Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113012377/yp3029sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012377/yp3029Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113012377/yp3029Isup5.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012377/yp3029IIsup3.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113012377/yp3029IIsup6.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012377/yp3029IIIsup4.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113012377/yp3029IIIsup7.mol |
CCDC references: 950451; 950452; 950453
For related literature, see: Ahmad et al. (2010); Cairns et al. (2002); Gahl et al. (2000, 2001, 2002); Kay et al. (2007); Kim et al. (2002); McCaughan et al. (2008); Schmidt et al. (2006); Smith et al. (2006); Steiner (2000); Suresh et al. (2006); Sweetman (2011); Touchman et al. (2000); Vedavathi & Vijayan (1979).
For the preparation of cysteamine tartrate monohydrate (cysteamine hydrogen tartrate), (I), millimolar amounts (1:1 ratio) of cysteamine and L-(+)-tartaric acid were weighed and transferred into a 50 ml conical flask. A small amount (5 ml) of hot ethanol was added to the mixture, and the flask and contents were placed in a water bath, with swirling, at 323 K. After 10 min both starting materials remained solid, and so to aid dissolution the flask was stirred and heated to 333 K on a hot plate. Further quantities of solvent were added dropwise to the mixture until a clear solution was obtained. The whole process lasted for about an hour and a total volume of 15 ml of ethanol was used. The solution was then filtered, covered with Parafilm and left in the fume cupboard for crystallization to take place by slow evaporation. After 5 d, clear rod-shaped crystals of (I) separated from the product mixture. The crystals were then collected by gravity filtration and allowed to dry on filter paper. Attempts to cut crystals of (I) to a smaller size without damaging the crystals were unsuccessful.
For the preparation of cystamine tartrate, (II), and cystamine tartrate dihydrate (cystamine hydrogen tartrate dihydrate), (III), millimolar amounts (1:1 ratio) of cystamine and L-(+)- tartaric acid were weighed and transferred into a 50 ml conical flask. Hot ethanol (5 ml) was added, resulting in the formation of a white precipitate, and the flask placed in a water bath at 323 K with swirling. Ethanol was added dropwise until a clear solution was obtained. A total volume of 20 ml of solvent was used. The solution was filtered, covered with Parafilm and left in the fume cupboard for crystallization to take place by slow evaporation. After 24 h, crystals [blades of (II) and needles of (III)] formed, and these were collected by gravity filtration and allowed to dry on filter paper. Product (III) also formed as a noncrystalline mass in the preparation of (I). Attempts to obtain high-quality crystals of (III) were only partially successful.
Where appropriate, idealized bond lengths for H atoms were C—H = 1.00 (CH) or 0.98 Å (CH2), O—H = 0.84 Å and N—H = 0.91 Å. For (I), the positions of the S-bound and water H atoms were refined freely, with Uiso(H) = 1.2Ueq(S) or 1.3Ueq(O), and the remaining H atoms were treated as riding on their attached atoms, with Uiso(H) = 1.2Ueq(carrier). For (II), all H atoms were treated in the riding model, with Uiso(H) = 1.2Ueq(carrier). For (III), the water H-atom positions were restrained, with O—H = 0.85 (2) Å and H···H = 1.34 (2) Å, and with Uiso(H) = 1.5Ueq(O). The remaining H atoms in (III) were treated in the riding model, with Uiso(H) = 1.2Ueq(carrier).
For all compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).
C2H8NS+·C4H5O6−·H2O | Z = 4 |
Mr = 245.25 | F(000) = 520 |
Orthorhombic, P212121 | Dx = 1.495 Mg m−3 |
Hall symbol: P 2ac 2ab | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0630 (2) Å | µ = 0.32 mm−1 |
b = 10.3833 (5) Å | T = 120 K |
c = 14.8591 (7) Å | Rod, colourless |
V = 1089.73 (8) Å3 | 0.84 × 0.12 × 0.1 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 2485 independent reflections |
Graphite monochromator | 2099 reflections with I > 2σ(I) |
Detector resolution: 9.091 pixels mm-1 | Rint = 0.051 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −9→8 |
Tmin = 0.620, Tmax = 0.746 | k = −13→13 |
9253 measured reflections | l = −17→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0455P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2485 reflections | Δρmax = 0.27 e Å−3 |
143 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1027 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.04 (9) |
C2H8NS+·C4H5O6−·H2O | V = 1089.73 (8) Å3 |
Mr = 245.25 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.0630 (2) Å | µ = 0.32 mm−1 |
b = 10.3833 (5) Å | T = 120 K |
c = 14.8591 (7) Å | 0.84 × 0.12 × 0.1 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 2485 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 2099 reflections with I > 2σ(I) |
Tmin = 0.620, Tmax = 0.746 | Rint = 0.051 |
9253 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | Δρmax = 0.27 e Å−3 |
S = 1.06 | Δρmin = −0.25 e Å−3 |
2485 reflections | Absolute structure: Flack (1983), 1027 Friedel pairs |
143 parameters | Absolute structure parameter: −0.04 (9) |
0 restraints |
