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
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).
Crystal data top
HO8S2·3(H4N) | Z = 4 |
Mr = 247.25 | F(000) = 520 |
Triclinic, P1 | Dx = 1.838 Mg m−3 |
a = 8.282 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.095 (5) Å | Cell parameters from 17019 reflections |
c = 11.613 (6) Å | θ = 5.4–64.5° |
α = 90.44 (5)° | µ = 0.62 mm−1 |
β = 110.07 (6)° | T = 126 K |
γ = 100.64 (5)° | Cube, colourless |
V = 893.6 (8) Å3 | 0.3 × 0.3 × 0.1 mm |
Data collection top
Stoe IPDS II diffractometer | 6139 independent reflections |
Radiation source: fine-focus sealed tube | 3270 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 0 pixels mm-1 | θmax = 32.1°, θmin = 2.7° |
rotation method scans | h = −12→12 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996) | k = −14→15 |
Tmin = 0.797, Tmax = 0.942 | l = −17→16 |
21478 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H 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 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
Crystal data top
HO8S2·3(H4N) | γ = 100.64 (5)° |
Mr = 247.25 | V = 893.6 (8) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.282 (4) Å | Mo Kα radiation |
b = 10.095 (5) Å | µ = 0.62 mm−1 |
c = 11.613 (6) Å | T = 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 = 0.942 | Rint = 0.057 |
21478 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.50 e Å−3 |
6139 reflections | Δρmin = −0.65 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
S1 | 0.27434 (8) | −0.45664 (6) | 0.30120 (6) | 0.01303 (14) | |
S2 | 0.73018 (8) | −0.53509 (6) | 0.19599 (6) | 0.01292 (14) | |
S3 | 0.28036 (8) | 0.04511 (6) | 0.08780 (6) | 0.01307 (14) | |
S4 | 0.73056 (8) | −0.03433 (6) | 0.41981 (6) | 0.01277 (14) | |
O1 | 0.4686 (3) | −0.4342 (2) | 0.32952 (19) | 0.0207 (4) | |
O2 | 0.5280 (3) | −0.5579 (2) | 0.1617 (2) | 0.0214 (4) | |
O3 | 0.2100 (3) | −0.60192 (18) | 0.30772 (18) | 0.0181 (4) | |
O4 | 0.7926 (3) | −0.39041 (18) | 0.19578 (18) | 0.0187 (4) | |
O5 | 0.2384 (3) | −0.3761 (2) | 0.39211 (18) | 0.0199 (4) | |
O6 | 0.7568 (3) | −0.6131 (2) | 0.10102 (18) | 0.0199 (4) | |
O7 | 0.1918 (3) | −0.4163 (2) | 0.17651 (18) | 0.0193 (4) | |
O8 | 0.8000 (3) | −0.5844 (2) | 0.31794 (18) | 0.0196 (4) | |
O9 | 0.4743 (3) | 0.0669 (2) | 0.15845 (19) | 0.0211 (4) | |
O10 | 0.5304 (3) | −0.0470 (2) | 0.3564 (2) | 0.0215 (4) | |
O11 | 0.2076 (3) | −0.10103 (17) | 0.07996 (17) | 0.0173 (4) | |
O12 | 0.8113 (3) | 0.10747 (18) | 0.42362 (17) | 0.0187 (4) | |
O13 | 0.2532 (3) | 0.0915 (2) | −0.03586 (18) | 0.0200 (4) | |
O14 | 0.7866 (3) | −0.1204 (2) | 0.34556 (18) | 0.0197 (4) | |
O15 | 0.2013 (3) | 0.12149 (19) | 0.15426 (17) | 0.0188 (4) | |
O16 | 0.7558 (3) | −0.0803 (2) | 0.54178 (18) | 0.0200 (4) | |
N1 | 0.5028 (3) | −0.2577 (3) | 0.6124 (2) | 0.0163 (5) | |
N2 | 0.5078 (3) | −0.7555 (3) | −0.1168 (2) | 0.0163 (5) | |
N3 | 0.1012 (3) | −0.6529 (3) | 0.5127 (2) | 0.0176 (5) | |
N4 | 0.0963 (3) | 0.3453 (3) | 0.0141 (2) | 0.0172 (5) | |
N5 | 0.0918 (4) | −0.1523 (3) | 0.2823 (3) | 0.0172 (5) | |
N6 | 0.1081 (4) | −0.1497 (3) | −0.2045 (2) | 0.0181 (5) | |
H1 | 0.499 (7) | −0.538 (5) | 0.220 (5) | 0.061 (15)* | |
H2 | 0.517 (6) | −0.011 (4) | 0.280 (4) | 0.051 (13)* | |
H3 | 0.549 (4) | −0.193 (3) | 0.596 (3) | 0.013 (8)* | |
H4 | 0.421 (6) | −0.317 (4) | 0.545 (4) | 0.043 (12)* | |
H5 | 0.587 (5) | −0.308 (4) | 0.642 (4) | 0.034 (10)* | |
H6 | 0.443 (6) | −0.246 (4) | 0.672 (4) | 0.039 (11)* | |
H7 | 0.428 (5) | −0.800 (3) | −0.087 (3) | 0.018 (8)* | |
H8 | 0.561 (4) | −0.672 (3) | −0.069 (3) | 0.018 (8)* | |
H9 | 0.467 (7) | −0.737 (5) | −0.188 (5) | 0.058 (14)* | |
H10 | 0.579 (7) | −0.794 (5) | −0.121 (4) | 0.046 (13)* | |
H11 | 0.134 (6) | −0.631 (5) | 0.453 (5) | 0.049 (13)* | |
H12 | 0.141 (6) | −0.712 (5) | 0.562 (4) | 0.045 (12)* | |
H13 | 0.126 (5) | −0.581 (4) | 0.558 (4) | 0.028 (10)* | |
H14 | 0.0000 | −0.680 (4) | 0.487 (3) | 0.027 (10)* | |
H15 | 0.137 (5) | 0.363 (4) | −0.040 (4) | 0.026 (10)* | |
H16 | 0.127 (5) | 0.284 (4) | 0.059 (4) | 0.036 (11)* | |
H17 | −0.016 (6) | 0.334 (4) | −0.026 (4) | 0.033 (10)* | |
H18 | 0.126 (5) | 0.417 (4) | 0.063 (4) | 0.027 (10)* | |
H19 | 0.112 (6) | −0.130 (5) | 0.222 (5) | 0.045 (13)* | |
H20 | 0.143 (4) | −0.087 (3) | 0.332 (3) | 0.014 (8)* | |
H21 | −0.012 (7) | −0.170 (4) | 0.264 (4) | 0.042 (13)* | |
H22 | 0.127 (5) | −0.216 (4) | 0.313 (3) | 0.021 (9)* | |
H23 | 0.141 (6) | −0.224 (4) | −0.173 (4) | 0.032 (10)* | |
H24 | 0.116 (5) | −0.128 (4) | −0.273 (4) | 0.022 (9)* | |
H25 | 0.009 (7) | −0.167 (5) | −0.218 (4) | 0.048 (14)* | |
H26 | 0.170 (5) | −0.073 (4) | −0.163 (4) | 0.035 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0132 (3) | 0.0123 (3) | 0.0135 (3) | 0.0036 (2) | 0.0041 (2) | 0.0011 (2) |
S2 | 0.0135 (3) | 0.0117 (3) | 0.0132 (3) | 0.0025 (2) | 0.0041 (2) | 0.0011 (2) |
S3 | 0.0137 (3) | 0.0119 (3) | 0.0149 (3) | 0.0030 (2) | 0.0064 (2) | 0.00196 (19) |
S4 | 0.0138 (3) | 0.0114 (3) | 0.0140 (3) | 0.0017 (2) | 0.0064 (2) | 0.000 |
O1 | 0.0134 (9) | 0.0222 (9) | 0.0243 (10) | 0.0028 (7) | 0.0042 (7) | 0.000 |
O2 | 0.0118 (9) | 0.0268 (10) | 0.0234 (10) | 0.0015 (7) | 0.0047 (8) | 0.0016 (7) |
O3 | 0.0212 (10) | 0.0134 (8) | 0.0211 (9) | 0.0038 (7) | 0.0089 (8) | 0.0028 (6) |
O4 | 0.0215 (10) | 0.0123 (8) | 0.0227 (9) | 0.0022 (7) | 0.0089 (8) | 0.000 |
O5 | 0.0212 (10) | 0.0217 (9) | 0.0169 (9) | 0.0058 (7) | 0.0061 (7) | −0.0031 (7) |
O6 | 0.0233 (10) | 0.0200 (9) | 0.0170 (9) | 0.0049 (7) | 0.0076 (7) | −0.0029 (7) |
