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The non-H atoms in the organic component of the title compound, C8H7N3OS2·H2O, are almost coplanar, as the dihedral angle between the two ring planes is only 1.8 (2)°; there is a wide C-C-C angle of 127.8 (3)° at the methine C atom linking the two rings. The mol­ecular components are linked into a three-dimensional framework structure by two-centre hydrogen bonds of N-H...O and O-H...N types, together with a three-centre O-H...(N,S) system. Comparisons are made with some (Z)-5-arylmethylidene-2-sulfanyl­idene-1,3-thia­zolidin-4-ones.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112043260/sf3183sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112043260/sf3183Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112043260/sf3183Isup3.cml
Supplementary material

CCDC reference: 914659

Comment top

We report here the molecular and supramolecular structure of (Z)-5-[(5-methyl-1H-imidazol-4-yl)methylidene]-2-sulfanylidene-1,3-thiazolidin-4-one monohydrate, (I) (Fig. 1), which we briefly compare with those of the related (Z)-5-arylmethlene-2-sulfanylidene-1,3-thiazolidin-4-ones (II)–(VIII) (Delgado et al., 2005, 2006) (see Scheme). Compound (I) was prepared using a base-catalysed condensation reaction between rhodanine (2-sulfanylidene-1,3-thiazolidin-4-one) and 4-methylimidazole-5-carbaldehyde in refluxing ethanol, whereas compounds (II)–(VIII) were all prepared by condensation reactions between rhodanine and the appropriately substituted aryl aldehydes using microwave radiation in solvent-free systems. Compounds (II)–(VIII) were obtained in solvent-free form by crystallization from solutions in dimethylformamide, whereas crystallization of compound (I) from a solution in ethanol provided a stoichiometric monohydrate.

Within the organic component of compound (I), the non-H atoms are almost coplanar, as shown by the values (Table 1) of the torsion angles S1—C5—C57—C54 and C5—C57—C54—N53; the dihedral angle between the mean planes through the two independent rings is 1.8 (2)°. At the same time, there is a wide C—C—C angle at methine atom C57 which links the two rings (Table 1), while of the exocyclic angles at C5 the value of S1—C5—C57 exceeds that of C4—C5—C57 by ca 5°. Although the values of the angles N53—C54—C57 and C55—C54—C57 differ by only ca 2°, in the simple analogue 1-methylimidazole-4-carboxaldehyde monohydrate, (IX) [Cambridge Structural Database (CSD; Allen, 2002) refcode BEHBIA; Cheruzel et al., 2003], the corresponding N—C—C and C—C—C angles are 121.0 (2) and 129.2 (2)°, respectively. These observations taken together suggest that the short intramolecular nonbonded S1···N53 contact, with an S···N distance of 3.048 (3) Å, somewhat shorter than the sum of the van der Waals radii (3.35 Å; Bondi, 1964), is strongly repulsive. This behaviour in compound (I) closely resembles that in compounds (II)–(VIII), each of which has an almost-planar molecular skeleton and a wide angle, ca 130°, at the linking methine C atom. Compounds (II)–(VIII) differ from compound (I) in that the short repulsive intramolecular contact is of the S···H—C type, rather than of the S···N type, as in (I). In every case, it appears that a distortion of the central C—C—C angles is energetically more economical in minimizing the effects of the repulsive contact that [than?] a rotation about the formal single bridge bond, viz. C54—C57 in (I) and the corresponding bonds in (II)–(VIII). However, in none of compounds (I)–(VIII) do the bond distances provide any evidence for the type of electronic polarization which could lead to the development of canonical forms having restricted rotation about the bond in question.

The molecular components of compound (I) are linked into a three-dimensional framework structure, which contains two-centre hydrogen bonds of N—H···O and O—H···N types, along with an almost-planar three-centre O—H···(N,S) system (Table 2): the sum of the bond angles at atom H11 is 357°. However, the formation of the framework structure is readily analysed in terms of three independent one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000) and their combinations.

