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The MxHy(AO4)z acid salts (M = Cs, Rb, K, Na, Li, NH4; A = S, Se, As, P) exhibit ferroelectric properties. The solid acids have low conductivity values and are of inter­est with regard to their thermal properties and proton conductivity. The crystal structure of caesium di­hydrogen orthophosphate mono­hydrogen orthophosphate dihydrate, Cs3(H1.5PO4)2·2H2O, has been solved. The com­pound crystallizes in the space group Pbca and forms a structure with strong hydrogen bonds connecting phosphate tetra­hedra that agrees well with the IR spectra. The dehydration of Cs3(H1.5PO4)2·2H2O with the loss of two water mol­ecules occurs at 348–433 K. Anhydrous Cs3(H1.5PO4)2 is stable up to 548 K and is then converted completely into caesium pyrophosphate (Cs4P2O7) and CsPO3. Anhydrous Cs3(H1.5PO4)2 crystallizes in the monoclinic C2 space group, with the unit-cell parameters a = 11.1693 (4), b = 6.4682 (2), c = 7.7442 (3) Å and β = 71.822 (2)°. The conductivities of both compounds have been measured. In contrast to crystal hydrate Cs3(H1.5PO4)2·2H2O, the dehydrated form has rather low conductivity values of ∼6 × 10−6–10−8 S cm−1 at 373–493 K, with an activation energy of 0.91 eV.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617012335/fn3241sup1.cif
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229617012335/fn3241Isup2.hkl
Contains datablock I

CCDC reference: 1555937

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2016); cell refinement: CrysAlis PRO (Rigaku OD, 2016); data reduction: CrysAlis PRO (Rigaku OD, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015) and ShelXle (Hübschle et al., 2011); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).

(I) top
Crystal data top
Cs3(H2PO4)(HPO4)·2H2ODx = 3.285 Mg m3
Mr = 627.73Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 9404 reflections
a = 7.4721 (5) Åθ = 2.7–29.2°
b = 11.4369 (8) ŵ = 8.85 mm1
c = 14.8509 (11) ÅT = 296 K
V = 1269.12 (15) Å3Block, colourless
Z = 40.20 × 0.05 × 0.02 mm
F(000) = 1128
Data collection top
Agilent Xcalibur Ruby Gemini ultra
diffractometer
1298 independent reflections
Radiation source: sealed X-ray tube1176 reflections with I > 2σ(I)
Detector resolution: 10.3457 pixels mm-1Rint = 0.086
ω scanθmax = 26.4°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2016)
h = 99
Tmin = 0.453, Tmax = 1.000k = 1414