O7 | 0.0198 (9) | 0.0228 (9) | 0.0152 (8) | 0.0072 (7) | 0.0043 (7) | 0.0050 (7) |
O8 | 0.0194 (9) | 0.0249 (10) | 0.0151 (8) | 0.0074 (7) | 0.0052 (7) | 0.0051 (7) |
O9 | 0.0126 (8) | 0.0220 (9) | 0.0266 (10) | 0.0026 (7) | 0.0048 (7) | 0.0039 (7) |
O10 | 0.0141 (9) | 0.0255 (10) | 0.0244 (10) | 0.0034 (7) | 0.0065 (7) | 0.000 |
O11 | 0.0198 (9) | 0.0115 (8) | 0.0211 (9) | 0.0033 (6) | 0.0077 (7) | 0.0018 (6) |
O12 | 0.0225 (10) | 0.0122 (8) | 0.0189 (9) | 0.000 | 0.0060 (7) | 0.0017 (6) |
O13 | 0.0235 (10) | 0.0213 (9) | 0.0153 (8) | 0.000 | 0.0091 (7) | 0.0040 (7) |
O14 | 0.0200 (9) | 0.0232 (9) | 0.0173 (9) | 0.0065 (7) | 0.0074 (7) | −0.0021 (7) |
O15 | 0.0206 (9) | 0.0215 (9) | 0.0174 (9) | 0.0072 (7) | 0.0089 (7) | 0.000 |
O16 | 0.0216 (10) | 0.0236 (9) | 0.0150 (8) | 0.000 | 0.0088 (7) | 0.0021 (7) |
N1 | 0.0165 (10) | 0.0135 (10) | 0.0196 (11) | 0.0021 (8) | 0.0075 (8) | 0.0026 (7) |
N2 | 0.0148 (11) | 0.0149 (10) | 0.0176 (11) | 0.0019 (8) | 0.0043 (9) | 0.000 |
N3 | 0.0182 (12) | 0.0157 (11) | 0.0164 (11) | 0.000 | 0.0049 (9) | 0.000 |
N4 | 0.0179 (12) | 0.0160 (11) | 0.0162 (11) | 0.0036 (8) | 0.0041 (9) | 0.0020 (8) |
N5 | 0.0184 (12) | 0.0151 (11) | 0.0190 (11) | 0.0038 (8) | 0.0075 (9) | 0.000 |
N6 | 0.0192 (12) | 0.0173 (11) | 0.0196 (12) | 0.0019 (9) | 0.0100 (9) | 0.0027 (8) |
Geometric parameters (Å, º) top
S1—O5 | 1.468 (2) | N1—H6 | 1.00 (5) |
S1—O7 | 1.471 (2) | N2—H7 | 0.90 (4) |
S1—O3 | 1.477 (2) | N2—H8 | 0.95 (3) |
S1—O1 | 1.500 (2) | N2—H9 | 0.81 (5) |
S2—O6 | 1.450 (2) | N2—H10 | 0.78 (5) |
S2—O4 | 1.457 (2) | N3—H11 | 0.84 (5) |
S2—O8 | 1.464 (2) | N3—H12 | 0.86 (5) |
S2—O2 | 1.554 (2) | N3—H13 | 0.84 (4) |
S3—O15 | 1.464 (2) | N3—H14 | 0.780 (6) |
S3—O13 | 1.469 (2) | N4—H15 | 0.82 (4) |
S3—O11 | 1.477 (2) | N4—H16 | 0.83 (4) |
S3—O9 | 1.505 (2) | N4—H17 | 0.87 (4) |
S4—O16 | 1.452 (2) | N4—H18 | 0.86 (4) |
S4—O12 | 1.457 (2) | N5—H19 | 0.80 (5) |
S4—O14 | 1.458 (2) | N5—H20 | 0.82 (3) |
S4—O10 | 1.546 (2) | N5—H21 | 0.80 (5) |
O2—H1 | 0.83 (5) | N5—H22 | 0.79 (4) |
O10—H2 | 0.94 (5) | N6—H23 | 0.89 (4) |
N1—H3 | 0.76 (3) | N6—H24 | 0.84 (4) |
N1—H4 | 0.95 (4) | N6—H25 | 0.76 (5) |
N1—H5 | 0.91 (4) | N6—H26 | 0.88 (4) |
| | | |
O5—S1—O7 | 110.70 (13) | H5—N1—H6 | 111 (4) |
O5—S1—O3 | 110.01 (13) | H7—N2—H8 | 108 (3) |
O7—S1—O3 | 110.25 (13) | H7—N2—H9 | 114 (4) |
O5—S1—O1 | 109.37 (13) | H8—N2—H9 | 106 (4) |
O7—S1—O1 | 108.47 (14) | H7—N2—H10 | 117 (4) |
O3—S1—O1 | 107.99 (13) | H8—N2—H10 | 110 (4) |
O6—S2—O4 | 112.52 (13) | H9—N2—H10 | 101 (5) |
O6—S2—O8 | 112.79 (14) | H11—N3—H12 | 124 (5) |
O4—S2—O8 | 112.22 (13) | H11—N3—H13 | 105 (4) |
O6—S2—O2 | 105.23 (14) | H12—N3—H13 | 105 (4) |
O4—S2—O2 | 106.78 (14) | H11—N3—H14 | 109 (4) |
O8—S2—O2 | 106.68 (14) | H12—N3—H14 | 104 (4) |
O15—S3—O13 | 110.94 (13) | H13—N3—H14 | 110 (4) |
O15—S3—O11 | 110.50 (13) | H15—N4—H16 | 119 (4) |
O13—S3—O11 | 110.32 (13) | H15—N4—H17 | 102 (4) |
O15—S3—O9 | 108.50 (13) | H16—N4—H17 | 115 (4) |
O13—S3—O9 | 108.79 (14) | H15—N4—H18 | 108 (4) |
O11—S3—O9 | 107.70 (13) | H16—N4—H18 | 105 (4) |
O16—S4—O12 | 112.32 (13) | H17—N4—H18 | 107 (4) |
O16—S4—O14 | 112.35 (14) | H19—N5—H20 | 104 (4) |
O12—S4—O14 | 111.73 (13) | H19—N5—H21 | 107 (5) |
O16—S4—O10 | 105.78 (14) | H20—N5—H21 | 116 (4) |
O12—S4—O10 | 107.24 (14) | H19—N5—H22 | 118 (5) |
O14—S4—O10 | 106.96 (13) | H20—N5—H22 | 106 (3) |
S2—O2—H1 | 113 (4) | H21—N5—H22 | 107 (4) |
S4—O10—H2 | 105 (3) | H23—N6—H24 | 120 (4) |
H3—N1—H4 | 116 (4) | H23—N6—H25 | 101 (4) |
H3—N1—H5 | 105 (4) | H24—N6—H25 | 104 (4) |
H4—N1—H5 | 101 (4) | H23—N6—H26 | 116 (4) |
H3—N1—H6 | 115 (4) | H24—N6—H26 | 96 (3) |
H4—N1—H6 | 107 (4) | H25—N6—H26 | 119 (5) |
Crystal data top
HO8S2·3(H4N) | F(000) = 126 |
Mr = 247.2 | Dx = 1.829 (2) Mg m−3 |
Monoclinic, P2/n | Neutron radiation, λ = 0.87 Å |
Hall symbol: -P 2yac | Cell parameters from 19 reflections |
a = 15.473 (8) Å | θ = 12.9–18.6° |
b = 5.849 (3) Å | µ = 0.002 mm−1 |
c = 10.131 (5) Å | T = 250 K |
β = 101.75 (5)° | Cube, colourless |
V = 897.7 (8) Å3 | 3 × 3 × 3 × 0 (radius) mm |
Z = 4 | |
Data collection top
4-circle diffractometer | Rint = 0.043 |
Radiation source: nuclear reactor | θmax = 37.5°, θmin = 3.3° |
Cu (220) monochromator | h = −21→0 |
ω scans | k = −8→3 |
1770 measured reflections | l = −13→14 |
1503 independent reflections | 2 standard reflections every 360 min min |
1092 reflections with I > 3σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.066 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.140 | (Δ/σ)max = 0.036 |
S = 3.26 | Δρmax = 0.97 e Å−3 |
1503 reflections | Δρmin = −1.59 e Å−3 |
208 parameters | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
0 restraints | Extinction coefficient: 87E2 (4) |
2 constraints | |
Crystal data top
HO8S2·3(H4N) | V = 897.7 (8) Å3 |
Mr = 247.2 | Z = 4 |
Monoclinic, P2/n | Neutron radiation, λ = 0.87 Å |
a = 15.473 (8) Å | µ = 0.002 mm−1 |
b = 5.849 (3) Å | T = 250 K |
c = 10.131 (5) Å | 3 × 3 × 3 × 0 (radius) mm |
β = 101.75 (5)° | |
Data collection top
4-circle diffractometer | Rint = 0.043 |
1770 measured reflections | 2 standard reflections every 360 min min |
1503 independent reflections | intensity decay: none |
1092 reflections with I > 3σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.140 | All H-atom parameters refined |
S = 3.26 | Δρmax = 0.97 e Å−3 |
1503 reflections | Δρmin = −1.59 e Å−3 |
208 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.3614 (5) | 0.4667 (11) | 0.4624 (6) | 0.025 (2) | |
