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 Fe
2(SO
4)
3. Studies of the compound at 100 and 200 K are reported. The analysis reveals the structural features of an alum, (H
5O
2)Fe(SO
4)
2·12H
2O. The Fe(H
2O)
6 unit is located on a centre of inversion at (
, 0,
), while the H
5O
2+ cation is located about an inversion centre at (
,
,
). The compound thus represents the first oxonium alum, although the unit cell is orthorhombic.
Supporting information
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·H2SO4·28H2O | F(000) = 1052 |
Mr = 501.22 | Dx = 1.685 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 39264 reflections |
a = 12.0692 (15) Å | θ = 1.8–29.6° |
b = 12.7108 (17) Å | µ = 1.07 mm−1 |
c = 12.882 (2) Å | T = 100 K |
V = 1976.2 (5) Å3 | Plate, violet |
Z = 4 | 0.15 × 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 focus | 1526 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.137 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 1.6° |
rotation method scans | h = −14→14 |
Absorption correction: integration (Coppens, 1970) | k = −15→15 |
Tmin = 0.850, Tmax = 0.908 | l = −15→15 |
51260 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | All 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 parameters | Δρmax = 0.66 e Å−3 |
14 restraints | Δρmin = −0.67 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Fe1 | 0.5000 | 0.0000 | 0.5000 | 0.0239 (2) | |
S1 | 0.81304 (6) | 0.19330 (5) | 0.69505 (5) | 0.0254 (2) | |
O1 | 0.48821 (17) | 0.15580 (16) | 0.48589 (16) | 0.0272 (5) | |
H1A | 0.434 (2) | 0.183 (3) | 0.461 (3) | 0.053 (12)* | |
H1B | 0.545 (2) | 0.188 (3) | 0.475 (3) | 0.055 (13)* | |
O2 | 0.48386 (18) | 0.01248 (16) | 0.65331 (16) | 0.0283 (5) | |
H2A | 0.479 (4) | −0.040 (3) | 0.690 (3) | 0.064 (14)* | |
H2B | 0.472 (4) | 0.064 (3) | 0.688 (3) | 0.062 (13)* | |
O3 | 0.66454 (19) | 0.01395 (15) | 0.51533 (16) | 0.0274 (5) | |
H3A | 0.691 (3) | 0.036 (3) | 0.569 (2) | 0.057 (12)* | |
H3B | 0.707 (3) | 0.021 (3) | 0.464 (2) | 0.047 (11)* | |
O4 | 0.75209 (17) | 0.09341 (15) | 0.69101 (15) | 0.0307 (5) | |
O5 | 0.81986 (16) | 0.23926 (16) | 0.58987 (15) | 0.0312 (5) | |
O6 | 0.75408 (17) | 0.26763 (15) | 0.76476 (16) | 0.0329 (5) | |
O7 | 0.92583 (17) | 0.17761 (14) | 0.73561 (16) | 0.0316 (5) | |
O8 | 0.80132 (18) | 0.03479 (16) | 0.35748 (16) | 0.0315 (5) | |
H8A | 0.795 (4) | 0.092 (2) | 0.329 (3) | 0.062 (13)* | |
H8B | 0.782 (3) | −0.007 (3) | 0.313 (2) | 0.048 (12)* | |
O9 | 0.55093 (18) | 0.34910 (15) | 0.72157 (16) | 0.0294 (5) | |
H9A | 0.613 (2) | 0.324 (4) | 0.719 (4) | 0.074 (16)* | |
H9B | 0.510 (3) | 0.300 (2) | 0.735 (3) | 0.047 (11)* | |
O10 | 0.66082 (18) | 0.27954 (16) | 0.45188 (16) | 0.0300 (5) | |
