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The structures of 5-(2-hy­droxy­ethyl)-2-[(pyridin-2-yl)amino]-1,3-thia­zolidin-4-one, C10H11N3O2S, (I), and ethyl 4-[(4-oxo-1,3-thia­zolidin-2-yl)amino]­benzoate, C12H12N2O3S, (II), which are identical to the entries with refcodes GACXOZ [Váňa et al. (2009). J. Heterocycl. Chem. 46, 635–639] and HEGLUC [Behbehani & Ibrahim (2012). Mol­ecules, 17, 6362–6385], respectively, in the Cambridge Structural Database [Allen (2002). Acta Cryst. B58, 380–388], have been redetermined at 130 K. This structural study shows that both investigated compounds exist in their crystal structures as the tautomer with the carbonyl–imine group in the five-membered heterocyclic ring and an exocyclic amine N atom, rather than the previously reported tautomer with a secondary amide group and an exocyclic imine N atom. The physico­chemical and spectroscopic data of the two investigated compounds are the same as those of GACXOZ and HEGLUC, respectively. In the thia­zolidin-4-one system of (I), the S and chiral C atoms, along with the hy­droxy­ethyl group, are disordered. The thia­zolidin-4-one fragment takes up two alternative locations in the crystal structure, which allows the mol­ecule to adopt R and S configurations. The occupancy factors of the disordered atoms are 0.883 (2) (for the R configuration) and 0.117 (2) (for the S configuration). In (I), the main factor that determines the crystal packing is a system of hydrogen bonds, involving both strong N—H...N and O—H...O and weak C—H...O hydrogen bonds, linking the mol­ecules into a three-dimensional hydrogen-bond network. On the other hand, in (II), the mol­ecules are linked via N—H...O hydrogen bonds into chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614015162/wq3065sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015162/wq3065Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015162/wq3065IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614015162/wq3065Isup4.cml
CML file for (I)

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614015162/wq3065IIsup5.cml
CML file for (II)

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614015162/wq3065sup6.pdf
Photochemical and spectroscopic data for (I) and (II)

CCDC references: 1010769; 1010770

Introduction top

1,3-Thia­zolidin-4-one derivatives are a well known class of patented drugs, among which are, for example, hypoglycaemic thia­zolidinediones (pioglitazone and its analogues), aldose redu­ctase inhibitors (epalrestat), anti-inflammatory agents (darbufelone) and new-generation diuretics (etozoline). In modern medicinal chemistry, the thia­zolidinone core is a powerful biophore for the rational design of `drug-like' molecules. Modern research into the pharmacological potential of 1,3-thia­zolidin-4-ones has allowed the establishment of a wide spectrum of pharmacological activities, including anti­cancer, anti-inflammatory, anti­viral, anti­parasitic, anti­microbial and anti­oxidant (Lesyk & Zimenkovsky, 2004; Lesyk et al., 2011).

It is worth noting that studies regarding amino–imino tautomerism in 2-amino­(imino)-1,3-thia­zolidin-4-one derivatives have been carried out continually for almost 50 years. The investigations have been performed on crystalline and liquid phases using different spectroscopic techniques, e.g. IR, UV, 1H and 13C NMR, or sometimes with calculations in quantum chemistry. X-ray crystallography is not commonly used among the analytical methods applied to structural studies concerning tautomerism. In the Cambridge Structural Database (CSD, Version 5.35; Allen, 2002), we found only 21 structures with the amine form (refcodes EKELEL FIVPIJ, FOWQOY, IHUFAS, IMPTHA01, IMPTHA12, IMTAZO01, INMTZO, JOBGOW, KUKZUM, PACPIU, PATAZO, PTHAZO10, SALYOT, SINQOW, SINQUC, TEBDAH, ULACAM, VELBEU, WOSMAS and YUQCAP) and 16 with the imino form (refcodes EHITZO, GACXOZ, HEGLUC, HEGMAJ, HEGMEN, HEGMIR, HEGMOX, IMTAZO, IOTAGP, IXTAZD10, RIPMOT, ROMXUN, SOHHIH, ULACEQ, VAMPUW and YARLIN), the latter set including two structures with an incorrectly specified tautomeric form.

As part of a programme aimed at the development of new biologically active compounds, we have prepared 5-(2-hy­droxy­ethyl)-2-[(pyridin-2-yl)amino]-1,3-thia­zolidin-4-one, (I) [CSD refcode GACXOZ; Váňa et al., 2009], and ethyl 4-[(4-oxo-1,3-thia­zolidin-2-yl)amino]­benzoate, (II) [CSD refcode HEGLUC; Behbehani & Ibrahim, 2012] (Scheme 1), and have made corrections to the inter­pretations of their previously published structures. According to the previous reports, the investigated compounds exist in tautomeric form A2, with a secondary amide group in the five-membered heterocyclic ring and an exocyclic imine N atom (see Scheme 2).

Experimental top

Synthesis and crystallization top

The title compounds were synthesized by methods used for obtaining 2-amino­(imino)-1,3-thia­zolidin-4-one derivatives (Subtel'na et al., 2010; Geronikaki et al., 2008; Ostapiuk et al., 2012). Compound (I) was prepared by the [2+3]-cyclo­condensation reaction of 3-bromo­tetra­hydro­furan-2-one (α-bromo-γ-butyrolactone) with 1-(pyridin-2-yl)thio­urea in the presence of fused sodium acetate in refluxing ethanol. Compound (II) was synthesized through cyclo­condensation of ethyl 4-(2-chloro­acetyl­amino)­benzoate and ammonium thio­cyanate in ethanol (Behbehani & Ibrahim, 2012). It is known that the above-mentioned reactions do not stop at the nucleophilic substitution stage (Geronikaki et al., 2008; Ostapiuk et al., 2012). The inter­mediate α-thio­cyanato­amide undergoes spontaneous cyclization/rearrangement to give the thia­zolidin-4-one derivative, (II).