S2 | 0.1343 (4) | 0.0314 (10) | 0.5395 (7) | 0.0218 (18) | |
N1 | 0.75 | 0.0214 (6) | 0.75 | 0.0280 (10) | |
N2 | 0.75 | 0.4803 (6) | 0.25 | 0.0298 (11) | |
N3 | 0.44921 (19) | 0.5239 (4) | 0.1557 (3) | 0.0317 (8) | |
N4 | 0.05054 (19) | 0.9689 (4) | 0.8504 (3) | 0.0324 (9) | |
O1 | 0.2641 (2) | 0.4315 (7) | 0.4463 (4) | 0.0382 (12) | |
O2 | 0.2339 (2) | 0.0620 (7) | 0.5610 (4) | 0.0381 (12) | |
O3 | 0.4011 (2) | 0.4449 (7) | 0.6054 (3) | 0.0320 (11) | |
O4 | 0.1012 (2) | 0.0006 (6) | 0.3945 (4) | 0.0328 (11) | |
O5 | 0.3769 (2) | 0.6950 (6) | 0.4132 (4) | 0.0345 (11) | |
O6 | 0.1200 (2) | 0.8291 (6) | 0.6154 (4) | 0.0336 (11) | |
O7 | 0.3956 (2) | 0.2909 (6) | 0.3836 (4) | 0.0341 (11) | |
O8 | 0.0982 (2) | 0.2365 (6) | 0.5884 (4) | 0.0343 (11) | |
H1 | 0.2489 | 0.2061 | 0.5143 | 0.0396 (17)* | 0.651 (14) |
H2 | 0.2511 | 0.2939 | 0.4857 | 0.0396 (17)* | 0.349 (14) |
H3 | 0.7138 (7) | 0.382 (3) | 0.1871 (13) | 0.108 (5) | |
H4 | 0.7849 (8) | 0.114 (2) | 0.8230 (10) | 0.092 (4) | |
H5 | 0.7045 (10) | 0.556 (3) | 0.274 (2) | 0.150 (8) | |
H6 | 0.7954 (10) | 0.946 (4) | 0.722 (2) | 0.167 (9) | |
H7 | 0.5100 (8) | 0.538 (2) | 0.1804 (15) | 0.094 (5) | |
H8 | 0.9872 (7) | 0.930 (2) | 0.8401 (12) | 0.080 (4) | |
H9 | 0.4259 (8) | 0.685 (2) | 0.1304 (11) | 0.089 (4) | |
H10 | 0.0804 (7) | 0.8798 (17) | 0.9281 (9) | 0.071 (3) | |
H11 | 0.4377 (7) | 0.413 (2) | 0.0783 (12) | 0.086 (4) | |
H12 | 0.0590 (6) | 0.1404 (13) | 0.8702 (8) | 0.062 (3) | |
H13 | 0.4277 (8) | 0.464 (2) | 0.2334 (10) | 0.086 (4) | |
H14 | 0.0721 (7) | 0.9245 (16) | 0.7654 (10) | 0.072 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.037 (4) | 0.027 (3) | 0.016 (3) | 0.007 (2) | 0.012 (3) | 0 |
S2 | 0.020 (3) | 0.020 (3) | 0.023 (3) | 0.004 (2) | 0 | 0 |
N1 | 0.0290 (17) | 0.0303 (15) | 0.0237 (18) | 0 | 0.0029 (13) | 0 |
N2 | 0.0370 (19) | 0.0299 (16) | 0.0227 (17) | 0 | 0.0062 (14) | 0 |
N3 | 0.0415 (15) | 0.0297 (13) | 0.0248 (13) | −0.0072 (10) | 0.0086 (10) | 0 |
N4 | 0.0377 (16) | 0.0251 (12) | 0.0343 (16) | −0.0056 (10) | 0.0072 (11) | −0.0026 (9) |
O1 | 0.0256 (17) | 0.047 (2) | 0.043 (2) | 0 | 0.0085 (15) | 0 |
O2 | 0.0294 (18) | 0.044 (2) | 0.041 (2) | 0 | 0.0077 (15) | 0 |
O3 | 0.0382 (19) | 0.0349 (18) | 0.0215 (17) | 0 | 0.0027 (14) | 0.0033 (13) |
O4 | 0.042 (2) | 0.0378 (19) | 0.0193 (17) | −0.0073 (15) | 0.0073 (15) | −0.0026 (13) |
O5 | 0.044 (2) | 0.0249 (17) | 0.0324 (18) | 0.0028 (15) | 0.0037 (14) | 0.0061 (14) |
O6 | 0.0410 (19) | 0.0287 (17) | 0.0320 (17) | 0.0055 (15) | 0.0098 (14) | 0.0110 (14) |
O7 | 0.041 (2) | 0.0297 (17) | 0.0358 (18) | 0 | 0.0179 (14) | −0.0105 (14) |
O8 | 0.0375 (19) | 0.0265 (17) | 0.0422 (19) | 0.0044 (15) | 0.0159 (15) | −0.0056 (15) |
H3 | 0.068 (6) | 0.141 (11) | 0.097 (8) | 0 | −0.024 (5) | −0.041 (9) |
H4 | 0.103 (8) | 0.090 (7) | 0.060 (5) | 0.011 (6) | −0.036 (5) | −0.025 (6) |
H5 | 0.073 (8) | 0.150 (13) | 0.215 (19) | 0.046 (8) | 0 | −0.078 (13) |
H6 | 0.077 (8) | 0.226 (19) | 0.187 (17) | 0.059 (9) | 0 | −0.120 (15) |
H7 | 0.053 (6) | 0.093 (8) | 0.129 (10) | 0 | 0 | −0.036 (7) |
H8 | 0.053 (5) | 0.094 (7) | 0.095 (7) | −0.022 (5) | 0.021 (5) | −0.040 (6) |
H9 | 0.110 (9) | 0.062 (6) | 0.085 (7) | 0 | 0 | 0.010 (5) |
H10 | 0.097 (7) | 0.061 (5) | 0.057 (5) | 0.008 (5) | 0.022 (5) | 0 |
H11 | 0.092 (7) | 0.083 (7) | 0.089 (7) | −0.035 (6) | 0.035 (6) | −0.042 (6) |
H12 | 0.087 (6) | 0.033 (4) | 0.060 (5) | 0 | 0 | −0.006 (3) |
H13 | 0.104 (8) | 0.116 (8) | 0.052 (5) | 0 | 0.045 (6) | 0.017 (5) |
H14 | 0.104 (7) | 0.062 (5) | 0.058 (5) | −0.017 (5) | 0.033 (5) | 0 |
Geometric parameters (Å, º) top
S1—O1 | 1.495 (8) | N2—H3 | 0.953 (14) |
S1—O3 | 1.460 (7) | N2—H3iv | 0.953 (14) |
S1—O5 | 1.462 (8) | N2—H5 | 0.906 (19) |
S1—O7 | 1.465 (8) | N2—H5iv | 0.906 (19) |
S2—O2 | 1.523 (7) | N3—H7 | 0.927 (12) |
S2—O4 | 1.465 (7) | N3—H9 | 1.023 (12) |
S2—O6i | 1.452 (7) | N3—H11 | 1.005 (12) |
S2—O8 | 1.452 (7) | N3—H13 | 0.980 (12) |
N1—H4 | 0.985 (10) | N4—H8v | 0.991 (11) |
N1—H4ii | 0.985 (10) | N4—H10 | 0.978 (10) |
N1—H6i | 0.92 (2) | N4—H12vi | 1.027 (8) |
N1—H6iii | 0.92 (2) | N4—H14 | 1.018 (11) |
| | | |
O1—S1—O3 | 107.9 (5) | H3—N2—H3iv | 105.4 (13) |
O1—S1—O5 | 108.7 (5) | H3—N2—H5 | 95.3 (14) |
O1—S1—O7 | 108.2 (4) | H3—N2—H5iv | 120.1 (17) |
O3—S1—O5 | 110.7 (4) | H3iv—N2—H5 | 120.1 (17) |
O3—S1—O7 | 110.7 (5) | H3iv—N2—H5iv | 95.3 (14) |
O5—S1—O7 | 110.6 (5) | H5—N2—H5iv | 121.4 (17) |
O2—S2—O4 | 107.1 (5) | H7—N3—H9 | 105.8 (10) |
O2—S2—O6i | 106.1 (4) | H7—N3—H11 | 106.0 (11) |
O2—S2—O8 | 107.6 (4) | H7—N3—H13 | 107.9 (12) |
O4—S2—O6i | 111.8 (4) | H9—N3—H11 | 113.6 (9) |
O4—S2—O8 | 111.3 (4) | H9—N3—H13 | 111.8 (11) |
O6i—S2—O8 | 112.5 (5) | H11—N3—H13 | 111.2 (10) |
H4—N1—H4ii | 113.1 (10) | H8v—N4—H10 | 104.9 (10) |
H4—N1—H6i | 99.0 (14) | H8v—N4—H12vi | 109.2 (9) |
H4—N1—H6iii | 111.8 (16) | H8v—N4—H14 | 109.9 (9) |
H4ii—N1—H6i | 111.8 (16) | H10—N4—H12vi | 110.0 (8) |
H4ii—N1—H6iii | 99.0 (14) | H10—N4—H14 | 111.3 (9) |
H6i—N1—H6iii | 122.9 (19) | H12vi—N4—H14 | 111.3 (8) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y, −z+3/2; (iii) −x+3/2, y−1, −z+3/2; (iv) −x+3/2, y, −z+1/2; (v) x−1, y, z; (vi) x, y+1, z. |
Crystal data top
HO8S2·3(H4N) | F(000) = 126 |
Mr = 247.2 | Dx = 1.835 (2) Mg m−3 |
Monoclinic, P2/n | Neutron radiation, λ = 0.87 Å |
Hall symbol: -P 2yac | Cell parameters from 19 reflections |
a = 15.534 (8) Å | θ = 12.9–18.6° |
b = 5.825 (3) Å | µ = 0.002 mm−1 |
c = 10.089 (5) Å | T = 150 K |