Within the selected asymmetric unit (Fig. 1), thiazolidine ring atom N3 acts as hydrogen-bond donor to water atom O1. In the first one-dimensional substructure, atom O1 at (x, y, z) acts as hydrogen-bond donor, via atom H12, to imidazole ring atom N53 at (x + 1/2, y, -z + 3/2), so generating a C22(9) (Bernstein et al., 1995) chain running parallel to the [100] direction and built from bimolecular units related to one another by the a-glide plane at z = 0.75 (Fig. 2).

Two further substructures take the form of chains running parallel to the [001] direction and comprising building blocks related, respectively, by a 21 screw axis and a c-glide plane. The simpler of these two substructures involves the organic component only, with no participation by the water molecule. Atom N51 at (x, y, z) acts as hydrogen-bond donor to carbonyl atom O4 at (-x + 1/2, -y + 1, z - 1/2), so forming a simple C(8) chain running parallel to the [001] direction and containing organic molecules which are related to one another by the 21 screw axis along (1/4, 1/2, z) (Fig. 3).

In the final substructure, atom O1 at (x, y, z) acts as hydrogen-bond donor, via atom H11, in a three-centre system to atoms N53 and S1, both at (x, -y + 3/2, z + 1/2). A database study (Allen et al., 1997) of two-centre hydrogen bonds having two-coordinate S atoms as the acceptors found that for O—H···S interactions, the mean H···S distance was 2.63 (4) Å and the mean O···S distance was 3.37 (5) Å. In general, the distances in three-centre interactions are expected to be longer than those in similar two-centre interactions, and this is well illustrated by the two O—H···N hydrogen bonds, one two-centre and one three-centre, present in compound (I) (Table 2). By way of comparison, the intermolecular component of a three-centre C—H···(S)2 system in compound (V) has H···S and C···S distances of 2.86 and 3.588 (2) Å, respectively (Delgado et al., 2005), fully consistent with the values for the O—H···S interaction in (I). This three-centre hydrogen bond in compound (I) gives rise to a C22(6)C22(9)[R12(6)] chain of rings running parallel to the [001] direction and containing bimolecular units related to one another by the c-glide plane at y = 0.75 (Fig. 4).

The combination of the two independent chains parallel to [001] generates a sheet lying parallel to (100), which contains equal numbers of R12(6) and R66(24) rings and which lies in the domain 0.0 < x < 0.5 (Fig. 5). A second such sheet, related to the first by inversion, lies in the domain 0.5 < x < 1.0, and the successive (100) sheets are linked by the chains parallel to [100] (Fig. 2) to form a continuous three-dimensional framework structure.

It is of interest briefly to compare the three-dimensional supramolecular aggregation in compound (I) with that in compounds (II)–(VIII), where the dimensionality is always less than three (Delgado et al., 2005, 2006). Compounds (II)–(VIII) all crystallize in solvent-free forms and the dominant mode of aggregation is the formation of cyclic R22(8) dimers built from pairs of N—H···O hydrogen bonds: the sole exception to this pattern occurs in compound (IV), where an R22(8) dimer is formed from paired N—H···S hydrogen bonds. There are no direction-specific interactions between the dimers in compounds (III) and (VIII), so that the aggregation here can be regarded as zero-dimensional. The aggregation in compounds (VI) and (VII) is one-dimensional: there are no further hydrogen bonds in the structures of compounds (VI) and (VII), but instead the dimers are linked into chains by, respectively, an aromatic ππ stacking interaction and a dipolar carbonyl–carbonyl interaction. By contrast, the dimeric units in copound (IV) are linked into a chain of rings by a C—H···O hydrogen bond, while those in compound (V) are linked into a chain of rings by a C—H···S hydrogen bond. Finally, in compound (II), where Z' = 2 and which forms the only two-dimensional aggregation so far observed in this series, three independent C—H···π(arene) hydrogen bonds link the dimeric units into complex sheets.

