (4)	1.11775 (16)	0.0336
O6	0.69811 (15)	0.6185 (4)	0.98300 (13)	0.0330
O7	0.60648 (16)	0.8078 (5)	1.07354 (17)	0.0383
O2	0.5508 (2)	0.2012 (7)	0.7736 (2)	0.0590
O3	0.5152 (2)	0.4894 (5)	0.6204 (3)	0.0708
H1	0.4788 (3)	−0.1907 (9)	0.6088 (3)	0.0442
H2	0.7630 (3)	0.3085 (8)	1.1411 (3)	0.0387

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0309 (7)	0.0330 (9)	0.0282 (7)	−0.0005 (6)	0.0160 (6)	−0.0005 (6)
Rb2	0.0292 (8)	0.0363 (8)	0.0311 (8)	0.0002 (6)	0.0145 (6)	0.0015 (6)
S1	0.0251 (18)	0.0195 (16)	0.035 (2)	−0.0005 (12)	0.0171 (16)	−0.0028 (13)
S2	0.0230 (17)	0.0198 (17)	0.0189 (16)	0.0019 (10)	0.0086 (14)	−0.0001 (10)
O1	0.0304 (11)	0.0334 (13)	0.0598 (14)	0.0008 (8)	0.0028 (10)	−0.0116 (9)
O5	0.0523 (12)	0.0234 (11)	0.0251 (8)	0.0047 (7)	0.0151 (8)	0.0024 (6)
O4	0.0305 (9)	0.0454 (12)	0.0434 (10)	0.0011 (8)	0.0200 (8)	−0.0076 (9)
O8	0.0388 (11)	0.0230 (9)	0.0378 (10)	−0.0041 (6)	0.0170 (8)	−0.0014 (7)
O6	0.0401 (10)	0.0354 (11)	0.0228 (8)	0.0046 (7)	0.0143 (7)	−0.0033 (6)
O7	0.0272 (10)	0.0502 (12)	0.0405 (11)	0.0054 (8)	0.0183 (8)	−0.0015 (9)
O2	0.0519 (15)	0.094 (2)	0.0429 (13)	−0.0074 (13)	0.0320 (12)	−0.0147 (12)
O3	0.0584 (17)	0.0263 (12)	0.120 (3)	0.0070 (9)	0.0358 (18)	0.0243 (13)
H1	0.0433 (19)	0.0348 (19)	0.0504 (19)	−0.0049 (15)	0.0186 (16)	−0.0064 (15)
H2	0.0470 (18)	0.0295 (16)	0.0384 (16)	0.0038 (13)	0.0192 (14)	0.0022 (13)

Geometric parameters (Å, º)

S1—O1	1.554 (4)	S2—O8	1.453 (4)
S1—O4	1.437 (4)	S2—O6	1.440 (4)
S1—O2	1.432 (5)	S2—O7	1.444 (4)
S1—O3	1.436 (4)	O1—H1	0.988 (5)
S2—O5	1.567 (4)	O5—H2	0.996 (4)
O1—S1—O4	108.3 (3)	O5—S2—O6	108.1 (2)
O1—S1—O2	106.7 (3)	O8—S2—O6	112.4 (3)
O4—S1—O2	113.0 (3)	O5—S2—O7	105.4 (3)
O1—S1—O3	100.9 (3)	O8—S2—O7	112.7 (2)
O4—S1—O3	111.9 (3)	O6—S2—O7	113.4 (3)
O2—S1—O3	115.0 (3)	S1—O1—H1	111.6 (3)
O5—S2—O8	103.9 (3)	S2—O5—H2	114.0 (3)

(rhs_300_dis) rubidium hydrogen sulfate

Crystal data

HO4S·Rb	F(000) = 240
Mr = 182.54	Dx = 2.877 Mg m^−3
Monoclinic, P21/n	Neutron radiation, λ = 0.85 Å
Hall symbol: -P 2yn	Cell parameters from 8517 reflections
a = 14.3602 (19) Å	θ = 0–0°
b = 4.6156 (6) Å	µ = 0.0 mm^−1
c = 14.413 (2) Å	T = 300 K
β = 118.069 (8)°	Block, colourless
V = 842.9 (2) Å^3	1.20 × 1.10 × 0.80 mm
Z = 8

Data collection

KOALA diffractometer	Rint = 0.091
Laue scans	θmax = 71.1°
8517 measured reflections	h = −18→16
1612 independent reflections	k = −5→5
1073 reflections with I > 2.0σ(I)	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.051	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 30.0 35.9 27.2 10.2 4.27
wR(F^2) = 0.096	(Δ/σ)max = 0.001
S = 0.91	Δρmax = 0.40 e Å^−3
1073 reflections	Δρmin = −0.41 e Å^−3
146 parameters	Extinction correction: Larson (1970), Equation 22
0 restraints	Extinction coefficient: 38 (3)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The crystal was placed on an Al pin with silicone grease.

Refinement. LAUEG SPECIFIC INFORMATION: HKL generation: wav = 0.850 to 1.700, d-space > 0.780 Image scale factors: refined Wavelength spectra model: 10 point spline + non-param, gamma = 300.0 Efficiency model: Quadratic in Y Extinction correction: off Harmonics (wav/2) correction: on Absorption correction: off Friedel pairs are merged Merge statistics using final weights: R = 6.2 ( 3.9)% wR2 = 7.7 ( 4.5)% GOOF = 1.7 ( 3458 reflns > 4 sig) R = 9.1 ( 6.2)% wR2 =10.7 ( 7.1)% GOOF = 1.5 (all 8517 reflns) Max. harmonic correction = 21.2 esds, 122 hkls corrected by > 1 esd Summary of refineable correction factors: File scale factor min= -3.4% max= 5.1% ave= 0.6% st.dev.= 2.1% Wavelength spectra min= -4.1% max= 3.1% ave= -0.1% st.dev.= 1.0% Refined efficiency min= -6.3% max= 2.7% ave= 0.3% st.dev.= 2.3% Sample absorption min= 0.0% max= 0.0% ave= 0.0% st.dev.= 0.0% Sample extinction min= 0.0% max= 0.0% ave= 0.0% st.dev.= 0.0% ### CheckCIF responses PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. S1 Check - The O ADPs of the S(1) HSO4 moiety are discussed in the text. In this disordered refinement they are still somewhat enlarged. See text for discussion. ABSMU01_ALERT_1_G Calculation of _exptl_absorpt_correction_mu not performed for this radiation type. - No absorption correction was required for this sample PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - No action taken PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ···.. (K) 293 Check - Correct PLAT300_ALERT_4_G Atom Site Occupancy of >O20 is Constrained at 0.501 Check - Final refined occupancies of oxygen atoms are reported. PLAT301_ALERT_3_G Main Residue Disorder ············ Percentage = 17 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT871_ALERT_4_G Laue technique Related ALERTS are Suppressed ··· ! Info