β = 101.52 (5)° | Cube, colourless |
V = 894.5 (8) Å3 | 3 × 3 × 3 × 0 (radius) mm |
Z = 4 | |
Data collection top
4-circle diffractometer | Rint = 0.024 |
Radiation source: nuclear reactor | θmax = 37.7°, θmin = 3.3° |
Cu (220) monochromator | h = −21→0 |
ω scans | k = −8→6 |
2379 measured reflections | l = −13→14 |
1689 independent reflections | 2 standard reflections every 360 min min |
1470 reflections with I > 3σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.058 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.139 | (Δ/σ)max = 0.031 |
S = 4.11 | Δρmax = 1.37 e Å−3 |
1689 reflections | Δρmin = −1.99 e Å−3 |
208 parameters | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
0 restraints | Extinction coefficient: 73E2 (3) |
2 constraints | |
Crystal data top
HO8S2·3(H4N) | V = 894.5 (8) Å3 |
Mr = 247.2 | Z = 4 |
Monoclinic, P2/n | Neutron radiation, λ = 0.87 Å |
a = 15.534 (8) Å | µ = 0.002 mm−1 |
b = 5.825 (3) Å | T = 150 K |
c = 10.089 (5) Å | 3 × 3 × 3 × 0 (radius) mm |
β = 101.52 (5)° | |
Data collection top
4-circle diffractometer | Rint = 0.024 |
2379 measured reflections | 2 standard reflections every 360 min min |
1689 independent reflections | intensity decay: none |
1470 reflections with I > 3σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.139 | All H-atom parameters refined |
S = 4.11 | Δρmax = 1.37 e Å−3 |
1689 reflections | Δρmin = −1.99 e Å−3 |
208 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.3602 (3) | 0.4656 (8) | 0.4630 (4) | 0.0141 (13) | |
S2 | 0.1338 (3) | 0.0286 (8) | 0.5391 (4) | 0.0141 (12) | |
N1 | 0.75 | 0.0227 (4) | 0.75 | 0.0193 (6) | |
N2 | 0.75 | 0.4804 (4) | 0.25 | 0.0202 (7) | |
N3 | 0.44974 (11) | 0.5217 (3) | 0.15727 (16) | 0.0198 (5) | |
N4 | 0.04859 (12) | 0.9678 (3) | 0.85166 (16) | 0.0215 (5) | |
O1 | 0.26294 (17) | 0.4288 (5) | 0.4480 (3) | 0.0268 (8) | |
O2 | 0.23344 (16) | 0.0602 (5) | 0.5628 (3) | 0.0244 (8) | |
O3 | 0.40045 (17) | 0.4357 (4) | 0.6066 (2) | 0.0186 (7) | |
O4 | 0.10211 (17) | −0.0096 (4) | 0.3938 (2) | 0.0186 (7) | |
O5 | 0.37510 (17) | 0.6991 (4) | 0.4172 (2) | 0.0196 (7) | |
O6 | 0.11943 (17) | 0.8307 (4) | 0.6202 (2) | 0.0202 (7) | |
O7 | 0.39405 (16) | 0.2949 (4) | 0.3790 (2) | 0.0191 (7) | |
O8 | 0.09759 (17) | 0.2408 (4) | 0.5843 (2) | 0.0194 (7) | |
H1 | 0.2489 | 0.2061 | 0.5143 | 0.0329 (13)* | 0.746 (12) |
H2 | 0.2511 | 0.2939 | 0.4857 | 0.0329 (13)* | 0.254 (12) |
H3 | 0.7151 (7) | 0.379 (2) | 0.1846 (11) | 0.106 (4) | |
H4 | 0.7857 (5) | 0.1200 (13) | 0.8227 (7) | 0.062 (2) | |
H5 | 0.7029 (7) | 0.557 (3) | 0.2753 (19) | 0.150 (7) | |
H6 | 0.7942 (8) | 0.942 (3) | 0.7170 (14) | 0.156 (7) | |
H7 | 0.5133 (4) | 0.5300 (11) | 0.1871 (7) | 0.053 (2) | |
H8 | 0.9850 (4) | 0.9298 (12) | 0.8403 (7) | 0.050 (2) | |
H9 | 0.4266 (4) | 0.6866 (9) | 0.1366 (5) | 0.0391 (16) | |
H10 | 0.0809 (4) | 0.8769 (9) | 0.9338 (5) | 0.0405 (17) | |
H11 | 0.4339 (4) | 0.4225 (9) | 0.0704 (5) | 0.0386 (16) | |
H12 | 0.0590 (4) | 0.1426 (8) | 0.8676 (5) | 0.0371 (16) | |
H13 | 0.4236 (4) | 0.4479 (9) | 0.2321 (5) | 0.0407 (17) | |
H14 | 0.0706 (4) | 0.9184 (9) | 0.7663 (5) | 0.0395 (16) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.021 (2) | 0.014 (2) | 0.0089 (19) | 0 | 0.0067 (16) | 0 |
S2 | 0.016 (2) | 0.015 (2) | 0.011 (2) | 0 | 0.0035 (15) | 0 |
N1 | 0.0225 (11) | 0.0200 (10) | 0.0149 (11) | 0 | 0.0026 (9) | 0 |
N2 | 0.0227 (11) | 0.0211 (10) | 0.0177 (11) | 0 | 0.0063 (9) | 0 |
N3 | 0.0243 (9) | 0.0180 (8) | 0.0177 (8) | −0.0031 (6) | 0.0057 (6) | 0 |
N4 | 0.0294 (10) | 0.0181 (8) | 0.0171 (9) | −0.0022 (6) | 0.0051 (6) | 0 |
O1 | 0.0182 (12) | 0.0334 (15) | 0.0292 (13) | 0 | 0.0059 (10) | 0 |
O2 | 0.0178 (12) | 0.0293 (13) | 0.0262 (13) | 0 | 0.0046 (10) | −0.0018 (9) |
O3 | 0.0285 (13) | 0.0159 (10) | 0.0109 (10) | 0 | 0.0031 (9) | 0.0016 (7) |
O4 | 0.0266 (12) | 0.0176 (11) | 0.0123 (11) | 0 | 0.0056 (9) | 0 |
O5 | 0.0283 (12) | 0.0134 (10) | 0.0166 (10) | 0.0023 (9) | 0.0034 (8) | 0 |
O6 | 0.0276 (12) | 0.0178 (11) | 0.0164 (10) | 0.0034 (9) | 0.0072 (9) | 0.0039 (8) |
O7 | 0.0257 (12) | 0.0161 (11) | 0.0172 (10) | 0.0015 (9) | 0.0085 (8) | −0.0031 (8) |
O8 | 0.0291 (12) | 0.0150 (11) | 0.0157 (10) | 0.0036 (9) | 0.0085 (8) | −0.0017 (8) |
H3 | 0.066 (5) | 0.140 (9) | 0.096 (7) | 0.029 (6) | −0.023 (5) | −0.067 (7) |
H4 | 0.059 (4) | 0.059 (4) | 0.055 (4) | 0.009 (3) | −0.019 (3) | −0.019 (3) |
H5 | 0.055 (6) | 0.158 (11) | 0.224 (16) | 0.045 (6) | 0 | −0.116 (11) |
H6 | 0.097 (8) | 0.217 (15) | 0.128 (10) | 0.103 (9) | −0.042 (7) | −0.109 (11) |
H7 | 0.028 (3) | 0.054 (4) | 0.072 (4) | 0 | 0 | −0.009 (3) |
H8 | 0.039 (3) | 0.054 (3) | 0.057 (4) | −0.005 (3) | 0.010 (2) | −0.019 (3) |
H9 | 0.044 (3) | 0.030 (3) | 0.041 (3) | 0.005 (2) | 0.003 (2) | 0 |
H10 | 0.062 (3) | 0.034 (3) | 0.025 (2) | 0.004 (2) | 0.006 (2) | 0.0068 (18) |
H11 | 0.048 (3) | 0.038 (3) | 0.032 (2) | −0.007 (2) | 0.012 (2) | −0.008 (2) |
H12 | 0.050 (3) | 0.022 (2) | 0.036 (3) | 0 | 0 | 0 |
H13 | 0.053 (3) | 0.039 (3) | 0.035 (3) | −0.006 (2) | 0.022 (2) | 0 |
H14 | 0.062 (3) | 0.035 (2) | 0.025 (2) | −0.003 (2) | 0.016 (2) | 0 |
Geometric parameters (Å, º) top
S1—O1 | 1.503 (6) | N2—H3 | 0.968 (11) |
S1—O3 | 1.469 (5) | N2—H3iv | 0.968 (11) |
S1—O5 | 1.470 (5) | N2—H5 | 0.935 (14) |
S1—O7 | 1.470 (5) | N2—H5iv | 0.935 (14) |
S2—O2 | 1.530 (6) | N3—H7 | 0.974 (6) |
S2—O4 | 1.467 (5) | N3—H9 | 1.033 (6) |
S2—O6i | 1.456 (5) | N3—H11 | 1.037 (5) |
S2—O8 | 1.468 (5) | N3—H13 | 1.020 (6) |