The physicochemical and spectroscopic data of (I) and (II) are the same as for GACXOZ and HEGLUC, respectively. Crystals suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of solutions in methanol [for (I)] and di­methyl­formamide [for (II)].

Refinement top

For both (I) and (II), N-bound H atoms were obtained from difference Fourier maps and refined freely. The remaining H atoms were positioned geometrically and refined within the riding-model approximation, with methyl C—H = 0.98, methyl­ene C—H = 0.99, methine C—H = 1.00, Csp2 C—H = 0.95 and O—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C,O) for methyl and hy­droxy H atoms. The methyl groups were refined as rigid groups, which were allowed to rotate. Non-H atoms of the disordered part of the molecule of (I) were obtained from difference Fourier maps. During refinement, the EADP instruction (SHELXL2014; Sheldrick, 2008) was used to constrain the displacement ellipsoids of the atoms in the alternative positions a and b. Bond distances between corresponding atoms were restrained with a SADI instruction. The H atoms of the OH groups of the hy­droxy­ethyl residues in positions a and b were separated in an arbitrary manner (DFIX instruction) with a distance of 0.61 Å. [Please rephrase without using software-specific terms.]

Results and discussion top

Tautomeric forms top

Our revision of the X-ray studies has shown that, in their crystal structures, compounds (I) and (II) adopt tautomeric form A1 rather than the previously suggested form A2 (Scheme 2 and Figs. 1 and 2). In both structures, the H atom was located at the exocyclic N atom (N6). This observation for (II) is supported by the presence of N6—H6···O18i hydrogen bonds (Table 2 and Fig. 3), in which atom N6 acts as a proton donor and carbonyl atom O18 as a proton acceptor. The formation of this N—H···O hydrogen bond is promoted by the anti­periplanar conformation of the C2—N3 and N6—H6 bonds [torsion angle N3—C2—N6—H6 = 180 (2)°].

In (I), the presence of N6—H6···N3i hydrogen bonds between the amidine groups (Table 3 and Fig. 4a) may lead to ambiguity about the amine/imine character of atoms N3 and N6. It is known that the presence of N—H···N hydrogen-bond contacts enhances the resonance effect, which is significant even for unassociated molecules. Therefore, one may be inclined to think that, for structure (I) forming hydrogen-bonded dimers, both tautomeric forms are possible, and the C2—N3 and C2—N6 bond lengths do not provide much useful information for solving this problem because of resonance inter­actions which render their lengths similar regardless of the tautomeric form. However, atom H6 was located and refined at this position and, in addition, analysis of the C2—N3 and C2—N6 bond lengths performed for tautomeric forms A1 and A2 did not confirm these suppositions.

The average C2—N3 and C2—N6 bond lengths in 20 2-amino-1,3-thia­zolidin-4-one derivatives deposited in the CSD and exhibiting the A1 tautomeric form are similar and adopt values of 1.325 (1) and 1.315 (2) Å, respectively (refcodes EKELEL, FIVPIJ, FOBQOY, IHUFAS, IMPTHA12, IMTAZO01, INMTZO, JOBGOW, KUKZUM, PACPIU, PTHAZO10, SALYOT, SINQOW, SINQUC, TEBDAH, ULACAM, VELBEU, VEQFAA, WOSMAS and YUQCAP; R < 0.07). These mean C2—N3 and C2—N6 bond lengths are inter­mediate between the lengths of single and double C—N bonds. In comparison with the usual literature CN double-bond value of 1.279 (1) Å (Allen et al., 1987), they are lengthened by about 33 and 16σ, respectively. On the other hand, they are shortened by about 26 and 24σ, respectively, compared with the mean value for a Csp2—N single-bond length [1.383 (2) Å]. This latter value was obtained from 117 structures of 2-imine-1,3-thia­zolidin-4-one derivatives substituted at N3 (R <0.07). Based on six records revealing the A2 tautomeric form, the average C2—N3 and C2—N6 bond lengths were calculated as 1.374 (3) and 1.280 (2) Å, respectively (refcodes EHITZO, HEGMAJ, HEGMEN, HEGMIR, HEGMOX and VAMPUV; R < 0.07), which are clearly different from one another. The former is similar to the normal Csp2—N single-bond length in heterocyclic rings, while the latter is close to a normal CN double-bond length.

Our observations thus indicate an unequal resonance effect in tautomeric forms A1 and A2, which allows the use of the C—N bond values to distinguish the forms. Crystal structure analysis of (I) and (II) shows that the inter­atomic lengths C2—N3 and C2—N6 [1.3256 (17) and 1.3385 (19) Å in (I), and 1.3182 (15) and 1.3282 (15) Å in (II)] have comparable values, which is a typical feature of tautomeric form A1.

