Chapter 2

Phase Transitions in Rubidium Hydrogen Sulfate: Crystal Structures at 293K and

200K

30

2.1 Introduction
The mechanism of the ferroelectric transition in NH4HSO4 was derived based on the disorder to order transition with the pseudo orthorhombic space group B2 1/a at room 31

temperature changing over to a non centrosymmetric space group Ba or B1 [78]. It was dreported that in the ferroelectric phase the sulfate groups get ordered to result in an asymmetry with respect to the center of inversion [78]. In this analysis the position of the hydrogen atom could not be determined though it was conjectured that the N-HO hydrogen bond could be responsible for the dielectric behavior of this crystal [83]. Since these studies are fairly old and hence less reliable due to disorder in the sulfate groups it is worthwhile to look into RbHSO 4, a member belonging to the same family. Preliminary studies as already mentioned in the foreword point out that the rubidium compound also exhibits a ferroelectric transition below -15C [83] despite the absence N-HO hydrogen bond. Since the heat of transition as determined by calorimetry is less than 25cal/mole [83], the disorder-order transition in the sulfate moiety is unlikely. NMR studies showed no sudden change in the proton second moment as the crystal becomes ferroelectric implying that the proton does not play an important role in the transition mechanism [88] unlike in the isomorphous NH4HSO4. Further NMR experiments showed a gradual decrease in the proton second moment with temperature, attributed to the gradual tunneling of the protons below the transition. This is consistent with the splitting of the proton 3100cm-1 band observed in IR experiments [85]. However, room temperature crystal structure determined by X-ray and neutron diffraction [85] assumes disorder in one sulfate and ordering of the hydrogen atoms in the paraelectric phase. In this study, the hydrogen atoms were located by neutron diffraction and the geometry of the O-HO hydrogen bonds were analyzed. Raman spectra recorded over the full temperature range form 6K to 480K indicate that there is no soft mode and the phase transition is of order-disorder type [125]. The spectra also confirm the structure proposed for the low temperature phase and the existence of the pseudo-orthorhombic symmetry. Subsequent reports involved the treatment of the two independent sulfate ions; one sulfate moiety exhibiting disorder while the other was ordered [86]. The mechanism of the ferroelectric phase transition was explained to be driven by the disorder in the sulfate moeities. The hydrogen atom attached to the disordered sulfate has larger thermal motion than the one connected to the sulfate moiety with no disorder. Hence it was concluded that the paraelectric phase indeed had disordered sulfate groups.

32

The studies related to RbHSO4 raise several questions particularly regarding the disorder-order transitions, the possible participation of the hydrogen atoms in the ferroelectric phase and more specifically the ferroelectric space group. It is of interest to point out that the crystal structure of the low temperature ferroelectric phase has not been determined by X-ray diffraction technique so far. It has been argued that the presence of strong orthorhombic pseudo symmetry implies the existence of a high temperature disordered phase [85]. It was also suggested that this high temperature phase would be paraelectric with the possibility of the migration of protons between two equivalent positions. The room temperature structure (293K) has been redetermined in an effort to resolve the features associated with disorder of the sulfate moiety. The structure of the ferroelectric phase (200K) has also been determined using the same single crystal. Preliminary high temperature powder X-ray diffraction studies have been performed to gain insights into the existence of a possible high temperature phase.

2.2 Experimental
Single crystals of RbHSO4 were grown by slow evaporation at 313K (40C) from an aqueous solution containing equimolar amounts of Rb2SO4 and H2SO4. The evaporation rate was slowed down considerably by sealing the 5ml beakers containing the solution in a thermostat. The crystals thus grown were examined under polarized light and found to be transparent and colorless. The composition of the crystals was confirmed by preliminary powder X-ray diffraction studies and by EDAX measurements. The crystals showed a sharp melting point at 207.7C (480.7K). Subsequent DTA measurements indicated no major change from 298K to the melting point. The selected crystal for the single crystal X-ray diffraction measured 0.53x0.3x0.2mm and the data were collected on a BRUKER AXS SMART APEX CCD [126] diffractometer.