N1—H4 | 1.002 (7) | N4—H8v | 0.997 (7) |
N1—H4ii | 1.002 (7) | N4—H10 | 1.026 (5) |
N1—H6i | 0.945 (15) | N4—H12vi | 1.038 (5) |
N1—H6iii | 0.945 (15) | N4—H14 | 1.029 (6) |
| | | |
O1—S1—O3 | 107.7 (3) | H3—N2—H3iv | 104.5 (10) |
O1—S1—O5 | 108.6 (3) | H3—N2—H5 | 96.7 (11) |
O1—S1—O7 | 108.3 (3) | H3—N2—H5iv | 117.9 (13) |
O3—S1—O5 | 110.9 (3) | H3iv—N2—H5 | 117.9 (13) |
O3—S1—O7 | 110.9 (3) | H3iv—N2—H5iv | 96.7 (11) |
O5—S1—O7 | 110.3 (3) | H5—N2—H5iv | 123.0 (13) |
O2—S2—O4 | 107.5 (4) | H7—N3—H9 | 107.8 (5) |
O2—S2—O6i | 105.7 (3) | H7—N3—H11 | 110.0 (6) |
O2—S2—O8 | 106.8 (3) | H7—N3—H13 | 108.7 (6) |
O4—S2—O6i | 112.6 (3) | H9—N3—H11 | 109.5 (4) |
O4—S2—O8 | 111.4 (3) | H9—N3—H13 | 111.6 (5) |
O6i—S2—O8 | 112.4 (4) | H11—N3—H13 | 109.2 (5) |
H4—N1—H4ii | 111.1 (6) | H8v—N4—H10 | 106.9 (5) |
H4—N1—H6i | 101.8 (9) | H8v—N4—H12vi | 110.9 (5) |
H4—N1—H6iii | 110.9 (10) | H8v—N4—H14 | 109.3 (5) |
H4ii—N1—H6i | 110.9 (10) | H10—N4—H12vi | 110.2 (4) |
H4ii—N1—H6iii | 101.8 (9) | H10—N4—H14 | 109.9 (5) |
H6i—N1—H6iii | 120.5 (14) | H12vi—N4—H14 | 109.6 (5) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y, −z+3/2; (iii) −x+3/2, y−1, −z+3/2; (iv) −x+3/2, y, −z+1/2; (v) x−1, y, z; (vi) x, y+1, z. |
Crystal data top
HO8S2·3(H4N) | F(000) = 253 |
Mr = 247.2 | Dx = 1.837 (2) Mg m−3 |
Monoclinic, P2/n | Neutron radiation, λ = 0.87 Å |
Hall symbol: -P 2yac | Cell parameters from 19 reflections |
a = 15.538 (8) Å | θ = 15.3–26.6° |
b = 11.641 (6) Å | µ = 0.002 mm−1 |
c = 10.085 (5) Å | T = 139 K |
β = 101.46 (5)° | Cube, colourless |
V = 1787.8 (16) Å3 | 3 × 3 × 3 × 0 (radius) mm |
Z = 8 | |
Data collection top
4-circle diffractometer | Rint = 0.03 |
Radiation source: nuclear reactor | θmax = 37.6°, θmin = 3.3° |
Cu (220) monochromator | h = −17→21 |
ω scans | k = −14→16 |
4208 measured reflections | l = −14→14 |
2689 independent reflections | 2 standard reflections every 240 min min |
1789 reflections with I > 3σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.083 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.166 | (Δ/σ)max = 0.039 |
S = 4.02 | Δρmax = 2.68 e Å−3 |
2689 reflections | Δρmin = −3.60 e Å−3 |
150 parameters | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
0 restraints | Extinction coefficient: 152E1 (7) |
2 constraints | |
Crystal data top
HO8S2·3(H4N) | V = 1787.8 (16) Å3 |
Mr = 247.2 | Z = 8 |
Monoclinic, P2/n | Neutron radiation, λ = 0.87 Å |
a = 15.538 (8) Å | µ = 0.002 mm−1 |
b = 11.641 (6) Å | T = 139 K |
c = 10.085 (5) Å | 3 × 3 × 3 × 0 (radius) mm |
β = 101.46 (5)° | |
Data collection top
4-circle diffractometer | Rint = 0.03 |
4208 measured reflections | 2 standard reflections every 240 min min |
2689 independent reflections | intensity decay: none |
1789 reflections with I > 3σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.083 | 0 restraints |
wR(F2) = 0.166 | All H-atom parameters refined |
S = 4.02 | Δρmax = 2.68 e Å−3 |
2689 reflections | Δρmin = −3.60 e Å−3 |
150 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.3586 (11) | 0.2295 (13) | 0.4589 (16) | 0.0088 | |
S2 | 0.1314 (14) | 0.0114 (16) | 0.538 (2) | 0.0104 | |
S3 | 0.3626 (11) | 0.7370 (13) | 0.4668 (16) | 0.0088 | |
S4 | 0.1359 (13) | 0.5176 (16) | 0.539 (2) | 0.0104 | |
N1 | 0.75 | 0.0085 (9) | 0.75 | 0.0158 | |
N2 | 0.75 | 0.2441 (7) | 0.25 | 0.016 | |
N3 | 0.4496 (7) | 0.2609 (10) | 0.1539 (8) | 0.0164 | |
N4 | 0.0497 (6) | 0.4876 (6) | 0.8522 (9) | 0.0174 | |
N5 | 0.75 | 0.5141 (9) | 0.75 | 0.0158 | |
N6 | 0.75 | 0.7368 (7) | 0.25 | 0.016 | |
N7 | 0.4498 (7) | 0.7606 (10) | 0.1594 (8) | 0.0164 | |
N8 | 0.0475 (6) | 0.9809 (6) | 0.8506 (9) | 0.0174 | |
O1 | 0.2614 (8) | 0.2151 (14) | 0.4494 (14) | 0.0232 | |
O2 | 0.2351 (10) | 0.0326 (12) | 0.5648 (16) | 0.0199 | |
O3 | 0.3958 (5) | 0.2198 (9) | 0.6063 (9) | 0.0151 | |
O4 | 0.1015 (12) | −0.0025 (13) | 0.3921 (15) | 0.0152 | |
O5 | 0.3733 (9) | 0.3485 (13) | 0.4154 (16) | 0.0163 | |
O6 | 0.1165 (7) | −0.0872 (9) | 0.6212 (11) | 0.0163 | |
O7 | 0.3943 (8) | 0.1440 (8) | 0.3764 (10) | 0.0159 | |
O8 | 0.0957 (7) | 0.1164 (7) | 0.5825 (10) | 0.0144 | |
O9 | 0.2649 (8) | 0.7146 (14) | 0.4443 (15) | 0.0232 | |
O10 | 0.2325 (10) | 0.5286 (12) | 0.5605 (16) | 0.0199 | |
O11 | 0.4045 (5) | 0.7173 (9) | 0.6069 (9) | 0.0151 | |
O12 | 0.1033 (12) | 0.4941 (13) | 0.3967 (15) | 0.0152 | |
O13 | 0.3769 (8) | 0.8507 (13) | 0.4180 (16) | 0.0163 | |
O14 | 0.1218 (7) | 0.4171 (9) | 0.6176 (11) | 0.0163 | |
O15 | 0.3944 (8) | 0.6506 (8) | 0.3826 (10) | 0.0159 | |
O16 | 0.0997 (7) | 0.6235 (7) | 0.5866 (10) | 0.0144 | |
H1 | 0.2489 | 0.10305 | 0.5143 | 0.0297* | 0.7114 |
H2 | 0.2511 | 0.14695 | 0.4857 | 0.0297* | 0.2886 |
H3 | 0.7092 (14) | 0.191 (3) | 0.187 (3) | 0.0881 | |
H4 | 0.7853 (18) | 0.0556 (19) | 0.825 (3) | 0.0524 | |
H5 | 0.7084 (16) | 0.293 (2) | 0.265 (4) | 0.1254 | |
H6 | 0.794 (2) | −0.040 (4) | 0.727 (4) | 0.1573 | |
H7 | 0.5196 (10) | 0.2633 (19) | 0.189 (2) | 0.0471 | |
H8 | −0.0124 (10) | 0.4691 (15) | 0.8313 (18) | 0.0444 | |
H9 | 0.4309 (12) | 0.342 (2) | 0.136 (2) | 0.0361 | |
H10 | 0.0772 (12) | 0.4368 (15) | 0.9375 (16) | 0.0339 | |
H11 | 0.4314 (13) | 0.211 (2) | 0.069 (2) | 0.0369 | |
H12 | 0.0616 (17) | 0.5670 (16) | 0.868 (3) | 0.0319 | |
H13 | 0.4198 (13) | 0.2266 (16) | 0.2358 (18) | 0.0383 | |
H14 | 0.0751 (12) | 0.4633 (17) | 0.769 (2) | 0.0323 | |
H15 | 0.2489 | 0.60305 | 0.5143 | 0.0297* | 0.7299 |
H16 | 0.2511 | 0.64695 | 0.4857 | 0.0297* | 0.2701 |
H17 | 0.7194 (15) | 0.687 (3) | 0.181 (3) | 0.0881 | |
