Buy article online - an online subscription or single-article purchase is required to access this article.
The highly disordered crystal structure of triammonium hydrogen disulfate, (NH
4)
3H(SO
4)
2, in the high-temperature phase I was studied using single-crystal neutron diffraction. It is known that the O atom involved in hydrogen bonding between neighbouring SO
4 tetrahedra is disordered and takes a split-atom position, building a two-dimensional hydrogen-bond network in the (001) plane. The H atoms in these SO
4-H-SO
4 hydrogen bonds are disordered and hence refined with a split-atom model. Moreover, from the much larger anisotropic mean-square displacements of ammonium protons the NH
groups were refined with a reasonable split-atom model, and their motional behaviour was also analysed by rigid-body treatment. Finally, careful consideration was given to show possible supplementary proton migration between the ammonium protons and those of the hydrogen bonds in this high-temperature phase.
Supporting information
Data collection: DIF4N (modified Linux version of DIF4); cell refinement: DIF4N; data reduction: PRON (Scherf, 1998); program(s) used to refine structure: Jana2006 (Petricek, Dusek & Palatinus, 2006); molecular graphics: Atoms 5.1; software used to prepare material for publication: Jana2006 (Petricek, Dusek & Palatinus, 2006).
Crystal data top
HO8S2·3(H4N) | Dx = 1.805 (2) Mg m−3 |
Mr = 247.2 | Neutron radiation, λ = 0.555 Å |
Trigonal, R3m | Cell parameters from 20 reflections |
Hall symbol: -R 3;-2" | θ = 8.4–12.0° |
a = 5.907 (3) Å | µ = 0.02 mm−1 |
c = 22.57 (1) Å | T = 413 K |
V = 682.0 (6) Å3 | Cuboid, colourless |
Z = 3 | 3 × 3 × 3 × 0 (radius) mm |
F(000) = 95 | |
Data collection top
Single-crystal diffractometer HEiDi | Rint = 0.065 |
Radiation source: nuclear reactor | θmax = 29.9°, θmin = 4.2° |
Cu (420) monochromator | h = −10→9 |
ω scans | k = −8→9 |
1164 measured reflections | l = −30→40 |
452 independent reflections | 3 standard reflections every 480 min min |
133 reflections with I > 3σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | 0 constraints |
R[F2 > 2σ(F2)] = 0.056 | All H-atom parameters refined |
wR(F2) = 0.109 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
S = 1.51 | (Δ/σ)max = 0.028 |
452 reflections | Δρmax = 4.89 e Å−3 |
48 parameters | Δρmin = −3.51 e Å−3 |
0 restraints | |
Crystal data top
HO8S2·3(H4N) | Z = 3 |
Mr = 247.2 | Neutron radiation, λ = 0.555 Å |
Trigonal, R3m | µ = 0.02 mm−1 |
a = 5.907 (3) Å | T = 413 K |
c = 22.57 (1) Å | 3 × 3 × 3 × 0 (radius) mm |
V = 682.0 (6) Å3 | |
Data collection top
Single-crystal diffractometer HEiDi | Rint = 0.065 |
