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A planar conformation of 1,3-thia­zolidine-2-thione (TZDTH), C3H5NS2, was crystallized for the first time. The new triclinic polymorph (P\overline{1}) obtained was compared in terms of its intra- and inter­molecular geometry with three previous reports of a monoclinic polymorph (P21/n). The packing is based on centrosymmetric dimers of TZDTH, linked by N—H...S hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106002484/fa1178sup1.cif
Contains datablocks global, 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106002484/fa11782sup2.hkl
Contains datablock 2

CCDC reference: 603189

Comment top

The heterocyclic thioamide 1,3-thiazolidine-2-thione, (2), exists in tautomeric equilibrium with its thiol form, 2-mercaptothiazoline, (1) (Raper et al., 1983). Besides the thiol–thione tautomerism, this molecular system can also be de-protonated to form the thiolate anion, (5). In the solid state, the most stable form is the thione, (2), as evidenced either by IR spectroscopy (Flakus et al., 2002) or by X-ray diffraction (Raper et al., 1983; Zhou et al., 1984; Flakus et al., 2002).

The tautomeric and canonic forms (1)–(5) are versatile ligands, as highlighted by the fact that 81 metal complex structures containing these ligands are deposited in the Cambridge Structural Database (CSD; updated August 2005; Allen, 2002). It is important to emphasize the pH-dependent coordination chemistry of these ligands. In neutral and acid media, where the thione tautomer (2) is the most stable form, usually the exocyclic S atom and the N atom are available as donor atoms (e.g. Rajalingam et al., 2001; Bell et al., 2001; Popovic et al., 2002), whereas in alkaline media, it is the S—C—N component of the thiolate anion that is involved in coordination to metals (e.g. Shi & Jiang, 2002; Du et al., 2002; Brandt & Sheldrick, 1998). An interesting complex with copper containing both forms (2) and (5) as donors has been observed by Raper et al. (1998). Form (3) has been observed by Abram et al. (1998) in an Au3+ complex.

The 1,3-thiazolidine-2-thione structure has been determined previously by X-ray diffraction as belonging to the space group P21/n (Raper et al., 1983; Zhou et al., 1984; Flakus et al., 2002) and in the present study as a new P1 triclinic polymorph. The cell parameters observed by Flakus et al. (2002) for the P21/n polymorph are a = 13.484 (5) Å, b = 5.452 (2) Å, c = 13.644 (5) Å and β = 94.71 (2)°. These values are very similar to those observed by Raper et al. (1983) and Zhou et al. (1984).

Fig. 1 shows an ORTEP-3 (Farrugia, 1997) view of (2). Pairs of centrosymmetrically related molecules linked by N—H···S hydrogen bonds are formed, as observed also for the P21/n polymorph. However, the new P1 polymorph has just one molecule in the asymmetric unit (Z = 2), whereas for the P21/n polymorph, there are two molecules in the asymmetric unit.

The main geometric parameters are given in Table 1. The intramolecular conformation was analyzed using Mogul (Bruno et al., 2004), a knowledge base of molecular geometry derived from the CSD. This study showed that all bond lengths and bond angles are in agreement with the expected values. Using Raper's arguments (reference?), the C—S1 bond distance and the localization of the proton at the N position both agree with the presence of (2), the thione form, instead of (1). Although the geometric parameters of the two polymorphs are very similar in terms of bond lengths and angles, comparison of these polymorphs by the Kabsch (1976) method showed them to be significantly different in terms of torsion angles. Fig. 2 shows the superposition of the two polymorphs, P1 (this work) and P21/n [Raper (Raper et al., 1983), Zhou (Zhou et al., 1984) and Flakus (Flakus et al., 2002)]. Since the asymmetric unit has two independent molecules in the monoclinic polymorph, the molecules compared with our P1 polymorph were labeled as 1 and 2 in Fig. 2. The deviations between analogous atoms given by the Kabsch method are presented in Table 2. The largest deviation between analogs takes place at methylene atom C2 [mean value equal to 0.25 (3) Å], except for Raper-2, for which the largest deviations occur between the N1 (0.51 Å) and S2 (0.29 Å) analogs. In other words, the main difference between the two polymorphs is in terms of their planarity. In the P1 polymorph, the molecule is flat; considering the non-H atoms, the largest deviation from the least-squares plane through all atoms in the molecule is 0.008 (1) Å for atom C2. On the other hand, in the P21/n polymorph the molecule is non-planar. A conformational analysis of (2) in the monoclinic form shows that the ring adopts an envelope conformation, with atom C2 in the flap position. The one exception is the Raper-2 molecule, which has a more distorted conformation (Fig. 2). Raper et al. (1983) argue that the non-planarity is due to the presence of methylene C atoms, which showed the largest deviations (from 0.11 to 0.18 Å) from the least-squares plane through the thioamide portion (S2/C3/S1/N1) of the molecule.