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rb1	0.79203 (11)	0.1405 (3)	0.91557 (10)	0.0298
Rb2	0.46098 (13)	0.7022 (3)	0.83616 (13)	0.0321
S1	0.5487 (3)	0.2159 (7)	0.6735 (3)	0.0250
S2	0.7071 (3)	0.7389 (6)	1.0791 (3)	0.0215
O1	0.45768 (16)	0.0150 (5)	0.5982 (2)	0.0482
O5	0.75763 (16)	0.5037 (4)	1.16737 (14)	0.0347
O4	0.64529 (14)	0.1176 (4)	0.67678 (15)	0.0387
O8	0.78115 (15)	0.9790 (3)	1.11769 (15)	0.0336
O6	0.69819 (14)	0.6185 (4)	0.98306 (12)	0.0327
O7	0.60649 (15)	0.8079 (5)	1.07346 (16)	0.0383
H1	0.4788 (3)	−0.1901 (8)	0.6089 (3)	0.0444
H2	0.7632 (3)	0.3094 (8)	1.1413 (2)	0.0389
O30	0.5132 (9)	0.480 (3)	0.6075 (8)	0.0411	0.5030
O31	0.5192 (14)	0.502 (3)	0.6404 (10)	0.0652	0.4970
O20	0.5466 (14)	0.235 (4)	0.7669 (13)	0.0541	0.5009
O21	0.5563 (11)	0.171 (3)	0.7803 (12)	0.0429	0.4991

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0307 (7)	0.0327 (8)	0.0283 (6)	−0.0007 (5)	0.0159 (5)	−0.0007 (5)
Rb2	0.0292 (8)	0.0369 (7)	0.0300 (8)	0.0003 (6)	0.0138 (6)	0.0013 (6)
S1	0.0252 (17)	0.0194 (15)	0.0338 (19)	−0.0005 (11)	0.0166 (15)	−0.0022 (12)
S2	0.0233 (17)	0.0198 (16)	0.0207 (15)	0.0021 (9)	0.0098 (13)	0.0002 (9)
O1	0.0302 (10)	0.0345 (12)	0.0587 (13)	0.0003 (7)	0.0035 (9)	−0.0116 (8)
O5	0.0521 (11)	0.0240 (10)	0.0248 (7)	0.0046 (6)	0.0153 (8)	0.0030 (6)
O4	0.0308 (9)	0.0448 (11)	0.0435 (9)	0.0017 (7)	0.0201 (7)	−0.0071 (8)
O8	0.0389 (10)	0.0228 (8)	0.0383 (9)	−0.0041 (6)	0.0175 (8)	−0.0014 (6)
O6	0.0402 (9)	0.0347 (10)	0.0229 (7)	0.0046 (7)	0.0146 (7)	−0.0032 (6)
O7	0.0272 (9)	0.0499 (11)	0.0407 (10)	0.0055 (7)	0.0184 (8)	−0.0019 (8)
H1	0.0426 (17)	0.0367 (18)	0.0487 (18)	−0.0054 (14)	0.0172 (14)	−0.0069 (14)
H2	0.0458 (17)	0.0310 (15)	0.0382 (14)	0.0034 (12)	0.0185 (13)	0.0023 (12)
O30	0.039 (3)	0.025 (3)	0.052 (4)	0.0019 (17)	0.015 (3)	0.010 (3)
O31	0.083 (6)	0.020 (3)	0.093 (9)	0.010 (3)	0.042 (7)	0.014 (5)
O20	0.056 (4)	0.083 (10)	0.032 (4)	0.022 (5)	0.028 (3)	0.004 (4)
O21	0.042 (5)	0.058 (6)	0.035 (4)	−0.011 (5)	0.023 (4)	−0.003 (4)

Geometric parameters (Å, º)

S1—O1	1.553 (4)	S2—O5	1.567 (3)
S1—O4	1.438 (4)	S2—O8	1.453 (4)
S1—O30	1.483 (13)	S2—O6	1.441 (4)
S1—O31	1.399 (15)	S2—O7	1.443 (4)
S1—O20	1.364 (16)	O1—H1	0.984 (5)
S1—O21	1.507 (17)	O5—H2	0.990 (4)
O1—S1—O4	108.5 (2)	O30—S1—O21	127.4 (8)
O1—S1—O30	97.0 (5)	O31—S1—O21	110.0 (9)
O4—S1—O30	108.4 (5)	O20—S1—O21	12.6 (14)
O1—S1—O31	107.7 (7)	O5—S2—O8	104.0 (2)
O4—S1—O31	116.2 (8)	O5—S2—O6	108.1 (2)
O30—S1—O31	17.7 (7)	O8—S2—O6	112.3 (3)
O1—S1—O20	109.0 (8)	O5—S2—O7	105.6 (2)
O4—S1—O20	117.2 (8)	O8—S2—O7	112.7 (2)
O30—S1—O20	114.7 (9)	O6—S2—O7	113.4 (3)
O31—S1—O20	97.5 (10)	S1—O1—H1	111.6 (3)
O1—S1—O21	105.3 (5)	S2—O5—H2	114.2 (3)
O4—S1—O21	108.6 (6)

(1) Rubidium hydrogensulfate

Crystal data

Rb·HO4S	F(000) = 688
Mr = 182.54	Dx = 2.877 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4265 reflections
a = 14.3602 (19) Å	θ = 3–28°
b = 4.6156 (6) Å	µ = 12.11 mm^−1
c = 14.413 (2) Å	T = 298 K
β = 118.069 (8)°	Block, colourless
V = 842.9 (2) Å^3	0.18 × 0.15 × 0.12 mm
Z = 8

