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Reaction between cyste­amine (systematic name: 2-amino­ethane­thiol, C2H7NS) and L-(+)-tartaric acid [systematic name: (2R,3R)-2,3-di­hydroxy­butane­dioic acid, C4H6O6] results in a mixture of cyste­amine tartrate(1-) monohydrate, C2H8NS+·C4H5O6-·H2O, (I), and cystamine bis­[tartrate(1-)] dihydrate, C4H14N2S22+·2C4H5O6-·2H2O, (III). Cystamine [systematic name: 2,2'-di­thio­bis­(ethyl­amine), C4H12N2S2], reacts with L-(+)-tartaric acid to produce a mixture of cystamine tartrate(2-), C4H14N2S22+·C4H4O62-, (II), and (III). In each crystal structure, the anions are linked by O-H...O hydrogen bonds that run parallel to the a axis. In addition, hydrogen bonding involving protonated amino groups in all three salts, and water mol­ecules in (I) and (III), leads to extensive three-dimensional hydrogen-bonding networks. All three salts crystallize in the ortho­rhom­bic space group P212121.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113012377/yp3029sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012377/yp3029Isup2.hkl
Contains datablock I

mol

MDL mol file https://doi.org/10.1107/S0108270113012377/yp3029Isup5.mol
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012377/yp3029IIsup3.hkl
Contains datablock II

mol

MDL mol file https://doi.org/10.1107/S0108270113012377/yp3029IIsup6.mol
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012377/yp3029IIIsup4.hkl
Contains datablock III

mol

MDL mol file https://doi.org/10.1107/S0108270113012377/yp3029IIIsup7.mol
Supplementary material

CCDC references: 950451; 950452; 950453

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. A view of (III), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the head-to-tail hydrogen-bonded chains of tartrate monoanions running parallel to [100] [O1···O6* = 2.489 (2) Å] and crosslinked by water molecules, which act as double donors and double acceptors of hydrogen bonds. Atoms labelled with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (x + 1, y, z), (x + 1/2, -y + 1/2, -z + 1), (-x + 1, y + 1/2, -z + 1/2) or (-x + 1, y - 1/2, -z + 1/2), respectively. Hydrogen bonds are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 5] Fig. 5. Part of the crystal structure of (I), showing the head-to-tail hydrogen-bonded chains of tartrate monoanions crosslinked by the protonated amino group of the cysteaminium cation. One of the three hydrogen bonds is bifurcated. Atoms labelled with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (x + 1, y, z), (-x + 2, y + 1/2, -z + 1/2) or (-x + 1, y + 1/2, -z + 1/2), respectively. Hydrogen bonds involving the amino groups are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 6] Fig. 6. A view of the packing of the ions in the unit cell of (I). Hydrogen bonds are shown as dashed lines.
[Figure 7] Fig. 7. Part of the crystal structure of (II), showing intramolecular [O3···O1 = 2.588 (4) Å and O4···O5 = 2.613 (4) Å] and intermolecular [O4···O2# = 2.613 (4) Å] hydrogen-bonded chains of tartrate anions running parallel to [100]. Atoms labelled with an asterisk (*) or a hash symbol (#) are at the symmetry positions (x + 1, y, z) or (x - 1, y, z), respectively. Hydrogen bonds are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 8] Fig. 8. Part of the crystal structure of (II), showing the tartrate anions crosslinked by the protonated amino groups of the cystaminium cation. Atoms labelled with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-x + 2, y + 1/2, -z + 1/2), (x - 1, y, z), (x - 3/2, -y + 1/2, -z) or (x - 1/2, -y + 1/2, -z), respectively. Hydrogen bonds are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 9] Fig. 9. A view of the packing of the ions in the unit cell of (II). Hydrogen bonds are shown as dashed lines.
[Figure 10] Fig. 10. Part of the crystal structure of (III), showing the intramolecular [O4···O5 = 2.576 (7) Å and O10···O11 = 2.682 (7) Å] and intermolecular [O1···O6* = 2.554 (7) Å and O8···O12* = 2.476 (7) Å] hydrogen-bonded chains of the two independent tartrate monoanions, running parallel to [100]. Atoms labelled with an asterisk (*) or a hash symbol (#) are at the symmetry positions (x + 1, y, z) or (x - 1, y, z), respectively. Hydrogen bonds are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 11] Fig. 11. Part of the crystal structure of (III), showing the hydrogen-bonded tartrate monoanions crosslinked by water molecules, which act as donors and acceptors of hydrogen bonds. Atoms labelled with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (-x, y - 1/2, -z + 1/2), (x + 1, y, z) or (x + 1/2, -y + 3/2, -z), respectively. Hydrogen bonds are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 12] Fig. 12. Part of the crystal structure of (III), showing the tartrate monoanions crosslinked by the protonated amino groups of the cystaminium cation. Atoms labelled with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (x, y - 1, z), (x + 1, y - 1, z) or (x + 1, y, z). Hydrogen bonds are shown as dashed lines and H atoms not involved in the interactions have been omitted.
[Figure 13] Fig. 13. A view of the packing of the ions in the unit cell of (III). Hydrogen bonds are shown as dashed lines.
