Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112043260/sf3183sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112043260/sf3183Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112043260/sf3183Isup3.cml |
CCDC reference: 914659
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).
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.
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°.
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).
C8H7N3OS2·H2O | F(000) = 1008 |
Mr = 243.32 | Dx = 1.558 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2384 reflections |
a = 7.4110 (6) Å | θ = 2.8–27.5° |
b = 16.2739 (18) Å | µ = 0.50 mm−1 |
c = 17.201 (2) Å | T = 120 K |
V = 2074.5 (4) Å3 | Plate, colourless |
Z = 8 | 0.40 × 0.28 × 0.10 mm |
Bruker–Nonius KappaCCD diffractometer | 2384 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 1449 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.119 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −21→17 |
Tmin = 0.826, Tmax = 0.952 | l = −22→22 |
23037 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-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 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C8H7N3OS2·H2O | V = 2074.5 (4) Å3 |
Mr = 243.32 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.4110 (6) Å | µ = 0.50 mm−1 |
b = 16.2739 (18) Å | T = 120 K |
c = 17.201 (2) Å | 0.40 × 0.28 × 0.10 mm |
Bruker–Nonius KappaCCD diffractometer | 2384 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1449 reflections with I > 2σ(I) |
Tmin = 0.826, Tmax = 0.952 | Rint = 0.119 |
23037 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.47 e Å−3 |
2384 reflections | Δρmin = −0.39 e Å−3 |
137 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.47426 (13) | 0.72683 (5) | 0.63974 (5) | 0.0228 (3) | |
C2 | 0.5126 (5) | 0.7666 (2) | 0.7330 (2) | 0.0224 (8) | |
S2 | 0.58807 (13) | 0.85987 (6) | 0.74867 (5) | 0.0256 (3) | |
N3 | 0.4701 (4) | 0.70945 (19) | 0.78858 (16) | 0.0235 (7) | |
H3 | 0.4801 | 0.7237 | 0.8483 | 0.028* | |
C4 | 0.4014 (5) | 0.6349 (2) | 0.7630 (2) | 0.0234 (8) | |
O4 | 0.3547 (4) | 0.57928 (16) | 0.80648 (14) | 0.0307 (7) | |
C5 | 0.3927 (5) | 0.6334 (2) | 0.6771 (2) | 0.0210 (8) | |
C57 | 0.3266 (5) | 0.5694 (2) | 0.6375 (2) | 0.0216 (8) | |
H57 | 0.2872 | 0.5239 | 0.6678 | 0.026* | |
N51 | 0.2541 (4) | 0.51311 (19) | 0.43903 (17) | 0.0248 (7) | |
H51 | 0.2324 | 0.4824 | 0.3967 | 0.030* | |
C52 | 0.3172 (5) | 0.5909 (2) | 0.4338 (2) | 0.0253 (8) | |
H52 | 0.3352 | 0.6188 | 0.3860 | 0.030* | |
N53 | 0.3509 (4) | 0.62340 (18) | 0.50189 (17) | 0.0225 (7) | |
C54 | 0.3082 (5) | 0.5612 (2) | 0.55531 (19) | 0.0213 (8) | |