2.3 Structure Determination and Refinement

2.3.1 At room temperature (293K) 33

The monoclinic symmetry, space group and the unit cell parameters were determined from the diffraction intensities measured using MoK radiation. The space group P21/n was selected to be the ideal choice based on the statistical evaluation of all 16,998 measurements. An examination of the distribution of intensities of equivalent reflections indicates the presence of the pseudo orthorhombic symmetry. The details of the data collection are listed in table 2.1. The data was collected in four batches covering a complete sphere of reciprocal space with each batch at different angles (=0, 90, 180, 270) and each frame covering 0.3 degrees in at 10 seconds exposure time. The crystal structure was solved by direct methods using the SHELXS97 [32] module in the WinGX [34] suite of software. The positional coordinates of rubidium and sulfur atoms obtained from the initial Fourier map were refined and the subsequent difference Fourier synthesis revealed the positions of all the remaining oxygen atoms in the structure. A careful examination of the thermal parameters, particularly those associated with the oxygen atoms indicate no unusual features relating to disorder. The hydrogen atoms were fixed corresponding to the value obtained from averaging neutron diffraction data for the O-H bond by restricting the O to H distance to 0.97 [127]. The details of the refinement are given in table 1. It must be mentioned that an empirical absorption correction was applied using the WinGX suite. The final residual density of 1.598 e-3 is clustered around the Rb atoms. There is no disorder in the sulfate moieties in the structure. The atomic coordinates along with the equivalent thermal parameters are listed in table 2.2. The coordinates were transformed to the P21/c cell as reported earlier [85] and refinements were repeated to verify the absence of disorder.

Table 2.1

34

Crystal data, measurement and structure refinement parameters for RbHSO4 Temperature Crystal habit Crystal color Crystal size(mm)* Crystal system Space group Cell dimensions (/) a b c 3 Volume ( ) Formula weight Density (g/cm )
3

293K Block Colorless 0.53x0.3x0.2 Monoclinic P21/n 14.3503(14) 4.6187(4) 14.3933(14) 118.03(1) 842.05(5) 182.5 2.88

120K Block Colorless 0.53x0.3x0.2 Monoclinic Pn 14.2667(12) 4.5878(4) 14.2924(12) 118.01(1) 825.94(12) 182.5 2.93 8 687.8

Z 8 F (000) 687.8 *The same crystal is used for both the data sets

Equipment (Mo K(graphite monochromator))() Scan mode range () Recording reciprocal space

Data collection BRUKER AXS SMART APEX CCD 0.7107 1.65-27.76 -18h18 -6k6 -18l18 16998 1895 12.13 SADABS SAINT

BRUKER AXS SMART APEX CCD 0.7107 2.66-26.57 -17h17 -5k5 -17l17 16489 3428 12.13 SADABS SAINT

Number of measured reflections Number of independent reflections (mm-1) Absorption correction Data reduction