1164 measured reflections | 3 standard reflections every 480 min min |
452 independent reflections | intensity decay: none |
133 reflections with I > 3σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.109 | All H-atom parameters refined |
S = 1.51 | Δρmax = 4.89 e Å−3 |
452 reflections | Δρmin = −3.51 e Å−3 |
48 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S | 0 | 0 | 0.4093 (3) | 0.052 (2) | |
N1 | 0 | 0 | 0 | 0.0569 (18) | |
N2 | 0 | 0 | 0.1993 (2) | 0.0642 (11) | |
O1 | 0.0379 (7) | −0.0379 (7) | 0.3435 (3) | 0.067 (3) | 0.3333 |
O2 | 0.1348 (2) | −0.1348 (2) | 0.57103 (13) | 0.0741 (13) | |
H1 | 0.464 (2) | −0.464 (2) | −0.0023 (12) | 0.063 (6)* | 0.1667 |
H4 | 0.0542 (17) | −0.0542 (17) | 0.1620 (6) | 0.093 (7) | 0.3333 |
H5 | 0.1381 (19) | −0.0321 (17) | 0.2122 (4) | 0.126 (7) | 0.5 |
H3 | 0.041 (4) | −0.041 (4) | −0.031 (2) | 0.087 (15)* | 0.1667 |
H2 | −0.0884 (12) | 0.0884 (12) | −0.0230 (8) | 0.116 (8) | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.062 (3) | 0.062 (3) | 0.031 (4) | 0.0311 (15) | 0 | 0 |
N1 | 0.058 (2) | 0.058 (2) | 0.055 (3) | 0.0290 (11) | 0 | 0 |
N2 | 0.0581 (12) | 0.0581 (12) | 0.077 (2) | 0.0290 (6) | 0 | 0 |
O1 | 0.074 (5) | 0.074 (5) | 0.050 (3) | 0.033 (3) | 0.0020 (15) | −0.0020 (15) |
O2 | 0.0814 (15) | 0.0814 (15) | 0.0809 (17) | 0.0568 (16) | −0.0015 (7) | 0.0015 (7) |
H4 | 0.088 (8) | 0.088 (8) | 0.091 (9) | 0.034 (7) | 0.027 (5) | −0.027 (5) |
H5 | 0.079 (7) | 0.096 (8) | 0.210 (9) | 0.050 (7) | 0.002 (5) | 0.038 (5) |
H2 | 0.119 (8) | 0.119 (8) | 0.139 (14) | 0.079 (9) | −0.015 (5) | 0.015 (5) |
Geometric parameters (Å, º) top
S—O1 | 1.535 (9) | N1—H2ii | 1.042 (12) |
S—O1i | 1.535 (9) | N1—H2vi | 1.042 (12) |
S—O1ii | 1.535 (9) | N1—H2vii | 1.042 (12) |
S—O2iii | 1.449 (3) | N1—H2viii | 1.042 (12) |
S—O2iv | 1.449 (3) | N2—H4 | 1.009 (14) |
S—O2v | 1.449 (3) | N2—H4i | 1.009 (14) |
N1—H3 | 0.82 (4) | N2—H4ii | 1.009 (14) |
N1—H3i | 0.82 (4) | N2—H5 | 0.970 (13) |
N1—H3ii | 0.82 (4) | N2—H5i | 0.970 (15) |
N1—H3vi | 0.82 (4) | N2—H5ii | 0.970 (10) |
N1—H3vii | 0.82 (4) | N2—H5ix | 0.970 (13) |
N1—H3viii | 0.82 (4) | N2—H5x | 0.970 (15) |
N1—H2 | 1.042 (12) | N2—H5xi | 0.970 (10) |
N1—H2i | 1.042 (12) | | |
| | | |
O1—S—O2iii | 122.5 (4) | H2—N1—H2i | 97.4 (10) |
O1—S—O2iv | 100.2 (3) | H2—N1—H2ii | 97.4 (10) |
O1—S—O2v | 100.2 (3) | H3vi—N1—H2 | 89 (2) |
O1i—S—O2iii | 100.2 (3) | H3vii—N1—H2 | 131 (2) |
O1i—S—O2iv | 100.2 (3) | H3viii—N1—H2 | 131 (2) |
O1i—S—O2v | 122.5 (4) | H2i—N1—H2ii | 97.4 (9) |
O1ii—S—O2iii | 100.2 (3) | H4—N2—H5 | 76.0 (9) |
O1ii—S—O2iv | 122.5 (4) | H4—N2—H5i | 130.6 (8) |
O1ii—S—O2v | 100.2 (3) | H4—N2—H5ii | 110.1 (8) |