(I) Cysteamine tartrate(1-) monohydrate top
Crystal data top
C2H8NS+·C4H5O6·H2OZ = 4
Mr = 245.25F(000) = 520
Orthorhombic, P212121Dx = 1.495 Mg m3
Hall symbol: P 2ac 2abMo Kα radiation, λ = 0.71073 Å
a = 7.0630 (2) ŵ = 0.32 mm1
b = 10.3833 (5) ÅT = 120 K
c = 14.8591 (7) ÅRod, colourless
V = 1089.73 (8) Å30.84 × 0.12 × 0.1 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2485 independent reflections
Graphite monochromator2099 reflections with I > 2σ(I)
Detector resolution: 9.091 pixels mm-1Rint = 0.051
ϕ and ω scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 98
Tmin = 0.620, Tmax = 0.746k = 1313
9253 measured reflectionsl = 1719
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H 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 reflectionsΔρmax = 0.27 e Å3
143 parametersΔρmin = 0.25 e Å3
0 restraintsAbsolute structure: Flack (1983), 1027 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (9)
Crystal data top
C2H8NS+·C4H5O6·H2OV = 1089.73 (8) Å3
Mr = 245.25Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.0630 (2) ŵ = 0.32 mm1
b = 10.3833 (5) ÅT = 120 K
c = 14.8591 (7) Å0.84 × 0.12 × 0.1 mm
Data collection top
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 = 0.746Rint = 0.051
9253 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093Δρmax = 0.27 e Å3
S = 1.06Δρmin = 0.25 e Å3
2485 reflectionsAbsolute structure: Flack (1983), 1027 Friedel pairs
143 parametersAbsolute structure parameter: 0.04 (9)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.62774 (18)0.08513 (14)0.46065 (10)0.0170 (3)
H10.74620.08370.45560.022*
O20.63688 (19)0.03004 (16)0.33240 (11)0.0231 (4)
O30.25893 (19)0.03363 (14)0.31731 (10)0.0181 (3)
H30.33780.03280.2750.023*
O40.31856 (19)0.23590 (14)0.31556 (10)0.0195 (3)
H40.41440.28130.32610.025*
O50.04770 (19)0.24127 (14)0.35304 (9)0.0184 (3)
O60.02037 (18)0.09647 (14)0.46333 (10)0.0172 (3)
C30.5516 (3)0.02653 (18)0.39225 (14)0.0146 (4)
C40.3354 (3)0.03150 (18)0.39253 (14)0.0135 (4)
H4A0.28940.01250.44820.016*
C50.2648 (3)0.17074 (18)0.39438 (14)0.0135 (4)
H50.32070.21580.44760.016*
C60.0480 (3)0.17104 (18)0.40290 (13)0.0139 (4)
S10.68437 (9)0.14607 (6)0.10095 (5)0.03652 (19)
H1S0.626 (4)0.220 (3)0.1665 (17)0.044*
N11.0543 (2)0.29928 (16)0.17750 (11)0.0171 (4)
H1A0.9480.34010.15790.021*
H1B1.15750.34870.1650.021*
H1C1.04630.28640.2380.021*
C10.9037 (3)0.0866 (2)0.14997 (17)0.0291 (5)
H1D0.88730.07860.21590.035*
H1E0.93010.00040.12580.035*
C21.0725 (3)0.1730 (2)0.13114 (16)0.0252 (5)
H2A1.18960.12970.15170.03*
H2B1.08320.18740.06550.03*
O70.62687 (19)0.38583 (14)0.35555 (10)0.0193 (3)
H7A0.72250.33350.36080.025*
H7B0.59450.40260.40360.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0080 (6)0.0246 (7)0.0184 (8)0.0003 (5)0.0003 (5)0.0019 (7)
O20.0151 (7)0.0303 (8)0.0238 (9)0.0060 (6)0.0011 (6)0.0076 (7)
O30.0137 (6)0.0219 (8)0.0186 (8)0.0025 (6)0.0005 (5)0.0069 (7)
O40.0148 (7)0.0218 (8)0.0220 (8)0.0029 (6)0.0001 (6)0.0063 (6)
O50.0129 (6)0.0237 (7)0.0187 (8)0.0035 (6)0.0006 (6)0.0031 (7)
O60.0102 (6)0.0231 (7)0.0181 (8)0.0006 (6)0.0007 (6)0.0026 (7)
C30.0139 (9)0.0150 (9)0.0151 (11)0.0010 (8)0.0011 (8)0.0024 (9)
C40.0097 (9)0.0150 (9)0.0157 (11)0.0018 (8)0.0010 (8)0.0001 (9)
C50.0136 (9)0.0137 (10)0.0133 (10)0.0022 (7)0.0002 (7)0.0014 (9)
C60.0132 (8)0.0159 (9)0.0127 (10)0.0002 (8)0.0002 (8)0.0047 (9)
S10.0340 (3)0.0297 (3)0.0458 (4)0.0100 (3)0.0083 (3)0.0049 (3)
