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Single-crystal neutron diffraction was used to investigate the H-atom disorder in triammonium hydrogen disulfate (TAHS), (NH4)3H(SO4)2, below room temperature. Crystal structure analysis of the monoclinic phase III shows an increase of proton ordering with decreasing temperature in the (SO4)H(SO4) dimer. Moreover, the NH4+ groups on a general position begin ordering in this phase. The monoclinic unit cell of TAHS-IV doubles in the b direction and a slight distortion of SO42− and NH4+ tetrahedra is observed. The order parameter introduced by Landau was determined for the second-order II/III and III/IV phase transitions from the intensities of the superstructure reflections. TAHS-V has a triclinic space group and the crystal structure seems to be completely ordered according to a structure analysis by single-crystal X-ray diffraction measurements. In addition, the decisive role of the dynamical disorder of different ammonium groups on successive phase transitions is discussed. Additional peaks were observed by X-ray powder diffraction measurements at ∼ 70 K on cooling, which refers to the V/VII phase transition. These additional peaks remained up to ∼ 85 K on heating. They were described with a doubling of the unit cell along all three principal crystallographic directions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052519213013092/hw5024sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213013092/hw5024Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213013092/hw5024IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213013092/hw5024IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213013092/hw5024IVsup5.hkl
Contains datablock IV

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052519213013092/hw5024sup6.pdf
Extra figures

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002) for (I); DIF4N (modified Linux version of DIF4) for (II), (III), (IV). Cell refinement: X-AREA (Stoe & Cie, 2002) for (I); DIF4N for (II), (III), (IV). Data reduction: X-RED (Stoe & Cie, 1996) for (I); PRON (Scherf, 1998) for (II), (III), (IV). Program(s) used to solve structure: SHELXL97 (Sheldrick, 1997) for (I). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); Jana2006 (Petricek, Dusek & Palatinus, 2006) for (II), (III), (IV). For all compounds, molecular graphics: Atoms 5.1. Software used to prepare material for publication: WinGX (Farrugia, 1999) for (I); Jana2006 (Petricek, Dusek & Palatinus, 2006) for (II), (III), (IV).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
(I) top
Crystal data top
HO8S2·3(H4N)Z = 4
Mr = 247.25F(000) = 520
Triclinic, P1Dx = 1.838 Mg m3
a = 8.282 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.095 (5) ÅCell parameters from 17019 reflections
c = 11.613 (6) Åθ = 5.4–64.5°
α = 90.44 (5)°µ = 0.62 mm1
β = 110.07 (6)°T = 126 K
γ = 100.64 (5)°Cube, colourless
V = 893.6 (8) Å30.3 × 0.3 × 0.1 mm
Data collection top
Stoe IPDS II
diffractometer
6139 independent reflections
Radiation source: fine-focus sealed tube3270 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 0 pixels mm-1θmax = 32.1°, θmin = 2.7°
rotation method scansh = 1212
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1996)
k = 1415
Tmin = 0.797, Tmax = 0.942l = 1716
21478 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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 0.94 w = 1/[σ2(Fo2) + (0.0555P)2]
where P = (Fo2 + 2Fc2)/3
6139 reflections(Δ/σ)max < 0.001
326 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
HO8S2·3(H4N)γ = 100.64 (5)°
Mr = 247.25V = 893.6 (8) Å3
Triclinic, P1Z = 4
a = 8.282 (4) ÅMo Kα radiation
b = 10.095 (5) ŵ = 0.62 mm1
c = 11.613 (6) ÅT = 126 K
α = 90.44 (5)°0.3 × 0.3 × 0.1 mm
β = 110.07 (6)°
Data collection top
Stoe IPDS II
diffractometer
6139 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1996)
3270 reflections with I > 2σ(I)
Tmin = 0.797, Tmax = 0.942Rint = 0.057
21478 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.50 e Å3
6139 reflectionsΔρmin = 0.65 e Å3
326 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
S10.27434 (8)0.45664 (6)0.30120 (6)0.01303 (14)
S20.73018 (8)0.53509 (6)0.19599 (6)0.01292 (14)
S30.28036 (8)0.04511 (6)0.08780 (6)0.01307 (14)
S40.73056 (8)0.03433 (6)0.41981 (6)0.01277 (14)
O10.4686 (3)0.4342 (2)0.32952 (19)0.0207 (4)
O20.5280 (3)0.5579 (2)0.1617 (2)0.0214 (4)
O30.2100 (3)0.60192 (18)0.30772 (18)0.0181 (4)
O40.7926 (3)0.39041 (18)0.19578 (18)0.0187 (4)
O50.2384 (3)0.3761 (2)0.39211 (18)0.0199 (4)
O60.7568 (3)0.6131 (2)0.10102 (18)0.0199 (4)
O70.1918 (3)0.4163 (2)0.17651 (18)0.0193 (4)
O80.8000 (3)0.5844 (2)0.31794 (18)0.0196 (4)
O90.4743 (3)0.0669 (2)0.15845 (19)0.0211 (4)
O100.5304 (3)0.0470 (2)0.3564 (2)0.0215 (4)
O110.2076 (3)0.10103 (17)0.07996 (17)0.0173 (4)
O120.8113 (3)0.10747 (18)0.42362 (17)0.0187 (4)
O130.2532 (3)0.0915 (2)0.03586 (18)0.0200 (4)
O140.7866 (3)0.1204 (2)0.34556 (18)0.0197 (4)
O150.2013 (3)0.12149 (19)0.15426 (17)0.0188 (4)
O160.7558 (3)0.0803 (2)0.54178 (18)0.0200 (4)
N10.5028 (3)0.2577 (3)0.6124 (2)0.0163 (5)
N20.5078 (3)0.7555 (3)0.1168 (2)0.0163 (5)