Related literature top

For related literature, see: Allen (1997, 2002); Bernstein et al. (1995); Bondi (1964); Cheruzel et al. (2003); Delgado et al. (2005, 2006); Ferguson et al. (1998a, 1998b); Gregson et al. (2000).

Experimental top

To a mixture of 4-methylimidazole-5-carbaldehyde (1.1 mmol) and 2-sulfanylidene-1,3-thiazolidin-4-one (1.0 mmol) in dry ethanol (10 ml) was added one drop of piperidine, and the mixture was then heated under reflux for 6 h. The resulting solid precipitate was collected by filtration and recrystallized from ethanol (yield 91%, m.p. 307–309 K). MS (EI, 70 eV) m/z (%): 225 (M+, 38), 139 (1), 138 (70), 137 (100), 69 (25), 42 (13). Crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation, at ambient temperature and in air, of a solution in ethanol.

Refinement top

All H atoms were located in difference maps. H atoms bonded to C atoms were subsequently treated as riding atoms in geometrically idealized positions, with C—H distances of 0.95 (imidazole and methine) or 0.98 Å (methyl), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and k = 1.2 otherwise. H atoms bonded to N atoms were permitted to ride at the positions located in the difference maps, with Uiso(H) = 1.2Ueq(N), giving N—H distances of 0.90 and 1.06 Å (see Table 2). H atoms bonded to O atoms were permitted to ride at the positions located in the difference maps, with Uiso(H) = 1.5Ueq(O), giving O—H distances of 0.86 and 0.88 Å (see Table 2) and an H—O—H angle of 103.9°.