Data collection

Bruker SMART diffractometer	1636 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 28.5°, θmin = 1.7°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −18→19
Tmin = 0.19, Tmax = 0.23	k = −6→6
8818 measured reflections	l = −18→19
1992 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.027	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 3.39 5.02 2.56 0.708
wR(F^2) = 0.057	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 1.19 e Å^−3
1987 reflections	Δρmin = −0.78 e Å^−3
137 parameters	Extinction correction: Larson (1970), Equation 22
58 restraints	Extinction coefficient: 13.1 (8)
Primary atom site location: Other

Special details

Refinement. ###CHECKCIF COMMENTS### Alert level C PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. S1 - S(1) tetrahedron may be refined with larger ADPs for O atoms or refined to a disordered model. Please see text for discussion. Alert level G PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 8 PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 58 - HS(1)O4 is modelled as the overlay of two possible orientations. Restraints are required to give a stable refinement PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ············.. 2 - CheckCIF bug, D-H atoms were refined anisotropically. PLAT301_ALERT_3_G Main Residue Disorder ············ Percentage = 25 PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found - CheckCIF bug, Chebychev polynomial weighting scheme used. Details given below. PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ···. ! - No action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rb1	0.70777 (3)	0.64082 (7)	0.58437 (3)	0.0279
Rb2	0.46118 (3)	0.70202 (7)	0.83628 (3)	0.0309
S1	0.54896 (7)	0.21607 (16)	0.67365 (8)	0.0252
S2	0.20686 (7)	0.76118 (16)	0.57925 (7)	0.0211
O5	0.2581 (2)	0.9949 (5)	0.66787 (19)	0.0331
O6	0.1979 (2)	0.8821 (6)	0.48282 (19)	0.0322
O7	0.2810 (2)	0.5209 (5)	0.6178 (2)	0.0322
O8	0.1063 (2)	0.6925 (6)	0.5735 (2)	0.0384
O10	0.462 (2)	0.035 (4)	0.5901 (12)	0.0345	0.4926
O11	0.454 (2)	−0.006 (4)	0.6070 (13)	0.0358	0.5074
O20	0.548 (3)	0.240 (5)	0.7682 (16)	0.0474	0.4817
O21	0.556 (2)	0.169 (4)	0.7787 (14)	0.0436	0.5183
O30	0.5110 (11)	0.478 (2)	0.6055 (7)	0.0358	0.5318
O31	0.5209 (15)	0.509 (3)	0.6428 (9)	0.0534	0.4682
O4	0.6455 (2)	0.1174 (6)	0.6772 (2)	0.0389
H1	0.4758	−0.1539	0.6029	0.0699*
H2	0.2652	1.1493	0.6455	0.0497*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.02901 (18)	0.02961 (18)	0.02711 (17)	0.00104 (13)	0.01488 (13)	0.00102 (13)
Rb2	0.02669 (18)	0.0362 (2)	0.02875 (19)	−0.00020 (14)	0.01208 (15)	0.00064 (14)
S1	0.0254 (4)	0.0187 (4)	0.0330 (5)	−0.0007 (3)	0.0148 (4)	−0.0027 (3)
S2	0.0228 (4)	0.0195 (3)	0.0204 (4)	−0.0018 (3)	0.0097 (3)	−0.0004 (3)
O5	0.0523 (16)	0.0212 (12)	0.0234 (12)	−0.0052 (11)	0.0157 (12)	−0.0017 (9)
O6	0.0390 (14)	0.0339 (13)	0.0229 (12)	−0.0053 (11)	0.0140 (11)	0.0016 (10)
O7	0.0375 (14)	0.0217 (12)	0.0378 (14)	0.0024 (10)	0.0182 (12)	0.0003 (10)
O8	0.0282 (14)	0.0501 (17)	0.0397 (16)	−0.0086 (12)	0.0182 (13)	0.0016 (12)
O10	0.030 (6)	0.023 (4)	0.035 (4)	−0.001 (3)	0.003 (4)	0.006 (3)
O11	0.023 (3)	0.023 (5)	0.054 (6)	−0.005 (4)	0.012 (5)	0.000 (4)
O20	0.050 (6)	0.060 (10)	0.034 (4)	0.017 (7)	0.022 (4)	0.001 (4)
O21	0.044 (8)	0.055 (9)	0.041 (3)	−0.012 (7)	0.027 (5)	−0.004 (4)
O30	0.039 (4)	0.020 (3)	0.041 (5)	−0.001 (2)	0.012 (4)	0.001 (3)
O31	0.071 (7)	0.016 (2)	0.065 (8)	0.005 (3)	0.026 (8)	0.000 (4)
O4	0.0304 (14)	0.0443 (16)	0.0448 (16)	0.0015 (12)	0.0201 (12)	−0.0084 (12)

Geometric parameters (Å, º)

S1—O10	1.515 (13)	S2—O5	1.566 (3)
S1—O11	1.608 (13)	S2—O6	1.446 (3)
S1—O20	1.375 (16)	S2—O7	1.455 (3)
S1—O21	1.487 (13)	S2—O8	1.442 (3)
S1—O30	1.488 (10)	O5—H2	0.808
S1—O31	1.421 (13)	O10—H1	0.895
S1—O4	1.437 (3)	O11—H1	0.763
O10—S1—O11	12.8 (12)	O11—S1—O4	110.4 (11)
O10—S1—O20	116.2 (16)	O20—S1—O4	116.9 (12)
O11—S1—O20	104.1 (16)	O21—S1—O4	108.5 (9)
O10—S1—O21	111.3 (12)	O30—S1—O4	109.2 (5)
O11—S1—O21	98.6 (11)	O31—S1—O4	116.1 (8)
O20—S1—O21	13.6 (16)	O5—S2—O6	108.25 (15)
O10—S1—O30	90.8 (9)	O5—S2—O7	103.61 (15)
O11—S1—O30	100.3 (7)	O6—S2—O7	112.30 (16)
O20—S1—O30	114.6 (9)	O5—S2—O8	105.75 (17)
O21—S1—O30	128.1 (9)	O6—S2—O8	113.31 (17)
O10—S1—O31	105.7 (10)	O7—S2—O8	112.81 (17)
O11—S1—O31	112.6 (11)	S2—O5—H2	112.4
O20—S1—O31	95.7 (11)	S1—O10—H1	110.6
O21—S1—O31	109.2 (9)	S1—O11—H1	111.1
O30—S1—O31	19.9 (5)	O10—H1—O11	23.4
O10—S1—O4	106.0 (12)