17880 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: difference Fourier map
wR(F2) = 0.074Only H-atom coordinates refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0383P)2 + 3.3232P]
where P = (Fo2 + 2Fc2)/3
1298 reflections(Δ/σ)max = 0.001
79 parametersΔρmax = 0.85 e Å3
1 restraintΔρmin = 1.14 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cs10.07728 (4)0.82817 (3)0.17311 (2)0.02937 (14)
Cs20.0000000.5000000.0000000.03806 (17)
P10.99034 (15)0.17285 (10)0.09057 (8)0.0220 (3)
O11.0725 (5)0.1525 (4)0.1823 (3)0.0364 (10)
O20.9101 (5)0.0612 (3)0.0501 (3)0.0389 (9)
H21.0000000.0000000.0000000.047*
O30.8240 (5)0.2562 (3)0.1086 (2)0.0337 (8)
H30.759 (7)0.262 (5)0.066 (3)0.040*
O41.1154 (5)0.2333 (4)0.0270 (3)0.0426 (9)
O50.3745 (7)0.0228 (4)0.2003 (3)0.0423 (10)
H5A0.282 (10)0.061 (6)0.198 (5)0.051*
H5B0.445 (9)0.066 (6)0.237 (5)0.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs10.0299 (2)0.0290 (2)0.0292 (2)0.00062 (11)0.00038 (12)0.00102 (11)
Cs20.0458 (3)0.0320 (3)0.0363 (3)0.00700 (19)0.0036 (2)0.00316 (18)
P10.0209 (6)0.0258 (6)0.0194 (6)0.0006 (4)0.0015 (4)0.0018 (5)
O10.028 (2)0.051 (2)0.030 (2)0.0072 (16)0.0026 (14)0.0015 (17)
O20.037 (2)0.0306 (19)0.049 (2)0.0061 (15)0.0049 (17)0.0183 (17)
O30.0289 (19)0.042 (2)0.030 (2)0.0121 (15)0.0054 (15)0.0126 (16)
O40.049 (2)0.046 (2)0.033 (2)0.0098 (19)0.0127 (18)0.0004 (18)
O50.046 (2)0.032 (2)0.049 (3)0.0103 (19)0.017 (2)0.0093 (19)
Geometric parameters (Å, º) top
Cs1—O1i3.146 (4)Cs2—O5viii3.130 (5)
Cs1—O5ii3.170 (5)Cs2—O4vi3.194 (4)
Cs1—O3iii3.253 (4)Cs2—O4ix3.194 (4)
Cs1—O5iv3.284 (4)Cs2—O2iii3.230 (4)
Cs1—O1v3.302 (4)Cs2—O2viii3.230 (4)
Cs1—O4v3.341 (4)Cs2—O3vi3.479 (4)
Cs1—O4vi3.376 (4)Cs2—O3ix3.479 (4)
Cs1—O3i3.424 (4)Cs2—P1vi3.9767 (12)
Cs1—O2vii3.465 (4)Cs2—P1ix3.9767 (12)
Cs1—O5iii3.534 (4)P1—O41.498 (4)
Cs1—O2vi3.549 (4)P1—O11.513 (4)
Cs1—O1vii3.712 (5)P1—O21.533 (4)
Cs2—O5iii3.130 (5)P1—O31.590 (4)
O1i—Cs1—O5ii127.65 (11)O2viii—Cs2—P1vi96.25 (7)
O1i—Cs1—O3iii73.22 (10)O3vi—Cs2—P1vi23.42 (6)
O5ii—Cs1—O3iii149.39 (10)O3ix—Cs2—P1vi156.58 (6)
O1i—Cs1—O5iv83.00 (11)O5iii—Cs2—P1ix76.26 (8)
O5ii—Cs1—O5iv76.96 (9)O5viii—Cs2—P1ix103.74 (8)
O3iii—Cs1—O5iv85.11 (11)O4vi—Cs2—P1ix159.35 (7)
O1i—Cs1—O1v82.24 (11)O4ix—Cs2—P1ix20.65 (7)
O5ii—Cs1—O1v82.35 (10)O2iii—Cs2—P1ix96.25 (7)
O3iii—Cs1—O1v126.06 (10)O2viii—Cs2—P1ix83.75 (7)
O5iv—Cs1—O1v138.97 (11)O3vi—Cs2—P1ix156.58 (6)
O1i—Cs1—O4v118.72 (10)O3ix—Cs2—P1ix23.42 (6)