Fig. 3 shows the packing of (2). The main intermolecular motif is the zero-dimensional network-forming dimer linked by N—H···S hydrogen bonds. The dimer forms parallel ribbons along the [010] direction. The dimers are also present in the monoclinic polymorph. However, in P21/n they do not form ribbons; they are stacked parallel to [010]. Despite the packing differences, the hydrogen-bond geometry mediating the dimers in P1 (Table 3) is very similar to that observed by Flakus et al. (2002).

Experimental top

We have been preparing soft analogs of the trispyrazolylborate ligand, [H(pz)3], Tp, such as hydrotris(2-mercaptothiazolyl)borate (Mt; Soares, Silva et al., 2004), hydrotris(2-methimazolyl)borate (Tm; Soares, Silva et al., 2004; Soares & Silva, 2002) and tetrakis(2-mercaptothiazolyl)borate (Mte; Soares, Menezes et al., 2004), as well trying to study their coordination chemistry. In an attempt to obtain a cobalt complex having Mte as supporting ligand, the appropriate reagents in a 1:1 molar ratio were placed in tetrahydrofuran (not dried) at room temperature. After 12 h, a green solution and a blue solid remained. The solution was filtered and was left at room temperature for three weeks, after which colorless crystals of (2) were obtained, together the desired complex.