H10A | 0.708 (2) | 0.267 (3) | 0.495 (2) | 0.037 (10)* | |
H10B | 0.691 (3) | 0.275 (3) | 0.3954 (19) | 0.046 (11)* | |
O11 | 0.57222 (19) | 0.44990 (18) | 0.54137 (17) | 0.0371 (5) | |
H11C | 0.5000 | 0.5000 | 0.5000 | 0.045* | |
H11A | 0.593 (4) | 0.402 (3) | 0.502 (3) | 0.077 (16)* | |
H11B | 0.552 (4) | 0.418 (4) | 0.596 (2) | 0.079 (15)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0300 (4) | 0.0155 (3) | 0.0261 (3) | 0.0004 (2) | −0.0001 (2) | −0.00010 (19) |
S1 | 0.0317 (4) | 0.0168 (4) | 0.0278 (4) | −0.0015 (2) | −0.0010 (3) | 0.0016 (2) |
O1 | 0.0291 (12) | 0.0171 (10) | 0.0355 (11) | 0.0009 (8) | −0.0026 (9) | 0.0009 (8) |
O2 | 0.0402 (12) | 0.0183 (10) | 0.0265 (11) | 0.0001 (8) | 0.0014 (9) | −0.0005 (8) |
O3 | 0.0317 (11) | 0.0224 (10) | 0.0280 (11) | −0.0002 (8) | 0.0002 (9) | −0.0034 (8) |
O4 | 0.0405 (11) | 0.0207 (10) | 0.0308 (10) | −0.0083 (8) | −0.0011 (9) | 0.0008 (8) |
O5 | 0.0344 (11) | 0.0284 (10) | 0.0309 (10) | −0.0043 (8) | −0.0017 (8) | 0.0068 (8) |
O6 | 0.0396 (12) | 0.0231 (10) | 0.0359 (11) | 0.0020 (8) | 0.0008 (9) | −0.0033 (8) |
O7 | 0.0373 (12) | 0.0206 (10) | 0.0369 (11) | −0.0003 (8) | −0.0053 (9) | 0.0030 (8) |
O8 | 0.0431 (12) | 0.0219 (10) | 0.0295 (11) | −0.0026 (9) | 0.0000 (9) | 0.0003 (9) |
O9 | 0.0364 (12) | 0.0198 (10) | 0.0319 (11) | −0.0005 (9) | 0.0020 (9) | 0.0005 (8) |
O10 | 0.0331 (11) | 0.0261 (10) | 0.0308 (11) | 0.0006 (8) | −0.0016 (10) | 0.0023 (9) |
O11 | 0.0486 (13) | 0.0304 (12) | 0.0324 (12) | 0.0044 (10) | 0.0025 (10) | 0.0028 (10) |
Geometric parameters (Å, º) top
Fe1—O2i | 1.991 (2) | Fe1—O3 | 2.004 (2) |
Fe1—O2 | 1.991 (2) | S1—O4 | 1.468 (2) |
Fe1—O1 | 1.994 (2) | S1—O7 | 1.472 (2) |
Fe1—O1i | 1.994 (2) | S1—O5 | 1.478 (2) |
Fe1—O3i | 2.004 (2) | S1—O6 | 1.485 (2) |
| | | |
O2i—Fe1—O2 | 180.0 | O2—Fe1—O3 | 89.55 (9) |
O2i—Fe1—O1 | 89.75 (8) | O1—Fe1—O3 | 89.53 (8) |
O2—Fe1—O1 | 90.25 (8) | O1i—Fe1—O3 | 90.47 (8) |
O2i—Fe1—O1i | 90.25 (8) | O3i—Fe1—O3 | 180.0 |
O2—Fe1—O1i | 89.75 (8) | O4—S1—O7 | 111.02 (12) |
O1—Fe1—O1i | 180.0 | O4—S1—O5 | 109.71 (12) |
O2i—Fe1—O3i | 89.55 (9) | O7—S1—O5 | 109.12 (12) |
O2—Fe1—O3i | 90.45 (9) | O4—S1—O6 | 109.36 (12) |
O1—Fe1—O3i | 90.47 (8) | O7—S1—O6 | 108.35 (12) |
O1i—Fe1—O3i | 89.53 (8) | O5—S1—O6 | 109.25 (12) |
O2i—Fe1—O3 | 90.45 (9) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5ii | 0.80 (2) | 1.82 (2) | 2.619 (3) | 173 (4) |
O1—H1B···O10 | 0.82 (2) | 1.84 (2) | 2.647 (3) | 171 (4) |
O2—H2A···O9iii | 0.82 (2) | 1.85 (2) | 2.662 (3) | 172 (5) |
O2—H2B···O7iv | 0.81 (2) | 1.83 (2) | 2.635 (3) | 172 (5) |
O3—H3A···O4 | 0.81 (2) | 1.88 (2) | 2.694 (3) | 177 (4) |
O3—H3B···O8 | 0.83 (2) | 1.80 (2) | 2.632 (3) | 178 (4) |