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular components of compound (I), showing the atom-labelling scheme and the N—H···O hydrogen bond within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of compound (I), showing the formation of a C22(9) chain parallel to [100]. For the sake of clarity, H atoms other than atoms H3, H11 and H12 have been omitted.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of a C(8) chain parallel to [001]. For the sake of clarity, the water molecule and H atoms other than atom H51 have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a C22(6)C22(9)[R12(6)] chain of rings parallel to [001]. For the sake of clarity, H atoms other than atoms H3, H11 and H12 have been omitted.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of compound (I), showing the formation of a sheet of R12(6) and R66(24) rings parallel to (100). For the sake of clarity, H atoms bonded to C atoms have been omitted.
(Z)-5-[(5-Methyl-1H-imidazol-4-yl)methylidene]-2-sulfanylidene- 1,3-thiazolidin-4-one monohydrate top
Crystal data top
C8H7N3OS2·H2OF(000) = 1008
Mr = 243.32Dx = 1.558 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2384 reflections
a = 7.4110 (6) Åθ = 2.8–27.5°
b = 16.2739 (18) ŵ = 0.50 mm1
c = 17.201 (2) ÅT = 120 K
V = 2074.5 (4) Å3Plate, colourless
Z = 80.40 × 0.28 × 0.10 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2384 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode1449 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.119
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2117
Tmin = 0.826, Tmax = 0.952l = 2222
23037 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0867P)2 + 0.5619P]
where P = (Fo2 + 2Fc2)/3
2384 reflections(Δ/σ)max = 0.001
137 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
C8H7N3OS2·H2OV = 2074.5 (4) Å3
Mr = 243.32Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.4110 (6) ŵ = 0.50 mm1
b = 16.2739 (18) ÅT = 120 K
c = 17.201 (2) Å0.40 × 0.28 × 0.10 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2384 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1449 reflections with I > 2σ(I)
Tmin = 0.826, Tmax = 0.952Rint = 0.119
23037 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.164H-atom parameters constrained
S = 1.08Δρmax = 0.47 e Å3
2384 reflectionsΔρmin = 0.39 e Å3
137 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.47426 (13)0.72683 (5)0.63974 (5)0.0228 (3)
C20.5126 (5)0.7666 (2)0.7330 (2)0.0224 (8)
S20.58807 (13)0.85987 (6)0.74867 (5)0.0256 (3)
N30.4701 (4)0.70945 (19)0.78858 (16)0.0235 (7)
H30.48010.72370.84830.028*
C40.4014 (5)0.6349 (2)0.7630 (2)0.0234 (8)
O40.3547 (4)0.57928 (16)0.80648 (14)0.0307 (7)
C50.3927 (5)0.6334 (2)0.6771 (2)0.0210 (8)
C570.3266 (5)0.5694 (2)0.6375 (2)0.0216 (8)
H570.28720.52390.66780.026*
N510.2541 (4)0.51311 (19)0.43903 (17)0.0248 (7)
H510.23240.48240.39670.030*
C520.3172 (5)0.5909 (2)0.4338 (2)0.0253 (8)
H520.33520.61880.38600.030*
N530.3509 (4)0.62340 (18)0.50189 (17)0.0225 (7)
C540.3082 (5)0.5612 (2)0.55531 (19)0.0213 (8)
C550.2464 (5)0.4923 (2)0.5162 (2)0.0241 (8)
C560.1835 (5)0.4106 (2)0.5454 (2)0.0319 (9)
H56A0.27910.38520.57660.048*
H56B0.15460.37500.50120.048*
H56C0.07550.41810.57760.048*
O10.5304 (4)0.73387 (15)0.94381 (14)0.0267 (6)
H110.50100.77290.97710.040*
H120.60910.70530.96820.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0305 (5)0.0221 (5)0.0158 (4)0.0029 (4)0.0005 (4)0.0000 (3)
C20.0203 (19)0.027 (2)0.0199 (18)0.0004 (16)0.0005 (14)0.0012 (15)
S20.0299 (5)0.0250 (5)0.0219 (5)0.0050 (4)0.0019 (4)0.0042 (4)
N30.0288 (17)0.0243 (16)0.0174 (15)0.0010 (14)0.0003 (13)0.0020 (12)
C40.0211 (18)0.028 (2)0.021 (2)0.0032 (16)0.0002 (15)0.0014 (16)
