Crystal structure of N,N′-[(ethane-1,2-diyl)bis(azanediylcarbonothioyl)]bis(benzamide)

A new symmetrical thiocarbonohydrazone derivative with two similar benzoylthioureido functional groups has been prepared and characterized.


Chemical context
Thiourea derivatives have been successfully used in the extraction of some transition metals (i.e. Cu II , Ni II and Co II ) from acidic media. Thiourea derivatives have also been shown to possess antibacterial, antifungal, antitubercular, antithyroid and insecticidal properties (Arslan et al., 2004;Cunha et al., 2007). The structures of several types of thiourea derivatives and its metal complexes have been determined in recent decades. These compounds possess two arms which can act as a tetradentate ligand coordinating through the S atom and the benzoyl O atom of each arm. Urea and thiourea derivatives can behave as catalysts through double interaction by hydrogen bonding with the substrate (Sigman & Jacobsen, 1998;Cortes-Clerget et al., 2016). Thiourea derivatives with alkyl bridges can adopt diverse conformations (Thiam et al., 2008;Pansuriya et al., 2011). We have recently begun to examine the coordination behaviour of a series of substituted benzoylthiourea derivatives that possess a number of interesting properties and reported a thioureido ligand in which the two thioureido moieties are bridged by a 1,2-phenylene ring (Thiam et al., 2008). In this paper, we report the synthesis and the characterization of a molecule where the two thioureidos are bridged by an ethane-1,2-diyl group. ISSN 2056-9890

Supramolecular features
In the crystal, the molecules, which feature an overall Z-form, have both halves roughly parallel to the ac plane, whereas the mid-point of the C1-C1a bond lies orthogonally parallel to the (100) plane. Molecular layers running almost parallel to the ac plane are formed by intermolecular C-HÁ Á ÁO and C-HÁ Á ÁS interactions (Table 1 and Fig. 2). These layers stack along the b direction. Despite the presence of phenyl rings, no interactions are observed in the crystal packing. However, the carbonyl function C3 O1 stacks on phenyl group C4-C9 of a neighbouring layer [O1Á Á ÁCg1 iv = 3.5543 (14) Å ; Cg1 is the centroid of ring C4-C9; symmetry code: (iv) Àx + 1, y + 1 2 , Àz + 1 2 ].

Database survey
Reflecting the interest in compounds similar to the title compound, no less than 35 associated structures are included in the Cambridge Structural Database (Version 5.38; Groom et al., 2016). The match APALEK (Abusaadiya et al., 2016) is the most similar structure to the title compound, the only difference being the substitution of the phenyl ring on the C3 position by a Cl atom. In both cases, the benzoyl functions of each thiourea subunit are trans with respect to the thiono S atom across the C-N bond. The 1-benzoyl-3-ethylthiourea fragment adopts a cis conformation with respect to the thiono S atom across the respective C-N bond. Six structures in which the spacer is different from the spacer in the symmetrical bis ( Table 1 Hydrogen-bond geometry (Å , ). Symmetry codes: (i) x; Ày þ 3 2 ; z À 1 2 ; (ii) Àx þ 1; Ày þ 1; Àz þ 1; (iii) x; Ày þ 3 2 ; z þ 1 2 .

Figure 2
Partial crystal packing of the title compound, showing C-HÁ Á ÁO (red dashed lines) and C-HÁ Á ÁS (yellow dashed lines) interactions (see Table 1 for details).

Synthesis and crystallization
All purchased chemicals and solvents were of reagent grade and were used without further purification. Melting points were determined with a Bü chi 570 melting-point apparatus and were uncorrected. To a mixture of 7.02 g (72 mmol) of potassium thiocyanate and 100 ml of acetone was added dropwise a solution of 10.116 g (72 mmol) of benzoyl chloride in 50 ml of acetone. The resulting mixture was stirred under reflux for 1 h and cooled to room temperature. A solution of 2.2 g (36.6 mmol) of 1,2-ethylenediamine in 20 ml of acetone was added. The yellow solution obtained was stirred at room temperature during 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and a white solid appeared after a few minutes. The compound was filtered off, washed with 3 Â 50 ml of water and dried under vacuum. The solid product was washed with water and purified by recrystallization from an ethanol/dichloromethane mixture (1:1 v/v). 12.3 g of the title compound were obtained (yield 88.5%). A small quantity of powder was recrystallized from 5 ml of DMF. Colourless single crystals suitable to XRD grew within six days.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. Aromatic H atoms were first located by HFIX and other H atoms were located in the difference Fourier map, positioned geometrically and allowed to ride on their respective parent atoms, with C-H = 0.93 (C ar H) or 0.97 Å (CH 2 ). The NH H atoms were located in a difference Fourier map and freely refined.   (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

N,N′-[(Ethane-1,2-diyl)bis(azanediylcarbonothioyl)]bis(benzamide)
Crystal data Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.