Experimental. Please note cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
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. Possible intramolecular H bonds with very small D—H···A angles are: N1—H1A···S1 0.91 2.87 3.2636 (16) Å 108° O3—H3···O2 0.84 2.28 2.679 (2) Å 110° |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.62774 (18) | 0.08513 (14) | 0.46065 (10) | 0.0170 (3) | |
H1 | 0.7462 | 0.0837 | 0.4556 | 0.022* | |
O2 | 0.63688 (19) | −0.03004 (16) | 0.33240 (11) | 0.0231 (4) | |
O3 | 0.25893 (19) | −0.03363 (14) | 0.31731 (10) | 0.0181 (3) | |
H3 | 0.3378 | −0.0328 | 0.275 | 0.023* | |
O4 | 0.31856 (19) | 0.23590 (14) | 0.31556 (10) | 0.0195 (3) | |
H4 | 0.4144 | 0.2813 | 0.3261 | 0.025* | |
O5 | −0.04770 (19) | 0.24127 (14) | 0.35304 (9) | 0.0184 (3) | |
O6 | −0.02037 (18) | 0.09647 (14) | 0.46333 (10) | 0.0172 (3) | |
C3 | 0.5516 (3) | 0.02653 (18) | 0.39225 (14) | 0.0146 (4) | |
C4 | 0.3354 (3) | 0.03150 (18) | 0.39253 (14) | 0.0135 (4) | |
H4A | 0.2894 | −0.0125 | 0.4482 | 0.016* | |
C5 | 0.2648 (3) | 0.17074 (18) | 0.39438 (14) | 0.0135 (4) | |
H5 | 0.3207 | 0.2158 | 0.4476 | 0.016* | |
C6 | 0.0480 (3) | 0.17104 (18) | 0.40290 (13) | 0.0139 (4) | |
S1 | 0.68437 (9) | 0.14607 (6) | 0.10095 (5) | 0.03652 (19) | |
H1S | 0.626 (4) | 0.220 (3) | 0.1665 (17) | 0.044* | |
N1 | 1.0543 (2) | 0.29928 (16) | 0.17750 (11) | 0.0171 (4) | |
H1A | 0.948 | 0.3401 | 0.1579 | 0.021* | |
H1B | 1.1575 | 0.3487 | 0.165 | 0.021* | |
H1C | 1.0463 | 0.2864 | 0.238 | 0.021* | |
C1 | 0.9037 (3) | 0.0866 (2) | 0.14997 (17) | 0.0291 (5) | |
H1D | 0.8873 | 0.0786 | 0.2159 | 0.035* | |
H1E | 0.9301 | −0.0004 | 0.1258 | 0.035* | |
C2 | 1.0725 (3) | 0.1730 (2) | 0.13114 (16) | 0.0252 (5) | |
H2A | 1.1896 | 0.1297 | 0.1517 | 0.03* | |
H2B | 1.0832 | 0.1874 | 0.0655 | 0.03* | |
O7 | 0.62687 (19) | 0.38583 (14) | 0.35555 (10) | 0.0193 (3) | |
H7A | 0.7225 | 0.3335 | 0.3608 | 0.025* | |
H7B | 0.5945 | 0.4026 | 0.4036 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0080 (6) | 0.0246 (7) | 0.0184 (8) | 0.0003 (5) | −0.0003 (5) | −0.0019 (7) |
O2 | 0.0151 (7) | 0.0303 (8) | 0.0238 (9) | 0.0060 (6) | 0.0011 (6) | −0.0076 (7) |
O3 | 0.0137 (6) | 0.0219 (8) | 0.0186 (8) | −0.0025 (6) | 0.0005 (5) | −0.0069 (7) |
O4 | 0.0148 (7) | 0.0218 (8) | 0.0220 (8) | −0.0029 (6) | 0.0001 (6) | 0.0063 (6) |
O5 | 0.0129 (6) | 0.0237 (7) | 0.0187 (8) | 0.0035 (6) | −0.0006 (6) | 0.0031 (7) |
O6 | 0.0102 (6) | 0.0231 (7) | 0.0181 (8) | −0.0006 (6) | 0.0007 (6) | 0.0026 (7) |
C3 | 0.0139 (9) | 0.0150 (9) | 0.0151 (11) | 0.0010 (8) | 0.0011 (8) | 0.0024 (9) |
C4 | 0.0097 (9) | 0.0150 (9) | 0.0157 (11) | −0.0018 (8) | 0.0010 (8) | −0.0001 (9) |
C5 | 0.0136 (9) | 0.0137 (10) | 0.0133 (10) | −0.0022 (7) | −0.0002 (7) | −0.0014 (9) |
C6 | 0.0132 (8) | 0.0159 (9) | 0.0127 (10) | −0.0002 (8) | −0.0002 (8) | −0.0047 (9) |
S1 | 0.0340 (3) | 0.0297 (3) | 0.0458 (4) | −0.0100 (3) | −0.0083 (3) | −0.0049 (3) |
N1 | 0.0123 (7) | 0.0186 (8) | 0.0205 (9) | −0.0003 (7) | −0.0002 (7) | 0.0025 (8) |
C1 | 0.0442 (14) | 0.0195 (11) | 0.0237 (13) | −0.0017 (10) | −0.0022 (10) | −0.0014 (11) |
C2 | 0.0294 (11) | 0.0255 (12) | 0.0206 (12) | 0.0056 (10) | 0.0010 (9) | −0.0053 (10) |
O7 | 0.0154 (7) | 0.0222 (8) | 0.0204 (8) | 0.0040 (6) | 0.0031 (6) | 0.0022 (7) |
O1—C3 | 1.301 (2) | S1—C1 | 1.820 (2) |
O1—H1 | 0.84 | S1—H1S | 1.31 (3) |
O2—C3 | 1.224 (2) | N1—C2 | 1.487 (3) |
O3—C4 | 1.414 (2) | N1—H1A | 0.91 |
O3—H3 | 0.84 | N1—H1B | 0.91 |
O4—C5 | 1.405 (2) | N1—H1C | 0.91 |
O4—H4 | 0.84 | C1—C2 | 1.518 (3) |
O5—C6 | 1.240 (2) | C1—H1D | 0.99 |
O6—C6 | 1.280 (2) | C1—H1E | 0.99 |
C3—C4 | 1.528 (3) | C2—H2A | 0.99 |
C4—C5 | 1.530 (3) | C2—H2B | 0.99 |
C4—H4A | 1 | O7—H7A | 0.8703 |
C5—C6 | 1.536 (3) | O7—H7B | 0.7698 |
C5—H5 | 1 | ||
C3—O1—H1 | 109.5 | C1—S1—H1S | 99.9 (11) |
C4—O3—H3 | 109.5 | C2—N1—H1A | 109.5 |
C5—O4—H4 | 109.5 | C2—N1—H1B | 109.5 |
O2—C3—O1 | 126.07 (17) | H1A—N1—H1B | 109.5 |
O2—C3—C4 | 120.65 (19) | C2—N1—H1C | 109.5 |
O1—C3—C4 | 113.27 (17) | H1A—N1—H1C | 109.5 |
O3—C4—C3 | 111.32 (17) | H1B—N1—H1C | 109.5 |
O3—C4—C5 | 109.99 (16) | C2—C1—S1 | 113.23 (16) |
C3—C4—C5 | 110.97 (16) | C2—C1—H1D | 108.9 |
O3—C4—H4A | 108.2 | S1—C1—H1D | 108.9 |
C3—C4—H4A | 108.2 | C2—C1—H1E | 108.9 |
C5—C4—H4A | 108.2 | S1—C1—H1E | 108.9 |
O4—C5—C4 | 110.62 (16) | H1D—C1—H1E | 107.7 |
O4—C5—C6 | 109.70 (16) | N1—C2—C1 | 111.58 (18) |
C4—C5—C6 | 109.17 (15) | N1—C2—H2A | 109.3 |
O4—C5—H5 | 109.1 | C1—C2—H2A | 109.3 |
C4—C5—H5 | 109.1 | N1—C2—H2B | 109.3 |
C6—C5—H5 | 109.1 | C1—C2—H2B | 109.3 |
O5—C6—O6 | 124.69 (17) | H2A—C2—H2B | 108 |
O5—C6—C5 | 119.68 (17) | H7A—O7—H7B | 106.8 |
O6—C6—C5 | 115.62 (16) | ||
O2—C3—C4—O3 | −0.7 (3) | C3—C4—C5—C6 | −175.13 (17) |
O1—C3—C4—O3 | −179.80 (15) | O4—C5—C6—O5 | −11.7 (2) |
O2—C3—C4—C5 | −123.6 (2) | C4—C5—C6—O5 | −133.06 (19) |
O1—C3—C4—C5 | 57.3 (2) | O4—C5—C6—O6 | 168.62 (16) |
O3—C4—C5—O4 | −59.54 (19) | C4—C5—C6—O6 | 47.3 (2) |
C3—C4—C5—O4 | 64.1 (2) | S1—C1—C2—N1 | 67.1 (2) |
O3—C4—C5—C6 | 61.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6i | 0.84 | 1.66 | 2.4885 (18) | 169 |
O3—H3···O7ii | 0.84 | 2.13 | 2.819 (2) | 139 |
O4—H4···O7 | 0.84 | 1.9 | 2.742 (2) | 177 |
N1—H1A···O3iii | 0.91 | 2 | 2.813 (2) | 148 |
N1—H1B···O2iv | 0.91 | 1.92 | 2.814 (2) | 166 |