C55 | 0.2464 (5) | 0.4923 (2) | 0.5162 (2) | 0.0241 (8) | |
C56 | 0.1835 (5) | 0.4106 (2) | 0.5454 (2) | 0.0319 (9) | |
H56A | 0.2791 | 0.3852 | 0.5766 | 0.048* | |
H56B | 0.1546 | 0.3750 | 0.5012 | 0.048* | |
H56C | 0.0755 | 0.4181 | 0.5776 | 0.048* | |
O1 | 0.5304 (4) | 0.73387 (15) | 0.94381 (14) | 0.0267 (6) | |
H11 | 0.5010 | 0.7729 | 0.9771 | 0.040* | |
H12 | 0.6091 | 0.7053 | 0.9682 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0305 (5) | 0.0221 (5) | 0.0158 (4) | −0.0029 (4) | −0.0005 (4) | 0.0000 (3) |
C2 | 0.0203 (19) | 0.027 (2) | 0.0199 (18) | 0.0004 (16) | −0.0005 (14) | −0.0012 (15) |
S2 | 0.0299 (5) | 0.0250 (5) | 0.0219 (5) | −0.0050 (4) | 0.0019 (4) | −0.0042 (4) |
N3 | 0.0288 (17) | 0.0243 (16) | 0.0174 (15) | −0.0010 (14) | 0.0003 (13) | −0.0020 (12) |
C4 | 0.0211 (18) | 0.028 (2) | 0.021 (2) | 0.0032 (16) | 0.0002 (15) | −0.0014 (16) |
O4 | 0.0497 (18) | 0.0258 (15) | 0.0167 (12) | −0.0059 (13) | 0.0012 (12) | 0.0061 (11) |
C5 | 0.0222 (19) | 0.024 (2) | 0.0172 (17) | −0.0005 (15) | −0.0001 (14) | 0.0038 (14) |
C57 | 0.0224 (19) | 0.0202 (18) | 0.0222 (18) | −0.0004 (15) | 0.0003 (15) | 0.0027 (15) |
N51 | 0.0220 (17) | 0.0298 (18) | 0.0226 (17) | 0.0040 (14) | −0.0015 (13) | −0.0076 (13) |
C52 | 0.027 (2) | 0.030 (2) | 0.0194 (18) | −0.0004 (17) | −0.0002 (16) | 0.0017 (16) |
N53 | 0.0260 (17) | 0.0242 (16) | 0.0174 (15) | −0.0006 (12) | 0.0001 (12) | 0.0002 (12) |
C54 | 0.0220 (18) | 0.0202 (19) | 0.0217 (17) | 0.0001 (15) | −0.0009 (14) | 0.0018 (15) |
C55 | 0.0214 (19) | 0.026 (2) | 0.025 (2) | 0.0039 (16) | −0.0008 (16) | −0.0023 (16) |
C56 | 0.032 (2) | 0.022 (2) | 0.042 (2) | −0.0013 (17) | −0.0032 (19) | −0.0019 (18) |
O1 | 0.0378 (15) | 0.0252 (14) | 0.0170 (12) | 0.0046 (12) | 0.0011 (11) | −0.0036 (10) |
S1—C2 | 1.754 (4) | N51—C55 | 1.372 (4) |
S1—C5 | 1.759 (4) | N51—H51 | 0.8973 |
C2—N3 | 1.371 (5) | C52—N53 | 1.309 (5) |
C2—S2 | 1.639 (4) | C52—H52 | 0.9500 |
N3—C4 | 1.387 (5) | N53—C54 | 1.404 (4) |
N3—H3 | 1.0563 | C54—C55 | 1.385 (5) |
C4—O4 | 1.225 (4) | C55—C56 | 1.495 (5) |
C4—C5 | 1.478 (5) | C56—H56A | 0.9800 |
C5—C57 | 1.337 (5) | C56—H56B | 0.9800 |
C57—C54 | 1.427 (5) | C56—H56C | 0.9800 |
C57—H57 | 0.9500 | O1—H11 | 0.8826 |
N51—C52 | 1.352 (5) | O1—H12 | 0.8564 |
C2—S1—C5 | 92.32 (17) | C55—N51—H51 | 129.8 |
N3—C2—S2 | 126.3 (3) | N53—C52—N51 | 112.7 (3) |
N3—C2—S1 | 110.5 (3) | N53—C52—H52 | 123.7 |
S2—C2—S1 | 123.2 (2) | N51—C52—H52 | 123.7 |
C2—N3—C4 | 117.2 (3) | C52—N53—C54 | 104.5 (3) |
C2—N3—H3 | 120.9 | C55—C54—N53 | 109.9 (3) |
C4—N3—H3 | 121.8 | N53—C54—C57 | 124.0 (3) |
O4—C4—N3 | 123.8 (3) | C55—C54—C57 | 126.0 (3) |
O4—C4—C5 | 125.8 (3) | N51—C55—C54 | 104.8 (3) |