N10.0123 (7)0.0186 (8)0.0205 (9)0.0003 (7)0.0002 (7)0.0025 (8)
C10.0442 (14)0.0195 (11)0.0237 (13)0.0017 (10)0.0022 (10)0.0014 (11)
C20.0294 (11)0.0255 (12)0.0206 (12)0.0056 (10)0.0010 (9)0.0053 (10)
O70.0154 (7)0.0222 (8)0.0204 (8)0.0040 (6)0.0031 (6)0.0022 (7)
Geometric parameters (Å, º) top
O1—C31.301 (2)S1—C11.820 (2)
O1—H10.84S1—H1S1.31 (3)
O2—C31.224 (2)N1—C21.487 (3)
O3—C41.414 (2)N1—H1A0.91
O3—H30.84N1—H1B0.91
O4—C51.405 (2)N1—H1C0.91
O4—H40.84C1—C21.518 (3)
O5—C61.240 (2)C1—H1D0.99
O6—C61.280 (2)C1—H1E0.99
C3—C41.528 (3)C2—H2A0.99
C4—C51.530 (3)C2—H2B0.99
C4—H4A1O7—H7A0.8703
C5—C61.536 (3)O7—H7B0.7698
C5—H51
C3—O1—H1109.5C1—S1—H1S99.9 (11)
C4—O3—H3109.5C2—N1—H1A109.5
C5—O4—H4109.5C2—N1—H1B109.5
O2—C3—O1126.07 (17)H1A—N1—H1B109.5
O2—C3—C4120.65 (19)C2—N1—H1C109.5
O1—C3—C4113.27 (17)H1A—N1—H1C109.5
O3—C4—C3111.32 (17)H1B—N1—H1C109.5
O3—C4—C5109.99 (16)C2—C1—S1113.23 (16)
C3—C4—C5110.97 (16)C2—C1—H1D108.9
O3—C4—H4A108.2S1—C1—H1D108.9
C3—C4—H4A108.2C2—C1—H1E108.9
C5—C4—H4A108.2S1—C1—H1E108.9
O4—C5—C4110.62 (16)H1D—C1—H1E107.7
O4—C5—C6109.70 (16)N1—C2—C1111.58 (18)
C4—C5—C6109.17 (15)N1—C2—H2A109.3
O4—C5—H5109.1C1—C2—H2A109.3
C4—C5—H5109.1N1—C2—H2B109.3
C6—C5—H5109.1C1—C2—H2B109.3
O5—C6—O6124.69 (17)H2A—C2—H2B108
O5—C6—C5119.68 (17)H7A—O7—H7B106.8
O6—C6—C5115.62 (16)
O2—C3—C4—O30.7 (3)C3—C4—C5—C6175.13 (17)
O1—C3—C4—O3179.80 (15)O4—C5—C6—O511.7 (2)
O2—C3—C4—C5123.6 (2)C4—C5—C6—O5133.06 (19)
O1—C3—C4—C557.3 (2)O4—C5—C6—O6168.62 (16)
O3—C4—C5—O459.54 (19)C4—C5—C6—O647.3 (2)
C3—C4—C5—O464.1 (2)S1—C1—C2—N167.1 (2)
O3—C4—C5—C661.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O6i0.841.662.4885 (18)169
O3—H3···O7ii0.842.132.819 (2)139
O4—H4···O70.841.92.742 (2)177
N1—H1A···O3iii0.9122.813 (2)148
N1—H1B···O2iv0.911.922.814 (2)166
N1—H1C···O5i0.911.892.772 (2)162
N1—H1C···O4i0.912.32.850 (2)118
O7—H7A···O5i0.871.892.7455 (19)168
O7—H7B···O6v0.772.142.8910 (19)166
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1/2, 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.
(II) Cystamine tartrate(2-) top
Crystal data top
C4H14N2S22+·C4H4O62Z = 4
Mr = 302.36F(000) = 640
Orthorhombic, P212121Dx = 1.516 Mg m3
Hall symbol: P 2ac 2abMo Kα radiation, λ = 0.71073 Å
a = 5.7281 (3) ŵ = 0.42 mm1
b = 9.3699 (5) ÅT = 120 K
c = 24.6770 (14) ÅBlade, colourless
V = 1324.46 (12) Å30.36 × 0.14 × 0.03 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3020 independent reflections
Graphite monochromator2273 reflections with I > 2σ(I)
Detector resolution: 9.091 pixels mm-1Rint = 0.083
ϕ and ω scansθmax = 27.6°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 77
Tmin = 0.613, Tmax = 0.746k = 1212
9158 measured reflectionsl = 3229
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H-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 reflectionsΔρmax = 0.55 e Å3
165 parametersΔρmin = 0.43 e Å3
0 restraintsAbsolute structure: Flack (1983), 1222 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.20 (13)
Crystal data top
C4H14N2S22+·C4H4O62V = 1324.46 (12) Å3
Mr = 302.36Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.7281 (3) ŵ = 0.42 mm1
b = 9.3699 (5) ÅT = 120 K
c = 24.6770 (14) Å0.36 × 0.14 × 0.03 mm
Data collection top
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 = 0.746Rint = 0.083
9158 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.139Δρmax = 0.55 e Å3
S = 1.05Δρmin = 0.43 e Å3
3020 reflectionsAbsolute structure: Flack (1983), 1222 Friedel pairs
