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The title compound, diiron(III) trisulfate-sulfuric acid-water (1/1/28), has been prepared at temperatures between 235 and 239 K from acid solutions of Fe2(SO4)3. Studies of the compound at 100 and 200 K are reported. The analysis reveals the structural features of an alum, (H5O2)Fe(SO4)2·12H2O. The Fe(H2O)6 unit is located on a centre of inversion at ({1 \over 2}, 0, {1 \over 2}), while the H5O2+ cation is located about an inversion centre at ({1 \over 2}{1 \over 2}{1 \over 2}). The compound thus represents the first oxonium alum, although the unit cell is ortho­rhom­bic.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113005969/ov3022sup1.cif
Contains datablocks I_100K, I_200K, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113005969/ov3022I_100Ksup4.hkl
Contains datablock I_100K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113005969/ov3022I_200Ksup5.hkl
Contains datablock I_200K

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

(I_100K) Diiron(III) trisulfate–sulfuric acid–water (1/1/28) top
Crystal data top
Fe2(SO4)3·H2SO4·28H2OF(000) = 1052
Mr = 501.22Dx = 1.685 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 39264 reflections
a = 12.0692 (15) Åθ = 1.8–29.6°
b = 12.7108 (17) ŵ = 1.07 mm1
c = 12.882 (2) ÅT = 100 K
V = 1976.2 (5) Å3Plate, violet
Z = 40.15 × 0.10 × 0.07 mm
Data collection top
Stoe IPDS 2
diffractometer
1740 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus1526 reflections with I > 2σ(I)
Plane graphite monochromatorRint = 0.137
Detector resolution: 6.67 pixels mm-1θmax = 25.0°, θmin = 1.6°
rotation method scansh = 1414
Absorption correction: integration
(Coppens, 1970)
k = 1515
Tmin = 0.850, Tmax = 0.908l = 1515
51260 measured reflections
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109All H-atom parameters refined
S = 1.10 w = 1/[σ2(Fo2) + (0.0709P)2 + 1.3832P]
where P = (Fo2 + 2Fc2)/3
1740 reflections(Δ/σ)max < 0.001
171 parametersΔρmax = 0.66 e Å3
14 restraintsΔρmin = 0.67 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.50000.00000.50000.0239 (2)
S10.81304 (6)0.19330 (5)0.69505 (5)0.0254 (2)
O10.48821 (17)0.15580 (16)0.48589 (16)0.0272 (5)
H1A0.434 (2)0.183 (3)0.461 (3)0.053 (12)*
H1B0.545 (2)0.188 (3)0.475 (3)0.055 (13)*
O20.48386 (18)0.01248 (16)0.65331 (16)0.0283 (5)
H2A0.479 (4)0.040 (3)0.690 (3)0.064 (14)*
H2B0.472 (4)0.064 (3)0.688 (3)0.062 (13)*
O30.66454 (19)0.01395 (15)0.51533 (16)0.0274 (5)
H3A0.691 (3)0.036 (3)0.569 (2)0.057 (12)*
H3B0.707 (3)0.021 (3)0.464 (2)0.047 (11)*
O40.75209 (17)0.09341 (15)0.69101 (15)0.0307 (5)
O50.81986 (16)0.23926 (16)0.58987 (15)0.0312 (5)
O60.75408 (17)0.26763 (15)0.76476 (16)0.0329 (5)
O70.92583 (17)0.17761 (14)0.73561 (16)0.0316 (5)
O80.80132 (18)0.03479 (16)0.35748 (16)0.0315 (5)