Refinement top

H atoms of the methylene group were positioned stereochemically and were refined with constrained displacement parameters [Uiso(H) = 1.2Ueq(Cmethylene), with methylene C—H distances of 0.99 Å]. The H atom of the amine group was located by difference Fourier synthesis and was refined isotropically.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. An ORTEP-3 (Farrugia, 1997) view of (2), showing the atom labeling and the dimer linked by N—H···S hydrogen bonds (dashed lines). Displacement ellipsoids are shown at the 50% probability level. [Symmetry code: (i) −x − 1, −y, z + 1.]
[Figure 2] Fig. 2. An ORTEP-3 (Farrugia, 1997) view of (2), showing the superposition of the P1 (black) and P21/n (gray) polymorphs.
[Figure 3] Fig. 3. The packing of (2), viewed along the [010] direction, showing the dimer formed by hydrogen bonds and the ribbons formed by parallel dimers.
1,3-thiazolidine-2-thione top
Crystal data top
C3H5NS2Z = 2
Mr = 119.22F(000) = 124
Triclinic, P1Dx = 1.586 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.4845 (2) ÅCell parameters from 5798 reflections
b = 6.4997 (3) Åθ = 0.4–27.5°
c = 7.6758 (3) ŵ = 0.90 mm1
α = 84.121 (2)°T = 120 K
β = 73.816 (3)°Needle, colorless
γ = 71.792 (3)°0.08 × 0.04 × 0.02 mm
V = 249.59 (2) Å3
Data collection top
Nonius KappaCCD
diffractometer
880 independent reflections
Radiation source: fine-focus sealed tube781 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromatorRint = 0.073
Detector resolution: 9 pixels mm-1θmax = 25.0°, θmin = 2.8°
ϕ scans and ω scans with κ offsetsh = 66
Absorption correction: multi-scan
(Blessing, 1995)
k = 77
Tmin = 0.919, Tmax = 0.984l = 99
7240 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.026 w = 1/[σ2(Fo2) + (0.027P)2 + 0.1265P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.063(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.26 e Å3
880 reflectionsΔρmin = 0.20 e Å3
59 parameters
Crystal data top
C3H5NS2γ = 71.792 (3)°
Mr = 119.22V = 249.59 (2) Å3
Triclinic, P1Z = 2
a = 5.4845 (2) ÅMo Kα radiation
b = 6.4997 (3) ŵ = 0.90 mm1
c = 7.6758 (3) ÅT = 120 K
α = 84.121 (2)°0.08 × 0.04 × 0.02 mm
β = 73.816 (3)°
Data collection top
Nonius KappaCCD
diffractometer
880 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
781 reflections with I > 2σ(I)
Tmin = 0.919, Tmax = 0.984Rint = 0.073
7240 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.063H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.26 e Å3
880 reflectionsΔρmin = 0.20 e Å3
59 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.33251 (9)0.27135 (7)0.38475 (6)0.02432 (17)
S20.20397 (10)0.03245 (8)0.16268 (7)0.02918 (18)
N10.1418 (3)0.1560 (2)0.3241 (2)0.0219 (4)
C30.1110 (4)0.0391 (3)0.3000 (2)0.0197 (4)
C20.3062 (4)0.2574 (3)0.1302 (3)0.0252 (4)
H2A0.34920.28920.00020.03*
H2B0.46590.32880.17470.03*
C10.0745 (4)0.3402 (3)0.2374 (3)0.0302 (5)
H1A0.01530.41050.1550.036*
H1B0.13060.44810.33030.036*
H10.282 (5)0.175 (4)0.390 (3)0.032 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0222 (3)0.0192 (3)0.0273 (3)0.0048 (2)0.0005 (2)0.0026 (2)
S20.0232 (3)0.0230 (3)0.0353 (3)0.0096 (2)0.0066 (2)0.0050 (2)
N10.0180 (8)0.0207 (9)0.0243 (8)0.0075 (7)0.0009 (7)0.0009 (7)
C30.0185 (9)0.0230 (10)0.0173 (9)0.0057 (8)0.0046 (7)0.0002 (7)
C20.0238 (10)0.0227 (11)0.0232 (10)0.0036 (8)0.0005 (8)0.0010 (8)
C10.0239 (11)0.0210 (11)0.0408 (12)0.0054 (8)0.0005 (9)0.0060 (9)
Geometric parameters (Å, º) top
S1—C31.671 (2)N1—H10.83 (2)
S2—C31.745 (2)C2—H2A0.99
S2—C21.812 (2)C2—H2B0.99
N1—C31.319 (2)C1—H1A0.99
N1—C11.456 (2)C1—H1B0.99
C2—C11.528 (3)
C3—S2—C293.76 (9)C2—C1—H1B110.1
C3—N1—C1119.46 (17)H1A—C1—H1B108.4
N1—C3—S1127.31 (15)C1—C2—H2A110.3
N1—C3—S2111.40 (14)S2—C2—H2A110.3
S1—C3—S2121.28 (11)C1—C2—H2B110.3
C1—C2—S2107.26 (13)S2—C2—H2B110.3
N1—C1—C2108.11 (15)H2A—C2—H2B108.5
N1—C1—H1A110.1C3—N1—H1120.8 (16)
C2—C1—H1A110.1C1—N1—H1119.7 (16)
N1—C1—H1B110.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.83 (3)2.53 (3)3.359 (2)172 (2)
Symmetry code: (i) x1, y, z+1.

Experimental details

Crystal data
Chemical formulaC3H5NS2
Mr119.22
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)5.4845 (2), 6.4997 (3), 7.6758 (3)
α, β, γ (°)84.121 (2), 73.816 (3), 71.792 (3)
V3)249.59 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.90
Crystal size (mm)0.08 × 0.04 × 0.02
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.919, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
7240, 880, 781
Rint0.073
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.063, 1.07
No. of reflections880
No. of parameters59
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.20

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) top
S1—C31.671 (2)N1—C31.319 (2)
S2—C31.745 (2)N1—C11.456 (2)
S2—C21.812 (2)C2—C11.528 (3)
C3—S2—C293.76 (9)S1—C3—S2121.28 (11)
C3—N1—C1119.46 (17)C1—C2—S2107.26 (13)
N1—C3—S1127.31 (15)N1—C1—C2108.11 (15)
N1—C3—S2111.40 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.83 (3)2.53 (3)3.359 (2)172 (2)
Symmetry code: (i) x1, y, z+1.
Deviations (Å) between analogous atoms given by the Kabsch (1976) method. Atom labeling as in Figure 2. top
AnalogsRaper-1Raper-2Zhou-1Zhou-2Flakus-1Flakus-2
C10.04960.01450.03100.06500.07130.0639
C20.23580.02480.20840.22630.28250.2822
C30.01220.02100.01890.01410.01840.0180
N10.05880.50790.03510.07540.08120.0721
S10.03140.01010.02090.03850.04620.0418
S20.02090.28540.01870.02350.02090.0187
 

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