(JB0003_ord) Rubidium hydrogensulfate

Crystal data

Rb·HO4S	F(000) = 688
Mr = 182.54	Dx = 2.871 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1777 reflections
a = 14.324 (3) Å	θ = 3–25°
b = 4.6263 (9) Å	µ = 12.09 mm^−1
c = 14.401 (7) Å	T = 293 K
β = 117.74 (3)°	Block, colourless
V = 844.7 (5) Å^3	0.20 × 0.12 × 0.10 mm
Z = 8

Data collection

Bruker Kappa Apex2 diffractometer	620 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 26.0°, θmin = 3.3°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −15→15
Tmin = 0.26, Tmax = 0.30	k = −5→5
3119 measured reflections	l = −13→13
754 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.023	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 6.83 11.1 6.67 2.86 0.686
wR(F^2) = 0.055	(Δ/σ)max = 0.0003437
S = 1.02	Δρmax = 0.35 e Å^−3
620 reflections	Δρmin = −0.35 e Å^−3
110 parameters	Extinction correction: Larson (1970), Equation 22
0 restraints	Extinction coefficient: 13 (2)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The crystal was placed in a Merrill-Basset HP cell using fluorinert FC70 as hydrostatic medium. The sample was subjected to a pressure of 0.14 GPa.

Refinement. ###CHECKCIF RESPONSES### Alert level A REFNR01_ALERT_3_A Ratio of reflections to parameters is < 6 for a centrosymmetric structure sine(theta)/lambda 0.6171 Proportion of unique data used 0.8223 Ratio reflections to parameters 5.6364 PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ······. 0.459 PLAT940_ALERT_3_B F**2 Refinement with I < n * Sigma(I) only The high pressure cell causes shading of a significant proportion of the sphere of reflections. This means that the completeness is reduced and as such the quality of the model is lower. As a result of the shading a reflection threshold of I>2.0σ(I) was used to give a stable refinement. PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. S1 PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ············.. 2 - Incorrect, donor atoms were refined anisotropically. PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m - Additional symmetry elements were discounted on the basis of systematic absences: Systematic absence exceptions: -21- -a- -c- -n- N 14 63 59 58 N I>3s 0 27 27 0 <I> 0.0 20.3 21.7 0.1 <I/s> 0.2 10.3 11.0 0.5 Identical indices and Friedel opposites combined before calculating R(sym) Option Space Group No. Type Axes CSD R(sym) N(eq) Syst. Abs. CFOM [A] P2(1)/n # 14 centro 1 19410 0.017 144 0.5 / 10.3 3.33 PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ···.. (K) 293 - Correct, room temperature collection. PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please - CheckCIF bug. Weighting scheme details are given below #########################################################################

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.70766 (7)	0.64030 (11)	0.58431 (9)	0.0316
Rb2	0.46111 (8)	0.70181 (12)	0.83617 (10)	0.0336
S1	0.54951 (19)	0.2157 (3)	0.6744 (3)	0.0268
S2	0.2065 (2)	0.7610 (3)	0.5785 (3)	0.0251
O1	0.4575 (5)	0.0149 (9)	0.5989 (7)	0.0503
O2	0.5507 (7)	0.2006 (13)	0.7734 (10)	0.0536
O3	0.5162 (6)	0.4920 (9)	0.6236 (8)	0.0729
O4	0.6452 (5)	0.1172 (9)	0.6774 (7)	0.0389
O5	0.2583 (5)	0.9943 (8)	0.6679 (6)	0.0400
O6	0.1979 (5)	0.8819 (8)	0.4830 (7)	0.0320
O7	0.2809 (5)	0.5208 (8)	0.6183 (6)	0.0375
O8	0.1068 (5)	0.6923 (9)	0.5743 (7)	0.0435
H1	0.4720	−0.1586	0.6069	0.0687*
H2	0.2615	1.1575	0.6459	0.0486*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0318 (7)	0.0315 (3)	0.0356 (13)	0.0008 (2)	0.0192 (8)	0.0005 (3)
Rb2	0.0292 (8)	0.0366 (3)	0.0359 (14)	−0.0002 (3)	0.0159 (9)	0.0003 (4)
S1	0.0252 (18)	0.0216 (7)	0.036 (3)	−0.0011 (6)	0.016 (2)	−0.0019 (8)
S2	0.0283 (17)	0.0207 (7)	0.031 (3)	−0.0024 (6)	0.017 (2)	−0.0006 (7)
O1	0.025 (5)	0.035 (3)	0.069 (13)	0.002 (2)	0.003 (7)	−0.011 (3)
O2	0.034 (8)	0.095 (5)	0.036 (17)	−0.011 (3)	0.019 (11)	−0.016 (4)
O3	0.054 (6)	0.027 (2)	0.130 (13)	0.006 (2)	0.036 (8)	0.020 (3)
O4	0.025 (5)	0.047 (3)	0.046 (11)	0.001 (2)	0.017 (7)	−0.008 (3)
O5	0.053 (5)	0.022 (2)	0.045 (10)	−0.0065 (19)	0.023 (7)	−0.003 (2)
O6	0.039 (5)	0.035 (2)	0.024 (10)	−0.006 (2)	0.016 (7)	0.003 (2)
O7	0.036 (5)	0.022 (2)	0.054 (9)	0.0063 (18)	0.022 (6)	0.006 (2)
O8	0.030 (6)	0.049 (3)	0.059 (11)	−0.006 (2)	0.027 (7)	0.001 (3)

Geometric parameters (Å, º)

S1—O1	1.565 (7)	S2—O6	1.436 (8)
S1—O2	1.419 (11)	S2—O7	1.460 (5)
S1—O3	1.440 (6)	S2—O8	1.437 (5)
S1—O4	1.426 (5)	O1—H1	0.824
S2—O5	1.576 (7)	O5—H2	0.828
O1—S1—O2	106.3 (4)	O5—S2—O7	102.7 (4)
O1—S1—O3	101.6 (5)	O6—S2—O7	113.2 (3)
O2—S1—O3	113.6 (5)	O5—S2—O8	105.5 (4)
O1—S1—O4	108.6 (3)	O6—S2—O8	113.9 (5)
O2—S1—O4	113.1 (5)	O7—S2—O8	112.2 (3)
O3—S1—O4	112.7 (4)	S1—O1—H1	113.9
O5—S2—O6	108.2 (3)	S2—O5—H2	113.7