H8A0.795 (4)0.092 (2)0.329 (3)0.062 (13)*
H8B0.782 (3)0.007 (3)0.313 (2)0.048 (12)*
O90.55093 (18)0.34910 (15)0.72157 (16)0.0294 (5)
H9A0.613 (2)0.324 (4)0.719 (4)0.074 (16)*
H9B0.510 (3)0.300 (2)0.735 (3)0.047 (11)*
O100.66082 (18)0.27954 (16)0.45188 (16)0.0300 (5)
H10A0.708 (2)0.267 (3)0.495 (2)0.037 (10)*
H10B0.691 (3)0.275 (3)0.3954 (19)0.046 (11)*
O110.57222 (19)0.44990 (18)0.54137 (17)0.0371 (5)
H11C0.50000.50000.50000.045*
H11A0.593 (4)0.402 (3)0.502 (3)0.077 (16)*
H11B0.552 (4)0.418 (4)0.596 (2)0.079 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0300 (4)0.0155 (3)0.0261 (3)0.0004 (2)0.0001 (2)0.00010 (19)
S10.0317 (4)0.0168 (4)0.0278 (4)0.0015 (2)0.0010 (3)0.0016 (2)
O10.0291 (12)0.0171 (10)0.0355 (11)0.0009 (8)0.0026 (9)0.0009 (8)
O20.0402 (12)0.0183 (10)0.0265 (11)0.0001 (8)0.0014 (9)0.0005 (8)
O30.0317 (11)0.0224 (10)0.0280 (11)0.0002 (8)0.0002 (9)0.0034 (8)
O40.0405 (11)0.0207 (10)0.0308 (10)0.0083 (8)0.0011 (9)0.0008 (8)
O50.0344 (11)0.0284 (10)0.0309 (10)0.0043 (8)0.0017 (8)0.0068 (8)
O60.0396 (12)0.0231 (10)0.0359 (11)0.0020 (8)0.0008 (9)0.0033 (8)
O70.0373 (12)0.0206 (10)0.0369 (11)0.0003 (8)0.0053 (9)0.0030 (8)
O80.0431 (12)0.0219 (10)0.0295 (11)0.0026 (9)0.0000 (9)0.0003 (9)
O90.0364 (12)0.0198 (10)0.0319 (11)0.0005 (9)0.0020 (9)0.0005 (8)
O100.0331 (11)0.0261 (10)0.0308 (11)0.0006 (8)0.0016 (10)0.0023 (9)
O110.0486 (13)0.0304 (12)0.0324 (12)0.0044 (10)0.0025 (10)0.0028 (10)
Geometric parameters (Å, º) top
Fe1—O2i1.991 (2)Fe1—O32.004 (2)
Fe1—O21.991 (2)S1—O41.468 (2)
Fe1—O11.994 (2)S1—O71.472 (2)
Fe1—O1i1.994 (2)S1—O51.478 (2)
Fe1—O3i2.004 (2)S1—O61.485 (2)
O2i—Fe1—O2180.0O2—Fe1—O389.55 (9)
O2i—Fe1—O189.75 (8)O1—Fe1—O389.53 (8)
O2—Fe1—O190.25 (8)O1i—Fe1—O390.47 (8)
O2i—Fe1—O1i90.25 (8)O3i—Fe1—O3180.0
O2—Fe1—O1i89.75 (8)O4—S1—O7111.02 (12)
O1—Fe1—O1i180.0O4—S1—O5109.71 (12)
O2i—Fe1—O3i89.55 (9)O7—S1—O5109.12 (12)
O2—Fe1—O3i90.45 (9)O4—S1—O6109.36 (12)
O1—Fe1—O3i90.47 (8)O7—S1—O6108.35 (12)
O1i—Fe1—O3i89.53 (8)O5—S1—O6109.25 (12)
O2i—Fe1—O390.45 (9)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O5ii0.80 (2)1.82 (2)2.619 (3)173 (4)
O1—H1B···O100.82 (2)1.84 (2)2.647 (3)171 (4)
O2—H2A···O9iii0.82 (2)1.85 (2)2.662 (3)172 (5)
O2—H2B···O7iv0.81 (2)1.83 (2)2.635 (3)172 (5)
O3—H3A···O40.81 (2)1.88 (2)2.694 (3)177 (4)
O3—H3B···O80.83 (2)1.80 (2)2.632 (3)178 (4)
O8—H8A···O6v0.82 (2)2.03 (2)2.839 (3)171 (4)
O8—H8B···O4vi0.82 (2)1.96 (2)2.769 (3)171 (4)
O9—H9A···O60.81 (2)1.94 (3)2.719 (3)160 (5)
O9—H9B···O7iv0.81 (2)1.90 (2)2.708 (3)175 (4)
O10—H10A···O50.81 (2)1.86 (2)2.666 (3)178 (4)
O10—H10B···O6v0.82 (2)1.93 (2)2.727 (3)167 (4)
O11—H11A···O100.83 (2)1.87 (2)2.676 (3)161 (5)
O11—H11B···O90.84 (2)1.84 (2)2.664 (3)164 (5)
Symmetry codes: (ii) x1/2, y+1/2, z+1; (iii) x+1, y1/2, z+3/2; (iv) x1/2, y, z+3/2; (v) x, y+1/2, z1/2; (vi) x+3/2, y, z1/2.