H18 | 0.7877 (18) | 0.5653 (19) | 0.818 (3) | 0.0524 | |
H19 | 0.6999 (17) | 0.764 (2) | 0.293 (3) | 0.1254 | |
H20 | 0.791 (2) | 0.476 (4) | 0.711 (4) | 0.1573 | |
H21 | 0.5099 (10) | 0.7685 (19) | 0.185 (2) | 0.0471 | |
H22 | −0.0190 (10) | 0.9615 (15) | 0.8469 (17) | 0.0444 | |
H23 | 0.4230 (12) | 0.844 (2) | 0.137 (3) | 0.0361 | |
H24 | 0.0842 (12) | 0.9401 (15) | 0.9285 (16) | 0.0339 | |
H25 | 0.4384 (13) | 0.710 (2) | 0.074 (2) | 0.0369 | |
H26 | 0.0583 (17) | 1.0741 (16) | 0.867 (3) | 0.0319 | |
H27 | 0.4275 (13) | 0.7212 (16) | 0.2284 (18) | 0.0383 | |
H28 | 0.0668 (12) | 0.9585 (17) | 0.765 (2) | 0.0323 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.006761 | 0.009876 | 0.009057 | 0 | 0 | 0 |
S2 | 0.007881 | 0.010467 | 0.013633 | 0 | 0.004308 | 0 |
S3 | 0.006761 | 0.009876 | 0.009057 | 0 | 0 | 0 |
S4 | 0.007881 | 0.010467 | 0.013633 | 0 | 0.004308 | 0 |
N1 | 0.01461 | 0.016356 | 0.015146 | 0 | 0 | 0 |
N2 | 0.013049 | 0.017107 | 0.016696 | 0 | 0 | 0 |
N3 | 0.017944 | 0.01629 | 0.014829 | −0.002136 | 0.002938 | 0 |
N4 | 0.017772 | 0.015359 | 0.018338 | −0.004564 | 0.001495 | −0.00192 |
N5 | 0.01461 | 0.016356 | 0.015146 | 0 | 0 | 0 |
N6 | 0.013049 | 0.017107 | 0.016696 | 0 | 0 | 0 |
N7 | 0.017944 | 0.01629 | 0.014829 | −0.002136 | 0.002938 | 0 |
N8 | 0.017772 | 0.015359 | 0.018338 | −0.004564 | 0.001495 | −0.00192 |
O1 | 0.006689 | 0.030716 | 0.03182 | 0 | 0.003253 | 0 |
O2 | 0.008485 | 0.025455 | 0.024265 | 0 | 0 | −0.002291 |
O3 | 0.017606 | 0.016509 | 0.011143 | 0 | 0.002392 | 0.001877 |
O4 | 0.015532 | 0.0186 | 0.011733 | 0 | 0.003116 | 0 |
O5 | 0.018489 | 0.011777 | 0.017199 | 0 | 0 | 0.001068 |
O6 | 0.018069 | 0.015933 | 0.016021 | 0.003119 | 0.005793 | 0.004394 |
O7 | 0.019062 | 0.012631 | 0.0166 | 0 | 0.004672 | −0.004793 |
O8 | 0.016609 | 0.01273 | 0.014622 | 0 | 0.0049 | −0.003982 |
O9 | 0.006689 | 0.030716 | 0.03182 | 0 | 0.003253 | 0 |
O10 | 0.008485 | 0.025455 | 0.024265 | 0 | 0 | −0.002291 |
O11 | 0.017606 | 0.016509 | 0.011143 | 0 | 0.002392 | 0.001877 |
O12 | 0.015532 | 0.0186 | 0.011733 | 0 | 0.003116 | 0 |
O13 | 0.018489 | 0.011777 | 0.017199 | 0 | 0 | 0.001068 |
O14 | 0.018069 | 0.015933 | 0.016021 | 0.003119 | 0.005793 | 0.004394 |
O15 | 0.019062 | 0.012631 | 0.0166 | 0 | 0.004672 | −0.004793 |
O16 | 0.016609 | 0.01273 | 0.014622 | 0 | 0.0049 | −0.003982 |
H3 | 0.055129 | 0.113597 | 0.082711 | 0.019348 | −0.017252 | −0.060916 |
H4 | 0.048974 | 0.048241 | 0.048311 | 0.007627 | −0.018848 | −0.017744 |
H5 | 0.061001 | 0.122359 | 0.182892 | 0.04213 | 0 | −0.093637 |
H6 | 0.092168 | 0.2041 | 0.140416 | 0.113586 | −0.061715 | −0.122949 |
H7 | 0.021336 | 0.048656 | 0.067781 | 0 | 0 | −0.009311 |
H8 | 0.021802 | 0.055165 | 0.0579 | −0.013453 | 0.011827 | −0.017294 |
H9 | 0.042578 | 0.024418 | 0.037912 | 0.003015 | 0 | 0 |
H10 | 0.043789 | 0.032865 | 0.026174 | 0 | 0.009934 | 0.006818 |
H11 | 0.046492 | 0.035088 | 0.029499 | −0.011241 | 0.008313 | −0.008293 |
H12 | 0.043181 | 0.017721 | 0.031832 | −0.003755 | 0 | −0.002522 |
H13 | 0.053027 | 0.036294 | 0.0314 | −0.003353 | 0.022742 | 0 |
H14 | 0.039876 | 0.034431 | 0.025271 | −0.00845 | 0.012708 | −0.002355 |
H17 | 0.055129 | 0.113597 | 0.082711 | 0.019348 | −0.017252 | −0.060916 |
H18 | 0.048974 | 0.048241 | 0.048311 | 0.007627 | −0.018848 | −0.017744 |
H19 | 0.061001 | 0.122359 | 0.182892 | 0.04213 | 0 | −0.093637 |
H20 | 0.092168 | 0.2041 | 0.140416 | 0.113586 | −0.061715 | −0.122949 |
H21 | 0.021336 | 0.048656 | 0.067781 | 0 | 0 | −0.009311 |
H22 | 0.021802 | 0.055165 | 0.0579 | −0.013453 | 0.011827 | −0.017294 |
H23 | 0.042578 | 0.024418 | 0.037912 | 0.003015 | 0 | 0 |
H24 | 0.043789 | 0.032865 | 0.026174 | 0 | 0.009934 | 0.006818 |
H25 | 0.046492 | 0.035088 | 0.029499 | −0.011241 | 0.008313 | −0.008293 |
H26 | 0.043181 | 0.017721 | 0.031832 | −0.003755 | 0 | −0.002522 |
H27 | 0.053027 | 0.036294 | 0.0314 | −0.003353 | 0.022742 | 0 |
H28 | 0.039876 | 0.034431 | 0.025271 | −0.00845 | 0.012708 | −0.002355 |
Geometric parameters (Å, º) top
S1—O1 | 1.50 (2) | N3—H7 | 1.075 (19) |
S1—O3 | 1.489 (18) | N3—H9 | 1.00 (3) |
S1—O5 | 1.48 (2) | N3—H11 | 1.03 (3) |
S1—O7 | 1.47 (2) | N3—H13 | 1.10 (2) |
S2—O2 | 1.60 (3) | N4—H8 | 0.971 (18) |
S2—O4 | 1.46 (3) | N4—H10 | 1.061 (18) |
S2—O6 | 1.47 (2) | N4—H12 | 0.95 (2) |
S2—O8 | 1.45 (2) | N4—H14 | 1.03 (2) |
S3—O9 | 1.51 (2) | N5—H18 | 1.01 (2) |
S3—O11 | 1.451 (17) | N5—H18i | 1.01 (2) |
S3—O13 | 1.44 (2) | N5—H20 | 0.93 (4) |
S3—O15 | 1.46 (2) | N5—H20i | 0.93 (4) |
S4—O10 | 1.48 (3) | N6—H17 | 0.96 (3) |
S4—O12 | 1.45 (3) | N6—H17ii | 0.96 (3) |
S4—O14 | 1.45 (2) | N6—H19 | 1.01 (3) |
S4—O16 | 1.47 (2) | N6—H19ii | 1.01 (3) |
N1—H4 | 1.00 (2) | N7—H21 | 0.922 (19) |
N1—H4i | 1.00 (2) | N7—H23 | 1.06 (3) |
N1—H6 | 0.95 (4) | N7—H25 | 1.03 (3) |
N1—H6i | 0.95 (4) | N7—H27 | 0.95 (2) |
N2—H3 | 1.01 (3) | N8—H22 | 1.051 (19) |
N2—H3ii | 1.01 (3) | N8—H24 | 0.995 (17) |
N2—H5 | 0.89 (3) | N8—H26 | 1.11 (2) |
N2—H5ii | 0.89 (3) | N8—H28 | 1.00 (2) |
| | | |
O1—S1—O3 | 103.9 (12) | H7—N3—H9 | 106.0 (19) |
O1—S1—O5 | 107.2 (12) | H7—N3—H11 | 113 (2) |
O1—S1—O7 | 112.0 (12) | H7—N3—H13 | 108.1 (17) |
O3—S1—O5 | 108.3 (11) | H9—N3—H11 | 111 (2) |
O3—S1—O7 | 113.5 (11) | H9—N3—H13 | 109 (2) |
O5—S1—O7 | 111.5 (14) | H11—N3—H13 | 110 (2) |
O2—S2—O4 | 107.1 (18) | H8—N4—H10 | 105.9 (16) |
O2—S2—O6 | 107.0 (14) | H8—N4—H12 | 114 (2) |
O2—S2—O8 | 104.7 (13) | H8—N4—H14 | 106.7 (16) |
O4—S2—O6 | 115.7 (14) | H10—N4—H12 | 111.9 (19) |
O4—S2—O8 | 109.8 (14) | H10—N4—H14 | 110.3 (16) |