(JB0005) rubidium hydrogen sulfate

Crystal data

HO4S·Rb	F(000) = 688
Mr = 182.54	Dx = 2.934 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 3627 reflections
a = 14.166 (5) Å	θ = 3–26°
b = 4.5982 (9) Å	µ = 12.36 mm^−1
c = 14.326 (4) Å	T = 293 K
β = 117.68 (3)°	Block, colourless
V = 826.4 (5) Å^3	0.20 × 0.12 × 0.10 mm
Z = 8

Data collection

Bruker Kappa Apex2 diffractometer	1149 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 26.1°, θmin = 3.3°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −16→15
Tmin = 0.24, Tmax = 0.29	k = −5→5
4613 measured reflections	l = −17→17
1240 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 22.4 35.5 18.6 5.57
R[F^2 > 2σ(F^2)] = 0.044	(Δ/σ)max = 0.0000811
wR(F^2) = 0.116	Δρmax = 0.84 e Å^−3
S = 0.83	Δρmin = −1.01 e Å^−3
1149 reflections	Extinction correction: Larson (1970), Equation 22
99 parameters	Extinction coefficient: 42 (7)
2 restraints	Absolute structure: Flack (1983), 562 Friedel-pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.236 (18)
Hydrogen site location: difference Fourier map

Special details

Experimental. The crystal was placed in a Merrill-Basset HP cell using fluorinert FC70 as hydrostatic medium. The sample was subjected to a pressure of 0.5 (1) GPa.

Refinement. ### CheckCIF responses ATOM007_ALERT_1_A _atom_site_aniso_label is missing Unique label identifying the atom site. PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 20 Report - Due to a combination of low-symmetry and the restricted number of unique reflections, the refinement was limited to an isotropic refinement. PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ······.0.417 Note PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 4 Report PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 114 Note PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.600 853 Report PLAT940_ALERT_3_B F**2 Refinement with I < n * Sigma(I) only ···.. Please Check PLAT090_ALERT_3_C Poor Data / Parameter Ratio (Zmax > 18) ······.. 6.83 Note PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 1 Note PLAT918_ALERT_3_C Reflection(s) with I(obs) much smaller I(calc) . 1 Check - The high pressure cell causes shading of a significant proportion of the sphere of reflections. This means that the completeness is reduced and as such the quality of the model is lower. As a result reflections are rejected at I/sig(I) > 2 to produce stable refinements. PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ············.. 4 Report - Not correct, all atoms refined. PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check PLAT113_ALERT_2_G ADDSYM Suggests Possible Pseudo/New Space group. Abm2 Check - Structure is pseudosymmetric, refinement in Abm2 leads to overlapped anions and higher agreement factors. PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ···.. (K) 293 Check - Correct. PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 4 Note H O4 S PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 7 Note Rb - No action taken. PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT960_ALERT_3_G Number of Intensities with I < - 2*sig(I) ··· 2 Check - No action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.2906 (4)	0.6328 (2)	0.4137 (3)	0.0255 (4)*
Rb2	0.0380 (3)	0.4708 (3)	0.6621 (3)	0.0304 (4)*
Rb3	0.2073 (4)	1.0993 (3)	0.0837 (3)	0.0254 (4)*
Rb4	−0.0391 (4)	0.0670 (3)	0.3351 (3)	0.0282 (4)*
S1	0.4530 (7)	1.0437 (7)	0.3275 (6)	0.0224 (8)*
S2	0.2037 (8)	1.0268 (8)	0.5751 (7)	0.0205 (8)*
S3	0.0530 (9)	0.5303 (7)	0.1765 (7)	0.0221 (7)*
S4	−0.2125 (9)	0.4977 (7)	0.4153 (8)	0.0187 (6)*
O1	0.5427 (18)	1.259 (2)	0.3870 (17)	0.038 (3)*
O2	0.454 (2)	1.016 (3)	0.2296 (19)	0.045 (4)*
O3	0.4944 (17)	0.781 (2)	0.4016 (15)	0.031 (3)*
O4	0.3519 (19)	1.170 (2)	0.3160 (18)	0.037 (3)*
O5	0.2516 (17)	1.2562 (18)	0.6624 (15)	0.025 (2)*
O6	0.1948 (19)	1.1474 (19)	0.4774 (16)	0.022 (2)*
O7	0.2869 (18)	0.7830 (19)	0.6225 (16)	0.031 (3)*
O8	0.104 (2)	0.959 (3)	0.572 (2)	0.048 (4)*
O9	−0.0404 (19)	0.721 (3)	0.0875 (18)	0.052 (4)*
O10	0.056 (3)	0.587 (2)	0.276 (2)	0.057 (4)*
O11	0.0126 (19)	0.239 (2)	0.1352 (18)	0.040 (3)*
O12	0.1490 (18)	0.6183 (17)	0.1735 (16)	0.026 (3)*
O13	−0.2566 (19)	0.2547 (19)	0.3307 (16)	0.027 (2)*
O14	−0.201 (2)	0.369 (2)	0.5102 (19)	0.033 (3)*
O15	−0.2817 (16)	0.7356 (17)	0.3849 (14)	0.022 (2)*
O16	−0.1047 (19)	0.5744 (19)	0.4279 (17)	0.031 (3)*
H1	0.5355	1.4279	0.3984	0.0290*
H2	0.2782	1.4060	0.6531	0.0273*
H3	−0.0231	0.8894	0.1053	0.0301*
H4	−0.2594	0.1035	0.3582	0.0220*

Geometric parameters (Å, º)