(I_200K) Diiron(III) trisulfate–sulfuric acid–water (1/1/28) top
Crystal data top
Fe2(SO4)3·H2SO4·28H2OF(000) = 1052
Mr = 501.22Dx = 1.683 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 11840 reflections
a = 12.0802 (19) Åθ = 2.7–29.6°
b = 12.7630 (19) ŵ = 1.07 mm1
c = 12.832 (2) ÅT = 200 K
V = 1978.5 (5) Å3Plate, violet
Z = 40.45 × 0.2 × 0.08 mm
Data collection top
Stoe IPDS 2
diffractometer
1737 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus1385 reflections with I > 2σ(I)
Plane graphite monochromatorRint = 0.147
Detector resolution: 6.67 pixels mm-1θmax = 25.0°, θmin = 1.6°
rotation method scansh = 1414
Absorption correction: integration
(Coppens, 1970)
k = 1515
Tmin = 0.707, Tmax = 0.886l = 1515
17528 measured reflections
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088All H-atom parameters refined
S = 1.01 w = 1/[σ2(Fo2) + (0.0602P)2 + 0.020P]
where P = (Fo2 + 2Fc2)/3
1737 reflections(Δ/σ)max < 0.001
180 parametersΔρmax = 0.45 e Å3
12 restraintsΔρmin = 0.68 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.50000.00000.50000.01046 (17)
S10.81319 (5)0.19418 (5)0.69455 (5)0.01312 (19)
O10.48873 (16)0.15490 (15)0.48543 (16)0.0153 (4)
H1A0.429 (2)0.180 (3)0.468 (4)0.053 (13)*
H1B0.5429 (19)0.190 (2)0.478 (2)0.008 (7)*
O20.48350 (17)0.01322 (15)0.65377 (15)0.0168 (4)
H2A0.477 (4)0.040 (2)0.688 (3)0.053 (13)*
H2B0.465 (4)0.066 (2)0.684 (3)0.045 (12)*
O30.66400 (17)0.01340 (16)0.51529 (16)0.0163 (4)
H3A0.690 (3)0.036 (3)0.569 (2)0.049 (13)*
H3B0.706 (3)0.023 (3)0.466 (2)0.033 (11)*
O40.75267 (19)0.09480 (17)0.69001 (16)0.0257 (5)
O50.82066 (16)0.24043 (17)0.58989 (16)0.0248 (5)
O60.75378 (19)0.26804 (16)0.76383 (17)0.0281 (5)
O70.92547 (17)0.17857 (15)0.73607 (17)0.0227 (5)
O80.80022 (19)0.03375 (18)0.35666 (17)0.0247 (5)
H8A0.785 (3)0.004 (3)0.309 (2)0.038 (12)*
H8B0.791 (4)0.090 (2)0.330 (3)0.053 (14)*
O90.55072 (19)0.34947 (16)0.72097 (16)0.0203 (5)
H9A0.613 (2)0.326 (3)0.728 (4)0.046 (13)*
H9B0.510 (3)0.301 (3)0.731 (4)0.056 (14)*