We thus submit that the original tautomeric assignments of GACXOZ and HEGLUC were incorrect, and propose they both be reassigned to the A1 form, supported by the evidence presented here. From the comparison of (I)/GACXOZ and (II)/HEGLUC it is clear that the molecules in pairs have the same geometry and, what is particularly important, very similar C2—N3 and C2—N6 bond lengths. In the first pair, the bond lengths are 1.326/1.322 and 1.338/1.337 Å, while in the second pair they have values of 1.318/1.308 and 1.328/1.333 Å, respectively. The structural differences relate to the position of the mobile N—H hydrogen only. We think that incorrect localization of the H atom at the endocyclic and not at the exocyclic N atom in GACXOZ and HEGLUC is most likely a result of the fact that the H atoms bonded to N atoms were positioned geometrically and were treated using a riding model, with the Uiso(H) parameter calculated and not refined. If Uiso(H) had been refined by the authors of the earlier papers, the mistake would have been noticed and corrected.

Further details of the structural analysis top

Some atoms in the crystal structure of (I) are disordered. This observation concerns the part of the molecule that includes atoms S1, C5, C14, C15 and O16 of the 2-hy­droxy­ethyl-1,3-thia­zolidin-4-one fragment. Each of these atoms takes up two alternative locations in the crystal structure, labelled a and b. This arrangement results in two different enanti­omers of the molecule, with atoms S1, C5, C14, C15 and O16 in position a having an R configuration and the atoms in position b have an S configuration (for the molecule shown in Fig. 1), and vice versa for a symmetry-related site. The occupancy factor for atoms S1, C5, C14, C15 and O16 in orientation a is 0.883 (2), while in orientation b the occupancy factor is 0.117 (2).

The thia­zolidine ring with atoms S1 and C5 in arrangement a is approximately planar (r.m.s. deviation = 0.0213 Å), while the ring with these atoms in arrangement b is folded (r.m.s. deviation = 0.1130 Å) and adopts a half-chair conformation [Cremer & Pople (1975) puckering parameters Q = 0.253 (8) Å and ϕ = 130.0 (16)°].

The pairs of bonds S1—C2/N6—C7 and C2—N6/C7—N8 are in a synperiplanar conformation. The torsion angles S1a/(S1b)—C2—N6—C7 and C2—N6—C7—N8 are 4.2 (2)/-14.7 (3) and -10.6 (2)°, respectively. The arrangements of the two alternative hy­droxy­ethyl residues are determined by torsion angles C5a—14a—C15a—O16a = 55.8 (2)° and C5b—C14b—C15b—O16b = 178.1 (14)°, from which the pairs of bonds C5a—C14a/C15a—O16a and C5b—C14b/C15b—O16b are synclinal and synperiplanar, respectively.

The heterocyclic and phenyl rings in (II) are both flat and approximately coplanar. The dihedral angle between their mean planes is 6.59 (6)°. Atoms C13, O14, O15 and C16 form a flat system (r.m.s. deviation = 0.0015 Å) that is twisted out of the mean plane of the phenyl ring by 2.23 (8)°. The remaining atom C17 is tlted from the flat system formed by atoms C13, O14, O15 and C16 by 0.201 (3) Å. Atoms C13 and C17 are in an anti­periplanar conformation [torsion angle C13—O15—C16—C17 = 172.17 (12)°]. On the other hand, the C13O14 carbonyl group is in a synperiplanar conformation in relation to the S1—C2 bond of the heterocyclic ring [torsion angle S1—C2···C13—O14 = -1.83 (18)°].

The partial double-bond character of the C2—N6 bond in (I) and (II) accounts for the hindered rotation of the 2-pyridyl­amino [in (I)] or phenyl­amino [in (II)] residues in the analysed structures. The dihedral angles between the cyclic systems are 11.67 (11)/27.4 (4)° for (I) and 6.59 (6)° for (II). The two values given for (I) result from the previously described disorder concerning the arrangement of atoms S1 and C5 in the crystal structure.

The main factor that determines the crystal packing and the formation of the supra­molecular structure of (I) is the system of hydrogen bonds, involving both strong N—H···N and O—H···O and weak C—H···O hydrogen bonds. The N6—H6···N3i and C12—H12···O13i hydrogen bonds link the molecules into centrosymmetric dimers and generate centrosymmetric R22(8) (Bernstein et al., 1995) ring motifs. Neighbouring dimers are linked through O16a—H16A···O13ii and O16b—H16B···O13ii hydrogen bonds to form the next centrosymmetric ring motif of R22(14) type (Fig. 4a). These contacts link the molecules of (I) into tapes extending along the [110] direction (Table 3, and Figs. 4a and 4b). Neighbouring molecular tapes are linked through nonclassical C10—H10···O16iii hydrogen bonds into layers parallel to the (111) plane, and these layers are connected by C14a—H14B···O16aiv hydrogen bonds, forming a three-dimensional hydrogen-bond network.

The molecules of (II) are linked in the crystal structure through N6—H6···O18i hydrogen bonds into chains extending along the [110] direction (Table 2 and Fig. 3).

Related literature top

For related literature, see: Allen (2002); Allen et al. (1987); Behbehani & Ibrahim (2012); Bernstein et al. (1995); Cremer & Pople (1975); Geronikaki et al. (2008); Lesyk & Zimenkovsky (2004); Lesyk et al. (2011); Ostapiuk et al. (2012); Sheldrick (2008); Subtel'na, Atamanyuk, Szymanska, Kieć-Kononowicz, Zimenkovsky, Vasylenko, Gzella & Lesyk (2010); Váňa et al. (2009).