N1—H1C···O5i | 0.91 | 1.89 | 2.772 (2) | 162 |
N1—H1C···O4i | 0.91 | 2.3 | 2.850 (2) | 118 |
O7—H7A···O5i | 0.87 | 1.89 | 2.7455 (19) | 168 |
O7—H7B···O6v | 0.77 | 2.14 | 2.8910 (19) | 166 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+2, y+1/2, −z+1/2; (v) x+1/2, −y+1/2, −z+1. |
C4H14N2S22+·C4H4O62− | Z = 4 |
Mr = 302.36 | F(000) = 640 |
Orthorhombic, P212121 | Dx = 1.516 Mg m−3 |
Hall symbol: P 2ac 2ab | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7281 (3) Å | µ = 0.42 mm−1 |
b = 9.3699 (5) Å | T = 120 K |
c = 24.6770 (14) Å | Blade, colourless |
V = 1324.46 (12) Å3 | 0.36 × 0.14 × 0.03 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3020 independent reflections |
Graphite monochromator | 2273 reflections with I > 2σ(I) |
Detector resolution: 9.091 pixels mm-1 | Rint = 0.083 |
ϕ and ω scans | θmax = 27.6°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −7→7 |
Tmin = 0.613, Tmax = 0.746 | k = −12→12 |
9158 measured reflections | l = −32→29 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0658P)2 + 0.2376P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3020 reflections | Δρmax = 0.55 e Å−3 |
165 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1222 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.20 (13) |
C4H14N2S22+·C4H4O62− | V = 1324.46 (12) Å3 |
Mr = 302.36 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.7281 (3) Å | µ = 0.42 mm−1 |
b = 9.3699 (5) Å | T = 120 K |
c = 24.6770 (14) Å | 0.36 × 0.14 × 0.03 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3020 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 2273 reflections with I > 2σ(I) |
Tmin = 0.613, Tmax = 0.746 | Rint = 0.083 |
9158 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.139 | Δρmax = 0.55 e Å−3 |
S = 1.05 | Δρmin = −0.43 e Å−3 |
3020 reflections | Absolute structure: Flack (1983), 1222 Friedel pairs |
165 parameters | Absolute structure parameter: 0.20 (13) |
0 restraints |
Experimental. Please note cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
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. Weak C—H···O is present: C2—H2E···O5 0.99 2.54 3.523 (5) Å 170° C3—H3···O6 0.99 2.48 3.252 (5) Å 134° C3—H3B···O5 0.99 2.35 3.329 (5) Å 172° |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.51833 (18) | 0.61447 (13) | 0.08424 (4) | 0.0255 (3) | |
S2 | 0.34754 (18) | 0.66345 (12) | 0.15428 (4) | 0.0239 (3) | |
N1 | 0.0816 (5) | 0.5917 (3) | 0.00651 (13) | 0.0174 (7) | |
H1A | 0.0583 | 0.6751 | 0.0246 | 0.021* | |
H1B | −0.0462 | 0.5716 | −0.014 | 0.021* | |
H1C | 0.2089 | 0.6003 | −0.0153 | 0.021* | |
N2 | 0.7591 (6) | 0.7169 (4) | 0.24357 (13) | 0.0204 (8) | |
H2A | 0.7465 | 0.7874 | 0.2184 | 0.024* | |
H2B | 0.9015 | 0.7221 | 0.2598 | 0.024* | |
H2C | 0.6453 | 0.7277 | 0.269 | 0.024* | |
C1 | 0.1205 (7) | 0.4747 (4) | 0.04598 (16) | 0.0190 (9) | |
H1D | 0.0576 | 0.3848 | 0.0308 | 0.023* | |
H1E | 0.0334 | 0.4961 | 0.0797 | 0.023* | |
C2 | 0.3756 (7) | 0.4539 (4) | 0.05965 (17) | 0.0221 (9) | |
H2D | 0.4585 | 0.42 | 0.0269 | 0.027* | |
H2E | 0.389 | 0.3786 | 0.0876 | 0.027* | |
C3 | 0.4820 (7) | 0.5435 (4) | 0.20243 (17) | 0.0220 (9) | |
H3A | 0.3884 | 0.5445 | 0.2361 | 0.026* | |
H3B | 0.4751 | 0.4455 | 0.1875 | 0.026* | |
C4 | 0.7332 (8) | 0.5765 (5) | 0.21688 (17) | 0.0234 (10) | |
H4A | 0.793 | 0.5012 | 0.2414 | 0.028* | |
H4B | 0.8289 | 0.5751 | 0.1835 | 0.028* | |
O1 | 0.9818 (5) | −0.1548 (3) | 0.06081 (11) | 0.0218 (6) | |
O2 | 1.2517 (5) | 0.0171 (4) | 0.06015 (11) | 0.0254 (7) | |
O3 | 0.8148 (5) | −0.0877 (3) | 0.15488 (11) | 0.0247 (7) | |
H3 | 0.7775 | −0.1475 | 0.131 | 0.03* | |
O4 | 0.7128 (5) | 0.1369 (3) | 0.07360 (10) | 0.0203 (6) | |
H4 | 0.5722 | 0.1312 | 0.083 | 0.024* | |
O5 | 0.4928 (5) | 0.2040 (3) | 0.16279 (11) | 0.0206 (6) | |
O6 | 0.8146 (5) | 0.2345 (3) | 0.21176 (11) | 0.0223 (7) | |
C5 | 1.0822 (6) | −0.0469 (4) | 0.08021 (17) | 0.0184 (9) | |
C6 | 0.9776 (7) | 0.0117 (4) | 0.13273 (15) | 0.0172 (8) | |
H6 | 1.1054 | 0.0293 | 0.1595 | 0.021* | |
C7 | 0.8542 (7) | 0.1527 (4) | 0.11986 (15) | 0.0166 (8) | |
H7 | 0.9755 | 0.2268 | 0.1121 | 0.02* | |
C8 | 0.7108 (7) | 0.2013 (4) | 0.16898 (16) | 0.0173 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0180 (5) | 0.0343 (6) | 0.0244 (5) | −0.0046 (5) | −0.0035 (4) | 0.0065 (5) |
S2 | 0.0195 (5) | 0.0218 (5) | 0.0303 (6) | 0.0012 (5) | −0.0043 (5) | −0.0018 (5) |
N1 | 0.0146 (15) | 0.0180 (18) | 0.0196 (18) | −0.0008 (15) | −0.0002 (13) | −0.0024 (14) |
N2 | 0.0183 (17) | 0.0205 (19) | 0.022 (2) | −0.0019 (16) | −0.0014 (14) | 0.0009 (15) |
C1 | 0.021 (2) | 0.017 (2) | 0.019 (2) | −0.0051 (19) | 0.0000 (16) | 0.0017 (17) |
C2 | 0.022 (2) | 0.024 (2) | 0.020 (2) | 0.002 (2) | −0.0015 (17) | 0.0039 (18) |
C3 | 0.025 (2) | 0.017 (2) | 0.024 (2) | 0.000 (2) | 0.0031 (18) | −0.0021 (17) |
C4 | 0.024 (2) | 0.023 (2) | 0.023 (2) | 0.0002 (19) | −0.0017 (17) | −0.0003 (18) |
O1 | 0.0215 (14) | 0.0178 (14) | 0.0261 (15) | 0.0036 (14) | −0.0022 (12) | −0.0052 (12) |
O2 | 0.0153 (14) | 0.0305 (18) | 0.0303 (17) | −0.0018 (14) | 0.0048 (12) | −0.0062 (14) |
O3 | 0.0314 (16) | 0.0200 (15) | 0.0228 (15) | −0.0043 (13) | 0.0017 (13) | 0.0036 (13) |
O4 | 0.0175 (13) | 0.0239 (16) | 0.0194 (15) | 0.0046 (13) | −0.0018 (11) | −0.0006 (12) |