Number of refined

Refinement 110 35

218

parameters Refinement method R [I>2I]/R[all data] wR [I>2I]/R[all data] g. o. f. Max/min e-3 Full matrix least squares 0.052/0.061 0.144/0.147 1.175 1.598/-1.811 Table 2.2 Fractional atomic coordinates and equivalent thermal parameters (Ueq) at 293K Ueq= -(22(U11(h.a*))2 + (U22(k.b*))2 + (U33(l.c*))2 + 2.U12.h.k.a*.b* + 2.U13.h.l.a*.c* + 2.U23.k.l.b*.c*) Atom x y z Ueq()2 Rb(1) 0.2925(5) 0.1388(1) 0.4154(1) 0.0238(2) Rb(2) -0.0388(1) -0.2981(2) 0.3363(1) 0.0257(2) S(1) 0.2068(1) -0.2615(3) 0.5793(1) 0.0161(3) S(2) 0.0489(1) 0.2155(4) 0.1734(1) 0.0174(2) O(1) 0.2578(4) -0.4985(10) 0.6678(3) 0.0268(11) O(2) 0.2814(4) -0.0230(10) 0.6175(3) 0.0262(10) O(3) 0.1986(4) -0.3845(11) 0.4831(3) 0.0277(11) O(4) 0.1053(4) -0.1929(12) 0.5730(3) 0.0322(12) O(5) 0.1458(4) 0.1158(12) 0.1772(4) 0.0318(3) O(6) 0.0171(6) 0.4932(13) 0.1213(6) 0.0615(11) O(7) 0.0522(5) 0.2008(17) 0.2747(4) 0.0516(17) O(8) -0.0431(4) -0.0151(12) 0.0974(4) 0.0398(14) H(1)# 0.2228 0.5024 0.7113 0.05 H(8)# 0.9182 0.1066 0.0296 0.05 # hydrogen atom coordinates and isotropic thermal parameters are fixed during refinements 2.3.2 At 200K The crystal used for the room temperature data was cooled to 200K at a ramp rate of 60K/hour and left to stabilize for 60 minutes (about 50K below Tc; reported Tc= 265K [83]). An Oxford cryosystem nitrogen open-flow cryostat was used for this. The temperature of 200K was maintained through out the data collection within 0.2K. The changes observed in the cell dimensions were as expected with a shrinkage in volume of 16.953. The space group is clearly determined to be non-centrosymmetric Pn (|E 2-1| 36 Full matrix least squares 0.078/0.081 0.209/0.208 1.035 1.573/-2.631

=0.766 with probability of being centrosymmetric 46.86% [128]). The corresponding values for the room temperature structure indeed point out to the centrosymmetric structure (|E2-1|=0.876 with probability of being centrosymmetric 80.05%). The absence of the 21 screw axis is indicated by the presence of a well-defined 050 reflection [I(050)=150.7(12)] (table 2.3). The data collection strategy was identical to that at room temperature and the details are listed in table 2.1. The structure was solved by direct methods using SHELXS97 [32] module in the WINGX suite [34]. As before, the heavy atoms were initially located and the difference Fourier synthesis gave the positions of all oxygen atoms in the structure. Once again, there was no disorder found on the sulfate moiety. The hydrogen atoms were fixed by restricting the O-H distance to 0.97 corresponding to the value obtained from averaging neutron diffraction data for the O-H bond [127]. The final residual density of 1.573 e -3 is clustered around the Rb atoms. The atomic coordinates along with the equivalent thermal parameters are listed in table 2.4. Table 2.3 Comparison of (0k0) k odd intensities for the paraelectric phase (P21/n) and the ferroelectric (Pn) Phase 0k0 010 030 050 Intensity(P21/n) 0.65(15) 0.29(5) -0.02(71) Intensity(Pn) 5.72(7) 3.00(3) 150.71(67)

Table 2.4 Fractional atomic coordinates and equivalent thermal parameters (Ueq) at 200K Atom x y z Ueq()2 Rb(1A) 0.4188(1) -0.1383(2) 0.4518(1) 0.0176(3) Rb(2A) 0.0898(1) 0.4267(3) 0.3730(1) 0.0174(3) Rb(1B) 0.3362(1) -0.5914(3) 0.1226(1) 0.0170(7) Rb(2B) 0.6675(1) 0.9789(1) 0.2008(1) 0.0187(3) S(1A) 0.3344(3) 0.4674(8) 0.6154(3) 0.0145(7) S(1B) -0.0792(3) 0.9957(8) 0.4571(3) 0.0135(6) S(2A) 0.1783(3) -0.0260(8) 0.2120(3) 0.0175(8) S(2B) 0.5805(3) -0.5445(8) 0.3663(3) 0.0157(7) 37