N3—C4—C5 | 110.4 (3) | N51—C55—C56 | 123.9 (3) |
C5—C57—C54 | 127.8 (3) | C54—C55—C56 | 131.3 (3) |
S1—C5—C57 | 127.8 (3) | C55—C56—H56A | 109.5 |
C4—C5—C57 | 122.6 (3) | C55—C56—H56B | 109.5 |
C4—C5—S1 | 109.6 (3) | H56A—C56—H56B | 109.5 |
C5—C57—H57 | 116.1 | C55—C56—H56C | 109.5 |
C54—C57—H57 | 116.1 | H56A—C56—H56C | 109.5 |
C52—N51—C55 | 108.0 (3) | H56B—C56—H56C | 109.5 |
C52—N51—H51 | 122.0 | H11—O1—H12 | 103.9 |
C5—S1—C2—N3 | 1.9 (3) | S1—C5—C57—C54 | 0.8 (6) |
C5—S1—C2—S2 | −177.8 (3) | C55—N51—C52—N53 | −0.4 (4) |
S2—C2—N3—C4 | 177.5 (3) | N51—C52—N53—C54 | 0.8 (4) |
S1—C2—N3—C4 | −2.2 (4) | C52—N53—C54—C55 | −0.9 (4) |
C2—N3—C4—O4 | −178.5 (4) | C52—N53—C54—C57 | 179.3 (3) |
C2—N3—C4—C5 | 1.2 (4) | C5—C57—C54—C55 | 176.9 (4) |
O4—C4—C5—C57 | 1.7 (6) | C5—C57—C54—N53 | −3.3 (6) |
N3—C4—C5—C57 | −178.0 (3) | C52—N51—C55—C54 | −0.2 (4) |
O4—C4—C5—S1 | −180.0 (3) | C52—N51—C55—C56 | −179.8 (3) |
N3—C4—C5—S1 | 0.3 (4) | N53—C54—C55—N51 | 0.7 (4) |
C2—S1—C5—C57 | 177.0 (4) | C57—C54—C55—N51 | −179.5 (3) |
C2—S1—C5—C4 | −1.3 (3) | N53—C54—C55—C56 | −179.7 (4) |
C4—C5—C57—C54 | 178.8 (3) | C57—C54—C55—C56 | 0.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 1.06 | 1.69 | 2.736 (4) | 169 |
N51—H51···O4i | 0.90 | 1.96 | 2.848 (4) | 171 |
O1—H11···N53ii | 0.88 | 2.07 | 2.857 (4) | 149 |
O1—H11···S1ii | 0.88 | 2.80 | 3.456 (3) | 132 |
O1—H12···N53iii | 0.86 | 2.29 | 3.122 (4) | 164 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) x+1/2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C8H7N3OS2·H2O |
Mr | 243.32 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 7.4110 (6), 16.2739 (18), 17.201 (2) |
V (Å3) | 2074.5 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.40 × 0.28 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.826, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23037, 2384, 1449 |
Rint | 0.119 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.164, 1.08 |
No. of reflections | 2384 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
C5—C57—C54 | 127.8 (3) | N53—C54—C57 | 124.0 (3) |
S1—C5—C57 | 127.8 (3) | C55—C54—C57 | 126.0 (3) |
C4—C5—C57 | 122.6 (3) | ||
S1—C5—C57—C54 | 0.8 (6) | C5—C57—C54—N53 | −3.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 1.06 | 1.69 | 2.736 (4) | 169 |
N51—H51···O4i | 0.90 | 1.96 | 2.848 (4) | 171 |
O1—H11···N53ii | 0.88 | 2.07 | 2.857 (4) | 149 |
O1—H11···S1ii | 0.88 | 2.80 | 3.456 (3) | 132 |
O1—H12···N53iii | 0.86 | 2.29 | 3.122 (4) | 164 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) x+1/2, y, −z+3/2. |
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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 π–π 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.