165 parametersAbsolute structure parameter: 0.20 (13)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.51833 (18)0.61447 (13)0.08424 (4)0.0255 (3)
S20.34754 (18)0.66345 (12)0.15428 (4)0.0239 (3)
N10.0816 (5)0.5917 (3)0.00651 (13)0.0174 (7)
H1A0.05830.67510.02460.021*
H1B0.04620.57160.0140.021*
H1C0.20890.60030.01530.021*
N20.7591 (6)0.7169 (4)0.24357 (13)0.0204 (8)
H2A0.74650.78740.21840.024*
H2B0.90150.72210.25980.024*
H2C0.64530.72770.2690.024*
C10.1205 (7)0.4747 (4)0.04598 (16)0.0190 (9)
H1D0.05760.38480.03080.023*
H1E0.03340.49610.07970.023*
C20.3756 (7)0.4539 (4)0.05965 (17)0.0221 (9)
H2D0.45850.420.02690.027*
H2E0.3890.37860.08760.027*
C30.4820 (7)0.5435 (4)0.20243 (17)0.0220 (9)
H3A0.38840.54450.23610.026*
H3B0.47510.44550.18750.026*
C40.7332 (8)0.5765 (5)0.21688 (17)0.0234 (10)
H4A0.7930.50120.24140.028*
H4B0.82890.57510.18350.028*
O10.9818 (5)0.1548 (3)0.06081 (11)0.0218 (6)
O21.2517 (5)0.0171 (4)0.06015 (11)0.0254 (7)
O30.8148 (5)0.0877 (3)0.15488 (11)0.0247 (7)
H30.77750.14750.1310.03*
O40.7128 (5)0.1369 (3)0.07360 (10)0.0203 (6)
H40.57220.13120.0830.024*
O50.4928 (5)0.2040 (3)0.16279 (11)0.0206 (6)
O60.8146 (5)0.2345 (3)0.21176 (11)0.0223 (7)
C51.0822 (6)0.0469 (4)0.08021 (17)0.0184 (9)
C60.9776 (7)0.0117 (4)0.13273 (15)0.0172 (8)
H61.10540.02930.15950.021*
C70.8542 (7)0.1527 (4)0.11986 (15)0.0166 (8)
H70.97550.22680.11210.02*
C80.7108 (7)0.2013 (4)0.16898 (16)0.0173 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0180 (5)0.0343 (6)0.0244 (5)0.0046 (5)0.0035 (4)0.0065 (5)
S20.0195 (5)0.0218 (5)0.0303 (6)0.0012 (5)0.0043 (5)0.0018 (5)
N10.0146 (15)0.0180 (18)0.0196 (18)0.0008 (15)0.0002 (13)0.0024 (14)
N20.0183 (17)0.0205 (19)0.022 (2)0.0019 (16)0.0014 (14)0.0009 (15)
C10.021 (2)0.017 (2)0.019 (2)0.0051 (19)0.0000 (16)0.0017 (17)
C20.022 (2)0.024 (2)0.020 (2)0.002 (2)0.0015 (17)0.0039 (18)
C30.025 (2)0.017 (2)0.024 (2)0.000 (2)0.0031 (18)0.0021 (17)
C40.024 (2)0.023 (2)0.023 (2)0.0002 (19)0.0017 (17)0.0003 (18)
O10.0215 (14)0.0178 (14)0.0261 (15)0.0036 (14)0.0022 (12)0.0052 (12)
O20.0153 (14)0.0305 (18)0.0303 (17)0.0018 (14)0.0048 (12)0.0062 (14)
O30.0314 (16)0.0200 (15)0.0228 (15)0.0043 (13)0.0017 (13)0.0036 (13)
O40.0175 (13)0.0239 (16)0.0194 (15)0.0046 (13)0.0018 (11)0.0006 (12)
O50.0154 (13)0.0230 (15)0.0234 (15)0.0002 (14)0.0006 (12)0.0013 (12)
O60.0194 (15)0.0268 (17)0.0206 (16)0.0028 (14)0.0015 (12)0.0062 (13)
C50.0134 (17)0.021 (2)0.021 (2)0.0066 (17)0.0043 (16)0.0020 (18)
C60.0165 (19)0.0176 (19)0.017 (2)0.0012 (19)0.0025 (15)0.0034 (16)
C70.0156 (17)0.016 (2)0.019 (2)0.0011 (18)0.0005 (16)0.0016 (16)
C80.023 (2)0.0081 (19)0.021 (2)0.0005 (16)0.0025 (16)0.0013 (16)
Geometric parameters (Å, º) top
S1—C21.817 (4)C3—H3A0.99
S1—S22.0384 (16)C3—H3B0.99
S2—C31.808 (4)C4—H4A0.99
N1—C11.483 (5)C4—H4B0.99
N1—H1A0.91O1—C51.257 (5)
N1—H1B0.91O2—C51.244 (5)
N1—H1C0.91O3—C61.427 (5)
N2—C41.479 (5)O3—H30.84
N2—H2A0.91O4—C71.408 (4)
N2—H2B0.91O4—H40.84
N2—H2C0.91O5—C81.258 (5)
C1—C21.513 (6)O6—C81.251 (5)
C1—H1D0.99C5—C61.530 (5)
C1—H1E0.99C6—C71.532 (5)
C2—H2D0.99C6—H61
C2—H2E0.99C7—C81.534 (5)
C3—C41.514 (6)C7—H71
C2—S1—S2104.70 (15)C4—C3—H3B108.4
C3—S2—S1102.28 (15)S2—C3—H3B108.4
C1—N1—H1A109.5H3A—C3—H3B107.4
C1—N1—H1B109.5N2—C4—C3112.5 (4)
H1A—N1—H1B109.5N2—C4—H4A109.1
C1—N1—H1C109.5C3—C4—H4A109.1
H1A—N1—H1C109.5N2—C4—H4B109.1
H1B—N1—H1C109.5C3—C4—H4B109.1
C4—N2—H2A109.5H4A—C4—H4B107.8