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012), OLEX2 (Dolomanov et al., 2009) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The disordered part b of the molecule is coloured grey, as distinct from the major component in black.
[Figure 2] Fig. 2. A view of the molecule of (II), showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. Part of the crystal structure of (II), showing the formation of the hydrogen-bonded chain along [110]. See Table 2 for symmetry code. H atoms not involved in hydrogen bonding have been omitted for clarity. Hydrogen bonds are shown as dashed lines.
[Figure 4] Fig. 4. (a) The molecular tape in (I), generated by the centrosymmetric dimers. For symmetry codes, see Table 3. H atoms not involved in hydrogen bonding have been omitted for clarity. (b) The molecular tape in (I), expanded along the [110] direction. Hydrogen bonds are shown as dashed lines. Grey shading denotes the disordered part of the molecule.
(I) 5-(2-Hydroxyethyl)-2-[(pyridin-2-yl)amino]-1,3-thiazolidin-4-one top
Crystal data top
C10H11N3O2SF(000) = 248
Mr = 237.28Dx = 1.491 Mg m3
Triclinic, P1Melting point = 459–461 K
a = 5.78910 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.8045 (2) ÅCell parameters from 3632 reflections
c = 10.9688 (3) Åθ = 3.0–29.1°
α = 90.638 (2)°µ = 0.29 mm1
β = 95.794 (2)°T = 130 K
γ = 107.990 (2)°Lath, colourless
V = 528.50 (3) Å30.42 × 0.22 × 0.10 mm
Z = 2
Data collection top
Agilent Xcalibur Atlas
diffractometer
2501 independent reflections
Radiation source: Enhance (Mo) X-ray Source2338 reflections with I > 2σ(I)
Detector resolution: 10.3088 pixels mm-1Rint = 0.016
ω scansθmax = 29.1°, θmin = 2.4°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
h = 67
Tmin = 0.939, Tmax = 1.000k = 1111
5332 measured reflectionsl = 1414
Refinement top
Refinement on F24 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0328P)2 + 0.2306P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
2501 reflectionsΔρmax = 0.34 e Å3
167 parametersΔρmin = 0.21 e Å3
Crystal data top
C10H11N3O2Sγ = 107.990 (2)°
Mr = 237.28V = 528.50 (3) Å3
Triclinic, P1Z = 2
a = 5.78910 (15) ÅMo Kα radiation
b = 8.8045 (2) ŵ = 0.29 mm1
c = 10.9688 (3) ÅT = 130 K
α = 90.638 (2)°0.42 × 0.22 × 0.10 mm
β = 95.794 (2)°
Data collection top
Agilent Xcalibur Atlas
diffractometer
2501 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
2338 reflections with I > 2σ(I)
Tmin = 0.939, Tmax = 1.000Rint = 0.016
5332 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0364 restraints
wR(F2) = 0.088H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.34 e Å3
2501 reflectionsΔρmin = 0.21 e Å3
167 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*/UeqOcc. (<1)
S1A0.40161 (15)0.38579 (7)0.27170 (4)0.01982 (15)0.883 (2)
C20.2062 (3)0.44461 (16)0.36246 (12)0.0199 (3)
N30.1772 (2)0.38288 (14)0.47166 (10)0.0214 (3)
C40.2935 (3)0.26908 (18)0.48923 (13)0.0267 (3)
N60.0916 (2)0.55040 (14)0.32764 (11)0.0206 (3)
H60.004 (4)0.572 (2)0.3822 (18)0.034 (5)*
C70.0942 (3)0.62302 (16)0.21345 (12)0.0202 (3)
N80.2530 (2)0.60269 (15)0.14094 (11)0.0230 (3)
C90.2538 (3)0.66848 (18)0.03061 (13)0.0259 (3)
H90.36400.65330.02340.031*
C100.1021 (3)0.75713 (19)0.00803 (13)0.0274 (3)
H100.10870.80260.08620.033*
C110.0599 (3)0.77766 (19)0.07079 (14)0.0274 (3)
H110.16520.83880.04720.033*
C120.0682 (3)0.70917 (18)0.18365 (13)0.0233 (3)
H120.17940.72020.23860.028*
O130.2882 (3)0.19347 (15)0.58229 (10)0.0383 (3)
