2-(5-Iodo-2-oxoindolin-3-yl­idene)hydrazinecarbo­thio­amide including an unknown solvate

Viviane Conceição Duarte de Bittencourt; Vanessa Carratu Gervini; Juliano Rosa de Menezes Vicenti; Jecika Maciel Velasques; Priscilla Jussiane Zambiazi

doi:10.1107/S1600536814010782

. 2014 May 17;70(Pt 6):o666–o667. doi: 10.1107/S1600536814010782

2-(5-Iodo-2-oxoindolin-3-ylidene)hydrazinecarbothioamide including an unknown solvate

Viviane Conceição Duarte de Bittencourt ^a, Vanessa Carratu Gervini ^a,^*, Juliano Rosa de Menezes Vicenti ^a, Jecika Maciel Velasques ^a, Priscilla Jussiane Zambiazi ^b

PMCID: PMC4051098 PMID: 24940248

Abstract

The molecule of the title compound, C₉H₇IN₄OS, is almost planar (r.m.s. deviation = 0.0373 Å). In the molecule, N—H⋯N and N—H⋯O hydrogen bonds generate, respectively, S(5) and S(6) ring motifs. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming chains propagating along [010]. These chains are linked via S⋯I contacts [3.4915 (16) Å], forming sheets lying parallel to (100). A region of disordered electron density, probably a disordered tetrahydrofuran solvent molecule, was treated using the SQUEEZE routine in PLATON [Spek (2009). Acta Cryst. D65, 148–155]. The formula mass and unit-cell characteristics were not taken into account during refinement.

Related literature

For the synthesis, see: Chiyanzu et al. (2003 ▶). For applications, see: Silva et al. (2001 ▶); Chiyanzu et al. (2003 ▶). For similar structures, see: de Bittencourt et al. (2014 ▶); Bandeira et al. (2013 ▶); de Oliveira et al. (2012 ▶). For S⋯I interactions, see: Auffinger et al. (2004 ▶). graphic file with name e-70-0o666-scheme1.jpg

Experimental

Crystal data

C₉H₇IN₄OS
M _r = 346.15
Monoclinic,
a = 33.765 (5) Å
b = 4.4569 (5) Å
c = 19.977 (3) Å
β = 123.100 (4)°
V = 2518.4 (6) Å³
Z = 8
Mo Kα radiation
μ = 2.69 mm⁻¹
T = 100 K
1.15 × 0.10 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: numerical (SADABS; Bruker, 2009 ▶) T _min = 0.701, T _max = 0.777
18679 measured reflections
2892 independent reflections
2577 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.062
S = 1.05
2892 reflections
161 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.50 e Å⁻³
Δρ_min = −1.52 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814010782/bg2528sup1.cif

e-70-0o666-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010782/bg2528Isup2.hkl

e-70-0o666-Isup2.hkl^{(139.1KB, hkl)}

Click here for additional data file.^{(3.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814010782/bg2528Isup3.cml

CCDC reference: 1002200

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H12⋯N3	0.85 (4)	2.28 (4)	2.633 (3)	105 (3)
N2—H21⋯O1	0.83 (4)	2.07 (4)	2.725 (3)	135 (3)
N4—H41⋯O1ⁱ	0.77 (3)	2.04 (4)	2.809 (3)	178 (3)
N1—H11⋯S1ⁱⁱ	0.79 (3)	2.66 (4)	3.448 (3)	170 (3)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We gratefully acknowledge Professor Dr Manfredo Hörner (Federal University of Santa Maria, Brazil) for his help and support with the X-ray measurements. We also acknowledge financial support through the DECIT/SCTIE-MS-CNPq-FAPERGS-Pronem-# 11/2029–1 and PRONEX-CNPq-FAPERGS projects.

supplementary crystallographic information

1. Comment

Isatins and their derivatives are described as compounds with technological applications, such as organic analytical chemistry and pigments and dyes (Silva et al., 2001). Particularly, halogen substituted isatins containing thiosemicarbazone fragment demonstrated biological activity against some trypanosomes (cruzain and rhodesain) and malaria (falcipain-2) parasites (Chiyanzu et al., 2003). In this paper, we describe the crystal structure of 2-(5-Iodo-2-oxoindolin-3-ylidene)-hydrazinecarbothioamide, C₉H₇ON₄SI. There is one molecule in the asymmetric unit (Figure 1), and it is very similar to that of the Cl analogue previously published by us (de Bittencourt et al., 2014). The molecule is almost planar (Bandeira et al., 2013; de Oliveira et al., 2012), displaying a r.m.s. deviation of 0.0373 Å for all fitted non-hydrogenoid atoms (with maximum deviation of 0.1057 (12) observed for S1 atom). Although the same intramolecular S(5) and S(6) ring motifs are verified (Table 1), the crystal packing differs totally when compared with the chloro substituted analog. In the present case, co-operative dimmers are formed through N1—H11···S1ⁱ interactions displaying distances of 2.67 (4) Å. The crystal structure is expanded along the [010] crystallographic direction through N4—H41···O1ⁱⁱ interactions with distances of 2.08 (4) Å, generating a one-dimensional polymer-like motif. One of the most interesting features are the S···Iⁱⁱⁱ contacts which further connects the molecules along the [001] crystallographic direction, presenting distances of 3.4915 (16) Å (Figure 2, symmetry codes: (i) –x, 2–y, –z; (ii) 1/2–x, -1/2 + y, 1/2–z; (iii) x, –y, 1/2 + z). Such S···I short interactions are related to be present in sulfur-containing proteins like cysteine and methionine (Auffinger et al., 2004), being mentioned to play an important hole in biological systems. As a second interesting feature, it was noted disordered solvent molecules occupying accessible voids of 83 Å³, suggestive of tetrahydrofuran, which was indeed used for crystallization. Due to this, collected data was treated using the SQUEEZE routine of the PLATON software (Spek, 2009) in order to remove solvent electronic density. The new HKP file generated was then used for further refinement of the final solvent free crystal structure. For solvent-voids position assignement in the unit cell, a solvent plot calculated by PLATON is shown in Figure 3.

2. Experimental

To 20 ml of ethanol it was mixed 500 mg (1.83 mmol s) of 5-iodo-isatine with 170 mg (1.83 mmol s) of thiosemicarbazide. Then, it was added ten drops of glacial acetic acid and the system was kept under reflux for four hours. After this time, the reaction mixture was cooled and an orange precipitated was filtered off under vacuum and dried at room temperature. m.p. 249–253 °C. Yield: 98%. Crystallization: needle single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporating a solution containing 30 mg of the product dissolved in 5 ml of tetrahydrofuran.