N30.1012 (3)0.6529 (3)0.5127 (2)0.0176 (5)
N40.0963 (3)0.3453 (3)0.0141 (2)0.0172 (5)
N50.0918 (4)0.1523 (3)0.2823 (3)0.0172 (5)
N60.1081 (4)0.1497 (3)0.2045 (2)0.0181 (5)
H10.499 (7)0.538 (5)0.220 (5)0.061 (15)*
H20.517 (6)0.011 (4)0.280 (4)0.051 (13)*
H30.549 (4)0.193 (3)0.596 (3)0.013 (8)*
H40.421 (6)0.317 (4)0.545 (4)0.043 (12)*
H50.587 (5)0.308 (4)0.642 (4)0.034 (10)*
H60.443 (6)0.246 (4)0.672 (4)0.039 (11)*
H70.428 (5)0.800 (3)0.087 (3)0.018 (8)*
H80.561 (4)0.672 (3)0.069 (3)0.018 (8)*
H90.467 (7)0.737 (5)0.188 (5)0.058 (14)*
H100.579 (7)0.794 (5)0.121 (4)0.046 (13)*
H110.134 (6)0.631 (5)0.453 (5)0.049 (13)*
H120.141 (6)0.712 (5)0.562 (4)0.045 (12)*
H130.126 (5)0.581 (4)0.558 (4)0.028 (10)*
H140.00000.680 (4)0.487 (3)0.027 (10)*
H150.137 (5)0.363 (4)0.040 (4)0.026 (10)*
H160.127 (5)0.284 (4)0.059 (4)0.036 (11)*
H170.016 (6)0.334 (4)0.026 (4)0.033 (10)*
H180.126 (5)0.417 (4)0.063 (4)0.027 (10)*
H190.112 (6)0.130 (5)0.222 (5)0.045 (13)*
H200.143 (4)0.087 (3)0.332 (3)0.014 (8)*
H210.012 (7)0.170 (4)0.264 (4)0.042 (13)*
H220.127 (5)0.216 (4)0.313 (3)0.021 (9)*
H230.141 (6)0.224 (4)0.173 (4)0.032 (10)*
H240.116 (5)0.128 (4)0.273 (4)0.022 (9)*
H250.009 (7)0.167 (5)0.218 (4)0.048 (14)*
H260.170 (5)0.073 (4)0.163 (4)0.035 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0132 (3)0.0123 (3)0.0135 (3)0.0036 (2)0.0041 (2)0.0011 (2)
S20.0135 (3)0.0117 (3)0.0132 (3)0.0025 (2)0.0041 (2)0.0011 (2)
S30.0137 (3)0.0119 (3)0.0149 (3)0.0030 (2)0.0064 (2)0.00196 (19)
S40.0138 (3)0.0114 (3)0.0140 (3)0.0017 (2)0.0064 (2)0.000
O10.0134 (9)0.0222 (9)0.0243 (10)0.0028 (7)0.0042 (7)0.000
O20.0118 (9)0.0268 (10)0.0234 (10)0.0015 (7)0.0047 (8)0.0016 (7)
O30.0212 (10)0.0134 (8)0.0211 (9)0.0038 (7)0.0089 (8)0.0028 (6)
O40.0215 (10)0.0123 (8)0.0227 (9)0.0022 (7)0.0089 (8)0.000
O50.0212 (10)0.0217 (9)0.0169 (9)0.0058 (7)0.0061 (7)0.0031 (7)
O60.0233 (10)0.0200 (9)0.0170 (9)0.0049 (7)0.0076 (7)0.0029 (7)
O70.0198 (9)0.0228 (9)0.0152 (8)0.0072 (7)0.0043 (7)0.0050 (7)
O80.0194 (9)0.0249 (10)0.0151 (8)0.0074 (7)0.0052 (7)0.0051 (7)
O90.0126 (8)0.0220 (9)0.0266 (10)0.0026 (7)0.0048 (7)0.0039 (7)
O100.0141 (9)0.0255 (10)0.0244 (10)0.0034 (7)0.0065 (7)0.000
O110.0198 (9)0.0115 (8)0.0211 (9)0.0033 (6)0.0077 (7)0.0018 (6)
O120.0225 (10)0.0122 (8)0.0189 (9)0.0000.0060 (7)0.0017 (6)
O130.0235 (10)0.0213 (9)0.0153 (8)0.0000.0091 (7)0.0040 (7)
O140.0200 (9)0.0232 (9)0.0173 (9)0.0065 (7)0.0074 (7)0.0021 (7)
O150.0206 (9)0.0215 (9)0.0174 (9)0.0072 (7)0.0089 (7)0.000
O160.0216 (10)0.0236 (9)0.0150 (8)0.0000.0088 (7)0.0021 (7)
N10.0165 (10)0.0135 (10)0.0196 (11)0.0021 (8)0.0075 (8)0.0026 (7)
N20.0148 (11)0.0149 (10)0.0176 (11)0.0019 (8)0.0043 (9)0.000
N30.0182 (12)0.0157 (11)0.0164 (11)0.0000.0049 (9)0.000
N40.0179 (12)0.0160 (11)0.0162 (11)0.0036 (8)0.0041 (9)0.0020 (8)
N50.0184 (12)0.0151 (11)0.0190 (11)0.0038 (8)0.0075 (9)0.000
N60.0192 (12)0.0173 (11)0.0196 (12)0.0019 (9)0.0100 (9)0.0027 (8)
Geometric parameters (Å, º) top
S1—O51.468 (2)N1—H61.00 (5)
S1—O71.471 (2)N2—H70.90 (4)
S1—O31.477 (2)N2—H80.95 (3)
S1—O11.500 (2)N2—H90.81 (5)
S2—O61.450 (2)N2—H100.78 (5)
S2—O41.457 (2)N3—H110.84 (5)
S2—O81.464 (2)N3—H120.86 (5)
S2—O21.554 (2)N3—H130.84 (4)
S3—O151.464 (2)N3—H140.780 (6)
S3—O131.469 (2)N4—H150.82 (4)
S3—O111.477 (2)N4—H160.83 (4)
S3—O91.505 (2)N4—H170.87 (4)
S4—O161.452 (2)N4—H180.86 (4)
S4—O121.457 (2)N5—H190.80 (5)
S4—O141.458 (2)N5—H200.82 (3)
S4—O101.546 (2)N5—H210.80 (5)
O2—H10.83 (5)N5—H220.79 (4)
O10—H20.94 (5)N6—H230.89 (4)
N1—H30.76 (3)N6—H240.84 (4)
N1—H40.95 (4)N6—H250.76 (5)
N1—H50.91 (4)N6—H260.88 (4)
O5—S1—O7110.70 (13)H5—N1—H6111 (4)
O5—S1—O3110.01 (13)H7—N2—H8108 (3)
O7—S1—O3110.25 (13)H7—N2—H9114 (4)
O5—S1—O1109.37 (13)H8—N2—H9106 (4)
O7—S1—O1108.47 (14)H7—N2—H10117 (4)
O3—S1—O1107.99 (13)H8—N2—H10110 (4)
O6—S2—O4112.52 (13)H9—N2—H10101 (5)
O6—S2—O8112.79 (14)H11—N3—H12124 (5)
O4—S2—O8112.22 (13)H11—N3—H13105 (4)
O6—S2—O2105.23 (14)H12—N3—H13105 (4)
O4—S2—O2106.78 (14)H11—N3—H14109 (4)
O8—S2—O2106.68 (14)H12—N3—H14104 (4)
O15—S3—O13110.94 (13)H13—N3—H14110 (4)
O15—S3—O11110.50 (13)H15—N4—H16119 (4)
O13—S3—O11110.32 (13)H15—N4—H17102 (4)
O15—S3—O9108.50 (13)H16—N4—H17115 (4)
O13—S3—O9108.79 (14)H15—N4—H18108 (4)
O11—S3—O9107.70 (13)H16—N4—H18105 (4)
O16—S4—O12112.32 (13)H17—N4—H18107 (4)
O16—S4—O14112.35 (14)H19—N5—H20104 (4)
O12—S4—O14111.73 (13)H19—N5—H21107 (5)
O16—S4—O10105.78 (14)H20—N5—H21116 (4)
O12—S4—O10107.24 (14)H19—N5—H22118 (5)
O14—S4—O10106.96 (13)H20—N5—H22106 (3)
S2—O2—H1113 (4)H21—N5—H22107 (4)
S4—O10—H2105 (3)H23—N6—H24120 (4)
H3—N1—H4116 (4)H23—N6—H25101 (4)
H3—N1—H5105 (4)H24—N6—H25104 (4)
H4—N1—H5101 (4)H23—N6—H26116 (4)
H3—N1—H6115 (4)H24—N6—H2696 (3)
H4—N1—H6107 (4)H25—N6—H26119 (5)
(II) top
Crystal data top
HO8S2·3(H4N)F(000) = 126
Mr = 247.2Dx = 1.829 (2) Mg m3
Monoclinic, P2/nNeutron radiation, λ = 0.87 Å
Hall symbol: -P 2yacCell parameters from 19 reflections
a = 15.473 (8) Åθ = 12.9–18.6°
b = 5.849 (3) ŵ = 0.002 mm1
c = 10.131 (5) ÅT = 250 K
β = 101.75 (5)°Cube, colourless
V = 897.7 (8) Å33 × 3 × 3 × 0 (radius) mm
Z = 4
Data collection top
4-circle
diffractometer
Rint = 0.043