O6—S2—O8 | 111.8 (17) | H12—N4—H14 | 108 (2) |
O9—S3—O11 | 111.2 (13) | H18—N5—H18i | 107 (2) |
O9—S3—O13 | 108.9 (13) | H18—N5—H20 | 103 (3) |
O9—S3—O15 | 103.8 (12) | H18—N5—H20i | 111 (3) |
O11—S3—O13 | 114.0 (12) | H18i—N5—H20 | 111 (3) |
O11—S3—O15 | 108.6 (11) | H18i—N5—H20i | 103 (3) |
O13—S3—O15 | 109.9 (14) | H20—N5—H20i | 122 (4) |
O10—S4—O12 | 107.8 (18) | H17—N6—H17ii | 105 (3) |
O10—S4—O14 | 104.4 (14) | H17—N6—H19 | 101 (2) |
O10—S4—O16 | 108.7 (14) | H17—N6—H19ii | 101 (2) |
O12—S4—O14 | 109.1 (14) | H17ii—N6—H19 | 101 (2) |
O12—S4—O16 | 113.5 (15) | H17ii—N6—H19ii | 101 (2) |
O14—S4—O16 | 112.8 (17) | H19—N6—H19ii | 144 (2) |
H4—N1—H4i | 114 (2) | H21—N7—H23 | 108 (2) |
H4—N1—H6 | 101 (3) | H21—N7—H25 | 107 (2) |
H4—N1—H6i | 117 (3) | H21—N7—H27 | 110 (2) |
H4i—N1—H6 | 117 (3) | H23—N7—H25 | 110 (2) |
H4i—N1—H6i | 101 (3) | H23—N7—H27 | 114 (2) |
H6—N1—H6i | 107 (4) | H25—N7—H27 | 108 (2) |
H3—N2—H3ii | 105 (3) | H22—N8—H24 | 109.4 (16) |
H3—N2—H5 | 96 (2) | H22—N8—H26 | 109.6 (18) |
H3—N2—H5ii | 132 (3) | H22—N8—H28 | 112.0 (16) |
H3ii—N2—H5 | 132 (3) | H24—N8—H26 | 107.6 (17) |
H3ii—N2—H5ii | 96 (2) | H24—N8—H28 | 109.3 (17) |
H5—N2—H5ii | 101 (3) | H26—N8—H28 | 109 (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 formula | HO8S2·3(H4N) | HO8S2·3(H4N) | HO8S2·3(H4N) | HO8S2·3(H4N) |
Mr | 247.25 | 247.2 | 247.2 | 247.2 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P2/n | Monoclinic, P2/n | Monoclinic, P2/n |
Temperature (K) | 126 | 250 | 150 | 139 |
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), 90 | 90, 101.52 (5), 90 | 90, 101.46 (5), 90 |
V (Å3) | 893.6 (8) | 897.7 (8) | 894.5 (8) | 1787.8 (16) |
Z | 4 | 4 | 4 | 8 |
Radiation type | Mo Kα | Neutron, λ = 0.87 Å | Neutron, λ = 0.87 Å | Neutron, λ = 0.87 Å |
µ (mm−1) | 0.62 | 0.002 | 0.002 | 0.002 |
Crystal size (mm) | 0.3 × 0.3 × 0.1 | 3 × 3 × 3 × 0 (radius) | 3 × 3 × 3 × 0 (radius) | 3 × 3 × 3 × 0 (radius) |
|
Data collection |
Diffractometer | Stoe IPDS II diffractometer | 4-circle diffractometer | 4-circle diffractometer | 4-circle diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 1996) | – | – | – |
Tmin, Tmax | 0.797, 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)] |
Rint | 0.057 | 0.043 | 0.024 | 0.03 |
(sin θ/λ)max (Å−1) | 0.747 | 0.700 | 0.703 | 0.702 |
|
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 reflections | 6139 | 1503 | 1689 | 2689 |
No. of parameters | 326 | 208 | 208 | 150 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.50, −0.65 | 0.97, −1.59 | 1.37, −1.99 | 2.68, −3.60 |
Selected geometric parameters (Å, º) for (I) topS1—O5 | 1.468 (2) | N1—H6 | 1.00 (5) |
S1—O7 | 1.471 (2) | N2—H7 | 0.90 (4) |
S1—O3 | 1.477 (2) | N2—H8 | 0.95 (3) |
S1—O1 | 1.500 (2) | N2—H9 | 0.81 (5) |
S2—O6 | 1.450 (2) | N2—H10 | 0.78 (5) |
S2—O4 | 1.457 (2) | N3—H11 | 0.84 (5) |
S2—O8 | 1.464 (2) | N3—H12 | 0.86 (5) |
S2—O2 | 1.554 (2) | N3—H13 | 0.84 (4) |
S3—O15 | 1.464 (2) | N3—H14 | 0.780 (6) |
S3—O13 | 1.469 (2) | N4—H15 | 0.82 (4) |
S3—O11 | 1.477 (2) | N4—H16 | 0.83 (4) |
S3—O9 | 1.505 (2) | N4—H17 | 0.87 (4) |
S4—O16 | 1.452 (2) | N4—H18 | 0.86 (4) |
S4—O12 | 1.457 (2) | N5—H19 | 0.80 (5) |
S4—O14 | 1.458 (2) | N5—H20 | 0.82 (3) |
S4—O10 | 1.546 (2) | N5—H21 | 0.80 (5) |
O2—H1 | 0.83 (5) | N5—H22 | 0.79 (4) |
O10—H2 | 0.94 (5) | N6—H23 | 0.89 (4) |
N1—H3 | 0.76 (3) | N6—H24 | 0.84 (4) |
N1—H4 | 0.95 (4) | N6—H25 | 0.76 (5) |
N1—H5 | 0.91 (4) | N6—H26 | 0.88 (4) |
| | | |
O5—S1—O7 | 110.70 (13) | H5—N1—H6 | 111 (4) |
O5—S1—O3 | 110.01 (13) | H7—N2—H8 | 108 (3) |
O7—S1—O3 | 110.25 (13) | H7—N2—H9 | 114 (4) |
O5—S1—O1 | 109.37 (13) | H8—N2—H9 | 106 (4) |
O7—S1—O1 | 108.47 (14) | H7—N2—H10 | 117 (4) |
O3—S1—O1 | 107.99 (13) | H8—N2—H10 | 110 (4) |
O6—S2—O4 | 112.52 (13) | H9—N2—H10 | 101 (5) |
O6—S2—O8 | 112.79 (14) | H11—N3—H12 | 124 (5) |
O4—S2—O8 | 112.22 (13) | H11—N3—H13 | 105 (4) |
O6—S2—O2 | 105.23 (14) | H12—N3—H13 | 105 (4) |
O4—S2—O2 | 106.78 (14) | H11—N3—H14 | 109 (4) |
O8—S2—O2 | 106.68 (14) | H12—N3—H14 | 104 (4) |
O15—S3—O13 | 110.94 (13) | H13—N3—H14 | 110 (4) |
O15—S3—O11 | 110.50 (13) | H15—N4—H16 | 119 (4) |
O13—S3—O11 | 110.32 (13) | H15—N4—H17 | 102 (4) |
O15—S3—O9 | 108.50 (13) | H16—N4—H17 | 115 (4) |
O13—S3—O9 | 108.79 (14) | H15—N4—H18 | 108 (4) |
O11—S3—O9 | 107.70 (13) | H16—N4—H18 | 105 (4) |
O16—S4—O12 | 112.32 (13) | H17—N4—H18 | 107 (4) |
O16—S4—O14 | 112.35 (14) | H19—N5—H20 | 104 (4) |
O12—S4—O14 | 111.73 (13) | H19—N5—H21 | 107 (5) |
O16—S4—O10 | 105.78 (14) | H20—N5—H21 | 116 (4) |
O12—S4—O10 | 107.24 (14) | H19—N5—H22 | 118 (5) |
O14—S4—O10 | 106.96 (13) | H20—N5—H22 | 106 (3) |
S2—O2—H1 | 113 (4) | H21—N5—H22 | 107 (4) |
S4—O10—H2 | 105 (3) | H23—N6—H24 | 120 (4) |
H3—N1—H4 | 116 (4) | H23—N6—H25 | 101 (4) |
H3—N1—H5 | 105 (4) | H24—N6—H25 | 104 (4) |
H4—N1—H5 | 101 (4) | H23—N6—H26 | 116 (4) |
H3—N1—H6 | 115 (4) | H24—N6—H26 | 96 (3) |
H4—N1—H6 | 107 (4) | H25—N6—H26 | 119 (5) |
Selected geometric parameters (Å, º) for (II) topS1—O1 | 1.495 (8) | N2—H3 | 0.953 (14) |
S1—O3 | 1.460 (7) | N2—H3iv | 0.953 (14) |
S1—O5 | 1.462 (8) | N2—H5 | 0.906 (19) |
S1—O7 | 1.465 (8) | N2—H5iv | 0.906 (19) |
S2—O2 | 1.523 (7) | N3—H7 | 0.927 (12) |
S2—O4 | 1.465 (7) | N3—H9 | 1.023 (12) |
S2—O6i | 1.452 (7) | N3—H11 | 1.005 (12) |
S2—O8 | 1.452 (7) | N3—H13 | 0.980 (12) |
N1—H4 | 0.985 (10) | N4—H8v | 0.991 (11) |
N1—H4ii | 0.985 (10) | N4—H10 | 0.978 (10) |
N1—H6i | 0.92 (2) | N4—H12vi | 1.027 (8) |
N1—H6iii | 0.92 (2) | N4—H14 | 1.018 (11) |