O2iii—S—O2iv | 111.0 (3) | H5—N2—H5i | 111.4 (8) |
O2iii—S—O2v | 111.0 (3) | H5—N2—H5ii | 111.4 (10) |
O2iv—S—O2v | 111.0 (3) | H5i—N2—H5ii | 111.4 (10) |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) y, x, −z+1; (iv) x−y, −y, −z+1; (v) −x, −x+y, −z+1; (vi) y, x, −z; (vii) x−y, −y, −z; (viii) −x, −x+y, −z; (ix) −y, −x, z; (x) −x+y, y, z; (xi) x, x−y, z. |
Experimental details
Crystal data |
Chemical formula | HO8S2·3(H4N) |
Mr | 247.2 |
Crystal system, space group | Trigonal, R3m |
Temperature (K) | 413 |
a, c (Å) | 5.907 (3), 22.57 (1) |
V (Å3) | 682.0 (6) |
Z | 3 |
Radiation type | Neutron, λ = 0.555 Å |
µ (mm−1) | 0.02 |
Crystal size (mm) | 3 × 3 × 3 × 0 (radius) |
|
Data collection |
Diffractometer | Single-crystal diffractometer HEiDi |
Absorption correction | – |
No. of measured, independent and observed [I > 3σ(I)] reflections | 1164, 452, 133 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.899 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.109, 1.51 |
No. of reflections | 452 |
No. of parameters | 48 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 4.89, −3.51 |
Selected geometric parameters (Å, º) topS—O1 | 1.535 (9) | N1—H2ii | 1.042 (12) |
S—O1i | 1.535 (9) | N1—H2vi | 1.042 (12) |
S—O1ii | 1.535 (9) | N1—H2vii | 1.042 (12) |
S—O2iii | 1.449 (3) | N1—H2viii | 1.042 (12) |
S—O2iv | 1.449 (3) | N2—H4 | 1.009 (14) |
S—O2v | 1.449 (3) | N2—H4i | 1.009 (14) |
N1—H3 | 0.82 (4) | N2—H4ii | 1.009 (14) |
N1—H3i | 0.82 (4) | N2—H5 | 0.970 (13) |
N1—H3ii | 0.82 (4) | N2—H5i | 0.970 (15) |
N1—H3vi | 0.82 (4) | N2—H5ii | 0.970 (10) |
N1—H3vii | 0.82 (4) | N2—H5ix | 0.970 (13) |
N1—H3viii | 0.82 (4) | N2—H5x | 0.970 (15) |
N1—H2 | 1.042 (12) | N2—H5xi | 0.970 (10) |
N1—H2i | 1.042 (12) | | |
| | | |
O1—S—O2iii | 122.5 (4) | H2—N1—H2i | 97.4 (10) |
O1—S—O2iv | 100.2 (3) | H2—N1—H2ii | 97.4 (10) |
O1—S—O2v | 100.2 (3) | H3vi—N1—H2 | 89 (2) |
O1i—S—O2iii | 100.2 (3) | H3vii—N1—H2 | 131 (2) |
O1i—S—O2iv | 100.2 (3) | H3viii—N1—H2 | 131 (2) |
O1i—S—O2v | 122.5 (4) | H2i—N1—H2ii | 97.4 (9) |
O1ii—S—O2iii | 100.2 (3) | H4—N2—H5 | 76.0 (9) |
O1ii—S—O2iv | 122.5 (4) | H4—N2—H5i | 130.6 (8) |
O1ii—S—O2v | 100.2 (3) | H4—N2—H5ii | 110.1 (8) |
O2iii—S—O2iv | 111.0 (3) | H5—N2—H5i | 111.4 (8) |
O2iii—S—O2v | 111.0 (3) | H5—N2—H5ii | 111.4 (10) |
O2iv—S—O2v | 111.0 (3) | H5i—N2—H5ii | 111.4 (10) |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) y, x, −z+1; (iv) x−y, −y, −z+1; (v) −x, −x+y, −z+1; (vi) y, x, −z; (vii) x−y, −y, −z; (viii) −x, −x+y, −z; (ix) −y, −x, z; (x) −x+y, y, z; (xi) x, x−y, z. |
Subscribe to Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.