Radiation source: nuclear reactorθmax = 37.5°, θmin = 3.3°
Cu (220) monochromatorh = 210
ω scansk = 83
1770 measured reflectionsl = 1314
1503 independent reflections2 standard reflections every 360 min min
1092 reflections with I > 3σ(I) intensity decay: none
Refinement top
Refinement on F2All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.066Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.140(Δ/σ)max = 0.036
S = 3.26Δρmax = 0.97 e Å3
1503 reflectionsΔρmin = 1.59 e Å3
208 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 87E2 (4)
2 constraints
Crystal data top
HO8S2·3(H4N)V = 897.7 (8) Å3
Mr = 247.2Z = 4
Monoclinic, P2/nNeutron radiation, λ = 0.87 Å
a = 15.473 (8) ŵ = 0.002 mm1
b = 5.849 (3) ÅT = 250 K
c = 10.131 (5) Å3 × 3 × 3 × 0 (radius) mm
β = 101.75 (5)°
Data collection top
4-circle
diffractometer
Rint = 0.043
1770 measured reflections2 standard reflections every 360 min min
1503 independent reflections intensity decay: none
1092 reflections with I > 3σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0660 restraints
wR(F2) = 0.140All H-atom parameters refined
S = 3.26Δρmax = 0.97 e Å3
1503 reflectionsΔρmin = 1.59 e Å3
208 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.3614 (5)0.4667 (11)0.4624 (6)0.025 (2)
S20.1343 (4)0.0314 (10)0.5395 (7)0.0218 (18)
N10.750.0214 (6)0.750.0280 (10)
N20.750.4803 (6)0.250.0298 (11)
N30.44921 (19)0.5239 (4)0.1557 (3)0.0317 (8)
N40.05054 (19)0.9689 (4)0.8504 (3)0.0324 (9)
O10.2641 (2)0.4315 (7)0.4463 (4)0.0382 (12)
O20.2339 (2)0.0620 (7)0.5610 (4)0.0381 (12)
O30.4011 (2)0.4449 (7)0.6054 (3)0.0320 (11)
O40.1012 (2)0.0006 (6)0.3945 (4)0.0328 (11)
O50.3769 (2)0.6950 (6)0.4132 (4)0.0345 (11)
O60.1200 (2)0.8291 (6)0.6154 (4)0.0336 (11)
O70.3956 (2)0.2909 (6)0.3836 (4)0.0341 (11)
O80.0982 (2)0.2365 (6)0.5884 (4)0.0343 (11)
H10.24890.20610.51430.0396 (17)*0.651 (14)
H20.25110.29390.48570.0396 (17)*0.349 (14)
H30.7138 (7)0.382 (3)0.1871 (13)0.108 (5)
H40.7849 (8)0.114 (2)0.8230 (10)0.092 (4)
H50.7045 (10)0.556 (3)0.274 (2)0.150 (8)
H60.7954 (10)0.946 (4)0.722 (2)0.167 (9)
H70.5100 (8)0.538 (2)0.1804 (15)0.094 (5)
H80.9872 (7)0.930 (2)0.8401 (12)0.080 (4)
H90.4259 (8)0.685 (2)0.1304 (11)0.089 (4)
H100.0804 (7)0.8798 (17)0.9281 (9)0.071 (3)
H110.4377 (7)0.413 (2)0.0783 (12)0.086 (4)
H120.0590 (6)0.1404 (13)0.8702 (8)0.062 (3)
H130.4277 (8)0.464 (2)0.2334 (10)0.086 (4)
H140.0721 (7)0.9245 (16)0.7654 (10)0.072 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.037 (4)0.027 (3)0.016 (3)0.007 (2)0.012 (3)0
S20.020 (3)0.020 (3)0.023 (3)0.004 (2)00
N10.0290 (17)0.0303 (15)0.0237 (18)00.0029 (13)0
N20.0370 (19)0.0299 (16)0.0227 (17)00.0062 (14)0
N30.0415 (15)0.0297 (13)0.0248 (13)0.0072 (10)0.0086 (10)0
N40.0377 (16)0.0251 (12)0.0343 (16)0.0056 (10)0.0072 (11)0.0026 (9)
O10.0256 (17)0.047 (2)0.043 (2)00.0085 (15)0
O20.0294 (18)0.044 (2)0.041 (2)00.0077 (15)0
O30.0382 (19)0.0349 (18)0.0215 (17)00.0027 (14)0.0033 (13)
O40.042 (2)0.0378 (19)0.0193 (17)0.0073 (15)0.0073 (15)0.0026 (13)
O50.044 (2)0.0249 (17)0.0324 (18)0.0028 (15)0.0037 (14)0.0061 (14)
O60.0410 (19)0.0287 (17)0.0320 (17)0.0055 (15)0.0098 (14)0.0110 (14)
O70.041 (2)0.0297 (17)0.0358 (18)00.0179 (14)0.0105 (14)
O80.0375 (19)0.0265 (17)0.0422 (19)0.0044 (15)0.0159 (15)0.0056 (15)
H30.068 (6)0.141 (11)0.097 (8)00.024 (5)0.041 (9)
H40.103 (8)0.090 (7)0.060 (5)0.011 (6)0.036 (5)0.025 (6)
H50.073 (8)0.150 (13)0.215 (19)0.046 (8)00.078 (13)
H60.077 (8)0.226 (19)0.187 (17)0.059 (9)00.120 (15)
H70.053 (6)0.093 (8)0.129 (10)000.036 (7)
H80.053 (5)0.094 (7)0.095 (7)0.022 (5)0.021 (5)0.040 (6)
H90.110 (9)0.062 (6)0.085 (7)000.010 (5)
H100.097 (7)0.061 (5)0.057 (5)0.008 (5)0.022 (5)0
H110.092 (7)0.083 (7)0.089 (7)0.035 (6)0.035 (6)0.042 (6)
H120.087 (6)0.033 (4)0.060 (5)000.006 (3)
H130.104 (8)0.116 (8)0.052 (5)00.045 (6)0.017 (5)
H140.104 (7)0.062 (5)0.058 (5)0.017 (5)0.033 (5)0
Geometric parameters (Å, º) top
S1—O11.495 (8)N2—H30.953 (14)
S1—O31.460 (7)N2—H3iv0.953 (14)
S1—O51.462 (8)N2—H50.906 (19)
S1—O71.465 (8)N2—H5iv0.906 (19)
S2—O21.523 (7)N3—H70.927 (12)
S2—O41.465 (7)N3—H91.023 (12)
S2—O6i1.452 (7)N3—H111.005 (12)
S2—O81.452 (7)N3—H130.980 (12)
N1—H40.985 (10)N4—H8v0.991 (11)
N1—H4ii0.985 (10)N4—H100.978 (10)
N1—H6i0.92 (2)N4—H12vi1.027 (8)
N1—H6iii0.92 (2)N4—H141.018 (11)
O1—S1—O3107.9 (5)H3—N2—H3iv105.4 (13)
O1—S1—O5108.7 (5)H3—N2—H595.3 (14)
O1—S1—O7108.2 (4)H3—N2—H5iv120.1 (17)
O3—S1—O5110.7 (4)H3iv—N2—H5120.1 (17)
O3—S1—O7110.7 (5)H3iv—N2—H5iv95.3 (14)
O5—S1—O7110.6 (5)H5—N2—H5iv121.4 (17)
O2—S2—O4107.1 (5)H7—N3—H9105.8 (10)
O2—S2—O6i106.1 (4)H7—N3—H11106.0 (11)
O2—S2—O8107.6 (4)H7—N3—H13107.9 (12)
O4—S2—O6i111.8 (4)H9—N3—H11113.6 (9)
O4—S2—O8111.3 (4)H9—N3—H13111.8 (11)
O6i—S2—O8112.5 (5)H11—N3—H13111.2 (10)
H4—N1—H4ii113.1 (10)H8v—N4—H10104.9 (10)
H4—N1—H6i99.0 (14)H8v—N4—H12vi109.2 (9)
H4—N1—H6iii111.8 (16)H8v—N4—H14109.9 (9)
H4ii—N1—H6i111.8 (16)H10—N4—H12vi110.0 (8)
H4ii—N1—H6iii99.0 (14)H10—N4—H14111.3 (9)
H6i—N1—H6iii122.9 (19)H12vi—N4—H14111.3 (8)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y, z+3/2; (iii) x+3/2, y1, z+3/2; (iv) x+3/2, y, z+1/2; (v) x1, y, z; (vi) x, y+1, z.