C15A0.5049 (3)0.0412 (2)0.2396 (2)0.0218 (4)0.883 (2)
H15A0.44410.07340.21280.026*0.883 (2)
H15B0.48800.10440.16700.026*0.883 (2)
C5A0.4400 (3)0.2454 (2)0.38628 (14)0.0206 (3)0.883 (2)
H5A0.61660.27360.41860.025*0.883 (2)
C14A0.3496 (3)0.07226 (19)0.33477 (15)0.0219 (3)0.883 (2)
H14A0.35110.00030.40300.026*0.883 (2)
H14B0.17860.04750.29700.026*0.883 (2)
O16A0.7567 (2)0.08204 (17)0.28591 (13)0.0269 (3)0.883 (2)
H16A0.77560.01590.33750.040*0.883 (2)
S1B0.3118 (10)0.3571 (5)0.2556 (4)0.01982 (15)0.117 (2)
C5B0.312 (3)0.2013 (16)0.3623 (11)0.0206 (3)0.117 (2)
H5B0.16850.10390.33870.025*0.117 (2)
C14B0.547 (2)0.1577 (14)0.3752 (11)0.0219 (3)0.117 (2)
H14C0.54570.08400.44280.026*0.117 (2)
H14D0.68920.25510.39390.026*0.117 (2)
C15B0.564 (3)0.077 (2)0.2534 (17)0.0218 (4)0.117 (2)
H15C0.42180.02070.23700.026*0.117 (2)
H15D0.55590.15020.18640.026*0.117 (2)
O16B0.778 (2)0.0357 (15)0.2525 (11)0.0269 (3)0.117 (2)
H16B0.77450.03890.30010.040*0.117 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0243 (3)0.0197 (2)0.0173 (2)0.0081 (2)0.0067 (2)0.00383 (16)
C20.0251 (7)0.0173 (6)0.0162 (6)0.0040 (5)0.0048 (5)0.0009 (5)
N30.0285 (7)0.0208 (6)0.0167 (5)0.0093 (5)0.0056 (5)0.0035 (4)
C40.0405 (9)0.0245 (7)0.0194 (7)0.0151 (7)0.0078 (6)0.0030 (6)
N60.0242 (6)0.0225 (6)0.0167 (5)0.0082 (5)0.0065 (5)0.0046 (5)
C70.0233 (7)0.0186 (6)0.0163 (6)0.0028 (5)0.0025 (5)0.0034 (5)
N80.0280 (7)0.0226 (6)0.0186 (6)0.0067 (5)0.0065 (5)0.0041 (5)
C90.0286 (8)0.0287 (8)0.0189 (7)0.0052 (6)0.0073 (6)0.0045 (6)
C100.0291 (8)0.0307 (8)0.0190 (7)0.0039 (6)0.0032 (6)0.0095 (6)
C110.0259 (8)0.0294 (8)0.0256 (7)0.0072 (6)0.0011 (6)0.0089 (6)
C120.0228 (7)0.0247 (7)0.0221 (7)0.0061 (6)0.0045 (5)0.0045 (6)
O130.0691 (9)0.0381 (7)0.0218 (5)0.0333 (6)0.0163 (5)0.0136 (5)
C15A0.0223 (11)0.0206 (11)0.0222 (8)0.0058 (8)0.0040 (8)0.0014 (7)
C5A0.0244 (9)0.0209 (8)0.0184 (7)0.0095 (7)0.0032 (6)0.0034 (6)
C14A0.0216 (8)0.0198 (8)0.0248 (8)0.0064 (6)0.0052 (6)0.0025 (6)
O16A0.0254 (7)0.0284 (8)0.0295 (8)0.0108 (5)0.0069 (5)0.0088 (6)
S1B0.0243 (3)0.0197 (2)0.0173 (2)0.0081 (2)0.0067 (2)0.00383 (16)
C5B0.0244 (9)0.0209 (8)0.0184 (7)0.0095 (7)0.0032 (6)0.0034 (6)
C14B0.0216 (8)0.0198 (8)0.0248 (8)0.0064 (6)0.0052 (6)0.0025 (6)
C15B0.0223 (11)0.0206 (11)0.0222 (8)0.0058 (8)0.0040 (8)0.0014 (7)
O16B0.0254 (7)0.0284 (8)0.0295 (8)0.0108 (5)0.0069 (5)0.0088 (6)
Geometric parameters (Å, º) top
S1A—C21.7655 (15)C12—H120.9500
S1A—C5A1.8178 (16)C15A—O16A1.427 (2)
C2—N31.3256 (17)C15A—C14A1.520 (3)
C2—N61.3385 (19)C15A—H15A0.9900
C2—S1B1.660 (5)C15A—H15B0.9900
N3—C41.3744 (19)C5A—C14A1.532 (2)
C4—O131.2227 (18)C5A—H5A1.0000
C4—C5A1.528 (2)C14A—H14A0.9900
C4—C5B1.535 (13)C14A—H14B0.9900
N6—C71.4119 (17)O16A—H16A0.8400
N6—H60.88 (2)S1B—C5B1.813 (13)
C7—N81.3251 (19)C5B—C14B1.520 (14)
C7—C121.396 (2)C5B—H5B1.0000
N8—C91.3473 (18)C14B—C15B1.533 (15)
C9—C101.384 (2)C14B—H14C0.9900
C9—H90.9500C14B—H14D0.9900
C10—C111.387 (2)C15B—O16B1.397 (16)
C10—H100.9500C15B—H15C0.9900
C11—C121.382 (2)C15B—H15D0.9900
C11—H110.9500O16B—H16B0.8400
C2—S1A—C5A89.64 (7)C14A—C15A—H15B109.2
N3—C2—N6118.87 (13)H15A—C15A—H15B107.9
N3—C2—S1B120.45 (18)C4—C5A—C14A111.18 (14)
N6—C2—S1B118.35 (18)C4—C5A—S1A105.24 (11)
N3—C2—S1A117.77 (11)C14A—C5A—S1A112.27 (11)
N6—C2—S1A123.35 (10)C4—C5A—H5A109.3
C2—N3—C4111.24 (12)C14A—C5A—H5A109.3
O13—C4—N3123.02 (14)S1A—C5A—H5A109.3
O13—C4—C5A121.08 (14)C15A—C14A—C5A112.54 (14)
N3—C4—C5A115.86 (12)C15A—C14A—H14A109.1