S1—O1	1.52 (2)	S3—O11	1.468 (15)
S1—O2	1.417 (19)	S3—O12	1.438 (19)
S1—O3	1.534 (16)	S4—O13	1.551 (17)
S1—O4	1.48 (2)	S4—O14	1.421 (19)
S2—O5	1.533 (18)	S4—O15	1.396 (15)
S2—O6	1.456 (17)	S4—O16	1.49 (2)
S2—O7	1.538 (19)	O1—H1	0.810
S2—O8	1.43 (2)	O5—H2	0.825
S3—O9	1.61 (3)	O9—H3	0.815
S3—O10	1.43 (2)	O13—H4	0.809
O1—S1—O2	102.7 (10)	O10—S3—O11	113.1 (9)
O1—S1—O3	100.0 (12)	O9—S3—O12	105.3 (10)
O2—S1—O3	116.0 (8)	O10—S3—O12	113.0 (15)
O1—S1—O4	108.7 (10)	O11—S3—O12	116.2 (8)
O2—S1—O4	112.4 (15)	O13—S4—O14	105.9 (9)
O3—S1—O4	115.1 (7)	O13—S4—O15	110.6 (13)
O5—S2—O6	109.3 (7)	O14—S4—O15	112.1 (8)
O5—S2—O7	100.6 (12)	O13—S4—O16	106.4 (9)
O6—S2—O7	114.1 (8)	O14—S4—O16	109.1 (17)
O5—S2—O8	103.3 (10)	O15—S4—O16	112.5 (7)
O6—S2—O8	114.3 (17)	S1—O1—H1	125.9
O7—S2—O8	113.6 (9)	S2—O5—H2	120.3
O9—S3—O10	108.8 (12)	S3—O9—H3	104.7
O9—S3—O11	98.9 (13)	S4—O13—H4	109.4

(JB0006) rubidium hydrogensulfate

Crystal data

HO4S·Rb	F(000) = 344
Mr = 182.54	Dx = 3.118 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1177 reflections
a = 7.3202 (7) Å	θ = 3–25°
b = 7.765 (2) Å	µ = 13.13 mm^−1
c = 7.3247 (8) Å	T = 293 K
β = 110.938 (7)°	Block, colourless
V = 388.83 (13) Å^3	0.20 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker Kappa Apex2 diffractometer	254 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 25.3°, θmin = 3.0°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −8→8
Tmin = 0.17, Tmax = 0.27	k = −3→4
1844 measured reflections	l = −7→7
295 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.073	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 9.15 14.4 7.72 2.50
S = 0.98	(Δ/σ)max = 0.0003004
254 reflections	Δρmax = 0.50 e Å^−3
55 parameters	Δρmin = −0.35 e Å^−3
34 restraints

Special details

Experimental. The crystal was placed in a Merrill-Basset HP cell using fluorinert FC70 as hydrostatic medium. The sample was subjected to a pressure of 1.1 (1) GPa.

Refinement. ###CHECKCIF RESPONSES### Alert level A REFNR01_ALERT_3_A Ratio of reflections to parameters is < 6 for a centrosymmetric structure sine(theta)/lambda 0.6016 Proportion of unique data used 0.8610 Ratio reflections to parameters 4.6182 PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ······.0.415 Note PLAT088_ALERT_3_A Poor Data / Parameter Ratio ··················.. 5.36 Note PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.600 151 Report PLAT940_ALERT_3_B F**2 Refinement with I < n * Sigma(I) only ···.. Please Check PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 4 Note - The high pressure cell causes shading of a significant proportion of the sphere of reflections. This means that the completeness is reduced and as such the quality of the model is lower. PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 5 Report PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 34 Note - Rigid-body, and rigid-bond restraints were applied to the HSO4 moiety. PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ············.. 1 Report - Not correct, all atoms were refined. PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check - Absorption correction was calculated in Sadabs. Reported tmin and tmax from Sadabs output PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ···.. (K) 293 Check - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 80 % - A resolution cut off was applied on the basis of rapidly increasing Rint at lower d. PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT957_ALERT_1_G Calculated (ThMax) and Actual (FCF) Kmax Differ 5 Units

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.79334 (9)	0.6264 (2)	0.79821 (10)	0.0312
O3	0.8951 (9)	0.2471 (18)	0.8668 (11)	0.0355
S1	0.7470 (2)	0.1201 (7)	0.7834 (3)	0.0239
O2	0.8078 (8)	−0.0168 (19)	0.6860 (9)	0.0370
O1	0.5713 (8)	0.2162 (17)	0.6291 (11)	0.0427
O4	0.6581 (8)	0.0545 (17)	0.9192 (9)	0.0275
H11	0.6019	0.2800	0.5549	0.0670*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0246 (4)	0.042 (2)	0.0268 (6)	−0.0019 (6)	0.0092 (3)	−0.0025 (6)
O3	0.042 (3)	0.032 (9)	0.035 (3)	−0.015 (3)	0.017 (2)	−0.012 (4)
S1	0.0215 (8)	0.027 (5)	0.0246 (12)	−0.0027 (10)	0.0099 (7)	−0.0055 (12)
O2	0.050 (3)	0.025 (9)	0.045 (4)	−0.005 (4)	0.028 (3)	−0.010 (5)
O1	0.029 (3)	0.053 (12)	0.047 (3)	0.007 (3)	0.015 (2)	0.018 (4)
O4	0.045 (3)	0.011 (12)	0.034 (3)	−0.009 (3)	0.022 (2)	−0.008 (3)

Geometric parameters (Å, º)

O3—S1	1.431 (11)	S1—O4	1.461 (7)
S1—O2	1.437 (12)	O1—H11	0.824
S1—O1	1.565 (8)
O3—S1—O2	113.6 (5)	O2—S1—O4	111.9 (7)
O3—S1—O1	106.4 (7)	O1—S1—O4	102.0 (4)
O2—S1—O1	108.3 (5)	S1—O1—H11	114.6
O3—S1—O4	113.8 (5)

(JB0008) Rubidium hydrogensulfate

Crystal data

HO4S·Rb	F(000) = 688
Mr = 182.54	Dx = 2.889 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2854 reflections
a = 14.3405 (7) Å	θ = 3–25°
b = 4.6150 (2) Å	µ = 12.16 mm^−1
c = 14.3723 (12) Å	T = 293 K
β = 118.054 (4)°	Block, colourless
V = 839.42 (9) Å^3	0.20 × 0.15 × 0.10 mm
Z = 8

Data collection

Unknown diffractometer	673 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.046
ω/2θ scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −16→16
Tmin = 0.09, Tmax = 0.30	k = −5→5
4260 measured reflections	l = −11→11
781 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.056	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 9.71 14.5 6.69 1.68
wR(F^2) = 0.157	(Δ/σ)max = 0.0001528
S = 0.99	Δρmax = 1.03 e Å^−3
780 reflections	Δρmin = −0.73 e Å^−3
110 parameters	Extinction correction: Larson (1970), Equation 22
20 restraints	Extinction coefficient: 14 (3)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The crystal was placed in a Merrill-Basset HP cell using fluorinert FC70 as hydrostatic medium. The sample was subjected to a pressure of 0.2 (1) GPa.