(III) top
Crystal data top
HO8S2·3(H4N)F(000) = 126
Mr = 247.2Dx = 1.835 (2) Mg m3
Monoclinic, P2/nNeutron radiation, λ = 0.87 Å
Hall symbol: -P 2yacCell parameters from 19 reflections
a = 15.534 (8) Åθ = 12.9–18.6°
b = 5.825 (3) ŵ = 0.002 mm1
c = 10.089 (5) ÅT = 150 K
β = 101.52 (5)°Cube, colourless
V = 894.5 (8) Å33 × 3 × 3 × 0 (radius) mm
Z = 4
Data collection top
4-circle
diffractometer
Rint = 0.024
Radiation source: nuclear reactorθmax = 37.7°, θmin = 3.3°
Cu (220) monochromatorh = 210
ω scansk = 86
2379 measured reflectionsl = 1314
1689 independent reflections2 standard reflections every 360 min min
1470 reflections with I > 3σ(I) intensity decay: none
Refinement top
Refinement on F2All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.058Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.139(Δ/σ)max = 0.031
S = 4.11Δρmax = 1.37 e Å3
1689 reflectionsΔρmin = 1.99 e Å3
208 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 73E2 (3)
2 constraints
Crystal data top
HO8S2·3(H4N)V = 894.5 (8) Å3
Mr = 247.2Z = 4
Monoclinic, P2/nNeutron radiation, λ = 0.87 Å
a = 15.534 (8) ŵ = 0.002 mm1
b = 5.825 (3) ÅT = 150 K
c = 10.089 (5) Å3 × 3 × 3 × 0 (radius) mm
β = 101.52 (5)°
Data collection top
4-circle
diffractometer
Rint = 0.024
2379 measured reflections2 standard reflections every 360 min min
1689 independent reflections intensity decay: none
1470 reflections with I > 3σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.139All H-atom parameters refined
S = 4.11Δρmax = 1.37 e Å3
1689 reflectionsΔρmin = 1.99 e Å3
208 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.3602 (3)0.4656 (8)0.4630 (4)0.0141 (13)
S20.1338 (3)0.0286 (8)0.5391 (4)0.0141 (12)
N10.750.0227 (4)0.750.0193 (6)
N20.750.4804 (4)0.250.0202 (7)
N30.44974 (11)0.5217 (3)0.15727 (16)0.0198 (5)
N40.04859 (12)0.9678 (3)0.85166 (16)0.0215 (5)
O10.26294 (17)0.4288 (5)0.4480 (3)0.0268 (8)
O20.23344 (16)0.0602 (5)0.5628 (3)0.0244 (8)
O30.40045 (17)0.4357 (4)0.6066 (2)0.0186 (7)
O40.10211 (17)0.0096 (4)0.3938 (2)0.0186 (7)
O50.37510 (17)0.6991 (4)0.4172 (2)0.0196 (7)
O60.11943 (17)0.8307 (4)0.6202 (2)0.0202 (7)
O70.39405 (16)0.2949 (4)0.3790 (2)0.0191 (7)
O80.09759 (17)0.2408 (4)0.5843 (2)0.0194 (7)
H10.24890.20610.51430.0329 (13)*0.746 (12)
H20.25110.29390.48570.0329 (13)*0.254 (12)
H30.7151 (7)0.379 (2)0.1846 (11)0.106 (4)
H40.7857 (5)0.1200 (13)0.8227 (7)0.062 (2)
H50.7029 (7)0.557 (3)0.2753 (19)0.150 (7)
H60.7942 (8)0.942 (3)0.7170 (14)0.156 (7)
H70.5133 (4)0.5300 (11)0.1871 (7)0.053 (2)
H80.9850 (4)0.9298 (12)0.8403 (7)0.050 (2)
H90.4266 (4)0.6866 (9)0.1366 (5)0.0391 (16)
H100.0809 (4)0.8769 (9)0.9338 (5)0.0405 (17)
H110.4339 (4)0.4225 (9)0.0704 (5)0.0386 (16)
H120.0590 (4)0.1426 (8)0.8676 (5)0.0371 (16)
H130.4236 (4)0.4479 (9)0.2321 (5)0.0407 (17)
H140.0706 (4)0.9184 (9)0.7663 (5)0.0395 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.021 (2)0.014 (2)0.0089 (19)00.0067 (16)0
S20.016 (2)0.015 (2)0.011 (2)00.0035 (15)0
N10.0225 (11)0.0200 (10)0.0149 (11)00.0026 (9)0
N20.0227 (11)0.0211 (10)0.0177 (11)00.0063 (9)0
N30.0243 (9)0.0180 (8)0.0177 (8)0.0031 (6)0.0057 (6)0
N40.0294 (10)0.0181 (8)0.0171 (9)0.0022 (6)0.0051 (6)0
O10.0182 (12)0.0334 (15)0.0292 (13)00.0059 (10)0
O20.0178 (12)0.0293 (13)0.0262 (13)00.0046 (10)0.0018 (9)
O30.0285 (13)0.0159 (10)0.0109 (10)00.0031 (9)0.0016 (7)
O40.0266 (12)0.0176 (11)0.0123 (11)00.0056 (9)0
O50.0283 (12)0.0134 (10)0.0166 (10)0.0023 (9)0.0034 (8)0
O60.0276 (12)0.0178 (11)0.0164 (10)0.0034 (9)0.0072 (9)0.0039 (8)
O70.0257 (12)0.0161 (11)0.0172 (10)0.0015 (9)0.0085 (8)0.0031 (8)
O80.0291 (12)0.0150 (11)0.0157 (10)0.0036 (9)0.0085 (8)0.0017 (8)
H30.066 (5)0.140 (9)0.096 (7)0.029 (6)0.023 (5)0.067 (7)
H40.059 (4)0.059 (4)0.055 (4)0.009 (3)0.019 (3)0.019 (3)
H50.055 (6)0.158 (11)0.224 (16)0.045 (6)00.116 (11)
H60.097 (8)0.217 (15)0.128 (10)0.103 (9)0.042 (7)0.109 (11)
H70.028 (3)0.054 (4)0.072 (4)000.009 (3)
H80.039 (3)0.054 (3)0.057 (4)0.005 (3)0.010 (2)0.019 (3)
H90.044 (3)0.030 (3)0.041 (3)0.005 (2)0.003 (2)0
H100.062 (3)0.034 (3)0.025 (2)0.004 (2)0.006 (2)0.0068 (18)
H110.048 (3)0.038 (3)0.032 (2)0.007 (2)0.012 (2)0.008 (2)
H120.050 (3)0.022 (2)0.036 (3)000
H130.053 (3)0.039 (3)0.035 (3)0.006 (2)0.022 (2)0
H140.062 (3)0.035 (2)0.025 (2)0.003 (2)0.016 (2)0
Geometric parameters (Å, º) top
S1—O11.503 (6)N2—H30.968 (11)
S1—O31.469 (5)N2—H3iv0.968 (11)
S1—O51.470 (5)N2—H50.935 (14)
S1—O71.470 (5)N2—H5iv0.935 (14)
S2—O21.530 (6)N3—H70.974 (6)
S2—O41.467 (5)N3—H91.033 (6)
S2—O6i1.456 (5)N3—H111.037 (5)
S2—O81.468 (5)N3—H131.020 (6)
N1—H41.002 (7)N4—H8v0.997 (7)
N1—H4ii1.002 (7)N4—H101.026 (5)
N1—H6i0.945 (15)N4—H12vi1.038 (5)
N1—H6iii0.945 (15)N4—H141.029 (6)