O5 | 0.0154 (13) | 0.0230 (15) | 0.0234 (15) | −0.0002 (14) | −0.0006 (12) | −0.0013 (12) |
O6 | 0.0194 (15) | 0.0268 (17) | 0.0206 (16) | 0.0028 (14) | −0.0015 (12) | −0.0062 (13) |
C5 | 0.0134 (17) | 0.021 (2) | 0.021 (2) | 0.0066 (17) | −0.0043 (16) | 0.0020 (18) |
C6 | 0.0165 (19) | 0.0176 (19) | 0.017 (2) | −0.0012 (19) | 0.0025 (15) | 0.0034 (16) |
C7 | 0.0156 (17) | 0.016 (2) | 0.019 (2) | −0.0011 (18) | −0.0005 (16) | −0.0016 (16) |
C8 | 0.023 (2) | 0.0081 (19) | 0.021 (2) | 0.0005 (16) | 0.0025 (16) | 0.0013 (16) |
S1—C2 | 1.817 (4) | C3—H3A | 0.99 |
S1—S2 | 2.0384 (16) | C3—H3B | 0.99 |
S2—C3 | 1.808 (4) | C4—H4A | 0.99 |
N1—C1 | 1.483 (5) | C4—H4B | 0.99 |
N1—H1A | 0.91 | O1—C5 | 1.257 (5) |
N1—H1B | 0.91 | O2—C5 | 1.244 (5) |
N1—H1C | 0.91 | O3—C6 | 1.427 (5) |
N2—C4 | 1.479 (5) | O3—H3 | 0.84 |
N2—H2A | 0.91 | O4—C7 | 1.408 (4) |
N2—H2B | 0.91 | O4—H4 | 0.84 |
N2—H2C | 0.91 | O5—C8 | 1.258 (5) |
C1—C2 | 1.513 (6) | O6—C8 | 1.251 (5) |
C1—H1D | 0.99 | C5—C6 | 1.530 (5) |
C1—H1E | 0.99 | C6—C7 | 1.532 (5) |
C2—H2D | 0.99 | C6—H6 | 1 |
C2—H2E | 0.99 | C7—C8 | 1.534 (5) |
C3—C4 | 1.514 (6) | C7—H7 | 1 |
C2—S1—S2 | 104.70 (15) | C4—C3—H3B | 108.4 |
C3—S2—S1 | 102.28 (15) | S2—C3—H3B | 108.4 |
C1—N1—H1A | 109.5 | H3A—C3—H3B | 107.4 |
C1—N1—H1B | 109.5 | N2—C4—C3 | 112.5 (4) |
H1A—N1—H1B | 109.5 | N2—C4—H4A | 109.1 |
C1—N1—H1C | 109.5 | C3—C4—H4A | 109.1 |
H1A—N1—H1C | 109.5 | N2—C4—H4B | 109.1 |
H1B—N1—H1C | 109.5 | C3—C4—H4B | 109.1 |
C4—N2—H2A | 109.5 | H4A—C4—H4B | 107.8 |
C4—N2—H2B | 109.5 | C6—O3—H3 | 109.5 |
H2A—N2—H2B | 109.5 | C7—O4—H4 | 109.5 |
C4—N2—H2C | 109.5 | O2—C5—O1 | 126.3 (4) |
H2A—N2—H2C | 109.5 | O2—C5—C6 | 118.0 (4) |
H2B—N2—H2C | 109.5 | O1—C5—C6 | 115.6 (4) |
N1—C1—C2 | 112.8 (3) | O3—C6—C5 | 110.2 (3) |
N1—C1—H1D | 109 | O3—C6—C7 | 109.9 (3) |
C2—C1—H1D | 109 | C5—C6—C7 | 108.4 (3) |
N1—C1—H1E | 109 | O3—C6—H6 | 109.4 |
C2—C1—H1E | 109 | C5—C6—H6 | 109.4 |
H1D—C1—H1E | 107.8 | C7—C6—H6 | 109.4 |
C1—C2—S1 | 113.7 (3) | O4—C7—C6 | 110.0 (3) |
C1—C2—H2D | 108.8 | O4—C7—C8 | 111.3 (3) |
S1—C2—H2D | 108.8 | C6—C7—C8 | 109.8 (3) |
C1—C2—H2E | 108.8 | O4—C7—H7 | 108.5 |
S1—C2—H2E | 108.8 | C6—C7—H7 | 108.5 |
H2D—C2—H2E | 107.7 | C8—C7—H7 | 108.5 |
C4—C3—S2 | 115.6 (3) | O6—C8—O5 | 124.7 (4) |
C4—C3—H3A | 108.4 | O6—C8—C7 | 119.1 (4) |
S2—C3—H3A | 108.4 | O5—C8—C7 | 116.2 (3) |
C2—S1—S2—C3 | 80.39 (19) | O3—C6—C7—O4 | −73.5 (4) |
N1—C1—C2—S1 | 55.3 (4) | C5—C6—C7—O4 | 47.1 (4) |
S2—S1—C2—C1 | 62.7 (3) | O3—C6—C7—C8 | 49.4 (4) |
S1—S2—C3—C4 | 69.9 (3) | C5—C6—C7—C8 | 170.0 (3) |
S2—C3—C4—N2 | 62.6 (4) | O4—C7—C8—O6 | −172.7 (3) |
O2—C5—C6—O3 | −169.6 (3) | C6—C7—C8—O6 | 65.2 (5) |
O1—C5—C6—O3 | 12.1 (5) | O4—C7—C8—O5 | 7.6 (5) |
O2—C5—C6—C7 | 70.0 (4) | C6—C7—C8—O5 | −114.5 (4) |
O1—C5—C6—C7 | −108.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.91 | 1.88 | 2.786 (4) | 175 |
N1—H1B···O2ii | 0.91 | 1.82 | 2.705 (4) | 162 |
N1—H1C···O1iii | 0.91 | 1.99 | 2.892 (4) | 170 |
N2—H2A···O3iv | 0.91 | 1.99 | 2.871 (4) | 161 |
N2—H2B···O6v | 0.91 | 1.77 | 2.684 (4) | 177 |
N2—H2C···O5vi | 0.91 | 1.87 | 2.727 (4) | 155 |
O3—H3···O1 | 0.84 | 2.09 | 2.588 (4) | 117 |
O3—H3···S1vii | 0.84 | 2.92 | 3.703 (3) | 156 |
O4—H4···O5 | 0.84 | 2.13 | 2.613 (4) | 116 |
O4—H4···O2viii | 0.84 | 2.2 | 2.889 (4) | 139 |
Symmetry codes: (i) x−1, y+1, z; (ii) x−3/2, −y+1/2, −z; (iii) x−1/2, −y+1/2, −z; (iv) x, y+1, z; (v) −x+2, y+1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) x, y−1, z; (viii) x−1, y, z. |
C4H14N2S22+·2C4H5O6−·2H2O | Z = 4 |
Mr = 488.48 | F(000) = 1032 |
Orthorhombic, P212121 | Dx = 1.556 Mg m−3 |
Hall symbol: P 2ac 2ab | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3425 (5) Å | µ = 0.33 mm−1 |
b = 10.5227 (8) Å | T = 120 K |
c = 26.983 (2) Å | Needle, colourless |
V = 2084.8 (3) Å3 | 0.22 × 0.02 × 0.02 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3527 independent reflections |
Graphite monochromator | 2471 reflections with I > 2σ(I) |
Detector resolution: 9.091 pixels mm-1 | Rint = 0.084 |
ϕ and ω scans | θmax = 25°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −8→8 |
Tmin = 0.363, Tmax = 1.0 | k = −12→12 |
12189 measured reflections | l = −32→30 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.078 | H-atom parameters constrained |
wR(F2) = 0.152 | w = 1/[σ2(Fo2) + (0.P)2 + 8.3475P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
3527 reflections | Δρmax = 0.42 e Å−3 |
271 parameters | Δρmin = −0.39 e Å−3 |
6 restraints | Absolute structure: Flack, (1983), 1396 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.1 (2) |
C4H14N2S22+·2C4H5O6−·2H2O | V = 2084.8 (3) Å3 |
Mr = 488.48 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3425 (5) Å | µ = 0.33 mm−1 |
b = 10.5227 (8) Å | T = 120 K |
c = 26.983 (2) Å | 0.22 × 0.02 × 0.02 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3527 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 2471 reflections with I > 2σ(I) |
Tmin = 0.363, Tmax = 1.0 | Rint = 0.084 |
12189 measured reflections |
R[F2 > 2σ(F2)] = 0.078 | H-atom parameters constrained |
wR(F2) = 0.152 | Δρmax = 0.42 e Å−3 |
S = 1.09 | Δρmin = −0.39 e Å−3 |
3527 reflections | Absolute structure: Flack, (1983), 1396 Friedel pairs |
271 parameters | Absolute structure parameter: −0.1 (2) |
6 restraints |