O100.66128 (17)0.27876 (17)0.45181 (17)0.0219 (5)
H10A0.714 (2)0.263 (3)0.489 (3)0.027 (10)*
H10B0.688 (4)0.273 (3)0.394 (2)0.052 (13)*
O11A0.5730 (3)0.4492 (3)0.5411 (3)0.0298 (7)0.80
H11C0.50000.50000.50000.036*
O11B0.5161 (16)0.4097 (13)0.5195 (11)0.038 (3)0.20
H11B0.540 (6)0.415 (5)0.590 (5)0.085 (19)*
H11A0.599 (5)0.398 (4)0.495 (4)0.069 (16)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0119 (3)0.0092 (3)0.0102 (3)0.0008 (2)0.0001 (2)0.0004 (2)
S10.0150 (3)0.0121 (3)0.0122 (3)0.0027 (3)0.0024 (3)0.0027 (2)
O10.0112 (10)0.0120 (9)0.0228 (11)0.0020 (8)0.0018 (8)0.0018 (8)
O20.0260 (11)0.0130 (10)0.0113 (10)0.0015 (9)0.0034 (8)0.0005 (8)
O30.0134 (10)0.0224 (10)0.0131 (11)0.0000 (8)0.0007 (8)0.0024 (9)
O40.0388 (12)0.0207 (11)0.0175 (10)0.0174 (9)0.0040 (10)0.0023 (8)
O50.0205 (10)0.0355 (12)0.0184 (11)0.0082 (9)0.0039 (9)0.0152 (9)
O60.0326 (12)0.0244 (11)0.0273 (12)0.0044 (9)0.0039 (10)0.0080 (10)
O70.0194 (11)0.0176 (9)0.0311 (12)0.0016 (8)0.0106 (9)0.0067 (9)
O80.0316 (12)0.0233 (12)0.0191 (12)0.0039 (10)0.0032 (10)0.0026 (10)
O90.0252 (12)0.0168 (10)0.0189 (11)0.0004 (9)0.0029 (9)0.0010 (8)
O100.0193 (11)0.0243 (11)0.0223 (12)0.0012 (8)0.0050 (10)0.0035 (10)
O11A0.0360 (19)0.0309 (18)0.0226 (17)0.0060 (16)0.0056 (16)0.0042 (15)
O11B0.051 (10)0.037 (8)0.027 (8)0.023 (8)0.013 (7)0.011 (6)
Geometric parameters (Å, º) top
Fe1—O11.9905 (19)S1—O41.465 (2)
Fe1—O1i1.9905 (19)S1—O51.470 (2)
Fe1—O2i1.990 (2)S1—O71.471 (2)
Fe1—O21.990 (2)S1—O61.481 (2)
Fe1—O3i1.998 (2)O11A—O11B0.90 (2)
Fe1—O31.998 (2)
O1—Fe1—O1i180.0O1i—Fe1—O390.46 (8)
O1—Fe1—O2i89.88 (8)O2i—Fe1—O390.30 (8)
O1i—Fe1—O2i90.12 (8)O2—Fe1—O389.70 (8)
O1—Fe1—O290.12 (8)O3i—Fe1—O3180.0
O1i—Fe1—O289.88 (8)O4—S1—O5110.00 (12)
O2i—Fe1—O2180.0O4—S1—O7110.94 (12)
O1—Fe1—O3i90.46 (8)O5—S1—O7109.20 (12)
O1i—Fe1—O3i89.54 (8)O4—S1—O6109.45 (13)
O2i—Fe1—O3i89.70 (8)O5—S1—O6108.82 (13)
O2—Fe1—O3i90.30 (8)O7—S1—O6108.40 (13)
O1—Fe1—O389.54 (8)
Symmetry code: (i) x+1, y, z+1.
 

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