O1—S1—O3107.7 (3)H3—N2—H3iv104.5 (10)
O1—S1—O5108.6 (3)H3—N2—H596.7 (11)
O1—S1—O7108.3 (3)H3—N2—H5iv117.9 (13)
O3—S1—O5110.9 (3)H3iv—N2—H5117.9 (13)
O3—S1—O7110.9 (3)H3iv—N2—H5iv96.7 (11)
O5—S1—O7110.3 (3)H5—N2—H5iv123.0 (13)
O2—S2—O4107.5 (4)H7—N3—H9107.8 (5)
O2—S2—O6i105.7 (3)H7—N3—H11110.0 (6)
O2—S2—O8106.8 (3)H7—N3—H13108.7 (6)
O4—S2—O6i112.6 (3)H9—N3—H11109.5 (4)
O4—S2—O8111.4 (3)H9—N3—H13111.6 (5)
O6i—S2—O8112.4 (4)H11—N3—H13109.2 (5)
H4—N1—H4ii111.1 (6)H8v—N4—H10106.9 (5)
H4—N1—H6i101.8 (9)H8v—N4—H12vi110.9 (5)
H4—N1—H6iii110.9 (10)H8v—N4—H14109.3 (5)
H4ii—N1—H6i110.9 (10)H10—N4—H12vi110.2 (4)
H4ii—N1—H6iii101.8 (9)H10—N4—H14109.9 (5)
H6i—N1—H6iii120.5 (14)H12vi—N4—H14109.6 (5)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y, z+3/2; (iii) x+3/2, y1, z+3/2; (iv) x+3/2, y, z+1/2; (v) x1, y, z; (vi) x, y+1, z.
(IV) top
Crystal data top
HO8S2·3(H4N)F(000) = 253
Mr = 247.2Dx = 1.837 (2) Mg m3
Monoclinic, P2/nNeutron radiation, λ = 0.87 Å
Hall symbol: -P 2yacCell parameters from 19 reflections
a = 15.538 (8) Åθ = 15.3–26.6°
b = 11.641 (6) ŵ = 0.002 mm1
c = 10.085 (5) ÅT = 139 K
β = 101.46 (5)°Cube, colourless
V = 1787.8 (16) Å33 × 3 × 3 × 0 (radius) mm
Z = 8
Data collection top
4-circle
diffractometer
Rint = 0.03
Radiation source: nuclear reactorθmax = 37.6°, θmin = 3.3°
Cu (220) monochromatorh = 1721
ω scansk = 1416
4208 measured reflectionsl = 1414
2689 independent reflections2 standard reflections every 240 min min
1789 reflections with I > 3σ(I) intensity decay: none
Refinement top
Refinement on F2All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.083Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.166(Δ/σ)max = 0.039
S = 4.02Δρmax = 2.68 e Å3
2689 reflectionsΔρmin = 3.60 e Å3
150 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 152E1 (7)
2 constraints
Crystal data top
HO8S2·3(H4N)V = 1787.8 (16) Å3
Mr = 247.2Z = 8
Monoclinic, P2/nNeutron radiation, λ = 0.87 Å
a = 15.538 (8) ŵ = 0.002 mm1
b = 11.641 (6) ÅT = 139 K
c = 10.085 (5) Å3 × 3 × 3 × 0 (radius) mm
β = 101.46 (5)°
Data collection top
4-circle
diffractometer
Rint = 0.03
4208 measured reflections2 standard reflections every 240 min min
2689 independent reflections intensity decay: none
1789 reflections with I > 3σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0830 restraints
wR(F2) = 0.166All H-atom parameters refined
S = 4.02Δρmax = 2.68 e Å3
2689 reflectionsΔρmin = 3.60 e Å3
150 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.3586 (11)0.2295 (13)0.4589 (16)0.0088
S20.1314 (14)0.0114 (16)0.538 (2)0.0104
S30.3626 (11)0.7370 (13)0.4668 (16)0.0088
S40.1359 (13)0.5176 (16)0.539 (2)0.0104
N10.750.0085 (9)0.750.0158
N20.750.2441 (7)0.250.016
N30.4496 (7)0.2609 (10)0.1539 (8)0.0164
N40.0497 (6)0.4876 (6)0.8522 (9)0.0174
N50.750.5141 (9)0.750.0158
N60.750.7368 (7)0.250.016
N70.4498 (7)0.7606 (10)0.1594 (8)0.0164
N80.0475 (6)0.9809 (6)0.8506 (9)0.0174
O10.2614 (8)0.2151 (14)0.4494 (14)0.0232
O20.2351 (10)0.0326 (12)0.5648 (16)0.0199
O30.3958 (5)0.2198 (9)0.6063 (9)0.0151
O40.1015 (12)0.0025 (13)0.3921 (15)0.0152
O50.3733 (9)0.3485 (13)0.4154 (16)0.0163
O60.1165 (7)0.0872 (9)0.6212 (11)0.0163
O70.3943 (8)0.1440 (8)0.3764 (10)0.0159
O80.0957 (7)0.1164 (7)0.5825 (10)0.0144
O90.2649 (8)0.7146 (14)0.4443 (15)0.0232
O100.2325 (10)0.5286 (12)0.5605 (16)0.0199
O110.4045 (5)0.7173 (9)0.6069 (9)0.0151
O120.1033 (12)0.4941 (13)0.3967 (15)0.0152
O130.3769 (8)0.8507 (13)0.4180 (16)0.0163
O140.1218 (7)0.4171 (9)0.6176 (11)0.0163
O150.3944 (8)0.6506 (8)0.3826 (10)0.0159
O160.0997 (7)0.6235 (7)0.5866 (10)0.0144
H10.24890.103050.51430.0297*0.7114
H20.25110.146950.48570.0297*0.2886
H30.7092 (14)0.191 (3)0.187 (3)0.0881
H40.7853 (18)0.0556 (19)0.825 (3)0.0524
H50.7084 (16)0.293 (2)0.265 (4)0.1254
H60.794 (2)0.040 (4)0.727 (4)0.1573
H70.5196 (10)0.2633 (19)0.189 (2)0.0471
H80.0124 (10)0.4691 (15)0.8313 (18)0.0444
H90.4309 (12)0.342 (2)0.136 (2)0.0361
H100.0772 (12)0.4368 (15)0.9375 (16)0.0339
H110.4314 (13)0.211 (2)0.069 (2)0.0369
H120.0616 (17)0.5670 (16)0.868 (3)0.0319
H130.4198 (13)0.2266 (16)0.2358 (18)0.0383
H140.0751 (12)0.4633 (17)0.769 (2)0.0323
H150.24890.603050.51430.0297*0.7299
H160.25110.646950.48570.0297*0.2701
H170.7194 (15)0.687 (3)0.181 (3)0.0881
H180.7877 (18)0.5653 (19)0.818 (3)0.0524
H190.6999 (17)0.764 (2)0.293 (3)0.1254
H200.791 (2)0.476 (4)0.711 (4)0.1573
H210.5099 (10)0.7685 (19)0.185 (2)0.0471
H220.0190 (10)0.9615 (15)0.8469 (17)0.0444
H230.4230 (12)0.844 (2)0.137 (3)0.0361
H240.0842 (12)0.9401 (15)0.9285 (16)0.0339
H250.4384 (13)0.710 (2)0.074 (2)0.0369
H260.0583 (17)1.0741 (16)0.867 (3)0.0319
H270.4275 (13)0.7212 (16)0.2284 (18)0.0383