O8—H8A···O6v | 0.82 (2) | 2.03 (2) | 2.839 (3) | 171 (4) |
O8—H8B···O4vi | 0.82 (2) | 1.96 (2) | 2.769 (3) | 171 (4) |
O9—H9A···O6 | 0.81 (2) | 1.94 (3) | 2.719 (3) | 160 (5) |
O9—H9B···O7iv | 0.81 (2) | 1.90 (2) | 2.708 (3) | 175 (4) |
O10—H10A···O5 | 0.81 (2) | 1.86 (2) | 2.666 (3) | 178 (4) |
O10—H10B···O6v | 0.82 (2) | 1.93 (2) | 2.727 (3) | 167 (4) |
O11—H11A···O10 | 0.83 (2) | 1.87 (2) | 2.676 (3) | 161 (5) |
O11—H11B···O9 | 0.84 (2) | 1.84 (2) | 2.664 (3) | 164 (5) |
Symmetry codes: (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1, y−1/2, −z+3/2; (iv) x−1/2, y, −z+3/2; (v) x, −y+1/2, z−1/2; (vi) −x+3/2, −y, z−1/2. |
(I_200K) Diiron(III) trisulfate–sulfuric acid–water (1/1/28)
top
Crystal data top
Fe2(SO4)3·H2SO4·28H2O | F(000) = 1052 |
Mr = 501.22 | Dx = 1.683 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 11840 reflections |
a = 12.0802 (19) Å | θ = 2.7–29.6° |
b = 12.7630 (19) Å | µ = 1.07 mm−1 |
c = 12.832 (2) Å | T = 200 K |
V = 1978.5 (5) Å3 | Plate, violet |
Z = 4 | 0.45 × 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 focus | 1385 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.147 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 1.6° |
rotation method scans | h = −14→14 |
Absorption correction: integration (Coppens, 1970) | k = −15→15 |
Tmin = 0.707, Tmax = 0.886 | l = −15→15 |
17528 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | All 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 parameters | Δρmax = 0.45 e Å−3 |
12 restraints | Δρmin = −0.68 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Fe1 | 0.5000 | 0.0000 | 0.5000 | 0.01046 (17) | |
S1 | 0.81319 (5) | 0.19418 (5) | 0.69455 (5) | 0.01312 (19) | |
O1 | 0.48873 (16) | 0.15490 (15) | 0.48543 (16) | 0.0153 (4) | |
H1A | 0.429 (2) | 0.180 (3) | 0.468 (4) | 0.053 (13)* | |
H1B | 0.5429 (19) | 0.190 (2) | 0.478 (2) | 0.008 (7)* | |
O2 | 0.48350 (17) | 0.01322 (15) | 0.65377 (15) | 0.0168 (4) | |
H2A | 0.477 (4) | −0.040 (2) | 0.688 (3) | 0.053 (13)* | |
H2B | 0.465 (4) | 0.066 (2) | 0.684 (3) | 0.045 (12)* | |
O3 | 0.66400 (17) | 0.01340 (16) | 0.51529 (16) | 0.0163 (4) | |
H3A | 0.690 (3) | 0.036 (3) | 0.569 (2) | 0.049 (13)* | |
H3B | 0.706 (3) | 0.023 (3) | 0.466 (2) | 0.033 (11)* | |
O4 | 0.75267 (19) | 0.09480 (17) | 0.69001 (16) | 0.0257 (5) | |
O5 | 0.82066 (16) | 0.24043 (17) | 0.58989 (16) | 0.0248 (5) | |
O6 | 0.75378 (19) | 0.26804 (16) | 0.76383 (17) | 0.0281 (5) | |
O7 | 0.92547 (17) | 0.17857 (15) | 0.73607 (17) | 0.0227 (5) | |
O8 | 0.80022 (19) | 0.03375 (18) | 0.35666 (17) | 0.0247 (5) | |
H8A | 0.785 (3) | −0.004 (3) | 0.309 (2) | 0.038 (12)* | |
H8B | 0.791 (4) | 0.090 (2) | 0.330 (3) | 0.053 (14)* | |
O9 | 0.55072 (19) | 0.34947 (16) | 0.72097 (16) | 0.0203 (5) | |