O13—C4—C5B123.3 (5)C5A—C14A—H14A109.1
N3—C4—C5B107.5 (4)C15A—C14A—H14B109.1
C2—N6—C7126.46 (13)C5A—C14A—H14B109.1
C2—N6—H6114.2 (13)H14A—C14A—H14B107.8
C7—N6—H6119.3 (13)C15A—O16A—H16A109.5
N8—C7—C12124.43 (13)C2—S1B—C5B87.4 (4)
N8—C7—N6116.53 (12)C14B—C5B—C4105.5 (9)
C12—C7—N6119.04 (13)C14B—C5B—S1B113.8 (9)
C7—N8—C9117.15 (13)C4—C5B—S1B106.5 (7)
N8—C9—C10123.26 (14)C14B—C5B—H5B110.3
N8—C9—H9118.4C4—C5B—H5B110.3
C10—C9—H9118.4S1B—C5B—H5B110.3
C9—C10—C11118.06 (13)C5B—C14B—C15B107.7 (11)
C9—C10—H10121.0C5B—C14B—H14C110.2
C11—C10—H10121.0C15B—C14B—H14C110.2
C12—C11—C10120.01 (14)C5B—C14B—H14D110.2
C12—C11—H11120.0C15B—C14B—H14D110.2
C10—C11—H11120.0H14C—C14B—H14D108.5
C11—C12—C7117.06 (14)O16B—C15B—C14B113.1 (13)
C11—C12—H12121.5O16B—C15B—H15C109.0
C7—C12—H12121.5C14B—C15B—H15C109.0
O16A—C15A—C14A112.19 (16)O16B—C15B—H15D109.0
O16A—C15A—H15A109.2C14B—C15B—H15D109.0
C14A—C15A—H15A109.2H15C—C15B—H15D107.8
O16A—C15A—H15B109.2C15B—O16B—H16B109.5
C5A_a—S1A_a—C2—N34.74 (12)C5B—C4—C5A—C14A43.3 (9)
C5A—S1A—C2—N6176.87 (13)O13—C4—C5A—S1A178.17 (14)
C5A—S1A—C2—S1B99.0 (5)N3—C4—C5A—S1A0.17 (18)
N6—C2—N3—C4175.93 (13)C5B—C4—C5A—S1A78.4 (10)
S1B—C2—N3—C413.5 (3)C2—S1A—C5A—C42.25 (12)
S1A—C2—N3—C45.60 (17)C2—S1A—C5A—C14A118.83 (13)
C2—N3—C4—O13178.53 (15)O16A—C15A—C14A—C5A55.8 (2)
C2—N3—C4—C5A3.5 (2)C4—C5A—C14A—C15A175.19 (15)
C2—N3—C4—C5B25.5 (6)S1A—C5A—C14A—C15A67.21 (17)
N3—C2—N6—C7177.41 (13)N3—C2—S1B—C5B3.1 (5)
S1B—C2—N6—C714.7 (3)N6—C2—S1B—C5B159.4 (5)
S1A—C2—N6—C74.2 (2)S1A—C2—S1B—C5B88.8 (7)
C2—N6—C7—N810.6 (2)O13—C4—C5B—C14B59.0 (11)
C2—N6—C7—C12168.97 (14)N3—C4—C5B—C14B148.0 (7)
C12—C7—N8—C90.9 (2)C5A—C4—C5B—C14B35.7 (7)
N6—C7—N8—C9178.62 (12)O13—C4—C5B—S1B179.7 (3)
C7—N8—C9—C101.3 (2)N3—C4—C5B—S1B26.7 (8)
N8—C9—C10—C110.6 (2)C5A—C4—C5B—S1B85.6 (11)
C9—C10—C11—C120.6 (2)C2—S1B—C5B—C14B132.4 (10)
C10—C11—C12—C71.0 (2)C2—S1B—C5B—C416.6 (7)
N8—C7—C12—C110.3 (2)C4—C5B—C14B—C15B175.6 (11)
N6—C7—C12—C11179.74 (13)S1B—C5B—C14B—C15B67.9 (14)
O13—C4—C5A—C14A60.0 (2)C5B—C14B—C15B—O16B178.1 (14)
N3—C4—C5A—C14A121.96 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.88 (2)2.10 (2)2.9733 (17)173 (2)
O16a—H16A···O13ii0.842.002.7940 (19)158
O16b—H16B···O13ii0.841.862.692 (12)168
C10—H10···O16aiii0.952.523.442 (2)164
C12—H12···O13i0.952.313.199 (2)155
C14a—H14B···O16aiv0.992.543.448 (2)152
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1; (iii) x+1, y+1, z; (iv) x1, y, z.
(II) Ethyl 4-[(4-oxothiazolidin-2-yl)amino]benzoate top
Crystal data top
C12H12N2O3SF(000) = 276
Mr = 264.30Dx = 1.496 Mg m3
Triclinic, P1Melting point = 461–462 K
a = 3.9850 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 5.5113 (3) ÅCell parameters from 5612 reflections
c = 26.8877 (14) Åθ = 2.3–29.0°
α = 84.483 (5)°µ = 0.28 mm1
β = 89.670 (5)°T = 130 K
γ = 86.338 (5)°Lath, colourless
V = 586.58 (6) Å30.40 × 0.34 × 0.05 mm
Z = 2
Data collection top
Agilent Xcalibur Atlas
diffractometer
2804 independent reflections
Radiation source: Enhance (Mo) X-ray Source2604 reflections with I > 2σ(I)
Detector resolution: 10.3088 pixels mm-1Rint = 0.017
ω scansθmax = 29.1°, θmin = 2.3°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
h = 55
Tmin = 0.908, Tmax = 1.000k = 77
7855 measured reflectionsl = 3535
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3017P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2804 reflectionsΔρmax = 0.54 e Å3
168 parametersΔρmin = 0.23 e Å3
Crystal data top