H280.0668 (12)0.9585 (17)0.765 (2)0.0323
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0067610.0098760.009057000
S20.0078810.0104670.01363300.0043080
S30.0067610.0098760.009057000
S40.0078810.0104670.01363300.0043080
N10.014610.0163560.015146000
N20.0130490.0171070.016696000
N30.0179440.016290.0148290.0021360.0029380
N40.0177720.0153590.0183380.0045640.0014950.00192
N50.014610.0163560.015146000
N60.0130490.0171070.016696000
N70.0179440.016290.0148290.0021360.0029380
N80.0177720.0153590.0183380.0045640.0014950.00192
O10.0066890.0307160.0318200.0032530
O20.0084850.0254550.024265000.002291
O30.0176060.0165090.01114300.0023920.001877
O40.0155320.01860.01173300.0031160
O50.0184890.0117770.017199000.001068
O60.0180690.0159330.0160210.0031190.0057930.004394
O70.0190620.0126310.016600.0046720.004793
O80.0166090.012730.01462200.00490.003982
O90.0066890.0307160.0318200.0032530
O100.0084850.0254550.024265000.002291
O110.0176060.0165090.01114300.0023920.001877
O120.0155320.01860.01173300.0031160
O130.0184890.0117770.017199000.001068
O140.0180690.0159330.0160210.0031190.0057930.004394
O150.0190620.0126310.016600.0046720.004793
O160.0166090.012730.01462200.00490.003982
H30.0551290.1135970.0827110.0193480.0172520.060916
H40.0489740.0482410.0483110.0076270.0188480.017744
H50.0610010.1223590.1828920.0421300.093637
H60.0921680.20410.1404160.1135860.0617150.122949
H70.0213360.0486560.067781000.009311
H80.0218020.0551650.05790.0134530.0118270.017294
H90.0425780.0244180.0379120.00301500
H100.0437890.0328650.02617400.0099340.006818
H110.0464920.0350880.0294990.0112410.0083130.008293
H120.0431810.0177210.0318320.00375500.002522
H130.0530270.0362940.03140.0033530.0227420
H140.0398760.0344310.0252710.008450.0127080.002355
H170.0551290.1135970.0827110.0193480.0172520.060916
H180.0489740.0482410.0483110.0076270.0188480.017744
H190.0610010.1223590.1828920.0421300.093637
H200.0921680.20410.1404160.1135860.0617150.122949
H210.0213360.0486560.067781000.009311
H220.0218020.0551650.05790.0134530.0118270.017294
H230.0425780.0244180.0379120.00301500
H240.0437890.0328650.02617400.0099340.006818
H250.0464920.0350880.0294990.0112410.0083130.008293
H260.0431810.0177210.0318320.00375500.002522
H270.0530270.0362940.03140.0033530.0227420
H280.0398760.0344310.0252710.008450.0127080.002355
Geometric parameters (Å, º) top
S1—O11.50 (2)N3—H71.075 (19)
S1—O31.489 (18)N3—H91.00 (3)
S1—O51.48 (2)N3—H111.03 (3)
S1—O71.47 (2)N3—H131.10 (2)
S2—O21.60 (3)N4—H80.971 (18)
S2—O41.46 (3)N4—H101.061 (18)
S2—O61.47 (2)N4—H120.95 (2)
S2—O81.45 (2)N4—H141.03 (2)
S3—O91.51 (2)N5—H181.01 (2)
S3—O111.451 (17)N5—H18i1.01 (2)
S3—O131.44 (2)N5—H200.93 (4)
S3—O151.46 (2)N5—H20i0.93 (4)
S4—O101.48 (3)N6—H170.96 (3)
S4—O121.45 (3)N6—H17ii0.96 (3)
S4—O141.45 (2)N6—H191.01 (3)
S4—O161.47 (2)N6—H19ii1.01 (3)
N1—H41.00 (2)N7—H210.922 (19)
N1—H4i1.00 (2)N7—H231.06 (3)
N1—H60.95 (4)N7—H251.03 (3)
N1—H6i0.95 (4)N7—H270.95 (2)
N2—H31.01 (3)N8—H221.051 (19)
N2—H3ii1.01 (3)N8—H240.995 (17)
N2—H50.89 (3)N8—H261.11 (2)
N2—H5ii0.89 (3)N8—H281.00 (2)
O1—S1—O3103.9 (12)H7—N3—H9106.0 (19)
O1—S1—O5107.2 (12)H7—N3—H11113 (2)
O1—S1—O7112.0 (12)H7—N3—H13108.1 (17)
O3—S1—O5108.3 (11)H9—N3—H11111 (2)
O3—S1—O7113.5 (11)H9—N3—H13109 (2)
O5—S1—O7111.5 (14)H11—N3—H13110 (2)
O2—S2—O4107.1 (18)H8—N4—H10105.9 (16)
O2—S2—O6107.0 (14)H8—N4—H12114 (2)
O2—S2—O8104.7 (13)H8—N4—H14106.7 (16)
O4—S2—O6115.7 (14)H10—N4—H12111.9 (19)
O4—S2—O8109.8 (14)H10—N4—H14110.3 (16)
O6—S2—O8111.8 (17)H12—N4—H14108 (2)
O9—S3—O11111.2 (13)H18—N5—H18i107 (2)
O9—S3—O13108.9 (13)H18—N5—H20103 (3)
O9—S3—O15103.8 (12)H18—N5—H20i111 (3)
O11—S3—O13114.0 (12)H18i—N5—H20111 (3)
O11—S3—O15108.6 (11)H18i—N5—H20i103 (3)
O13—S3—O15109.9 (14)H20—N5—H20i122 (4)
O10—S4—O12107.8 (18)H17—N6—H17ii105 (3)
O10—S4—O14104.4 (14)H17—N6—H19101 (2)
O10—S4—O16108.7 (14)H17—N6—H19ii101 (2)
O12—S4—O14109.1 (14)H17ii—N6—H19101 (2)
O12—S4—O16113.5 (15)H17ii—N6—H19ii101 (2)
O14—S4—O16112.8 (17)H19—N6—H19ii144 (2)
H4—N1—H4i114 (2)H21—N7—H23108 (2)
H4—N1—H6101 (3)H21—N7—H25107 (2)
H4—N1—H6i117 (3)H21—N7—H27110 (2)
H4i—N1—H6117 (3)H23—N7—H25110 (2)
H4i—N1—H6i101 (3)H23—N7—H27114 (2)
H6—N1—H6i107 (4)H25—N7—H27108 (2)
H3—N2—H3ii105 (3)H22—N8—H24109.4 (16)
H3—N2—H596 (2)H22—N8—H26109.6 (18)
H3—N2—H5ii132 (3)H22—N8—H28112.0 (16)
H3ii—N2—H5132 (3)H24—N8—H26107.6 (17)
H3ii—N2—H5ii96 (2)H24—N8—H28109.3 (17)
H5—N2—H5ii101 (3)H26—N8—H28109 (2)
Symmetry codes: (i) x+3/2, y, z+3/2; (ii) x+3/2, y, z+1/2.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaHO8S2·3(H4N)HO8S2·3(H4N)HO8S2·3(H4N)HO8S2·3(H4N)
Mr247.25247.2247.2247.2
Crystal system, space groupTriclinic, P1Monoclinic, P2/nMonoclinic, P2/nMonoclinic, P2/n