Experimental. Please note cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
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. A possible intramolecular H bond with a very small D—H···A angle is: O3—H3···O2 0.84 2.35 2.700 (7) Å 106° Weak C—H···O hydrogen is present: C2—H2D···O11 0.99 2.55 3.310 (9) Å 134° C11—H11A···O8 1.00 2.59 3.392 (9) Å 137° C11—H11A···O12 1.00 2.59 3.540 (9) Å 160° |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.7357 (3) | 0.03187 (18) | 0.13999 (8) | 0.0344 (5) | |
S2 | 0.4847 (3) | −0.00251 (19) | 0.16935 (7) | 0.0334 (5) | |
N1 | 0.6674 (8) | 0.4198 (6) | 0.1346 (2) | 0.0291 (15) | |
H1A | 0.7715 | 0.4372 | 0.1176 | 0.035* | |
H1B | 0.6513 | 0.4789 | 0.1588 | 0.035* | |
H1C | 0.5709 | 0.4218 | 0.1134 | 0.035* | |
N2 | 0.4048 (8) | −0.2558 (6) | 0.1048 (2) | 0.0267 (15) | |
H2A | 0.4989 | −0.2589 | 0.1267 | 0.032* | |
H2B | 0.4202 | −0.317 | 0.0813 | 0.032* | |
H2C | 0.2981 | −0.2693 | 0.1211 | 0.032* | |
C1 | 0.6814 (12) | 0.2911 (7) | 0.1573 (3) | 0.037 (2) | |
H1D | 0.5665 | 0.2701 | 0.1747 | 0.044* | |
H1E | 0.7816 | 0.2898 | 0.1819 | 0.044* | |
C2 | 0.7178 (12) | 0.1946 (6) | 0.1171 (3) | 0.035 (2) | |
H2D | 0.8326 | 0.2173 | 0.1 | 0.042* | |
H2E | 0.6183 | 0.1988 | 0.0924 | 0.042* | |
C3 | 0.3405 (10) | −0.0263 (7) | 0.1156 (3) | 0.0326 (19) | |
H3A | 0.2157 | −0.0458 | 0.1272 | 0.039* | |
H3B | 0.3348 | 0.0544 | 0.0968 | 0.039* | |
C4 | 0.4004 (11) | −0.1302 (7) | 0.0809 (3) | 0.0323 (19) | |
H4A | 0.3162 | −0.1333 | 0.0522 | 0.039* | |
H4B | 0.5235 | −0.1099 | 0.0681 | 0.039* | |
O1 | 0.3585 (7) | 0.6867 (5) | 0.23471 (19) | 0.0323 (14) | |
H1 | 0.4724 | 0.681 | 0.2329 | 0.048* | |
O2 | 0.3594 (7) | 0.5104 (5) | 0.1891 (2) | 0.0407 (14) | |
O3 | −0.0053 (7) | 0.4852 (5) | 0.1973 (2) | 0.0417 (14) | |
H3 | 0.0525 | 0.4658 | 0.1715 | 0.063* | |
O4 | 0.0684 (7) | 0.7351 (5) | 0.15084 (18) | 0.0360 (14) | |
H4 | −0.0155 | 0.7293 | 0.1298 | 0.054* | |
O5 | −0.2776 (7) | 0.6958 (4) | 0.15477 (17) | 0.0295 (13) | |
O6 | −0.2942 (7) | 0.6986 (5) | 0.23731 (18) | 0.0340 (14) | |
C5 | 0.2848 (10) | 0.5904 (8) | 0.2128 (3) | 0.0311 (18) | |
C6 | 0.0774 (10) | 0.5891 (7) | 0.2199 (3) | 0.0275 (18) | |
H6 | 0.0508 | 0.5857 | 0.2562 | 0.033* | |
C7 | −0.0032 (11) | 0.7149 (7) | 0.1986 (3) | 0.0293 (18) | |
H7 | 0.032 | 0.7874 | 0.2205 | 0.035* | |
C8 | −0.2110 (10) | 0.7027 (6) | 0.1977 (3) | 0.0248 (18) | |
O7 | 0.6171 (6) | 0.5848 (5) | 0.0360 (2) | 0.0323 (13) | |
O8 | 0.6364 (6) | 0.4089 (5) | −0.01008 (19) | 0.0319 (13) | |
O9 | 0.2648 (6) | 0.6175 (4) | 0.01331 (17) | 0.0267 (11) | |
H9 | 0.3061 | 0.6726 | −0.0062 | 0.04* | |
O10 | 0.3270 (7) | 0.4047 (5) | 0.08339 (17) | 0.0352 (13) | |
H10 | 0.2406 | 0.4198 | 0.1029 | 0.053* | |
O11 | −0.0205 (7) | 0.4277 (5) | 0.07573 (19) | 0.0351 (13) | |
O12 | −0.0271 (6) | 0.3977 (4) | −0.00650 (19) | 0.0302 (12) | |
H12 | −0.1396 | 0.4096 | −0.0033 | 0.045* | |
C9 | 0.5497 (9) | 0.5001 (8) | 0.0105 (3) | 0.0290 (17) | |
C10 | 0.3420 (9) | 0.4979 (7) | 0.0020 (2) | 0.0244 (16) | |
H10A | 0.3169 | 0.477 | −0.0335 | 0.029* | |
C11 | 0.2599 (10) | 0.3952 (7) | 0.0348 (3) | 0.0283 (17) | |
H11A | 0.2923 | 0.3099 | 0.021 | 0.034* | |
C12 | 0.0505 (10) | 0.4091 (7) | 0.0355 (3) | 0.0296 (19) | |
O13 | 0.9326 (7) | 0.7207 (4) | 0.04844 (18) | 0.0311 (13) | |
H13A | 0.8559 | 0.6618 | 0.0536 | 0.047* | |
H13B | 1.0294 | 0.6821 | 0.0403 | 0.047* | |
O14 | 0.1419 (8) | 0.2478 (5) | 0.1701 (2) | 0.0541 (17) | |
H14A | 0.2319 | 0.2525 | 0.15 | 0.081* | |
H14B | 0.1906 | 0.2105 | 0.1955 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0365 (11) | 0.0256 (10) | 0.0410 (11) | −0.0013 (9) | −0.0018 (10) | −0.0029 (10) |
S2 | 0.0455 (12) | 0.0242 (10) | 0.0305 (9) | −0.0045 (10) | 0.0046 (10) | −0.0016 (9) |
N1 | 0.025 (3) | 0.031 (4) | 0.030 (3) | 0.001 (3) | 0.003 (3) | 0.004 (3) |
N2 | 0.029 (4) | 0.023 (4) | 0.028 (3) | 0.002 (3) | −0.003 (3) | −0.003 (3) |
C1 | 0.044 (5) | 0.035 (5) | 0.032 (5) | 0.003 (4) | −0.001 (4) | −0.001 (4) |
C2 | 0.054 (6) | 0.015 (4) | 0.035 (4) | −0.001 (4) | 0.004 (4) | 0.003 (3) |
C3 | 0.042 (5) | 0.022 (5) | 0.034 (4) | 0.001 (4) | −0.003 (4) | 0.007 (4) |
C4 | 0.040 (5) | 0.023 (4) | 0.034 (5) | −0.008 (4) | 0.002 (4) | 0.003 (4) |
O1 | 0.028 (3) | 0.034 (3) | 0.034 (3) | −0.002 (3) | 0.003 (2) | −0.009 (3) |
O2 | 0.039 (3) | 0.030 (3) | 0.053 (4) | 0.001 (3) | 0.006 (3) | −0.011 (3) |
O3 | 0.032 (3) | 0.035 (3) | 0.059 (3) | −0.007 (3) | −0.001 (3) | −0.009 (3) |
O4 | 0.026 (3) | 0.050 (4) | 0.032 (3) | −0.001 (3) | −0.002 (2) | 0.011 (3) |
O5 | 0.035 (3) | 0.028 (3) | 0.025 (3) | 0.003 (2) | −0.002 (2) | −0.001 (2) |
O6 | 0.024 (3) | 0.048 (4) | 0.030 (3) | −0.005 (3) | 0.010 (3) | −0.005 (3) |
C5 | 0.032 (5) | 0.037 (5) | 0.025 (4) | 0.001 (4) | −0.004 (4) | 0.002 (4) |
C6 | 0.034 (5) | 0.021 (4) | 0.027 (4) | 0.002 (4) | 0.000 (3) | 0.000 (4) |
C7 | 0.029 (5) | 0.023 (4) | 0.036 (4) | −0.001 (4) | 0.002 (4) | −0.008 (4) |
C8 | 0.033 (5) | 0.008 (4) | 0.033 (4) | 0.005 (3) | 0.002 (4) | 0.001 (3) |
O7 | 0.026 (3) | 0.017 (3) | 0.054 (4) | 0.000 (2) | 0.000 (3) | −0.008 (3) |
O8 | 0.035 (3) | 0.021 (3) | 0.039 (3) | 0.005 (2) | 0.005 (3) | −0.009 (3) |
O9 | 0.029 (3) | 0.019 (3) | 0.032 (3) | 0.006 (2) | 0.002 (2) | 0.005 (2) |