O5ii—Cs1—O4v80.16 (11)P1vi—Cs2—P1ix180.00 (4)
O3iii—Cs1—O4v111.11 (9)O5iii—Cs2—Cs1x135.51 (9)
O5iv—Cs1—O4v155.38 (11)O5viii—Cs2—Cs1x44.49 (9)
O1v—Cs1—O4v44.33 (9)O4vi—Cs2—Cs1x47.57 (8)
O1i—Cs1—O4vi108.40 (9)O4ix—Cs2—Cs1x132.43 (8)
O5ii—Cs1—O4vi123.86 (11)O2iii—Cs2—Cs1x51.24 (8)
O3iii—Cs1—O4vi45.19 (9)O2viii—Cs2—Cs1x128.76 (8)
O5iv—Cs1—O4vi116.64 (11)O3vi—Cs2—Cs1x69.65 (6)
O1v—Cs1—O4vi104.34 (10)O3ix—Cs2—Cs1x110.35 (6)
O4v—Cs1—O4vi69.74 (3)P1vi—Cs2—Cs1x53.948 (17)
O1i—Cs1—O3i43.73 (9)P1ix—Cs2—Cs1x126.052 (18)
O5ii—Cs1—O3i84.10 (10)O5iii—Cs2—Cs1xi44.49 (9)
O3iii—Cs1—O3i114.61 (10)O5viii—Cs2—Cs1xi135.51 (9)
O5iv—Cs1—O3i73.77 (11)O4vi—Cs2—Cs1xi132.43 (8)
O1v—Cs1—O3i69.13 (9)O4ix—Cs2—Cs1xi47.57 (8)
O4v—Cs1—O3i112.88 (9)O2iii—Cs2—Cs1xi128.76 (8)
O4vi—Cs1—O3i151.03 (9)O2viii—Cs2—Cs1xi51.24 (8)
O1i—Cs1—O2vii136.30 (9)O3vi—Cs2—Cs1xi110.35 (6)
O5ii—Cs1—O2vii77.26 (10)O3ix—Cs2—Cs1xi69.65 (6)
O3iii—Cs1—O2vii72.97 (9)P1vi—Cs2—Cs1xi126.052 (17)
O5iv—Cs1—O2vii67.31 (10)P1ix—Cs2—Cs1xi53.948 (17)
O1v—Cs1—O2vii140.87 (9)Cs1x—Cs2—Cs1xi180.0
O4v—Cs1—O2vii98.91 (9)O4—P1—O1112.7 (2)
O4vi—Cs1—O2vii62.76 (9)O4—P1—O2112.4 (2)
O3i—Cs1—O2vii139.62 (9)O1—P1—O2112.6 (3)
O1i—Cs1—O5iii47.72 (11)O4—P1—O3108.5 (2)
O5ii—Cs1—O5iii127.44 (7)O1—P1—O3104.9 (2)
O3iii—Cs1—O5iii82.97 (11)O2—P1—O3105.1 (2)
O5iv—Cs1—O5iii130.65 (5)O4—P1—Cs1xii57.93 (16)
O1v—Cs1—O5iii46.61 (10)O1—P1—Cs1xii56.54 (16)
O4v—Cs1—O5iii71.53 (10)O2—P1—Cs1xii146.05 (15)
O4vi—Cs1—O5iii86.45 (11)O3—P1—Cs1xii108.83 (14)
O3i—Cs1—O5iii68.44 (10)O4—P1—Cs1vi57.03 (16)
O2vii—Cs1—O5iii149.01 (10)O1—P1—Cs1vi160.89 (15)
O1i—Cs1—O2vi150.96 (9)O2—P1—Cs1vi63.79 (17)
O5ii—Cs1—O2vi81.37 (10)O3—P1—Cs1vi93.97 (14)
O3iii—Cs1—O2vi80.78 (9)Cs1xii—P1—Cs1vi114.88 (3)
O5iv—Cs1—O2vi107.78 (10)O4—P1—Cs1xiii115.50 (16)
O1v—Cs1—O2vi103.57 (9)O1—P1—Cs1xiii47.43 (16)
O4v—Cs1—O2vi59.38 (9)O2—P1—Cs1xiii132.10 (16)
O4vi—Cs1—O2vi42.57 (9)O3—P1—Cs1xiii58.82 (13)
O3i—Cs1—O2vi164.55 (8)Cs1xii—P1—Cs1xiii67.79 (2)
O2vii—Cs1—O2vi40.78 (11)Cs1vi—P1—Cs1xiii149.62 (3)
O5iii—Cs1—O2vi117.14 (9)O4—P1—Cs2xiv48.76 (16)
O1i—Cs1—O1vii127.56 (6)O1—P1—Cs2xiv116.25 (18)
O5ii—Cs1—O1vii45.60 (9)O2—P1—Cs2xiv131.13 (17)
O3iii—Cs1—O1vii104.76 (9)O3—P1—Cs2xiv60.45 (15)
O5iv—Cs1—O1vii45.34 (10)Cs1xii—P1—Cs2xiv70.21 (2)
O1v—Cs1—O1vii127.89 (7)Cs1vi—P1—Cs2xiv70.71 (2)
O4v—Cs1—O1vii110.79 (9)Cs1xiii—P1—Cs2xiv83.12 (2)
O4vi—Cs1—O1vii103.69 (9)O4—P1—Cs1xv121.58 (17)
O3i—Cs1—O1vii101.96 (9)O1—P1—Cs1xv61.79 (17)