C4—N2—H2B109.5C6—O3—H3109.5
H2A—N2—H2B109.5C7—O4—H4109.5
C4—N2—H2C109.5O2—C5—O1126.3 (4)
H2A—N2—H2C109.5O2—C5—C6118.0 (4)
H2B—N2—H2C109.5O1—C5—C6115.6 (4)
N1—C1—C2112.8 (3)O3—C6—C5110.2 (3)
N1—C1—H1D109O3—C6—C7109.9 (3)
C2—C1—H1D109C5—C6—C7108.4 (3)
N1—C1—H1E109O3—C6—H6109.4
C2—C1—H1E109C5—C6—H6109.4
H1D—C1—H1E107.8C7—C6—H6109.4
C1—C2—S1113.7 (3)O4—C7—C6110.0 (3)
C1—C2—H2D108.8O4—C7—C8111.3 (3)
S1—C2—H2D108.8C6—C7—C8109.8 (3)
C1—C2—H2E108.8O4—C7—H7108.5
S1—C2—H2E108.8C6—C7—H7108.5
H2D—C2—H2E107.7C8—C7—H7108.5
C4—C3—S2115.6 (3)O6—C8—O5124.7 (4)
C4—C3—H3A108.4O6—C8—C7119.1 (4)
S2—C3—H3A108.4O5—C8—C7116.2 (3)
C2—S1—S2—C380.39 (19)O3—C6—C7—O473.5 (4)
N1—C1—C2—S155.3 (4)C5—C6—C7—O447.1 (4)
S2—S1—C2—C162.7 (3)O3—C6—C7—C849.4 (4)
S1—S2—C3—C469.9 (3)C5—C6—C7—C8170.0 (3)
S2—C3—C4—N262.6 (4)O4—C7—C8—O6172.7 (3)
O2—C5—C6—O3169.6 (3)C6—C7—C8—O665.2 (5)
O1—C5—C6—O312.1 (5)O4—C7—C8—O57.6 (5)
O2—C5—C6—C770.0 (4)C6—C7—C8—O5114.5 (4)
O1—C5—C6—C7108.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.911.882.786 (4)175
N1—H1B···O2ii0.911.822.705 (4)162
N1—H1C···O1iii0.911.992.892 (4)170
N2—H2A···O3iv0.911.992.871 (4)161
N2—H2B···O6v0.911.772.684 (4)177
N2—H2C···O5vi0.911.872.727 (4)155
O3—H3···O10.842.092.588 (4)117
O3—H3···S1vii0.842.923.703 (3)156
O4—H4···O50.842.132.613 (4)116
O4—H4···O2viii0.842.22.889 (4)139
Symmetry codes: (i) x1, y+1, z; (ii) x3/2, y+1/2, z; (iii) x1/2, 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, y1, z; (viii) x1, y, z.
(III) Cystamine bis[tartrate(1-)] dihydrate top
Crystal data top
C4H14N2S22+·2C4H5O6·2H2OZ = 4
Mr = 488.48F(000) = 1032
Orthorhombic, P212121Dx = 1.556 Mg m3
Hall symbol: P 2ac 2abMo Kα radiation, λ = 0.71073 Å
a = 7.3425 (5) ŵ = 0.33 mm1
b = 10.5227 (8) ÅT = 120 K
c = 26.983 (2) ÅNeedle, colourless
V = 2084.8 (3) Å30.22 × 0.02 × 0.02 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3527 independent reflections
Graphite monochromator2471 reflections with I > 2σ(I)
Detector resolution: 9.091 pixels mm-1Rint = 0.084
ϕ and ω scansθmax = 25°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 88
Tmin = 0.363, Tmax = 1.0k = 1212
12189 measured reflectionsl = 3230
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.078H-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 reflectionsΔρmax = 0.42 e Å3
271 parametersΔρmin = 0.39 e Å3
6 restraintsAbsolute structure: Flack, (1983), 1396 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.1 (2)
Crystal data top
C4H14N2S22+·2C4H5O6·2H2OV = 2084.8 (3) Å3
Mr = 488.48Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.3425 (5) ŵ = 0.33 mm1
b = 10.5227 (8) ÅT = 120 K
c = 26.983 (2) Å0.22 × 0.02 × 0.02 mm
Data collection top
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 = 1.0Rint = 0.084
12189 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.152Δρmax = 0.42 e Å3
S = 1.09Δρmin = 0.39 e Å3
3527 reflectionsAbsolute structure: Flack, (1983), 1396 Friedel pairs
271 parametersAbsolute structure parameter: 0.1 (2)
6 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.7357 (3)0.03187 (18)0.13999 (8)0.0344 (5)
S20.4847 (3)0.00251 (19)0.16935 (7)0.0334 (5)
N10.6674 (8)0.4198 (6)0.1346 (2)0.0291 (15)
H1A0.77150.43720.11760.035*
H1B0.65130.47890.15880.035*
H1C0.57090.42180.11340.035*
N20.4048 (8)0.2558 (6)0.1048 (2)0.0267 (15)
H2A0.49890.25890.12670.032*
H2B0.42020.3170.08130.032*
H2C0.29810.26930.12110.032*
C10.6814 (12)0.2911 (7)0.1573 (3)0.037 (2)