O40.0497 (18)0.0258 (15)0.0167 (12)0.0059 (13)0.0012 (12)0.0061 (11)
C50.0222 (19)0.024 (2)0.0172 (17)0.0005 (15)0.0001 (14)0.0038 (14)
C570.0224 (19)0.0202 (18)0.0222 (18)0.0004 (15)0.0003 (15)0.0027 (15)
N510.0220 (17)0.0298 (18)0.0226 (17)0.0040 (14)0.0015 (13)0.0076 (13)
C520.027 (2)0.030 (2)0.0194 (18)0.0004 (17)0.0002 (16)0.0017 (16)
N530.0260 (17)0.0242 (16)0.0174 (15)0.0006 (12)0.0001 (12)0.0002 (12)
C540.0220 (18)0.0202 (19)0.0217 (17)0.0001 (15)0.0009 (14)0.0018 (15)
C550.0214 (19)0.026 (2)0.025 (2)0.0039 (16)0.0008 (16)0.0023 (16)
C560.032 (2)0.022 (2)0.042 (2)0.0013 (17)0.0032 (19)0.0019 (18)
O10.0378 (15)0.0252 (14)0.0170 (12)0.0046 (12)0.0011 (11)0.0036 (10)
Geometric parameters (Å, º) top
S1—C21.754 (4)N51—C551.372 (4)
S1—C51.759 (4)N51—H510.8973
C2—N31.371 (5)C52—N531.309 (5)
C2—S21.639 (4)C52—H520.9500
N3—C41.387 (5)N53—C541.404 (4)
N3—H31.0563C54—C551.385 (5)
C4—O41.225 (4)C55—C561.495 (5)
C4—C51.478 (5)C56—H56A0.9800
C5—C571.337 (5)C56—H56B0.9800
C57—C541.427 (5)C56—H56C0.9800
C57—H570.9500O1—H110.8826
N51—C521.352 (5)O1—H120.8564
C2—S1—C592.32 (17)C55—N51—H51129.8
N3—C2—S2126.3 (3)N53—C52—N51112.7 (3)
N3—C2—S1110.5 (3)N53—C52—H52123.7
S2—C2—S1123.2 (2)N51—C52—H52123.7
C2—N3—C4117.2 (3)C52—N53—C54104.5 (3)
C2—N3—H3120.9C55—C54—N53109.9 (3)
C4—N3—H3121.8N53—C54—C57124.0 (3)
O4—C4—N3123.8 (3)C55—C54—C57126.0 (3)
O4—C4—C5125.8 (3)N51—C55—C54104.8 (3)
N3—C4—C5110.4 (3)N51—C55—C56123.9 (3)
C5—C57—C54127.8 (3)C54—C55—C56131.3 (3)
S1—C5—C57127.8 (3)C55—C56—H56A109.5
C4—C5—C57122.6 (3)C55—C56—H56B109.5
C4—C5—S1109.6 (3)H56A—C56—H56B109.5
C5—C57—H57116.1C55—C56—H56C109.5
C54—C57—H57116.1H56A—C56—H56C109.5
C52—N51—C55108.0 (3)H56B—C56—H56C109.5
C52—N51—H51122.0H11—O1—H12103.9
C5—S1—C2—N31.9 (3)S1—C5—C57—C540.8 (6)
C5—S1—C2—S2177.8 (3)C55—N51—C52—N530.4 (4)
S2—C2—N3—C4177.5 (3)N51—C52—N53—C540.8 (4)
S1—C2—N3—C42.2 (4)C52—N53—C54—C550.9 (4)
C2—N3—C4—O4178.5 (4)C52—N53—C54—C57179.3 (3)
C2—N3—C4—C51.2 (4)C5—C57—C54—C55176.9 (4)
O4—C4—C5—C571.7 (6)C5—C57—C54—N533.3 (6)
N3—C4—C5—C57178.0 (3)C52—N51—C55—C540.2 (4)
O4—C4—C5—S1180.0 (3)C52—N51—C55—C56179.8 (3)
N3—C4—C5—S10.3 (4)N53—C54—C55—N510.7 (4)
C2—S1—C5—C57177.0 (4)C57—C54—C55—N51179.5 (3)
C2—S1—C5—C41.3 (3)N53—C54—C55—C56179.7 (4)
C4—C5—C57—C54178.8 (3)C57—C54—C55—C560.1 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O11.061.692.736 (4)169
N51—H51···O4i0.901.962.848 (4)171
O1—H11···N53ii0.882.072.857 (4)149
O1—H11···S1ii0.882.803.456 (3)132
O1—H12···N53iii0.862.293.122 (4)164
Symmetry codes: (i) x+1/2, y+1, z1/2; (ii) x, y+3/2, z+1/2; (iii) x+1/2, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC8H7N3OS2·H2O
Mr243.32
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)120
a, b, c (Å)7.4110 (6), 16.2739 (18), 17.201 (2)
V3)2074.5 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.50
Crystal size (mm)0.40 × 0.28 × 0.10
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.826, 0.952
No. of measured, independent and
observed [I > 2σ(I)] reflections
23037, 2384, 1449
Rint0.119
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.164, 1.08
No. of reflections2384
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.47, 0.39

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond and torsion angles (º) top
C5—C57—C54127.8 (3)N53—C54—C57124.0 (3)
S1—C5—C57127.8 (3)C55—C54—C57126.0 (3)
C4—C5—C57122.6 (3)
S1—C5—C57—C540.8 (6)C5—C57—C54—N533.3 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O11.061.692.736 (4)169
N51—H51···O4i0.901.962.848 (4)171
O1—H11···N53ii0.882.072.857 (4)149
O1—H11···S1ii0.882.803.456 (3)132
O1—H12···N53iii0.862.293.122 (4)164
Symmetry codes: (i) x+1/2, y+1, z1/2; (ii) x, y+3/2, z+1/2; (iii) x+1/2, y, z+3/2.
 

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