Temperature (K)126250150139
a, b, c (Å)8.282 (4), 10.095 (5), 11.613 (6)15.473 (8), 5.849 (3), 10.131 (5)15.534 (8), 5.825 (3), 10.089 (5)15.538 (8), 11.641 (6), 10.085 (5)
α, β, γ (°)90.44 (5), 110.07 (6), 100.64 (5)90, 101.75 (5), 9090, 101.52 (5), 9090, 101.46 (5), 90
V3)893.6 (8)897.7 (8)894.5 (8)1787.8 (16)
Z4448
Radiation typeMo KαNeutron, λ = 0.87 ÅNeutron, λ = 0.87 ÅNeutron, λ = 0.87 Å
µ (mm1)0.620.0020.0020.002
Crystal size (mm)0.3 × 0.3 × 0.13 × 3 × 3 × 0 (radius)3 × 3 × 3 × 0 (radius)3 × 3 × 3 × 0 (radius)
Data collection
DiffractometerStoe IPDS II
diffractometer
4-circle
diffractometer
4-circle
diffractometer
4-circle
diffractometer
Absorption correctionNumerical
(X-SHAPE; Stoe & Cie, 1996)
Tmin, Tmax0.797, 0.942
No. of measured, independent and
observed reflections
21478, 6139, 3270 [I > 2σ(I)]1770, 1503, 1092 [I > 3σ(I)]2379, 1689, 1470 [I > 3σ(I)]4208, 2689, 1789 [I > 3σ(I)]
Rint0.0570.0430.0240.03
(sin θ/λ)max1)0.7470.7000.7030.702
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.117, 0.94 0.066, 0.140, 3.26 0.058, 0.139, 4.11 0.083, 0.166, 4.02
No. of reflections6139150316892689
No. of parameters326208208150
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementAll H-atom parameters refinedAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.50, 0.650.97, 1.591.37, 1.992.68, 3.60

Computer programs: X-AREA (Stoe & Cie, 2002), DIF4N (modified Linux version of DIF4), DIF4N, X-RED (Stoe & Cie, 1996), PRON (Scherf, 1998), SHELXL97 (Sheldrick, 1997), Jana2006 (Petricek, Dusek & Palatinus, 2006), Atoms 5.1, WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) for (I) top
S1—O51.468 (2)N1—H61.00 (5)
S1—O71.471 (2)N2—H70.90 (4)
S1—O31.477 (2)N2—H80.95 (3)
S1—O11.500 (2)N2—H90.81 (5)
S2—O61.450 (2)N2—H100.78 (5)
S2—O41.457 (2)N3—H110.84 (5)
S2—O81.464 (2)N3—H120.86 (5)
S2—O21.554 (2)N3—H130.84 (4)
S3—O151.464 (2)N3—H140.780 (6)
S3—O131.469 (2)N4—H150.82 (4)
S3—O111.477 (2)N4—H160.83 (4)
S3—O91.505 (2)N4—H170.87 (4)
S4—O161.452 (2)N4—H180.86 (4)
S4—O121.457 (2)N5—H190.80 (5)
S4—O141.458 (2)N5—H200.82 (3)
S4—O101.546 (2)N5—H210.80 (5)
O2—H10.83 (5)N5—H220.79 (4)
O10—H20.94 (5)N6—H230.89 (4)
N1—H30.76 (3)N6—H240.84 (4)
N1—H40.95 (4)N6—H250.76 (5)
N1—H50.91 (4)N6—H260.88 (4)
O5—S1—O7110.70 (13)H5—N1—H6111 (4)
O5—S1—O3110.01 (13)H7—N2—H8108 (3)
O7—S1—O3110.25 (13)H7—N2—H9114 (4)
O5—S1—O1109.37 (13)H8—N2—H9106 (4)
O7—S1—O1108.47 (14)H7—N2—H10117 (4)
O3—S1—O1107.99 (13)H8—N2—H10110 (4)
O6—S2—O4112.52 (13)H9—N2—H10101 (5)
O6—S2—O8112.79 (14)H11—N3—H12124 (5)
O4—S2—O8112.22 (13)H11—N3—H13105 (4)
O6—S2—O2105.23 (14)H12—N3—H13105 (4)
O4—S2—O2106.78 (14)H11—N3—H14109 (4)
O8—S2—O2106.68 (14)H12—N3—H14104 (4)
O15—S3—O13110.94 (13)H13—N3—H14110 (4)
O15—S3—O11110.50 (13)H15—N4—H16119 (4)
O13—S3—O11110.32 (13)H15—N4—H17102 (4)
O15—S3—O9108.50 (13)H16—N4—H17115 (4)
O13—S3—O9108.79 (14)H15—N4—H18108 (4)
O11—S3—O9107.70 (13)H16—N4—H18105 (4)
O16—S4—O12112.32 (13)H17—N4—H18107 (4)
O16—S4—O14112.35 (14)H19—N5—H20104 (4)
O12—S4—O14111.73 (13)H19—N5—H21107 (5)
O16—S4—O10105.78 (14)H20—N5—H21116 (4)
O12—S4—O10107.24 (14)H19—N5—H22118 (5)
O14—S4—O10106.96 (13)H20—N5—H22106 (3)
S2—O2—H1113 (4)H21—N5—H22107 (4)
S4—O10—H2105 (3)H23—N6—H24120 (4)
H3—N1—H4116 (4)H23—N6—H25101 (4)
H3—N1—H5105 (4)H24—N6—H25104 (4)
H4—N1—H5101 (4)H23—N6—H26116 (4)
H3—N1—H6115 (4)H24—N6—H2696 (3)
H4—N1—H6107 (4)H25—N6—H26119 (5)
Selected geometric parameters (Å, º) for (II) top
S1—O11.495 (8)N2—H30.953 (14)
S1—O31.460 (7)N2—H3iv0.953 (14)
S1—O51.462 (8)N2—H50.906 (19)
S1—O71.465 (8)N2—H5iv0.906 (19)
S2—O21.523 (7)N3—H70.927 (12)
S2—O41.465 (7)N3—H91.023 (12)
S2—O6i1.452 (7)N3—H111.005 (12)
S2—O81.452 (7)N3—H130.980 (12)
N1—H40.985 (10)N4—H8v0.991 (11)
N1—H4ii0.985 (10)N4—H100.978 (10)
N1—H6i0.92 (2)N4—H12vi1.027 (8)
N1—H6iii0.92 (2)N4—H141.018 (11)
O1—S1—O3107.9 (5)H3—N2—H3iv105.4 (13)
O1—S1—O5108.7 (5)H3—N2—H595.3 (14)
O1—S1—O7108.2 (4)H3—N2—H5iv120.1 (17)
O3—S1—O5110.7 (4)H3iv—N2—H5120.1 (17)
O3—S1—O7110.7 (5)H3iv—N2—H5iv95.3 (14)
O5—S1—O7110.6 (5)H5—N2—H5iv121.4 (17)
O2—S2—O4107.1 (5)H7—N3—H9105.8 (10)
O2—S2—O6i106.1 (4)H7—N3—H11106.0 (11)
O2—S2—O8107.6 (4)H7—N3—H13107.9 (12)
O4—S2—O6i111.8 (4)H9—N3—H11113.6 (9)
O4—S2—O8111.3 (4)H9—N3—H13111.8 (11)
O6i—S2—O8112.5 (5)H11—N3—H13111.2 (10)
H4—N1—H4ii113.1 (10)H8v—N4—H10104.9 (10)
H4—N1—H6i99.0 (14)H8v—N4—H12vi109.2 (9)
H4—N1—H6iii111.8 (16)H8v—N4—H14109.9 (9)
H4ii—N1—H6i111.8 (16)H10—N4—H12vi110.0 (8)
H4ii—N1—H6iii99.0 (14)H10—N4—H14111.3 (9)
H6i—N1—H6iii122.9 (19)H12vi—N4—H14111.3 (8)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y, z+3/2; (iii) x+3/2, y1, z+3/2; (iv) x+3/2, y, z+1/2; (v) x1, y, z; (vi) x, y+1, z.