Refinement. ### CheckCIF responses PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ······. 0.524 Note PLAT088_ALERT_3_B Poor Data / Parameter Ratio ··················.. 7.10 Note PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.595 492 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 2 Note PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 3 Report - The high pressure cell causes shading of a significant proportion of the sphere of reflections. This means that the completeness is reduced and as such the quality of the model is lower. As a result reflections are rejected at I/sig(I) > 2 to produce stable refinements. PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. S1 Check - Two oxygen atom sites on the HS(1)O4 moiety are enlarged, as discussed in the text this is due to the presence of two disorder sites enclosed within the O ADPs. PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 10 Report PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 20 Note - Rigid-body, and rigid-bond restraits applied to the HSO4 moieties. PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ············.. 2 Report - Not correct, all atoms refined. PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check And 3 other PLAT112 Alerts - Structure is pseudosymmetric, refinement in Abm2 leads to overlapped anions and higher agreement factors. PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ···.. (K) 293 Check - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 68 % - Resolution cut off applied on the basis of rapidly increasing Rint values PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT958_ALERT_1_G Calculated (ThMax) and Actual (FCF) Lmax Differ 6 Units PLAT960_ALERT_3_G Number of Intensities with I < - 2*sig(I) ··· 1 Check - No action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.70777 (9)	0.6398 (2)	0.58454 (14)	0.0326
Rb2	0.46120 (10)	0.7021 (3)	0.83642 (15)	0.0357
S1	0.5491 (3)	0.2144 (6)	0.6739 (4)	0.0295
S2	0.2063 (2)	0.7605 (6)	0.5788 (3)	0.0265
O1	0.4584 (7)	0.012 (2)	0.6002 (11)	0.0473
O2	0.5521 (9)	0.202 (3)	0.7746 (15)	0.0609
O3	0.5153 (9)	0.489 (2)	0.6218 (13)	0.0665
O4	0.6463 (7)	0.117 (2)	0.6768 (11)	0.0413
O5	0.2579 (7)	0.9962 (18)	0.6677 (9)	0.0358
O6	0.1979 (7)	0.8856 (19)	0.4832 (11)	0.0364
O7	0.2813 (7)	0.5250 (17)	0.6193 (10)	0.0386
O8	0.1062 (7)	0.692 (2)	0.5744 (11)	0.0425
H1	0.4723	−0.1615	0.6089	0.0687*
H2	0.2615	1.1587	0.6461	0.0486*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0343 (8)	0.0301 (9)	0.0325 (16)	0.0006 (5)	0.0150 (9)	0.0010 (5)
Rb2	0.0314 (8)	0.0363 (9)	0.0355 (17)	0.0002 (5)	0.0125 (9)	0.0010 (6)
S1	0.0362 (18)	0.0221 (17)	0.034 (3)	−0.0019 (12)	0.019 (2)	−0.0033 (12)
S2	0.0318 (17)	0.0171 (17)	0.028 (4)	−0.0021 (10)	0.012 (2)	−0.0001 (11)
O1	0.035 (4)	0.040 (5)	0.049 (8)	−0.002 (3)	0.005 (5)	−0.010 (4)
O2	0.057 (6)	0.096 (9)	0.038 (6)	−0.006 (6)	0.029 (7)	−0.016 (5)
O3	0.064 (6)	0.031 (4)	0.096 (11)	0.007 (4)	0.031 (8)	0.020 (4)
O4	0.034 (4)	0.051 (6)	0.041 (10)	−0.001 (3)	0.019 (5)	−0.008 (5)
O5	0.053 (5)	0.025 (4)	0.021 (6)	−0.004 (3)	0.011 (5)	0.000 (3)
O6	0.040 (5)	0.044 (5)	0.021 (6)	0.001 (4)	0.011 (5)	0.001 (3)
O7	0.046 (4)	0.022 (4)	0.047 (9)	0.007 (3)	0.021 (6)	0.009 (3)
O8	0.033 (4)	0.050 (6)	0.042 (11)	−0.005 (3)	0.015 (5)	0.003 (4)

Geometric parameters (Å, º)

S1—O1	1.547 (10)	S2—O6	1.443 (14)
S1—O2	1.429 (19)	S2—O7	1.445 (9)
S1—O3	1.435 (10)	S2—O8	1.441 (10)
S1—O4	1.445 (10)	O1—H1	0.820
S2—O5	1.573 (10)	O5—H2	0.822
O1—S1—O2	106.5 (8)	O5—S2—O7	102.5 (6)
O1—S1—O3	102.0 (7)	O6—S2—O7	113.5 (7)
O2—S1—O3	113.8 (9)	O5—S2—O8	105.5 (7)
O1—S1—O4	108.8 (6)	O6—S2—O8	114.2 (7)
O2—S1—O4	112.9 (8)	O7—S2—O8	112.9 (6)
O3—S1—O4	112.0 (7)	S1—O1—H1	114.8
O5—S2—O6	107.1 (6)	S2—O5—H2	114.4

(jb0009) rubidium hydrogensulfate

Crystal data

HO4S·Rb	F(000) = 688
Mr = 182.54	Dx = 2.914 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2455 reflections
a = 14.334 (5) Å	θ = 3–25°
b = 4.6197 (17) Å	µ = 12.27 mm^−1
c = 14.361 (9) Å	T = 293 K
β = 118.94 (3)°	Block, colourless
V = 832.2 (7) Å^3	0.20 × 0.15 × 0.10 mm
Z = 8

Data collection

Bruker Kappa Apex2 diffractometer	658 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.048
ω scans	θmax = 24.7°, θmin = 3.3°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −16→16
Tmin = 0.08, Tmax = 0.29	k = −5→5
4115 measured reflections	l = −11→11
754 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.069	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 7.24 9.98 4.57 0.838
wR(F^2) = 0.139	(Δ/σ)max = 0.0000913
S = 1.04	Δρmax = 1.27 e Å^−3
658 reflections	Δρmin = −0.99 e Å^−3
110 parameters	Extinction correction: Larson (1970), Equation 22
68 restraints	Extinction coefficient: 9 (2)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. The crystal was placed in a Merrill-Basset HP cell using fluorinert FC70 as hydrostatic medium. The sample was subjected to a pressure of 0.4 (1) GPa.