C12H12N2O3Sγ = 86.338 (5)°
Mr = 264.30V = 586.58 (6) Å3
Triclinic, P1Z = 2
a = 3.9850 (2) ÅMo Kα radiation
b = 5.5113 (3) ŵ = 0.28 mm1
c = 26.8877 (14) ÅT = 130 K
α = 84.483 (5)°0.40 × 0.34 × 0.05 mm
β = 89.670 (5)°
Data collection top
Agilent Xcalibur Atlas
diffractometer
2804 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
2604 reflections with I > 2σ(I)
Tmin = 0.908, Tmax = 1.000Rint = 0.017
7855 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.54 e Å3
2804 reflectionsΔρmin = 0.23 e Å3
168 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
S10.90166 (7)0.46485 (5)0.05976 (2)0.01454 (9)
C20.7690 (3)0.4621 (2)0.12301 (4)0.0130 (2)
N30.5653 (3)0.64554 (18)0.13492 (4)0.0152 (2)
C40.4898 (3)0.8077 (2)0.09439 (4)0.0145 (2)
C50.6724 (3)0.7546 (2)0.04612 (4)0.0151 (2)
H5A0.82770.88360.03600.018*
H5B0.50920.74680.01880.018*
N60.8822 (3)0.27244 (18)0.15391 (4)0.0148 (2)
H61.014 (4)0.167 (3)0.1409 (7)0.028 (4)*
C70.8121 (3)0.2168 (2)0.20533 (4)0.0142 (2)
C80.6325 (3)0.3760 (2)0.23453 (5)0.0177 (2)
H80.54750.53210.22030.021*
C90.5797 (3)0.3034 (2)0.28469 (5)0.0188 (3)
H90.45850.41110.30490.023*
C100.7019 (3)0.0748 (2)0.30575 (4)0.0168 (2)
C110.8843 (3)0.0814 (2)0.27639 (5)0.0185 (2)
H110.97110.23680.29080.022*
C120.9398 (3)0.0119 (2)0.22645 (5)0.0174 (2)
H121.06430.11910.20650.021*
C130.6394 (3)0.0095 (2)0.35919 (5)0.0198 (3)
O140.7419 (3)0.20429 (19)0.37957 (4)0.0322 (3)
O150.4537 (3)0.15882 (17)0.38186 (3)0.0237 (2)
C160.3732 (4)0.0971 (3)0.43390 (5)0.0244 (3)
H16A0.58000.04400.45320.029*
H16B0.21800.03670.43740.029*
C170.2087 (4)0.3256 (3)0.45242 (5)0.0288 (3)
H17A0.00850.37850.43230.043*
H17B0.36740.45490.44960.043*
H17C0.14350.29170.48750.043*
O180.2933 (2)0.98859 (16)0.09484 (3)0.01938 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01742 (16)0.01331 (14)0.01236 (14)0.00285 (11)0.00282 (10)0.00122 (10)
C20.0132 (5)0.0136 (5)0.0126 (5)0.0021 (4)0.0011 (4)0.0021 (4)
N30.0167 (5)0.0141 (5)0.0145 (5)0.0019 (4)0.0017 (4)0.0020 (4)
C40.0147 (5)0.0137 (5)0.0153 (5)0.0005 (4)0.0011 (4)0.0033 (4)
C50.0167 (6)0.0129 (5)0.0149 (5)0.0025 (4)0.0020 (4)0.0000 (4)
N60.0170 (5)0.0129 (5)0.0141 (5)0.0028 (4)0.0021 (4)0.0023 (4)
C70.0155 (5)0.0136 (5)0.0136 (5)0.0012 (4)0.0004 (4)0.0015 (4)
C80.0233 (6)0.0133 (5)0.0161 (6)0.0023 (5)0.0015 (5)0.0007 (4)
C90.0238 (6)0.0157 (6)0.0166 (6)0.0020 (5)0.0023 (5)0.0020 (4)
C100.0190 (6)0.0162 (6)0.0150 (6)0.0019 (5)0.0004 (4)0.0002 (4)
C110.0224 (6)0.0136 (5)0.0187 (6)0.0015 (5)0.0010 (5)0.0002 (4)
C120.0205 (6)0.0133 (5)0.0182 (6)0.0025 (5)0.0005 (5)0.0019 (4)
C130.0238 (6)0.0185 (6)0.0166 (6)0.0004 (5)0.0008 (5)0.0003 (5)
O140.0480 (7)0.0236 (5)0.0217 (5)0.0104 (5)0.0064 (4)0.0063 (4)
O150.0336 (5)0.0215 (5)0.0143 (4)0.0049 (4)0.0051 (4)0.0020 (3)
C160.0315 (7)0.0260 (7)0.0142 (6)0.0027 (6)0.0048 (5)0.0024 (5)
C170.0338 (8)0.0298 (7)0.0214 (7)0.0054 (6)0.0058 (6)0.0011 (5)
O180.0223 (5)0.0150 (4)0.0201 (4)0.0060 (3)0.0021 (3)0.0024 (3)
Geometric parameters (Å, º) top
S1—C21.7770 (12)C9—H90.9500
S1—C51.7957 (12)C10—C111.3918 (18)
C2—N31.3182 (15)C10—C131.4915 (17)
C2—N61.3282 (15)C11—C121.3811 (17)
N3—C41.3634 (15)C11—H110.9500
C4—O181.2287 (15)C12—H120.9500
C4—C51.5279 (16)C13—O141.2054 (16)
C5—H5A0.9900C13—O151.3400 (16)
C5—H5B0.9900O15—C161.4470 (15)
N6—C71.4171 (15)C16—C171.5081 (19)
N6—H60.859 (19)C16—H16A0.9900
C7—C81.3946 (17)C16—H16B0.9900
C7—C121.3977 (16)C17—H17A0.9800
C8—C91.3881 (17)C17—H17B0.9800
C8—H80.9500C17—H17C0.9800