Selected geometric parameters (Å, º) for (III) top
S1—O11.503 (6)N2—H30.968 (11)
S1—O31.469 (5)N2—H3iv0.968 (11)
S1—O51.470 (5)N2—H50.935 (14)
S1—O71.470 (5)N2—H5iv0.935 (14)
S2—O21.530 (6)N3—H70.974 (6)
S2—O41.467 (5)N3—H91.033 (6)
S2—O6i1.456 (5)N3—H111.037 (5)
S2—O81.468 (5)N3—H131.020 (6)
N1—H41.002 (7)N4—H8v0.997 (7)
N1—H4ii1.002 (7)N4—H101.026 (5)
N1—H6i0.945 (15)N4—H12vi1.038 (5)
N1—H6iii0.945 (15)N4—H141.029 (6)
O1—S1—O3107.7 (3)H3—N2—H3iv104.5 (10)
O1—S1—O5108.6 (3)H3—N2—H596.7 (11)
O1—S1—O7108.3 (3)H3—N2—H5iv117.9 (13)
O3—S1—O5110.9 (3)H3iv—N2—H5117.9 (13)
O3—S1—O7110.9 (3)H3iv—N2—H5iv96.7 (11)
O5—S1—O7110.3 (3)H5—N2—H5iv123.0 (13)
O2—S2—O4107.5 (4)H7—N3—H9107.8 (5)
O2—S2—O6i105.7 (3)H7—N3—H11110.0 (6)
O2—S2—O8106.8 (3)H7—N3—H13108.7 (6)
O4—S2—O6i112.6 (3)H9—N3—H11109.5 (4)
O4—S2—O8111.4 (3)H9—N3—H13111.6 (5)
O6i—S2—O8112.4 (4)H11—N3—H13109.2 (5)
H4—N1—H4ii111.1 (6)H8v—N4—H10106.9 (5)
H4—N1—H6i101.8 (9)H8v—N4—H12vi110.9 (5)
H4—N1—H6iii110.9 (10)H8v—N4—H14109.3 (5)
H4ii—N1—H6i110.9 (10)H10—N4—H12vi110.2 (4)
H4ii—N1—H6iii101.8 (9)H10—N4—H14109.9 (5)
H6i—N1—H6iii120.5 (14)H12vi—N4—H14109.6 (5)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y, z+3/2; (iii) x+3/2, y1, z+3/2; (iv) x+3/2, y, z+1/2; (v) x1, y, z; (vi) x, y+1, z.
Selected geometric parameters (Å, º) for (IV) top
S1—O11.50 (2)N3—H71.075 (19)
S1—O31.489 (18)N3—H91.00 (3)
S1—O51.48 (2)N3—H111.03 (3)
S1—O71.47 (2)N3—H131.10 (2)
S2—O21.60 (3)N4—H80.971 (18)
S2—O41.46 (3)N4—H101.061 (18)
S2—O61.47 (2)N4—H120.95 (2)
S2—O81.45 (2)N4—H141.03 (2)
S3—O91.51 (2)N5—H181.01 (2)
S3—O111.451 (17)N5—H18i1.01 (2)
S3—O131.44 (2)N5—H200.93 (4)
S3—O151.46 (2)N5—H20i0.93 (4)
S4—O101.48 (3)N6—H170.96 (3)
S4—O121.45 (3)N6—H17ii0.96 (3)
S4—O141.45 (2)N6—H191.01 (3)
S4—O161.47 (2)N6—H19ii1.01 (3)
N1—H41.00 (2)N7—H210.922 (19)
N1—H4i1.00 (2)N7—H231.06 (3)
N1—H60.95 (4)N7—H251.03 (3)
N1—H6i0.95 (4)N7—H270.95 (2)
N2—H31.01 (3)N8—H221.051 (19)
N2—H3ii1.01 (3)N8—H240.995 (17)
N2—H50.89 (3)N8—H261.11 (2)
N2—H5ii0.89 (3)N8—H281.00 (2)
O1—S1—O3103.9 (12)H7—N3—H9106.0 (19)
O1—S1—O5107.2 (12)H7—N3—H11113 (2)
O1—S1—O7112.0 (12)H7—N3—H13108.1 (17)
O3—S1—O5108.3 (11)H9—N3—H11111 (2)
O3—S1—O7113.5 (11)H9—N3—H13109 (2)
O5—S1—O7111.5 (14)H11—N3—H13110 (2)
O2—S2—O4107.1 (18)H8—N4—H10105.9 (16)
O2—S2—O6107.0 (14)H8—N4—H12114 (2)
O2—S2—O8104.7 (13)H8—N4—H14106.7 (16)
O4—S2—O6115.7 (14)H10—N4—H12111.9 (19)
O4—S2—O8109.8 (14)H10—N4—H14110.3 (16)
O6—S2—O8111.8 (17)H12—N4—H14108 (2)
O9—S3—O11111.2 (13)H18—N5—H18i107 (2)
O9—S3—O13108.9 (13)H18—N5—H20103 (3)
O9—S3—O15103.8 (12)H18—N5—H20i111 (3)
O11—S3—O13114.0 (12)H18i—N5—H20111 (3)
O11—S3—O15108.6 (11)H18i—N5—H20i103 (3)
O13—S3—O15109.9 (14)H20—N5—H20i122 (4)
O10—S4—O12107.8 (18)H17—N6—H17ii105 (3)
O10—S4—O14104.4 (14)H17—N6—H19101 (2)
O10—S4—O16108.7 (14)H17—N6—H19ii101 (2)
O12—S4—O14109.1 (14)H17ii—N6—H19101 (2)
O12—S4—O16113.5 (15)H17ii—N6—H19ii101 (2)
O14—S4—O16112.8 (17)H19—N6—H19ii144 (2)
H4—N1—H4i114 (2)H21—N7—H23108 (2)
H4—N1—H6101 (3)H21—N7—H25107 (2)
H4—N1—H6i117 (3)H21—N7—H27110 (2)
H4i—N1—H6117 (3)H23—N7—H25110 (2)
H4i—N1—H6i101 (3)H23—N7—H27114 (2)
H6—N1—H6i107 (4)H25—N7—H27108 (2)
H3—N2—H3ii105 (3)H22—N8—H24109.4 (16)
H3—N2—H596 (2)H22—N8—H26109.6 (18)
H3—N2—H5ii132 (3)H22—N8—H28112.0 (16)
H3ii—N2—H5132 (3)H24—N8—H26107.6 (17)
H3ii—N2—H5ii96 (2)H24—N8—H28109.3 (17)
H5—N2—H5ii101 (3)H26—N8—H28109 (2)
Symmetry codes: (i) x+3/2, y, z+3/2; (ii) x+3/2, y, z+1/2.
 

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