H1D0.56650.27010.17470.044*
H1E0.78160.28980.18190.044*
C20.7178 (12)0.1946 (6)0.1171 (3)0.035 (2)
H2D0.83260.21730.10.042*
H2E0.61830.19880.09240.042*
C30.3405 (10)0.0263 (7)0.1156 (3)0.0326 (19)
H3A0.21570.04580.12720.039*
H3B0.33480.05440.09680.039*
C40.4004 (11)0.1302 (7)0.0809 (3)0.0323 (19)
H4A0.31620.13330.05220.039*
H4B0.52350.10990.06810.039*
O10.3585 (7)0.6867 (5)0.23471 (19)0.0323 (14)
H10.47240.6810.23290.048*
O20.3594 (7)0.5104 (5)0.1891 (2)0.0407 (14)
O30.0053 (7)0.4852 (5)0.1973 (2)0.0417 (14)
H30.05250.46580.17150.063*
O40.0684 (7)0.7351 (5)0.15084 (18)0.0360 (14)
H40.01550.72930.12980.054*
O50.2776 (7)0.6958 (4)0.15477 (17)0.0295 (13)
O60.2942 (7)0.6986 (5)0.23731 (18)0.0340 (14)
C50.2848 (10)0.5904 (8)0.2128 (3)0.0311 (18)
C60.0774 (10)0.5891 (7)0.2199 (3)0.0275 (18)
H60.05080.58570.25620.033*
C70.0032 (11)0.7149 (7)0.1986 (3)0.0293 (18)
H70.0320.78740.22050.035*
C80.2110 (10)0.7027 (6)0.1977 (3)0.0248 (18)
O70.6171 (6)0.5848 (5)0.0360 (2)0.0323 (13)
O80.6364 (6)0.4089 (5)0.01008 (19)0.0319 (13)
O90.2648 (6)0.6175 (4)0.01331 (17)0.0267 (11)
H90.30610.67260.00620.04*
O100.3270 (7)0.4047 (5)0.08339 (17)0.0352 (13)
H100.24060.41980.10290.053*
O110.0205 (7)0.4277 (5)0.07573 (19)0.0351 (13)
O120.0271 (6)0.3977 (4)0.00650 (19)0.0302 (12)
H120.13960.40960.00330.045*
C90.5497 (9)0.5001 (8)0.0105 (3)0.0290 (17)
C100.3420 (9)0.4979 (7)0.0020 (2)0.0244 (16)
H10A0.31690.4770.03350.029*
C110.2599 (10)0.3952 (7)0.0348 (3)0.0283 (17)
H11A0.29230.30990.0210.034*
C120.0505 (10)0.4091 (7)0.0355 (3)0.0296 (19)
O130.9326 (7)0.7207 (4)0.04844 (18)0.0311 (13)
H13A0.85590.66180.05360.047*
H13B1.02940.68210.04030.047*
O140.1419 (8)0.2478 (5)0.1701 (2)0.0541 (17)
H14A0.23190.25250.150.081*
H14B0.19060.21050.19550.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0365 (11)0.0256 (10)0.0410 (11)0.0013 (9)0.0018 (10)0.0029 (10)
S20.0455 (12)0.0242 (10)0.0305 (9)0.0045 (10)0.0046 (10)0.0016 (9)
N10.025 (3)0.031 (4)0.030 (3)0.001 (3)0.003 (3)0.004 (3)
N20.029 (4)0.023 (4)0.028 (3)0.002 (3)0.003 (3)0.003 (3)
C10.044 (5)0.035 (5)0.032 (5)0.003 (4)0.001 (4)0.001 (4)
C20.054 (6)0.015 (4)0.035 (4)0.001 (4)0.004 (4)0.003 (3)
C30.042 (5)0.022 (5)0.034 (4)0.001 (4)0.003 (4)0.007 (4)
C40.040 (5)0.023 (4)0.034 (5)0.008 (4)0.002 (4)0.003 (4)
O10.028 (3)0.034 (3)0.034 (3)0.002 (3)0.003 (2)0.009 (3)
O20.039 (3)0.030 (3)0.053 (4)0.001 (3)0.006 (3)0.011 (3)
O30.032 (3)0.035 (3)0.059 (3)0.007 (3)0.001 (3)0.009 (3)
O40.026 (3)0.050 (4)0.032 (3)0.001 (3)0.002 (2)0.011 (3)
O50.035 (3)0.028 (3)0.025 (3)0.003 (2)0.002 (2)0.001 (2)
O60.024 (3)0.048 (4)0.030 (3)0.005 (3)0.010 (3)0.005 (3)
C50.032 (5)0.037 (5)0.025 (4)0.001 (4)0.004 (4)0.002 (4)
C60.034 (5)0.021 (4)0.027 (4)0.002 (4)0.000 (3)0.000 (4)
C70.029 (5)0.023 (4)0.036 (4)0.001 (4)0.002 (4)0.008 (4)
C80.033 (5)0.008 (4)0.033 (4)0.005 (3)0.002 (4)0.001 (3)
O70.026 (3)0.017 (3)0.054 (4)0.000 (2)0.000 (3)0.008 (3)
O80.035 (3)0.021 (3)0.039 (3)0.005 (2)0.005 (3)0.009 (3)
O90.029 (3)0.019 (3)0.032 (3)0.006 (2)0.002 (2)0.005 (2)
O100.038 (3)0.043 (3)0.026 (3)0.006 (3)0.003 (3)0.007 (3)
O110.026 (3)0.040 (3)0.040 (3)0.001 (3)0.003 (3)0.008 (3)
O120.024 (3)0.025 (3)0.042 (3)0.002 (2)0.001 (3)0.003 (3)
C90.034 (4)0.025 (4)0.028 (4)0.002 (4)0.005 (4)0.008 (4)
C100.032 (4)0.018 (4)0.024 (4)0.002 (3)0.002 (3)0.003 (4)
C110.022 (4)0.029 (4)0.034 (4)0.001 (4)0.005 (4)0.002 (4)