O(1A) 0.3891(9) 0.2338(22) 0.7073(8) 0.0234(22) O(2A) 0.4076(8) 0.7099(23) 0.6518(8) 0.0233(21) O(3A) 0.3261(9) 0.3399(24) 0.5198(9) 0.0195(25) O(4A) 0.2320(9) 0.5327(28) 0.6108(9) 0.0232(24) O(5A) 0.2756(10) -0.1108(26) 0.2143(10) 0.0279(23) O(6A) 0.1520(10) 0.2731(22) 0.1823(11) 0.0424(34) O(7A) 0.1791(11) -0.0898(28) 0.3123(10) 0.0323(30) O(8A) 0.0857(8) -0.2114(27) 0.1259(9) 0.0293(24) O(1B) -0.1261(7) 1.2383(21) 0.3701(7) 0.0183(19) O(2B) -0.1572(7) 0.7608(22) 0.4172(8) 0.0197(20) O(3B) -0.0686(11) 1.1170(24) 0.5558(9) 0.0252(28) O(4B) 0.0210(9) 0.9144(26) 0.4654(9) 0.0238(25) O(5B) 0.4829(9) -0.6682(25) 0.3605(9) 0.0208(18) O(6B) 0.6145(8) -0.2876(24) 0.4356(8) 0.0280(23) O(7B) 0.5756(10) -0.4970(31) 0.2648(10) 0.0311(29) O(8B) 0.6737(8) -0.7680(25) 0.4283(10) 0.0208(25) # H(1A) 0.3457 0.2050 0.7423 0.05 H(1B)# 0.9098 0.2313 0.3263 0.05 H(8A)# 0.0412 0.9119 0.0664 0.05 # H(8B) 0.6574 0.1190 0.4772 0.05 # hydrogen atom coordinates and isotropic thermal parameters fixed during refinements 2.3.3 Structure at elevated temperature The crystals of RbHSO4 were ground and the powder specimen was mounted in a high temperature furnace on a STOE STADI/P diffractometer in the Debye-Scherrer mode. The sample was mounted in a Lindemann capillary of dimension 0.3mm and rotated during data collection. Data were collected at room temperature and then in steps of 10 up to 488K. Figure 2.1 compares the room temperature powder X-ray diffraction pattern with that collected at 488K.

38

Figure 2.1: Powder X-ray diffraction pattern of RbHSO4 at 298K and 463K

The appearance of the new peaks starts at 393K. It has been suggested that the pseudo orthorhombic phase would revert to a fully orthorhombic phase at higher temperature [85]. However, an examination of the patterns indicates the contrary with the appearance of extra peaks at 2=25.47 (d=3.47) and another at 2=26.38 (d=3.376). There is also an indication of new peaks in the region of 30 in 2 , which show a deviation from orthorhombic pseudo symmetry accompanying the phase transition. Further, the powder pattern reverts back to the monoclinic phase at 293K. A careful analysis and characterization of the high temperature phase will reveal the finer details of the reversible transition.

2.4 Results and Discussion

39

The bond lengths, bond angles and bond valence sum are given in tables 2.5 and 2.6 [129,130] for the room temperature and 200K structures respectively. Figures 2.2 and 2.3 depict the ORTEP [131] plots with 50% probability ellipsoids. Figures 2.4 and 2.5 give the corresponding packing diagrams [131] for both the paraelectric and ferroelectric phases. Table 2.5 Selected Bond lengths (), bond angles ( ) and bond valence sum at 293K Rb(1)-O(3) Rb(1)-O(5) Rb(1)-O(2) Rb(1)-O(7) Rb(1)-O(5) Rb(1)-O(8) Rb(1)-O(3) Rb(1)-O(6) Rb(1)-O(6) Rb(1)-O(5) valence sum Rb(2)-O(1) Rb(2)-O(3) Rb(2)-O(4) Rb(2)-O(7) Rb(2)-O(4) Rb(2)-O(1) Rb(2)-O(2) Rb(2)-O(4) Rb(2)-O(7) valence sum 3.134(6) 3.068(5) 3.075(6) 3.079(6) 3.077(5) 3.033(5) 2.972(6) 3.095(9) 3.252(6) 3.077(5) 1.09 3.255(6) 3.076(5) 3.082(5) 2.983(8) 3.051(6) 3.255(6) 3.104(4) 2.988(6) 2.991(8) 1.00 S(1)-O(1) S(1)-O(2) S(1)-O(3) S(1)-O(4) valence sum S(2)-O(5) S(2)-O(6) S(2)-O(7) S(2)-O(8) valence sum O(1)-S(1)-O(2) O(1)-S(1)-O(3) O(1)-S(1)-O(4) O(2)-S(1)-O(3) O(2)-S(1)-O(4) O(3)-S(1)-O(4) O(5)-S(2)-O(8) O(5)-S(2)-O(6) O(5)-S(2)-O(7) O(7)-S(2)-O(8) O(6)-S(2)-O(7) O(6)-S(2)-O(8) 1.576(5) 1.450(5) 1.447(6) 1.453(6) 5.94 1.440(7) 1.446(7) 1.438(7) 1.567(5) 6.09 104.0(3) 107.4(3) 105.8(3) 112.1(3) 113.3(3) 113.3(3) 108.7(3) 111.6(5) 112.1(4) 107.2(4) 114.7(5) 101.8(4)

