A monoclinic polymorph of (1E,5E)-1,5-bis­(2-hy­droxy­benzyl­idene)thio­carbono­hydrazide

Bonell Schmitt; Thomas Gerber; Eric Hosten; Richard Betz

doi:10.1107/S1600536811030340

. 2011 Jul 30;67(Pt 8):o2206–o2207. doi: 10.1107/S1600536811030340

A monoclinic polymorph of (1E,5E)-1,5-bis(2-hydroxybenzylidene)thiocarbonohydrazide

Bonell Schmitt ^a, Thomas Gerber ^a, Eric Hosten ^a, Richard Betz ^a,^*

PMCID: PMC3213636 PMID: 22091213

Abstract

The title compound, C₁₅H₁₄N₄O₂S, is a derivative of thioureadihydrazide. In contrast to the previously reported polymorph (orthorhombic, space group Pbca, Z = 8), the current study revealed monoclinic symmetry (space group P2₁/n, Z = 4). The molecule shows non-crystallographic C ₂ as well as approximate C _s symmetry. Intramolecular bifurcated O—H⋯(N,S) hydrogen bonds, are present. In the crystal, intermolecular N—H⋯S hydrogen bonds and C—H⋯π contacts connect the molecules into undulating chains along the b axis. The shortest centroid–centroid distance between two aromatic systems is 4.5285 (12) Å.

Related literature

For the crystal structure of the orthorhombic polymorph of the title compound reported without three-dimensional coordinates, see: Yanping et al. (1999 ▶). For the crystal structure of a methylated derivative of the title compound, see: Affan et al. (2010 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). Structures containing similar C=S distances were retrieved from the Cambridge Structural Database (Allen, 2002 ▶). For chelate ligands in coordination chemistry, see: Gade (1998 ▶).

Experimental

Crystal data

C₁₅H₁₄N₄O₂S
M _r = 314.36
Monoclinic,
a = 5.6020 (1) Å
b = 7.4260 (2) Å
c = 34.5220 (8) Å
β = 91.225 (1)°
V = 1435.80 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 200 K
0.20 × 0.17 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.879, T _max = 1.000
13304 measured reflections
3578 independent reflections
2830 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.116
S = 1.11
3578 reflections
209 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030340/kj2182sup1.cif

e-67-o2206-sup1.cif^{(17.4KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536811030340/kj2182Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030340/kj2182Isup3.hkl

e-67-o2206-Isup3.hkl^{(175.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811030340/kj2182Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

C _g1 and C _g2 are the centroids of the C11–C16 and C21–C26 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H81⋯N2	0.84	1.87	2.597 (2)	144
O1—H81⋯S1	0.84	2.99	3.7096 (14)	145
O2—H82⋯N4	0.84	1.89	2.617 (2)	144
O2—H82⋯S1	0.84	3.08	3.8135 (16)	147
N1—H71⋯S1ⁱ	0.86 (2)	2.53 (2)	3.3514 (17)	159 (2)
N3—H73⋯S1ⁱ	0.85 (3)	2.82 (3)	3.5605 (18)	147 (2)
C16—H16⋯C_g2ⁱ	0.95	2.81	3.423 (2)	123
C26—H26⋯C_g1ⁱ	0.95	2.74	3.438 (2)	130

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Mrs Gisela Bräuer for helpful discussions.

supplementary crystallographic information

Comment

Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of resultant coordination compounds in relation to coordination compounds exclusively applying comparable monodentate ligands (Gade, 1998). Combining different donor atoms, a molecular set-up to accomodate a large variety of metal centers of variable Lewis acidity is at hand. In this aspect, the title compound seemed particularily interesting due to its use as strictly neutral or – depending on the pH value – as anionic or cationic ligand. In addition, due to the set-up of its donor atoms, a multitude of differently-sized chelate ligands can be formed. The presence of a thioketo group as well as amino groups, hydroxyl groups and imine-type nitrogen atoms further enhances the versatility of the title compound's ligating abilities. In our continuous interest in elucidating the rules influencing the formation of coordination compounds with different set-ups of NOS-donor atoms, we determined the crystal structure of the title compound to enable comparative studies with geometric parameters in envisioned coordination compounds. Although the compound has been reported to crystallize in the orthorhombic space group Pbca (Yanping et al., 1999), we found a monoclinic polymorph. Furthermore, no three-dimensional coordinates have been deposited for the former structure solution. The molecular and crystal structure of a methyl-substituted derivative of the title compound is apparent in the literature as well (Affan et al., 2010).

The molecule is essentially planar. The least-squares planes defined by the carbon atoms of the phenyl groups (including the respective C=N moiety) intersect at an angle of only 5.33 (8) °. The least-squares plane defined by the atoms of the central N₂C=S motif encloses angles of 7.26 (8) ° and 11.75 (7) ° with the aforementioned least-squares planes, respectively (Fig. 1). The C=N double bonds are invariably (E)-configured. The length of the C=S bond is in good agreement with values reported for other thioketones whose crystal structural data have been deposited with the Cambridge Structural Database (Allen, 2002), the reported range being 1.297–1.864 Å.

In the crystal structure, intra- as well as intermolecular hydrogen bonds are apparent. While the intramolecular hydrogen bond – stemming from the hydroxyl group – shows bifurcation between the sulfur atom as well as the imine-type nitrogen atom, the intermolecular hydrogen bonds exclusively have the sulfur atom as acceptor. The presence of the sulfur-supported hydrogen bond is complemented by the results of IR spectroscopy that show the presence of three bands in the region for hydrogen bonds between oxygen, nitrogen and sulfur. In addition, C–H···π contacts can be observed that involve hydrogen atoms on the aromatic system. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the bifurcated hydrogen bond is S(6)S(9) on the unitary level while the amino-group-supported hydrogen bonds necessitate a C¹₁(4)C¹₁(4) descriptor on the same level. A binary descriptor of R¹₂(6) emphasizes the "chelation" of the sulfur atom by the two secondary amino groups. In total, the molecules are connected to waved, zigzag-type chains along the crystallographic b axis. The shortest intercentroid distance between two π-systems was measured at 4.5285 (12) Å and involves both aromatic moieties (Fig. 2).

Experimental

The compound was prepared upon reacting thiocarbohydrazide (0.50 mmol) with ortho-hydroxybenzaldehyde (1.00 mmol) in refluxing ethanol (15 ml) under nitrogen in analogy to a published procedure (Yanping et al., 1999). Crystals suitable for the X-ray diffraction study were obtained upon slow evaporation of the reaction mixture.