C120.038 (5)0.009 (4)0.042 (5)0.005 (3)0.006 (4)0.006 (4)
O130.038 (3)0.016 (3)0.039 (3)0.004 (2)0.002 (3)0.002 (3)
O140.056 (4)0.044 (4)0.063 (4)0.010 (3)0.008 (3)0.008 (4)
Geometric parameters (Å, º) top
S1—C21.825 (7)O4—H40.8401
S1—S22.038 (3)O5—C81.261 (8)
S2—C31.813 (7)O6—C81.231 (8)
N1—C11.490 (9)C5—C61.535 (10)
N1—H1A0.91C6—C71.560 (10)
N1—H1B0.9101C6—H61
N1—H1C0.9099C7—C81.531 (10)
N2—C41.471 (9)C7—H71
N2—H2A0.91O7—C91.229 (8)
N2—H2B0.9099O8—C91.278 (8)
N2—H2C0.91O9—C101.414 (8)
C1—C21.511 (9)O9—H90.8401
C1—H1D0.99O10—C111.405 (8)
C1—H1E0.99O10—H100.84
C2—H2D0.99O11—C121.220 (9)
C2—H2E0.99O12—C121.275 (9)
C3—C41.506 (10)O12—H120.84
C3—H3A0.99C9—C101.542 (9)
C3—H3B0.99C10—C111.522 (9)
C4—H4A0.99C10—H10A1
C4—H4B0.99C11—C121.544 (10)
O1—C51.292 (9)C11—H11A1
O1—H10.84O13—H13A0.8485
O2—C51.191 (8)O13—H13B0.8473
O3—C61.392 (9)O14—H14A0.8558
O3—H30.8399O14—H14B0.8663
O4—C71.407 (8)
C2—S1—S2103.5 (3)O2—C5—O1127.5 (7)
C3—S2—S1104.0 (3)O2—C5—C6121.1 (7)
C1—N1—H1A109.5O1—C5—C6111.4 (7)
C1—N1—H1B109.5O3—C6—C5112.6 (6)
H1A—N1—H1B109.5O3—C6—C7109.8 (6)
C1—N1—H1C109.5C5—C6—C7108.8 (6)
H1A—N1—H1C109.5O3—C6—H6108.5
H1B—N1—H1C109.5C5—C6—H6108.5
C4—N2—H2A109.5C7—C6—H6108.5
C4—N2—H2B109.5O4—C7—C8111.8 (6)
H2A—N2—H2B109.5O4—C7—C6108.9 (6)
C4—N2—H2C109.4C8—C7—C6108.2 (6)
H2A—N2—H2C109.5O4—C7—H7109.3
H2B—N2—H2C109.5C8—C7—H7109.3
N1—C1—C2109.1 (6)C6—C7—H7109.3
N1—C1—H1D109.9O6—C8—O5127.1 (7)
C2—C1—H1D109.9O6—C8—C7119.0 (6)
N1—C1—H1E109.9O5—C8—C7113.9 (6)
C2—C1—H1E109.9C10—O9—H9109.5
H1D—C1—H1E108.3C11—O10—H10109.5
C1—C2—S1113.6 (5)C12—O12—H12109.5
C1—C2—H2D108.8O7—C9—O8125.9 (7)
S1—C2—H2D108.8O7—C9—C10119.5 (7)
C1—C2—H2E108.8O8—C9—C10114.6 (7)
S1—C2—H2E108.8O9—C10—C11110.3 (5)
H2D—C2—H2E107.7O9—C10—C9110.5 (6)
C4—C3—S2115.3 (5)C11—C10—C9108.4 (6)
C4—C3—H3A108.4O9—C10—H10A109.2
S2—C3—H3A108.4C11—C10—H10A109.2
C4—C3—H3B108.4C9—C10—H10A109.2
S2—C3—H3B108.4O10—C11—C10110.7 (6)
H3A—C3—H3B107.5O10—C11—C12109.3 (6)
N2—C4—C3112.7 (6)C10—C11—C12109.6 (6)
N2—C4—H4A109.1O10—C11—H11A109.1
C3—C4—H4A109.1C10—C11—H11A109.1
N2—C4—H4B109.1C12—C11—H11A109.1
C3—C4—H4B109.1O11—C12—O12128.0 (7)
H4A—C4—H4B107.8O11—C12—C11116.9 (7)
C5—O1—H1109.5O12—C12—C11115.1 (7)
C6—O3—H3109.5H13A—O13—H13B104.5
C7—O4—H4109.5H14A—O14—H14B102
C2—S1—S2—C375.3 (4)O4—C7—C8—O58.9 (9)
N1—C1—C2—S1179.4 (5)C6—C7—C8—O5111.0 (7)
S2—S1—C2—C162.4 (6)O7—C9—C10—O917.5 (9)
S1—S2—C3—C456.8 (6)O8—C9—C10—O9163.4 (6)
S2—C3—C4—N261.0 (8)O7—C9—C10—C11103.5 (8)
O2—C5—C6—O31.6 (11)O8—C9—C10—C1175.6 (7)
O1—C5—C6—O3179.1 (6)O9—C10—C11—O1073.6 (7)
O2—C5—C6—C7120.4 (8)C9—C10—C11—O1047.5 (8)
O1—C5—C6—C758.9 (8)O9—C10—C11—C1247.0 (8)
O3—C6—C7—O475.0 (7)C9—C10—C11—C12168.2 (6)
C5—C6—C7—O448.6 (8)O10—C11—C12—O111.4 (9)
O3—C6—C7—C846.7 (8)C10—C11—C12—O11120.1 (7)
C5—C6—C7—C8170.4 (6)O10—C11—C12—O12177.8 (6)
O4—C7—C8—O6172.1 (6)C10—C11—C12—O1260.8 (8)
C6—C7—C8—O667.9 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O11i0.911.92.789 (8)164
N1—H1B···O20.912.322.861 (8)118
N1—H1B···O5i0.912.342.983 (8)127
N1—H1C···O100.911.972.859 (7)164
N2—H2A···O5ii0.911.872.741 (8)160
N2—H2B···O7iii0.912.162.948 (8)145
N2—H2B···O9iii0.912.272.987 (7)136
N2—H2C···O4iii0.911.872.767 (7)169
O1—H1···O6i0.841.732.554 (7)167
O3—H3···O140.842.392.819 (8)113
O4—H4···O50.842.072.576 (7)118
O4—H4···O13iv0.842.232.941 (7)143
O9—H9···O13v0.841.852.682 (7)171
O10—H10···O110.842.052.572 (7)119
O12—H12···O8iv0.841.662.476 (7)165
O13—H13A···O70.851.992.743 (7)148