H9A | 0.613 (2) | 0.326 (3) | 0.728 (4) | 0.046 (13)* | |
H9B | 0.510 (3) | 0.301 (3) | 0.731 (4) | 0.056 (14)* | |
O10 | 0.66128 (17) | 0.27876 (17) | 0.45181 (17) | 0.0219 (5) | |
H10A | 0.714 (2) | 0.263 (3) | 0.489 (3) | 0.027 (10)* | |
H10B | 0.688 (4) | 0.273 (3) | 0.394 (2) | 0.052 (13)* | |
O11A | 0.5730 (3) | 0.4492 (3) | 0.5411 (3) | 0.0298 (7) | 0.80 |
H11C | 0.5000 | 0.5000 | 0.5000 | 0.036* | |
O11B | 0.5161 (16) | 0.4097 (13) | 0.5195 (11) | 0.038 (3) | 0.20 |
H11B | 0.540 (6) | 0.415 (5) | 0.590 (5) | 0.085 (19)* | |
H11A | 0.599 (5) | 0.398 (4) | 0.495 (4) | 0.069 (16)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0119 (3) | 0.0092 (3) | 0.0102 (3) | 0.0008 (2) | −0.0001 (2) | −0.0004 (2) |
S1 | 0.0150 (3) | 0.0121 (3) | 0.0122 (3) | −0.0027 (3) | −0.0024 (3) | 0.0027 (2) |
O1 | 0.0112 (10) | 0.0120 (9) | 0.0228 (11) | −0.0020 (8) | −0.0018 (8) | 0.0018 (8) |
O2 | 0.0260 (11) | 0.0130 (10) | 0.0113 (10) | 0.0015 (9) | 0.0034 (8) | −0.0005 (8) |
O3 | 0.0134 (10) | 0.0224 (10) | 0.0131 (11) | 0.0000 (8) | 0.0007 (8) | −0.0024 (9) |
O4 | 0.0388 (12) | 0.0207 (11) | 0.0175 (10) | −0.0174 (9) | −0.0040 (10) | 0.0023 (8) |
O5 | 0.0205 (10) | 0.0355 (12) | 0.0184 (11) | −0.0082 (9) | −0.0039 (9) | 0.0152 (9) |
O6 | 0.0326 (12) | 0.0244 (11) | 0.0273 (12) | 0.0044 (9) | 0.0039 (10) | −0.0080 (10) |
O7 | 0.0194 (11) | 0.0176 (9) | 0.0311 (12) | −0.0016 (8) | −0.0106 (9) | 0.0067 (9) |
O8 | 0.0316 (12) | 0.0233 (12) | 0.0191 (12) | −0.0039 (10) | 0.0032 (10) | −0.0026 (10) |
O9 | 0.0252 (12) | 0.0168 (10) | 0.0189 (11) | 0.0004 (9) | 0.0029 (9) | −0.0010 (8) |
O10 | 0.0193 (11) | 0.0243 (11) | 0.0223 (12) | −0.0012 (8) | −0.0050 (10) | 0.0035 (10) |
O11A | 0.0360 (19) | 0.0309 (18) | 0.0226 (17) | 0.0060 (16) | 0.0056 (16) | 0.0042 (15) |
O11B | 0.051 (10) | 0.037 (8) | 0.027 (8) | 0.023 (8) | 0.013 (7) | 0.011 (6) |
Geometric parameters (Å, º) top
Fe1—O1 | 1.9905 (19) | S1—O4 | 1.465 (2) |
Fe1—O1i | 1.9905 (19) | S1—O5 | 1.470 (2) |
Fe1—O2i | 1.990 (2) | S1—O7 | 1.471 (2) |
Fe1—O2 | 1.990 (2) | S1—O6 | 1.481 (2) |
Fe1—O3i | 1.998 (2) | O11A—O11B | 0.90 (2) |
Fe1—O3 | 1.998 (2) | | |
| | | |
O1—Fe1—O1i | 180.0 | O1i—Fe1—O3 | 90.46 (8) |
O1—Fe1—O2i | 89.88 (8) | O2i—Fe1—O3 | 90.30 (8) |
O1i—Fe1—O2i | 90.12 (8) | O2—Fe1—O3 | 89.70 (8) |
O1—Fe1—O2 | 90.12 (8) | O3i—Fe1—O3 | 180.0 |
O1i—Fe1—O2 | 89.88 (8) | O4—S1—O5 | 110.00 (12) |
O2i—Fe1—O2 | 180.0 | O4—S1—O7 | 110.94 (12) |
O1—Fe1—O3i | 90.46 (8) | O5—S1—O7 | 109.20 (12) |
O1i—Fe1—O3i | 89.54 (8) | O4—S1—O6 | 109.45 (13) |
O2i—Fe1—O3i | 89.70 (8) | O5—S1—O6 | 108.82 (13) |
O2—Fe1—O3i | 90.30 (8) | O7—S1—O6 | 108.40 (13) |
O1—Fe1—O3 | 89.54 (8) | | |
Symmetry code: (i) −x+1, −y, −z+1. |