O2vii—Cs1—O1vii41.17 (8)O2—P1—Cs1xv52.45 (16)
O5iii—Cs1—O1vii169.82 (10)O3—P1—Cs1xv129.64 (16)
O2vi—Cs1—O1vii71.25 (8)Cs1xii—P1—Cs1xv102.09 (3)
O5iii—Cs2—O5viii180.00 (15)Cs1vi—P1—Cs1xv107.94 (3)
O5iii—Cs2—O4vi96.92 (11)Cs1xiii—P1—Cs1xv100.53 (3)
O5viii—Cs2—O4vi83.08 (11)Cs2xiv—P1—Cs1xv169.71 (3)
O5iii—Cs2—O4ix83.08 (11)P1—O1—Cs1xiii111.82 (19)
O5viii—Cs2—O4ix96.92 (11)P1—O1—Cs1xii100.98 (19)
O4vi—Cs2—O4ix180.00 (14)Cs1xiii—O1—Cs1xii85.50 (11)
O5iii—Cs2—O2iii92.72 (11)P1—O1—Cs1xv97.16 (19)
O5viii—Cs2—O2iii87.28 (11)Cs1xiii—O1—Cs1xv131.82 (13)
O4vi—Cs2—O2iii64.26 (10)Cs1xii—O1—Cs1xv126.80 (10)
O4ix—Cs2—O2iii115.74 (10)P1—O2—Cs2xvi129.92 (19)
O5iii—Cs2—O2viii87.28 (11)P1—O2—Cs1xv107.01 (19)
O5viii—Cs2—O2viii92.72 (11)Cs2xvi—O2—Cs1xv107.25 (10)
O4vi—Cs2—O2viii115.74 (10)P1—O2—Cs1vi93.40 (18)
O4ix—Cs2—O2viii64.26 (10)Cs2xvi—O2—Cs1vi83.54 (9)
O2iii—Cs2—O2viii180.0Cs1xv—O2—Cs1vi139.22 (11)
O5iii—Cs2—O3vi105.11 (9)P1—O3—Cs1xi157.2 (2)
O5viii—Cs2—O3vi74.89 (9)P1—O3—Cs1xiii97.79 (15)
O4vi—Cs2—O3vi43.86 (9)Cs1xi—O3—Cs1xiii81.91 (8)
O4ix—Cs2—O3vi136.14 (9)P1—O3—Cs2xiv96.13 (17)
O2iii—Cs2—O3vi106.96 (9)Cs1xi—O3—Cs2xiv106.39 (10)
O2viii—Cs2—O3vi73.04 (9)Cs1xiii—O3—Cs2xiv99.49 (9)
O5iii—Cs2—O3ix74.89 (9)P1—O4—Cs2xiv110.6 (2)
O5viii—Cs2—O3ix105.11 (9)P1—O4—Cs1xii99.74 (19)
O4vi—Cs2—O3ix136.14 (9)Cs2xiv—O4—Cs1xii87.54 (10)
O4ix—Cs2—O3ix43.86 (9)P1—O4—Cs1vi101.11 (19)
O2iii—Cs2—O3ix73.04 (9)Cs2xiv—O4—Cs1vi88.48 (10)
O2viii—Cs2—O3ix106.96 (9)Cs1xii—O4—Cs1vi158.85 (12)
O3vi—Cs2—O3ix180.0Cs2xvi—O5—Cs1xvii91.74 (11)
O5iii—Cs2—P1vi103.74 (8)Cs2xvi—O5—Cs1xviii110.45 (13)
O5viii—Cs2—P1vi76.26 (8)Cs1xvii—O5—Cs1xviii85.42 (11)
O4vi—Cs2—P1vi20.65 (7)Cs2xvi—O5—Cs1xi86.75 (11)
O4ix—Cs2—P1vi159.35 (7)Cs1xvii—O5—Cs1xi138.66 (14)
O2iii—Cs2—P1vi83.75 (7)Cs1xviii—O5—Cs1xi133.48 (14)
O4—P1—O1—Cs1xiii104.4 (2)O4—P1—O3—Cs1xi163.2 (5)
O2—P1—O1—Cs1xiii127.1 (2)O1—P1—O3—Cs1xi76.1 (5)
O3—P1—O1—Cs1xiii13.4 (2)O2—P1—O3—Cs1xi42.8 (5)
Cs1xii—P1—O1—Cs1xiii89.52 (19)Cs1xii—P1—O3—Cs1xi135.3 (4)
Cs1vi—P1—O1—Cs1xiii158.0 (4)Cs1vi—P1—O3—Cs1xi106.7 (5)
Cs2xiv—P1—O1—Cs1xiii50.6 (2)Cs1xiii—P1—O3—Cs1xi87.6 (5)
Cs1xv—P1—O1—Cs1xiii140.7 (2)Cs2xiv—P1—O3—Cs1xi171.9 (5)
O4—P1—O1—Cs1xii14.9 (2)Cs1xv—P1—O3—Cs1xi10.6 (6)
O2—P1—O1—Cs1xii143.33 (17)O4—P1—O3—Cs1xiii109.2 (2)
O3—P1—O1—Cs1xii102.95 (18)O1—P1—O3—Cs1xiii11.5 (2)
Cs1vi—P1—O1—Cs1xii68.5 (6)O2—P1—O3—Cs1xiii130.43 (19)
Cs1xiii—P1—O1—Cs1xii89.52 (19)Cs1xii—P1—O3—Cs1xiii47.68 (13)