O13—H13B···O9i0.851.992.833 (7)170
O14—H14A···O100.862.513.170 (8)135
O14—H14B···O6vi0.871.972.786 (8)156
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1, z; (iii) x, y1, z; (iv) x1, y, z; (v) x1/2, y+3/2, z; (vi) x, y1/2, z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC2H8NS+·C4H5O6·H2OC4H14N2S22+·C4H4O62C4H14N2S22+·2C4H5O6·2H2O
Mr245.25302.36488.48
Crystal system, space groupOrthorhombic, P212121Orthorhombic, P212121Orthorhombic, P212121
Temperature (K)120120120
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)
V3)1089.73 (8)1324.46 (12)2084.8 (3)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.320.420.33
Crystal size (mm)0.84 × 0.12 × 0.10.36 × 0.14 × 0.030.22 × 0.02 × 0.02
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2007)
Multi-scan
(SADABS; Sheldrick, 2007)
Multi-scan
(SADABS; Sheldrick, 2007)
Tmin, Tmax0.620, 0.7460.613, 0.7460.363, 1.0
No. of measured, independent and
observed [I > 2σ(I)] reflections
9253, 2485, 2099 9158, 3020, 2273 12189, 3527, 2471
Rint0.0510.0830.084
(sin θ/λ)max1)0.6510.6530.595
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 reflections248530203527
No. of parameters143165271
No. of restraints006
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.250.55, 0.430.42, 0.39
Absolute structureFlack (1983), 1027 Friedel pairsFlack (1983), 1222 Friedel pairsFlack, (1983), 1396 Friedel pairs
Absolute structure parameter0.04 (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).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O6i0.841.662.4885 (18)169.3
O3—H3···O7ii0.842.132.819 (2)139
O4—H4···O70.841.92.742 (2)177.2
N1—H1A···O3iii0.9122.813 (2)148.2
N1—H1B···O2iv0.911.922.814 (2)165.9
N1—H1C···O5i0.911.892.772 (2)161.8
N1—H1C···O4i0.912.32.850 (2)118.4
O7—H7A···O5i0.871.892.7455 (19)168.1
O7—H7B···O6v0.772.142.8910 (19)166.4
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1/2, 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.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.911.882.786 (4)174.9
N1—H1B···O2ii0.911.822.705 (4)162.2
N1—H1C···O1iii0.911.992.892 (4)170.2
N2—H2A···O3iv0.911.992.871 (4)161.3
N2—H2B···O6v0.911.772.684 (4)177.1
N2—H2C···O5vi0.911.872.727 (4)155.3
O3—H3···O10.842.092.588 (4)117.4
O3—H3···S1vii0.842.923.703 (3)156.4
O4—H4···O50.842.132.613 (4)116.1
O4—H4···O2viii0.842.22.889 (4)139.4
Symmetry codes: (i) x1, y+1, z; (ii) x3/2, y+1/2, z; (iii) x1/2, 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, y1, z; (viii) x1, y, z.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O11i0.911.92.789 (8)164.4
N1—H1B···O20.912.322.861 (8)118.1
N1—H1B···O5i0.912.342.983 (8)127.1
N1—H1C···O100.911.972.859 (7)164.2
N2—H2A···O5ii0.911.872.741 (8)159.8
N2—H2B···O7iii0.912.162.948 (8)144.7
N2—H2B···O9iii0.912.272.987 (7)135.7
N2—H2C···O4iii0.911.872.767 (7)169
O1—H1···O6i0.841.732.554 (7)167.4
O3—H3···O140.842.392.819 (8)112.6
O4—H4···O50.842.072.576 (7)118.3
O4—H4···O13iv0.842.232.941 (7)142.5
O9—H9···O13v0.841.852.682 (7)170.6
O10—H10···O110.842.052.572 (7)119.3
O12—H12···O8iv0.841.662.476 (7)164.8
O13—H13A···O70.851.992.743 (7)147.5
O13—H13B···O9i0.851.992.833 (7)170
O14—H14A···O100.862.513.170 (8)134.9
O14—H14B···O6vi0.871.972.786 (8)156.3
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1, z; (iii) x, y1, z; (iv) x1, y, z; (v) x1/2, y+3/2, z; (vi) x, y1/2, z+1/2.
 

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