40

Figure 2.2: ORTEP of RbHSO4 at 293K

Figure 2.3: ORTEP of RbHSO4 at 200K 41

Table 2.6 Bond lengths (), bond angles ( ) and bond valence sum at 200K Rb(1A)-O(5A) Rb(1A)-O(7A) Rb(1A)-O(6B) Rb(1A)-O(3A) Rb(1A)-O(5B) Rb(1A)-O(8A) Rb(1A)-O(3A) Rb(1A)-O(5B) Rb(1A)-O(2A) valence sum Rb(1B)-O(3B) Rb(1B)-O(3B) Rb(1B)-O(2B) Rb(1B)-O(6B) Rb(1B)-O(8B) Rb(1B)-O(6A) Rb(1B)-O(5A) Rb(1B)-O(5B) Rb(1B)-O(7B) Rb(1B)-O(5A) valence sum 3.028(12) 3.049(12) 2.987(13) 2.954(13) 3.090(13) 2.981(10) 3.103(13) 2.883(13) 3.017(13) 1.21 3.125(13) 2.946(14) 3.078(12) 3.086(8) 3.112(10) 3.184(17) 2.901(14) 3.067(11) 3.070(11) 3.036(14) 1.19 Rb(2A)O(4B) Rb(2A)-O(7A) Rb(2A)-O(3A) Rb(2A)-O(4A) Rb(2A)-O(4B) Rb(2A)-O(7A) Rb(2A)-O(1B) Rb(2A)-O(1A) Rb(2A)-O(2A) valence sum Rb(2B)-O(4B) Rb(2B)-O(3B) Rb(2B)-O(2B) Rb(2B)-O(1A) Rb(2B)-O(7B) Rb(2B)-O(7B) Rb(2B)-O(4A) Rb(2B)-O(4A) Rb(2B)-O(4A) valence sum 2.986(13) 3.007(15) 3.046(10) 3.065(11) 3.074(13) 2.886(15) 3.177(11) 3.139(9) 3.071(8) 1.10 3.054(11) 3.049(12) 3.044(8) 3.269(13) 2.917(15) 3.069(15) 3.021(13) 2.941(14) 3.094(8) 1.10 S(1A)-O(1A) S(1A)-O(2A) S(1A)-O(3A) S(1A)-O(4A) valence sum S(1B)-O(4B) S(1B)-O(2B) S(1B)-O(3B) S(1B)-O(1B) valence sum S(2A)-O(5A) S(2A)-O(6A) S(2A)-O(7A) S(2A)-O(8A) valence sum S(2B)-O(5B) S(2B)-O(6B) S(2B)-O(7B) S(2B)-O(8B) valence sum 1.586(10) 1.441(14) 1.436(14) 1.461(10) 5.97 1.428(14) 1.462(10) 1.461(14) 1.567(10) 5.97 1.426(16) 1.434(11) 1.457(16) 1.568(10) 6.11 1.468(14) 1.465(12) 1.433(15) 1.581(11) 5.86