Refinement. ### CheckCIF responses Alert level A REFNR01_ALERT_3_A Ratio of reflections to parameters is < 6 for a centrosymmetric structure sine(theta)/lambda 0.5881 Proportion of unique data used 0.8727 Ratio reflections to parameters 5.9818 PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ············ 18.53 Degree PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ······. 0.592 Note PLAT088_ALERT_3_B Poor Data / Parameter Ratio ··················.. 6.85 Note PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.588 475 Report PLAT940_ALERT_3_B F**2 Refinement with I < n * Sigma(I) only ···.. Please Check THETM01_ALERT_3_C The value of sine(theta_max)/wavelength is less than 0.590 Calculated sin(theta_max)/wavelength = 0.5881 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 2 Note PLAT918_ALERT_3_C Reflection(s) with I(obs) much smaller I(calc) . 4 Check PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 3 Report PLAT960_ALERT_3_G Number of Intensities with I < - 2*sig(I) ··· 2 Check - The high pressure cell causes shading of a significant proportion of the sphere of reflections. This means that the completeness is reduced and as such the quality of the model is lower. As a result data to parameter ratios are very much lowered requiring numerous restraints to ensure stable refinements. PLAT939_ALERT_3_A Large Value of Not (SHELXL) Weight Optimized S. 1064.21 - No significant deviations from the normal probability plot are found for this dataset. Outliers due to shading are typically removed by the I/sig(I)>2 reflection condition. PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···..S1 Check - Two oxygen atom sites on the HS(1)O4 moiety are enlarged, as discussed in the text this is due to the presence of two disorder sites enclosed within the O ADPs. PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 10 Report PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 28 Note - Rigid-body, and rigid-bond restraints were applied to the HSO4 moiety. PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ············.. 2 Report - Not correct, all atoms were refined to confirm their identity. PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check - SADABS absorption tmin and tmax reported. PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· 2 Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check - Structure is pseudosymmetric, refinement in Abm2 leads to overlapped anions and higher agreement factors. PLAT199_ALERT_1_G Reported _cell_measurement_temperature ···.. (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ···.. (K) 293 Check - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 75 % - A resolution cut off was applied on the basis of rapidly increasing Rint at lower d. PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT958_ALERT_1_G Calculated (ThMax) and Actual (FCF) Lmax Differ 5 Units - No action taken

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.70808 (13)	0.6355 (3)	0.58474 (18)	0.0315
Rb2	0.46156 (14)	0.7021 (3)	0.8368 (2)	0.0358
S1	0.5486 (3)	0.2130 (8)	0.6733 (5)	0.0297
S2	0.2072 (3)	0.7629 (7)	0.5789 (5)	0.0279
O1	0.4565 (9)	0.009 (3)	0.5980 (13)	0.0496
O2	0.5516 (13)	0.206 (3)	0.7752 (19)	0.0612
O3	0.5140 (11)	0.494 (3)	0.6189 (15)	0.0666
O4	0.6464 (9)	0.113 (2)	0.6775 (13)	0.0403
O5	0.2574 (9)	0.998 (2)	0.6686 (11)	0.0368
O6	0.1968 (9)	0.891 (2)	0.4833 (13)	0.0358
O7	0.2829 (9)	0.527 (2)	0.6189 (11)	0.0358
O8	0.1054 (10)	0.690 (2)	0.5740 (14)	0.0422
H1	0.4704	−0.1647	0.6067	0.0687*
H2	0.2610	1.1606	0.6470	0.0486*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0307 (9)	0.0301 (11)	0.0312 (19)	0.0007 (6)	0.0129 (10)	0.0018 (6)
Rb2	0.0283 (10)	0.0350 (11)	0.039 (2)	0.0000 (6)	0.0121 (11)	0.0005 (7)
S1	0.030 (2)	0.024 (2)	0.032 (4)	−0.0035 (15)	0.013 (3)	−0.0047 (16)
S2	0.025 (2)	0.021 (2)	0.030 (4)	−0.0015 (14)	0.008 (3)	0.0031 (15)
O1	0.035 (5)	0.040 (6)	0.058 (11)	−0.007 (4)	0.009 (7)	−0.022 (6)
O2	0.054 (8)	0.095 (10)	0.038 (8)	−0.007 (7)	0.024 (8)	−0.016 (6)
O3	0.056 (8)	0.033 (5)	0.098 (13)	0.007 (4)	0.028 (10)	0.022 (6)
O4	0.033 (4)	0.039 (6)	0.046 (13)	0.000 (4)	0.018 (7)	−0.008 (5)
O5	0.048 (6)	0.011 (5)	0.038 (7)	−0.001 (4)	0.010 (6)	0.004 (3)
O6	0.031 (6)	0.036 (6)	0.036 (7)	0.001 (4)	0.012 (6)	0.010 (4)
O7	0.040 (5)	0.013 (5)	0.044 (10)	0.001 (3)	0.012 (7)	0.005 (4)
O8	0.040 (5)	0.036 (7)	0.058 (13)	−0.010 (4)	0.029 (7)	−0.007 (5)

Geometric parameters (Å, º)

S1—O1	1.556 (12)	S2—O6	1.436 (16)
S1—O2	1.44 (2)	S2—O7	1.445 (11)
S1—O3	1.471 (13)	S2—O8	1.464 (13)
S1—O4	1.450 (13)	O1—H1	0.821
S2—O5	1.569 (13)	O5—H2	0.823
O1—S1—O2	106.8 (9)	O5—S2—O7	103.7 (7)
O1—S1—O3	102.2 (9)	O6—S2—O7	113.7 (9)
O2—S1—O3	113.3 (10)	O5—S2—O8	104.4 (8)
O1—S1—O4	108.3 (7)	O6—S2—O8	114.1 (8)
O2—S1—O4	113.4 (10)	O7—S2—O8	112.7 (7)
O3—S1—O4	112.0 (9)	S1—O1—H1	115.1
O5—S2—O6	107.0 (8)	S2—O5—H2	114.2