O10 | 0.038 (3) | 0.043 (3) | 0.026 (3) | −0.006 (3) | 0.003 (3) | 0.007 (3) |
O11 | 0.026 (3) | 0.040 (3) | 0.040 (3) | 0.001 (3) | 0.003 (3) | 0.008 (3) |
O12 | 0.024 (3) | 0.025 (3) | 0.042 (3) | 0.002 (2) | 0.001 (3) | −0.003 (3) |
C9 | 0.034 (4) | 0.025 (4) | 0.028 (4) | −0.002 (4) | 0.005 (4) | 0.008 (4) |
C10 | 0.032 (4) | 0.018 (4) | 0.024 (4) | 0.002 (3) | 0.002 (3) | −0.003 (4) |
C11 | 0.022 (4) | 0.029 (4) | 0.034 (4) | 0.001 (4) | −0.005 (4) | 0.002 (4) |
C12 | 0.038 (5) | 0.009 (4) | 0.042 (5) | −0.005 (3) | 0.006 (4) | 0.006 (4) |
O13 | 0.038 (3) | 0.016 (3) | 0.039 (3) | 0.004 (2) | 0.002 (3) | 0.002 (3) |
O14 | 0.056 (4) | 0.044 (4) | 0.063 (4) | 0.010 (3) | −0.008 (3) | 0.008 (4) |
S1—C2 | 1.825 (7) | O4—H4 | 0.8401 |
S1—S2 | 2.038 (3) | O5—C8 | 1.261 (8) |
S2—C3 | 1.813 (7) | O6—C8 | 1.231 (8) |
N1—C1 | 1.490 (9) | C5—C6 | 1.535 (10) |
N1—H1A | 0.91 | C6—C7 | 1.560 (10) |
N1—H1B | 0.9101 | C6—H6 | 1 |
N1—H1C | 0.9099 | C7—C8 | 1.531 (10) |
N2—C4 | 1.471 (9) | C7—H7 | 1 |
N2—H2A | 0.91 | O7—C9 | 1.229 (8) |
N2—H2B | 0.9099 | O8—C9 | 1.278 (8) |
N2—H2C | 0.91 | O9—C10 | 1.414 (8) |
C1—C2 | 1.511 (9) | O9—H9 | 0.8401 |
C1—H1D | 0.99 | O10—C11 | 1.405 (8) |
C1—H1E | 0.99 | O10—H10 | 0.84 |
C2—H2D | 0.99 | O11—C12 | 1.220 (9) |
C2—H2E | 0.99 | O12—C12 | 1.275 (9) |
C3—C4 | 1.506 (10) | O12—H12 | 0.84 |
C3—H3A | 0.99 | C9—C10 | 1.542 (9) |
C3—H3B | 0.99 | C10—C11 | 1.522 (9) |
C4—H4A | 0.99 | C10—H10A | 1 |
C4—H4B | 0.99 | C11—C12 | 1.544 (10) |
O1—C5 | 1.292 (9) | C11—H11A | 1 |
O1—H1 | 0.84 | O13—H13A | 0.8485 |
O2—C5 | 1.191 (8) | O13—H13B | 0.8473 |
O3—C6 | 1.392 (9) | O14—H14A | 0.8558 |
O3—H3 | 0.8399 | O14—H14B | 0.8663 |
O4—C7 | 1.407 (8) | ||
C2—S1—S2 | 103.5 (3) | O2—C5—O1 | 127.5 (7) |
C3—S2—S1 | 104.0 (3) | O2—C5—C6 | 121.1 (7) |
C1—N1—H1A | 109.5 | O1—C5—C6 | 111.4 (7) |
C1—N1—H1B | 109.5 | O3—C6—C5 | 112.6 (6) |
H1A—N1—H1B | 109.5 | O3—C6—C7 | 109.8 (6) |
C1—N1—H1C | 109.5 | C5—C6—C7 | 108.8 (6) |
H1A—N1—H1C | 109.5 | O3—C6—H6 | 108.5 |
H1B—N1—H1C | 109.5 | C5—C6—H6 | 108.5 |
C4—N2—H2A | 109.5 | C7—C6—H6 | 108.5 |
C4—N2—H2B | 109.5 | O4—C7—C8 | 111.8 (6) |
H2A—N2—H2B | 109.5 | O4—C7—C6 | 108.9 (6) |
C4—N2—H2C | 109.4 | C8—C7—C6 | 108.2 (6) |
H2A—N2—H2C | 109.5 | O4—C7—H7 | 109.3 |
H2B—N2—H2C | 109.5 | C8—C7—H7 | 109.3 |
N1—C1—C2 | 109.1 (6) | C6—C7—H7 | 109.3 |
N1—C1—H1D | 109.9 | O6—C8—O5 | 127.1 (7) |
C2—C1—H1D | 109.9 | O6—C8—C7 | 119.0 (6) |
N1—C1—H1E | 109.9 | O5—C8—C7 | 113.9 (6) |
C2—C1—H1E | 109.9 | C10—O9—H9 | 109.5 |
H1D—C1—H1E | 108.3 | C11—O10—H10 | 109.5 |
C1—C2—S1 | 113.6 (5) | C12—O12—H12 | 109.5 |
C1—C2—H2D | 108.8 | O7—C9—O8 | 125.9 (7) |
S1—C2—H2D | 108.8 | O7—C9—C10 | 119.5 (7) |
C1—C2—H2E | 108.8 | O8—C9—C10 | 114.6 (7) |
S1—C2—H2E | 108.8 | O9—C10—C11 | 110.3 (5) |
H2D—C2—H2E | 107.7 | O9—C10—C9 | 110.5 (6) |
C4—C3—S2 | 115.3 (5) | C11—C10—C9 | 108.4 (6) |
C4—C3—H3A | 108.4 | O9—C10—H10A | 109.2 |
S2—C3—H3A | 108.4 | C11—C10—H10A | 109.2 |
C4—C3—H3B | 108.4 | C9—C10—H10A | 109.2 |
S2—C3—H3B | 108.4 | O10—C11—C10 | 110.7 (6) |
H3A—C3—H3B | 107.5 | O10—C11—C12 | 109.3 (6) |
N2—C4—C3 | 112.7 (6) | C10—C11—C12 | 109.6 (6) |
N2—C4—H4A | 109.1 | O10—C11—H11A | 109.1 |
C3—C4—H4A | 109.1 | C10—C11—H11A | 109.1 |
N2—C4—H4B | 109.1 | C12—C11—H11A | 109.1 |
C3—C4—H4B | 109.1 | O11—C12—O12 | 128.0 (7) |
H4A—C4—H4B | 107.8 | O11—C12—C11 | 116.9 (7) |
C5—O1—H1 | 109.5 | O12—C12—C11 | 115.1 (7) |
C6—O3—H3 | 109.5 | H13A—O13—H13B | 104.5 |
C7—O4—H4 | 109.5 | H14A—O14—H14B | 102 |
C2—S1—S2—C3 | 75.3 (4) | O4—C7—C8—O5 | 8.9 (9) |
N1—C1—C2—S1 | −179.4 (5) | C6—C7—C8—O5 | −111.0 (7) |
S2—S1—C2—C1 | 62.4 (6) | O7—C9—C10—O9 | 17.5 (9) |
S1—S2—C3—C4 | 56.8 (6) | O8—C9—C10—O9 | −163.4 (6) |
S2—C3—C4—N2 | 61.0 (8) | O7—C9—C10—C11 | −103.5 (8) |
O2—C5—C6—O3 | 1.6 (11) | O8—C9—C10—C11 | 75.6 (7) |
O1—C5—C6—O3 | −179.1 (6) | O9—C10—C11—O10 | −73.6 (7) |
O2—C5—C6—C7 | −120.4 (8) | C9—C10—C11—O10 | 47.5 (8) |
O1—C5—C6—C7 | 58.9 (8) | O9—C10—C11—C12 | 47.0 (8) |
O3—C6—C7—O4 | −75.0 (7) | C9—C10—C11—C12 | 168.2 (6) |
C5—C6—C7—O4 | 48.6 (8) | O10—C11—C12—O11 | 1.4 (9) |
O3—C6—C7—C8 | 46.7 (8) | C10—C11—C12—O11 | −120.1 (7) |
C5—C6—C7—C8 | 170.4 (6) | O10—C11—C12—O12 | −177.8 (6) |
O4—C7—C8—O6 | −172.1 (6) | C10—C11—C12—O12 | 60.8 (8) |
C6—C7—C8—O6 | 67.9 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O11i | 0.91 | 1.9 | 2.789 (8) | 164 |
N1—H1B···O2 | 0.91 | 2.32 | 2.861 (8) | 118 |
N1—H1B···O5i | 0.91 | 2.34 | 2.983 (8) | 127 |
N1—H1C···O10 | 0.91 | 1.97 | 2.859 (7) | 164 |
N2—H2A···O5ii | 0.91 | 1.87 | 2.741 (8) | 160 |
N2—H2B···O7iii | 0.91 | 2.16 | 2.948 (8) | 145 |
N2—H2B···O9iii | 0.91 | 2.27 | 2.987 (7) | 136 |
N2—H2C···O4iii | 0.91 | 1.87 | 2.767 (7) | 169 |
O1—H1···O6i | 0.84 | 1.73 | 2.554 (7) | 167 |
O3—H3···O14 | 0.84 | 2.39 | 2.819 (8) | 113 |
O4—H4···O5 | 0.84 | 2.07 | 2.576 (7) | 118 |
O4—H4···O13iv | 0.84 | 2.23 | 2.941 (7) | 143 |
O9—H9···O13v | 0.84 | 1.85 | 2.682 (7) | 171 |
O10—H10···O11 | 0.84 | 2.05 | 2.572 (7) | 119 |
O12—H12···O8iv | 0.84 | 1.66 | 2.476 (7) | 165 |
O13—H13A···O7 | 0.85 | 1.99 | 2.743 (7) | 148 |
O13—H13B···O9i | 0.85 | 1.99 | 2.833 (7) | 170 |
O14—H14A···O10 | 0.86 | 2.51 | 3.170 (8) | 135 |