O(3A)-S(1A)-O(4A) O(3A)-S(1A)-O(1A) O(3A)-S(1A)-O(2A) O(2A)-S(1A)-O(4A) O(1A)-S(1A)-O(2A) O(1A)-S(1A)-O(4A) O(4B)-S(1B)-O(2B) O(4B)-S(1B)-O(3B) O(4B)-S(1B)-O(1B) O(2B)-S(1B)-O(3B) O(2B)-S(1B)-O(1B) O(3B)-S(1B)-O(1B)

113.9(8) 107.5(6) 112.1(7) 113.3(7) 103.4(6) 105.6(7) 112.9(8) 112.0(8) 106.9(7) 112.0(8) 104.5(6) 108.06)

O(7A)-S(2A)-O(6A) O(7A)-S(2A)-O(8A) O(7A)-S(2A)-O(5A) O(5A)-S(2A)-O(8A) O(6A)-S(2A)-O(8A) O(5A)-S(2A)-O(6A) O(6B)-S(2B)-O(5B) O(6B)-S(2B)-O(8B) O(6B)-S(2B)-O(7B) O(5B)-S(2B)-O(8B) O(5B)-S(2B)-O(7B) O(8B)-S(2B)-O(7B)

111.4(8) 106.2(8) 111.2(9) 108.8(8) 106.3(8) 112.6(9) 110.6(7) 102.3(6) 114.2(7) 107.6(6) 113.8(8) 107.4(8)

42

Figure 2.4: Packing diagram of the paraelectric phase of RbHSO4 at 293K along b axis

Figure2.5: Packing diagram of the ferroelectric phase of RbHSO4 at 200K along b axis 43

The main feature of the room temperature structure as determined in this study is the absence of disorder in either of the sulfate moeities. The suggestion that the disorder in the sulfate moiety is the major cause for paraelectric to ferroelectric transition appears to be erroneous [86]. The bond valence sum for the sulfur atoms at room temperature do not indicate any significant distortion of the sulfate tetrahedra. The bond lengths associated with the sulfate group at room temperature do not show any significant deviation or distortion. However, the lengthening of the bonds S(1)-O(1) and S(2)-O(8) suggest the presence of the proton on these oxygen atoms. The cell dimensions show the expected contraction on cooling to 200K and the crystal retains the monoclinic symmetry. The sulfate moieties now display variable bond lengths in the range 1.428 to 1.468 (table2.6). The longer bonds [S(1B)-O(1B)=1.567;S(1A)O(1A)=1.586(10); S(2A)-O(8A)=1.568(10); S(2B)-O(2B)=1.581(11)] are characteristic of the presence of the hydrogen atom. Bond valence [130] features also suggest significant deviation and corresponding distortion in the sulfate tetrahedra. It might be argued that these deviations in bond lengths together with significant changes in the BVS around sulfur are the cause for the phase transition. The bond valence sum on Rb atoms suggest that the Rb atoms are more compact in the ferroelectric phase as compared to the room temperature phase. Indeed, the coordination around one of the Rb(1) in the room temperature phase changes from 10 to 9 (figures 2.6 and 2.7). There are no hydrogen bonds observed in both the phases.

44

Figure 2.6: Coordination around Rb(1) atom at 293K

Figure 2.7: Coordination around Rb(1) atom at 200K 45

2.5 Conclusions
The determination of the single crystal structures of RbHSO 4 at 293K and 200K has demonstrated the nature of distortion responsible for the phase transition from the paraelectric to the ferroelectric phase. We also found the absence of disorder in the positional coordinates of individual atoms in the structure at room temperature. The order-disorder mechanism proposed for NH4HSO4 apparently is not applicable to RbHSO4. The sulfate tetrahedra are nearly ideal in the paraelectric phase with the extension of one S-O bond in the direction of the hydrogen bond. The corresponding sulfate tetrahedra in the ferroelectric phase show considerable distortions from the ideal geometry. There is a change in the Rb coordination in the low temperature phase.

46