C9—C101.3902 (17)
C2—S1—C589.35 (5)C9—C10—C11119.57 (11)
N3—C2—N6125.95 (11)C9—C10—C13121.63 (12)
N3—C2—S1117.49 (9)C11—C10—C13118.79 (11)
N6—C2—S1116.55 (9)C12—C11—C10120.38 (11)
C2—N3—C4111.51 (10)C12—C11—H11119.8
O18—C4—N3124.59 (11)C10—C11—H11119.8
O18—C4—C5119.87 (10)C11—C12—C7119.75 (11)
N3—C4—C5115.53 (10)C11—C12—H12120.1
C4—C5—S1105.83 (8)C7—C12—H12120.1
C4—C5—H5A110.6O14—C13—O15124.04 (12)
S1—C5—H5A110.6O14—C13—C10124.54 (12)
C4—C5—H5B110.6O15—C13—C10111.42 (11)
S1—C5—H5B110.6C13—O15—C16116.64 (10)
H5A—C5—H5B108.7O15—C16—C17106.36 (11)
C2—N6—C7129.30 (10)O15—C16—H16A110.5
C2—N6—H6115.7 (12)C17—C16—H16A110.5
C7—N6—H6115.0 (12)O15—C16—H16B110.5
C8—C7—C12120.37 (11)C17—C16—H16B110.5
C8—C7—N6123.86 (11)H16A—C16—H16B108.6
C12—C7—N6115.76 (11)C16—C17—H17A109.5
C9—C8—C7119.11 (11)C16—C17—H17B109.5
C9—C8—H8120.4H17A—C17—H17B109.5
C7—C8—H8120.4C16—C17—H17C109.5
C8—C9—C10120.81 (12)H17A—C17—H17C109.5
C8—C9—H9119.6H17B—C17—H17C109.5
C10—C9—H9119.6
C5—S1—C2—N32.42 (10)C7—C8—C9—C100.3 (2)
C5—S1—C2—N6178.37 (10)C8—C9—C10—C111.1 (2)
N6—C2—N3—C4178.45 (11)C8—C9—C10—C13178.21 (12)
S1—C2—N3—C40.67 (14)C9—C10—C11—C120.94 (19)
C2—N3—C4—O18176.49 (11)C13—C10—C11—C12178.37 (12)
C2—N3—C4—C54.32 (15)C10—C11—C12—C70.04 (19)
O18—C4—C5—S1174.96 (9)C8—C7—C12—C110.75 (19)
N3—C4—C5—S15.82 (13)N6—C7—C12—C11179.87 (11)
C2—S1—C5—C44.21 (8)C9—C10—C13—O14179.18 (13)
N3—C2—N6—C71.3 (2)C11—C10—C13—O141.5 (2)
S1—C2—N6—C7177.79 (10)C9—C10—C13—O150.89 (18)
C2—N6—C7—C88.0 (2)C11—C10—C13—O15178.41 (11)
C2—N6—C7—C12172.90 (12)O14—C13—O15—C160.5 (2)
C12—C7—C8—C90.62 (19)C10—C13—O15—C16179.45 (11)
N6—C7—C8—C9179.66 (11)C13—O15—C16—C17172.17 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···O18i0.857 (17)1.954 (17)2.7882 (14)164.3 (17)
Symmetry code: (i) x+1, y1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H11N3O2SC12H12N2O3S
Mr237.28264.30
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)130130
a, b, c (Å)5.78910 (15), 8.8045 (2), 10.9688 (3)3.9850 (2), 5.5113 (3), 26.8877 (14)
α, β, γ (°)90.638 (2), 95.794 (2), 107.990 (2)84.483 (5), 89.670 (5), 86.338 (5)
V3)528.50 (3)586.58 (6)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.290.28
Crystal size (mm)0.42 × 0.22 × 0.100.40 × 0.34 × 0.05
Data collection
DiffractometerAgilent Xcalibur Atlas
diffractometer
Agilent Xcalibur Atlas
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Multi-scan
(CrysAlis PRO; Agilent, 2010)
Tmin, Tmax0.939, 1.0000.908, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
5332, 2501, 2338 7855, 2804, 2604
Rint0.0160.017
(sin θ/λ)max1)0.6840.684
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.088, 1.13 0.030, 0.078, 1.05
No. of reflections25012804
No. of parameters167168
No. of restraints40
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.210.54, 0.23

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012), OLEX2 (Dolomanov et al., 2009) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N6—H6···O18i0.857 (17)1.954 (17)2.7882 (14)164.3 (17)
Symmetry code: (i) x+1, y1, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.88 (2)2.10 (2)2.9733 (17)173 (2)
O16a—H16A···O13ii0.842.002.7940 (19)158
O16b—H16B···O13ii0.841.862.692 (12)168
C10—H10···O16aiii0.952.523.442 (2)164
C12—H12···O13i0.952.313.199 (2)155
C14a—H14B···O16aiv0.992.543.448 (2)152
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1; (iii) x+1, y+1, z; (iv) x1, y, z.
 

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