O14—H14B···O6vi | 0.87 | 1.97 | 2.786 (8) | 156 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) x, y−1, z; (iv) x−1, y, z; (v) x−1/2, −y+3/2, −z; (vi) −x, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C2H8NS+·C4H5O6−·H2O | C4H14N2S22+·C4H4O62− | C4H14N2S22+·2C4H5O6−·2H2O |
Mr | 245.25 | 302.36 | 488.48 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 7.0630 (2), 10.3833 (5), 14.8591 (7) | 5.7281 (3), 9.3699 (5), 24.6770 (14) | 7.3425 (5), 10.5227 (8), 26.983 (2) |
V (Å3) | 1089.73 (8) | 1324.46 (12) | 2084.8 (3) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.32 | 0.42 | 0.33 |
Crystal size (mm) | 0.84 × 0.12 × 0.1 | 0.36 × 0.14 × 0.03 | 0.22 × 0.02 × 0.02 |
Data collection | |||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) | Multi-scan (SADABS; Sheldrick, 2007) | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.620, 0.746 | 0.613, 0.746 | 0.363, 1.0 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9253, 2485, 2099 | 9158, 3020, 2273 | 12189, 3527, 2471 |
Rint | 0.051 | 0.083 | 0.084 |
(sin θ/λ)max (Å−1) | 0.651 | 0.653 | 0.595 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.093, 1.06 | 0.060, 0.139, 1.05 | 0.078, 0.152, 1.09 |
No. of reflections | 2485 | 3020 | 3527 |
No. of parameters | 143 | 165 | 271 |
No. of restraints | 0 | 0 | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.25 | 0.55, −0.43 | 0.42, −0.39 |
Absolute structure | Flack (1983), 1027 Friedel pairs | Flack (1983), 1222 Friedel pairs | Flack, (1983), 1396 Friedel pairs |
Absolute structure parameter | −0.04 (9) | 0.20 (13) | −0.1 (2) |
Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6i | 0.84 | 1.66 | 2.4885 (18) | 169.3 |
O3—H3···O7ii | 0.84 | 2.13 | 2.819 (2) | 139 |
O4—H4···O7 | 0.84 | 1.9 | 2.742 (2) | 177.2 |
N1—H1A···O3iii | 0.91 | 2 | 2.813 (2) | 148.2 |
N1—H1B···O2iv | 0.91 | 1.92 | 2.814 (2) | 165.9 |
N1—H1C···O5i | 0.91 | 1.89 | 2.772 (2) | 161.8 |
N1—H1C···O4i | 0.91 | 2.3 | 2.850 (2) | 118.4 |
O7—H7A···O5i | 0.87 | 1.89 | 2.7455 (19) | 168.1 |
O7—H7B···O6v | 0.77 | 2.14 | 2.8910 (19) | 166.4 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+2, y+1/2, −z+1/2; (v) x+1/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.91 | 1.88 | 2.786 (4) | 174.9 |
N1—H1B···O2ii | 0.91 | 1.82 | 2.705 (4) | 162.2 |
N1—H1C···O1iii | 0.91 | 1.99 | 2.892 (4) | 170.2 |
N2—H2A···O3iv | 0.91 | 1.99 | 2.871 (4) | 161.3 |
N2—H2B···O6v | 0.91 | 1.77 | 2.684 (4) | 177.1 |
N2—H2C···O5vi | 0.91 | 1.87 | 2.727 (4) | 155.3 |
O3—H3···O1 | 0.84 | 2.09 | 2.588 (4) | 117.4 |
O3—H3···S1vii | 0.84 | 2.92 | 3.703 (3) | 156.4 |
O4—H4···O5 | 0.84 | 2.13 | 2.613 (4) | 116.1 |
O4—H4···O2viii | 0.84 | 2.2 | 2.889 (4) | 139.4 |
Symmetry codes: (i) x−1, y+1, z; (ii) x−3/2, −y+1/2, −z; (iii) x−1/2, −y+1/2, −z; (iv) x, y+1, z; (v) −x+2, y+1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) x, y−1, z; (viii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O11i | 0.91 | 1.9 | 2.789 (8) | 164.4 |
N1—H1B···O2 | 0.91 | 2.32 | 2.861 (8) | 118.1 |
N1—H1B···O5i | 0.91 | 2.34 | 2.983 (8) | 127.1 |
N1—H1C···O10 | 0.91 | 1.97 | 2.859 (7) | 164.2 |
N2—H2A···O5ii | 0.91 | 1.87 | 2.741 (8) | 159.8 |
N2—H2B···O7iii | 0.91 | 2.16 | 2.948 (8) | 144.7 |
N2—H2B···O9iii | 0.91 | 2.27 | 2.987 (7) | 135.7 |
N2—H2C···O4iii | 0.91 | 1.87 | 2.767 (7) | 169 |
O1—H1···O6i | 0.84 | 1.73 | 2.554 (7) | 167.4 |
O3—H3···O14 | 0.84 | 2.39 | 2.819 (8) | 112.6 |
O4—H4···O5 | 0.84 | 2.07 | 2.576 (7) | 118.3 |
O4—H4···O13iv | 0.84 | 2.23 | 2.941 (7) | 142.5 |
O9—H9···O13v | 0.84 | 1.85 | 2.682 (7) | 170.6 |
O10—H10···O11 | 0.84 | 2.05 | 2.572 (7) | 119.3 |
O12—H12···O8iv | 0.84 | 1.66 | 2.476 (7) | 164.8 |
O13—H13A···O7 | 0.85 | 1.99 | 2.743 (7) | 147.5 |
O13—H13B···O9i | 0.85 | 1.99 | 2.833 (7) | 170 |
O14—H14A···O10 | 0.86 | 2.51 | 3.170 (8) | 134.9 |
O14—H14B···O6vi | 0.87 | 1.97 | 2.786 (8) | 156.3 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) x, y−1, z; (iv) x−1, y, z; (v) x−1/2, −y+3/2, −z; (vi) −x, y−1/2, −z+1/2. |
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Nephropathic cystinosis is a rare autosomal recessive disease that is characterized by raised lysosomal levels of cystine in the cells of most organs. If untreated, the disease results in death from renal failure by the second decade of life. The condition is characterized by poor growth, renal Fanconi syndrome, renal glomerular failure, and impairment of other tissues and organs (e.g. thyroid, pancreas, central nervous system). If treatment is started just after birth this can attenuate the rate of renal failure, but glomerular damage present at the time of diagnosis (usually about 12 months of age) is irreversible and may result in the need for renal transplant (Gahl et al., 2000, 2001, 2002; Cairns et al., 2002). Although novel prodrug strategies are being researched (Kay et al., 2007; McCaughan et al., 2008), the main treatment for the disorder remains the administration of the aminothiol cysteamine as the ditartrate salt, in the commercial preparation Cystagon (Manufacturer and location?). Cysteamine lowers intracellular levels of cystine by forming a cysteamine–cysteine mixed disulfide that is spatially similar in structure to the amino acid lysine, and can egress the lysosome using the undamaged excretion pathway for lysine (Touchman et al., 2000). The thiol cysteamine is known to auto-oxidize to form cystamine (Scheme 1).