| | | |
O1—S1—O3 | 107.9 (5) | H3—N2—H3iv | 105.4 (13) |
O1—S1—O5 | 108.7 (5) | H3—N2—H5 | 95.3 (14) |
O1—S1—O7 | 108.2 (4) | H3—N2—H5iv | 120.1 (17) |
O3—S1—O5 | 110.7 (4) | H3iv—N2—H5 | 120.1 (17) |
O3—S1—O7 | 110.7 (5) | H3iv—N2—H5iv | 95.3 (14) |
O5—S1—O7 | 110.6 (5) | H5—N2—H5iv | 121.4 (17) |
O2—S2—O4 | 107.1 (5) | H7—N3—H9 | 105.8 (10) |
O2—S2—O6i | 106.1 (4) | H7—N3—H11 | 106.0 (11) |
O2—S2—O8 | 107.6 (4) | H7—N3—H13 | 107.9 (12) |
O4—S2—O6i | 111.8 (4) | H9—N3—H11 | 113.6 (9) |
O4—S2—O8 | 111.3 (4) | H9—N3—H13 | 111.8 (11) |
O6i—S2—O8 | 112.5 (5) | H11—N3—H13 | 111.2 (10) |
H4—N1—H4ii | 113.1 (10) | H8v—N4—H10 | 104.9 (10) |
H4—N1—H6i | 99.0 (14) | H8v—N4—H12vi | 109.2 (9) |
H4—N1—H6iii | 111.8 (16) | H8v—N4—H14 | 109.9 (9) |
H4ii—N1—H6i | 111.8 (16) | H10—N4—H12vi | 110.0 (8) |
H4ii—N1—H6iii | 99.0 (14) | H10—N4—H14 | 111.3 (9) |
H6i—N1—H6iii | 122.9 (19) | H12vi—N4—H14 | 111.3 (8) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y, −z+3/2; (iii) −x+3/2, y−1, −z+3/2; (iv) −x+3/2, y, −z+1/2; (v) x−1, y, z; (vi) x, y+1, z. |
Selected geometric parameters (Å, º) for (III) topS1—O1 | 1.503 (6) | N2—H3 | 0.968 (11) |
S1—O3 | 1.469 (5) | N2—H3iv | 0.968 (11) |
S1—O5 | 1.470 (5) | N2—H5 | 0.935 (14) |
S1—O7 | 1.470 (5) | N2—H5iv | 0.935 (14) |
S2—O2 | 1.530 (6) | N3—H7 | 0.974 (6) |
S2—O4 | 1.467 (5) | N3—H9 | 1.033 (6) |
S2—O6i | 1.456 (5) | N3—H11 | 1.037 (5) |
S2—O8 | 1.468 (5) | N3—H13 | 1.020 (6) |
N1—H4 | 1.002 (7) | N4—H8v | 0.997 (7) |
N1—H4ii | 1.002 (7) | N4—H10 | 1.026 (5) |
N1—H6i | 0.945 (15) | N4—H12vi | 1.038 (5) |
N1—H6iii | 0.945 (15) | N4—H14 | 1.029 (6) |
| | | |
O1—S1—O3 | 107.7 (3) | H3—N2—H3iv | 104.5 (10) |
O1—S1—O5 | 108.6 (3) | H3—N2—H5 | 96.7 (11) |
O1—S1—O7 | 108.3 (3) | H3—N2—H5iv | 117.9 (13) |
O3—S1—O5 | 110.9 (3) | H3iv—N2—H5 | 117.9 (13) |
O3—S1—O7 | 110.9 (3) | H3iv—N2—H5iv | 96.7 (11) |
O5—S1—O7 | 110.3 (3) | H5—N2—H5iv | 123.0 (13) |
O2—S2—O4 | 107.5 (4) | H7—N3—H9 | 107.8 (5) |
O2—S2—O6i | 105.7 (3) | H7—N3—H11 | 110.0 (6) |
O2—S2—O8 | 106.8 (3) | H7—N3—H13 | 108.7 (6) |
O4—S2—O6i | 112.6 (3) | H9—N3—H11 | 109.5 (4) |
O4—S2—O8 | 111.4 (3) | H9—N3—H13 | 111.6 (5) |
O6i—S2—O8 | 112.4 (4) | H11—N3—H13 | 109.2 (5) |
H4—N1—H4ii | 111.1 (6) | H8v—N4—H10 | 106.9 (5) |
H4—N1—H6i | 101.8 (9) | H8v—N4—H12vi | 110.9 (5) |
H4—N1—H6iii | 110.9 (10) | H8v—N4—H14 | 109.3 (5) |
H4ii—N1—H6i | 110.9 (10) | H10—N4—H12vi | 110.2 (4) |
H4ii—N1—H6iii | 101.8 (9) | H10—N4—H14 | 109.9 (5) |
H6i—N1—H6iii | 120.5 (14) | H12vi—N4—H14 | 109.6 (5) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y, −z+3/2; (iii) −x+3/2, y−1, −z+3/2; (iv) −x+3/2, y, −z+1/2; (v) x−1, y, z; (vi) x, y+1, z. |
Selected geometric parameters (Å, º) for (IV) topS1—O1 | 1.50 (2) | N3—H7 | 1.075 (19) |
S1—O3 | 1.489 (18) | N3—H9 | 1.00 (3) |
S1—O5 | 1.48 (2) | N3—H11 | 1.03 (3) |
S1—O7 | 1.47 (2) | N3—H13 | 1.10 (2) |
S2—O2 | 1.60 (3) | N4—H8 | 0.971 (18) |
S2—O4 | 1.46 (3) | N4—H10 | 1.061 (18) |
S2—O6 | 1.47 (2) | N4—H12 | 0.95 (2) |
S2—O8 | 1.45 (2) | N4—H14 | 1.03 (2) |
S3—O9 | 1.51 (2) | N5—H18 | 1.01 (2) |
S3—O11 | 1.451 (17) | N5—H18i | 1.01 (2) |
S3—O13 | 1.44 (2) | N5—H20 | 0.93 (4) |
S3—O15 | 1.46 (2) | N5—H20i | 0.93 (4) |
S4—O10 | 1.48 (3) | N6—H17 | 0.96 (3) |
S4—O12 | 1.45 (3) | N6—H17ii | 0.96 (3) |
S4—O14 | 1.45 (2) | N6—H19 | 1.01 (3) |
S4—O16 | 1.47 (2) | N6—H19ii | 1.01 (3) |
N1—H4 | 1.00 (2) | N7—H21 | 0.922 (19) |
N1—H4i | 1.00 (2) | N7—H23 | 1.06 (3) |
N1—H6 | 0.95 (4) | N7—H25 | 1.03 (3) |
N1—H6i | 0.95 (4) | N7—H27 | 0.95 (2) |
N2—H3 | 1.01 (3) | N8—H22 | 1.051 (19) |
N2—H3ii | 1.01 (3) | N8—H24 | 0.995 (17) |
N2—H5 | 0.89 (3) | N8—H26 | 1.11 (2) |
N2—H5ii | 0.89 (3) | N8—H28 | 1.00 (2) |
| | | |
O1—S1—O3 | 103.9 (12) | H7—N3—H9 | 106.0 (19) |
O1—S1—O5 | 107.2 (12) | H7—N3—H11 | 113 (2) |
O1—S1—O7 | 112.0 (12) | H7—N3—H13 | 108.1 (17) |
O3—S1—O5 | 108.3 (11) | H9—N3—H11 | 111 (2) |
O3—S1—O7 | 113.5 (11) | H9—N3—H13 | 109 (2) |
O5—S1—O7 | 111.5 (14) | H11—N3—H13 | 110 (2) |
O2—S2—O4 | 107.1 (18) | H8—N4—H10 | 105.9 (16) |
O2—S2—O6 | 107.0 (14) | H8—N4—H12 | 114 (2) |
O2—S2—O8 | 104.7 (13) | H8—N4—H14 | 106.7 (16) |
O4—S2—O6 | 115.7 (14) | H10—N4—H12 | 111.9 (19) |
O4—S2—O8 | 109.8 (14) | H10—N4—H14 | 110.3 (16) |
O6—S2—O8 | 111.8 (17) | H12—N4—H14 | 108 (2) |
O9—S3—O11 | 111.2 (13) | H18—N5—H18i | 107 (2) |
O9—S3—O13 | 108.9 (13) | H18—N5—H20 | 103 (3) |
O9—S3—O15 | 103.8 (12) | H18—N5—H20i | 111 (3) |
O11—S3—O13 | 114.0 (12) | H18i—N5—H20 | 111 (3) |
O11—S3—O15 | 108.6 (11) | H18i—N5—H20i | 103 (3) |
O13—S3—O15 | 109.9 (14) | H20—N5—H20i | 122 (4) |
O10—S4—O12 | 107.8 (18) | H17—N6—H17ii | 105 (3) |
O10—S4—O14 | 104.4 (14) | H17—N6—H19 | 101 (2) |
O10—S4—O16 | 108.7 (14) | H17—N6—H19ii | 101 (2) |
O12—S4—O14 | 109.1 (14) | H17ii—N6—H19 | 101 (2) |
O12—S4—O16 | 113.5 (15) | H17ii—N6—H19ii | 101 (2) |
O14—S4—O16 | 112.8 (17) | H19—N6—H19ii | 144 (2) |
H4—N1—H4i | 114 (2) | H21—N7—H23 | 108 (2) |
H4—N1—H6 | 101 (3) | H21—N7—H25 | 107 (2) |
H4—N1—H6i | 117 (3) | H21—N7—H27 | 110 (2) |
H4i—N1—H6 | 117 (3) | H23—N7—H25 | 110 (2) |
H4i—N1—H6i | 101 (3) | H23—N7—H27 | 114 (2) |
H6—N1—H6i | 107 (4) | H25—N7—H27 | 108 (2) |
H3—N2—H3ii | 105 (3) | H22—N8—H24 | 109.4 (16) |
H3—N2—H5 | 96 (2) | H22—N8—H26 | 109.6 (18) |
H3—N2—H5ii | 132 (3) | H22—N8—H28 | 112.0 (16) |
H3ii—N2—H5 | 132 (3) | H24—N8—H26 | 107.6 (17) |
H3ii—N2—H5ii | 96 (2) | H24—N8—H28 | 109.3 (17) |
H5—N2—H5ii | 101 (3) | H26—N8—H28 | 109 (2) |
Symmetry codes: (i) −x+3/2, y, −z+3/2; (ii) −x+3/2, y, −z+1/2. |