Cs2xiv—P1—O1—Cs1xii38.89 (16)Cs1vi—P1—O3—Cs1xiii165.66 (8)
Cs1xv—P1—O1—Cs1xii129.74 (15)Cs2xiv—P1—O3—Cs1xiii100.49 (12)
O4—P1—O1—Cs1xv114.8 (2)Cs1xv—P1—O3—Cs1xiii77.06 (16)
O2—P1—O1—Cs1xv13.6 (2)O4—P1—O3—Cs2xiv8.7 (2)
O3—P1—O1—Cs1xv127.31 (17)O1—P1—O3—Cs2xiv112.02 (19)
Cs1xii—P1—O1—Cs1xv129.74 (15)O2—P1—O3—Cs2xiv129.08 (19)
Cs1vi—P1—O1—Cs1xv61.3 (6)Cs1xii—P1—O3—Cs2xiv52.81 (11)
Cs1xiii—P1—O1—Cs1xv140.7 (2)Cs1vi—P1—O3—Cs2xiv65.17 (8)
Cs2xiv—P1—O1—Cs1xv168.64 (4)Cs1xiii—P1—O3—Cs2xiv100.49 (12)
O4—P1—O2—Cs2xvi115.2 (3)Cs1xv—P1—O3—Cs2xiv177.55 (6)
O1—P1—O2—Cs2xvi116.2 (3)O1—P1—O4—Cs2xiv105.7 (2)
O3—P1—O2—Cs2xvi2.6 (3)O2—P1—O4—Cs2xiv125.8 (2)
Cs1xii—P1—O2—Cs2xvi179.36 (6)O3—P1—O4—Cs2xiv10.0 (2)
Cs1vi—P1—O2—Cs2xvi84.4 (2)Cs1xii—P1—O4—Cs2xiv91.03 (17)
Cs1xiii—P1—O2—Cs2xvi63.9 (3)Cs1vi—P1—O4—Cs2xiv92.57 (19)
Cs2xiv—P1—O2—Cs2xvi61.2 (3)Cs1xiii—P1—O4—Cs2xiv53.5 (2)
Cs1xv—P1—O2—Cs2xvi131.3 (3)Cs1xv—P1—O4—Cs2xiv175.58 (5)
O4—P1—O2—Cs1xv113.4 (2)O1—P1—O4—Cs1xii14.7 (2)
O1—P1—O2—Cs1xv15.1 (2)O2—P1—O4—Cs1xii143.19 (18)
O3—P1—O2—Cs1xv128.78 (17)O3—P1—O4—Cs1xii101.07 (18)
Cs1xii—P1—O2—Cs1xv48.0 (3)Cs1vi—P1—O4—Cs1xii176.4 (2)
Cs1vi—P1—O2—Cs1xv144.24 (16)Cs1xiii—P1—O4—Cs1xii37.52 (18)
Cs1xiii—P1—O2—Cs1xv67.4 (2)Cs2xiv—P1—O4—Cs1xii91.03 (17)
Cs2xiv—P1—O2—Cs1xv167.51 (6)Cs1xv—P1—O4—Cs1xii84.55 (15)
O4—P1—O2—Cs1vi30.8 (2)O1—P1—O4—Cs1vi161.71 (19)
O1—P1—O2—Cs1vi159.38 (16)O2—P1—O4—Cs1vi33.2 (2)
O3—P1—O2—Cs1vi86.98 (17)O3—P1—O4—Cs1vi82.53 (19)
Cs1xii—P1—O2—Cs1vi96.2 (3)Cs1xii—P1—O4—Cs1vi176.4 (2)
Cs1xiii—P1—O2—Cs1vi148.33 (11)Cs1xiii—P1—O4—Cs1vi146.08 (7)
Cs2xiv—P1—O2—Cs1vi23.27 (19)Cs2xiv—P1—O4—Cs1vi92.57 (19)
Cs1xv—P1—O2—Cs1vi144.24 (16)Cs1xv—P1—O4—Cs1vi91.85 (15)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z; (iv) x1/2, y+1, z+1/2; (v) x+3/2, y+1/2, z; (vi) x+1, y+1, z; (vii) x1, y+1, z; (viii) x1/2, y+1/2, z; (ix) x1, y, z; (x) x1/2, y+3/2, z; (xi) x+1/2, y1/2, z; (xii) x+3/2, y1/2, z; (xiii) x+1, y1/2, z+1/2; (xiv) x+1, y, z; (xv) x+1, y1, z; (xvi) x+1/2, y+1/2, z; (xvii) x, y1, z; (xviii) x+1/2, y1, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O2xix1.22 (1)1.22 (1)2.445 (7)180 (1)
O3—H3···O4viii0.80 (2)1.75 (2)2.549 (5)177 (6)
O5—H5A···O1ix0.82 (8)1.90 (8)2.713 (6)175 (7)
O5—H5B···O1xx0.90 (8)1.82 (8)2.725 (6)176 (7)
Symmetry codes: (viii) x1/2, y+1/2, z; (ix) x1, y, z; (xix) x+2, y, z; (xx) x1/2, y, z+1/2.
 

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