The known 2R,3R absolute configuration of L-(+)-tartaric acid can establish the absolute configuration of its chiral associations, where it can exist as a neutral molecule, a tartrate monoanion or a tartrate dianion. Its use in pharmaceutical salts also includes metoprolol tartrate, a β-adrenoceptor blocking agent used for migraines, and zolpidem tartrate, a hyponotic used for insomnia (Sweetman, 2011).
In this study, we have reacted cysteamine and cystamine with L-(+)-tartaric acid, and report on the formation and absolute molecular configuration of the three crystalline products, cysteamine tartrate(1-) monohydrate, (I), cystamine tartrate(2-), (II), and cystamine bis[tartrate(1-)] dihydrate, (III) (Scheme 2; Figs. 1–3).
For (I), the cysteamine moiety remains unoxidized and salt formation results from the transfer of a proton from one of the two carboxylic acid groups in the tartaric acid molecule to the amino group in cysteamine. This results in a monohydrated tartrate monoanion (also known as a hydrogen tartrate anion or semi-tartrate anion) associated with a cysteaminium cation. In the carboxylic acid group, the single-bond character of C3—O1 = 1.301 (2) Å compares with the double-bond length of C3—O2 = 1.224 (2) Å, whereas the lengths of the bonds in the carboxylate group, C6—O5 = 1.240 (2) Å and C6—O6 = 1.280 (2) Å, are closer to each other, but not equal, due to differences in hydrogen bonding. The conformation of the cation is described by the torsion angle S1—C1—C2—N1 = 76.1 (2)° and differs from values of 61.7 (2), -60.3 (4) and 60.7 (4)° found in cysteamine hydrochloride (Ahmad et al., 2010; Kim et al., 2002), where chloride anions are engaged in hydrogen bonding. The S—H bond of 1.31 (3) Å compares with the value of 1.30 (5) Å in thiosalicylic acid (Steiner, 2000) and there are no short intermolecular contacts around the S atom. The tartrate monoanions are linked into chains running parallel to (100) by a strong head-to-tail O1—H1···O6 hydrogen bond, with O1···O6 = 2.489 (2) Å. These chains are then interlinked by water molecules (Fig. 4) and cysteaminium cations (via the three H atoms of the protonated amino group; Fig. 5). One of these three H atoms, H1C, is involved in bifurcated hydrogen bonding. The resulting honeycomb or columnar packing structure (Fig. 6) is similar to those found in quinolinium hydrogen (2R,3R)-tartrate monohydrate (Smith et al., 2006) and pyridinium (2R,3R)-tartrate (Suresh et al., 2006). Hydrogen bonds are given in Table 1.
Product (II) is an anhydrous salt formed by the transfer of both H atoms from the two carboxylic acid groups in L(+)-tartaric acid to the two amino groups in cystamine. (When cysteamine is the starting material, cystamine is formed by auto-oxidation of cysteamine.) Similarities in bond character in the carboxylate groups are shown by C5—O1 = 1.257 (5) Å, C5—O2 = 1.244 (5) Å, C8—O5 = 1.258 (5) Å and C8—O6 = 1.251 (5) Å. The disulfide bond [S1—S2 = 2.038 (2) Å] adopts a gauche orientation, with the torsion angle C2—S1—S2—C3 = 75.3 (4)°, and as the five torsion angles around this bond are all positive it may be designated +RHSpiral (Schmidt et al., 2006). The tartrate anions (Fig. 7) are linked into chains running parallel to (100) by a single O4—H4···O2 hydrogen bond (Table 2). In addition, each cystaminium cation is hydrogen-bonded to six tartrate anions via the two protonated amino groups (Fig. 8), resulting in the overall crystal packing shown in Fig. 9. Hydrogen bonds are listed in Table 2.
The quality of the data set related to the crystal for (III) was not as good as those obtained for (I) and (II), and discussion of the fine details of the product structure needs to be approached with caution. As in (II), both amino groups have acquired an additional H atom. Each of these two protons appears to have transferred from separate tartaric acid molecules, leaving a single charge on each tartrate monoanion. Evidence for this is based on bond lengths, such as that for the carboxylic acid group, C5—O1 = 1.292 (9) Å and C5—O2 = 1.191 (9) Å, and, in the same anion, the carboxylate group has C8—O5 = 1.261 (8) Å and C8—O6 = 1.231 (8) Å. In the second tartrate monoanion, the bond character is less obvious but the carboxylic acid group has C12—O11 = 1.220 (9) Å and C12—O12 = 1.274 (9) Å, while in the carboxylate group these bonds are C9—O7 = 1.229 (9) Å and C9—O8 = 1.278 (8) Å. In this second anion, the O8···O12 intermolecular separation is very short at 2.476 (7) Å, and although a difference Fourier map indicated that atom H12 was closer to O12 than O8, a sharing of the donor–acceptor roles of these two O atoms could explain the similarities in C—O bond lengths. Refinements of other models involving H3O+ formation were unsatisfactory. The disulfide bond [S1—S2 = 2.038 (3) Å] adopts a gauche orientation, with the torsion angle C2—S1—S2—C3 = 80.4 (2)°, and may be designated +/-RHSpiral (Schmidt et al., 2006). Here, N1—C1—C2—S1 = -179.6 (4)°, and this trans-planar arrangement is also present in cystamine hydrochloride (Vedavathi & Vijayan, 1979), whereas in (II) this arrangement is gauche. As in (I), each tartrate monoanion of (III) is linked into chains (Fig. 10) running parallel to (100) by a strong head-to-tail O1—H1···O6 hydrogen bond, with O1—O6 = 2.554 (7) Å. These chains are crosslinked by two independent water molecules (Fig. 11) acting as acceptors and donors of hydrogen bonds. Furthermore, each protonated amino group is linked to four tartrate monoanions (Fig. 12), with one of the three protons, H4, engaged in bifurcated hydrogen-bond formation. Numerous hydrogen bonds are present and some have short donor–acceptor separations (Table 3). The resulting crystal packing is shown in Fig. 13.