N-[(Morpholin-4-yl)carbonothio­yl]-4-nitro­benzamide

Sohail Saeed; Rashid Mehmood; Wing-Tak Wong; Ghulam Waris; Abdul Manan

doi:10.1107/S1600536810018763

. 2010 May 22;66(Pt 6):o1431–o1432. doi: 10.1107/S1600536810018763

N-[(Morpholin-4-yl)carbonothioyl]-4-nitrobenzamide

Sohail Saeed ^a,^*, Rashid Mehmood ^a, Wing-Tak Wong ^b, Ghulam Waris ^c, Abdul Manan ^c

PMCID: PMC2979403 PMID: 21579507

Abstract

In the title compound, C₁₂H₁₃N₃O₄S, the nitro group is slightly twisted [6.58 (11)°] from the benzene ring plane. The morpholine ring adopts a chair form. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into chains along [110]. There are also π–π contacts [centroid–centroid distance = 3.8301 (11) Å] and C—H⋯π interactions to stack neighbouring benzene rings and link the chains into a three-dimensional network. C—H⋯O and C—H⋯S interactions are also observed.

Related literature

For the use of thiourea derivatives in the analysis of transition metals, see: Arslan et al. (2003 ▶). For the biological and agrochemical activity of thioureas and their transition metal complexes, see: Saeed et al. (2008 ▶, 2009 ▶, 2010 ▶); Che et al. (1999 ▶); Saeed & Parvez (2005 ▶). For their catalytic properties, see: Gu et al. (2007 ▶). For thioureas as ligands in coordination chemistry, see: Burrows et al. (1999 ▶); Henderson et al. (2002 ▶); Schuster et al. (1990 ▶).

Experimental

Crystal data

C₁₂H₁₃N₃O₄S
M _r = 295.31
Triclinic,
a = 6.9867 (11) Å
b = 7.4047 (11) Å
c = 14.261 (2) Å
α = 88.654 (2)°
β = 82.805 (2)°
γ = 65.638 (2)°
V = 666.46 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.943, T _max = 0.980
4478 measured reflections
2916 independent reflections
2485 reflections with I > 2σ(I)
R _int = 0.009

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.106
S = 1.09
2916 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 1996 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT and CrystalStructure (Rigaku/MSC and Rigaku, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018763/sj2785sup1.cif

e-66-o1431-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018763/sj2785Isup2.hkl

e-66-o1431-Isup2.hkl^{(143.1KB, hkl)}

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

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

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O4ⁱ	0.82 (2)	2.27 (2)	3.0947 (17)	178.1 (18)
C3—H3⋯O1ⁱⁱ	0.93	2.43	3.206 (2)	141
C6—H6⋯O3ⁱⁱⁱ	0.93	2.65	3.377 (2)	135
C9—H9B⋯O4^iv	0.97	2.67	3.590 (2)	159
C10—H10A⋯S1^v	0.97	2.98	3.7913 (18)	142
C12—H12B⋯S1^vi	0.97	2.97	3.7196 (18)	135
C2—H2⋯Cg1^vii	0.93	3.45	3.682 (2)	83

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

The authors are grateful to the Department of Chemistry, Research Complex, Allama Iqbal Open University, and the Hong Kong Polytechnic University for providing laboratory and analytical facilities.

supplementary crystallographic information

Comment

Cobalt, nickel and copper are essential elements for biological systems and are present in trace quantities. In each case, trace analysis of these elements requires pre-concentration prior to their analysis. Thiourea derivatives are selective analytical reagents, especially for the determination of transition metals in complex inferring matrices (Arslan et al., 2003). The biological activity of complexes with thiourea derivatives has been successfully screened for various biological actions. Thioureas and their transition metal complexes are found to exhibit a wide range of biological activities including anticancer (Saeed et al., 2010), antifungal (Saeed et al., 2008), antiviral, antibacterial (Saeed et al., 2009), anti-tubercular, anti-thyroidal, herbicidal and insecticidal activities, organocatalyst (Gu et al., 2007). Thioureas also have a long history as ligands in coordination chemistry and coordinate to a metal via sulfur and oxygen (Burrows et al., 1999). These hard and soft donor atoms provide a multitude of bonding possibilities (Henderson et al., 2002). Hydrogen bonding behavior of some thioureas has been investigated and it is found that intramolecular hydrogen bonds between the carbonyl oxygen and a hydrogen atom on N' is common. The complexing capacity of thiourea derivatives has been reported in several papers (Schuster et al., 1990). Some acyl thioureas have been found to possess pesticidal activities and promote plant growth (Saeed & Parvez, 2005) while some have been shown to have notable positive effect on the germination of maize seeds as well as on the chlorophyll contents in seedling leaves (Che et al., 1999). With the simultaneous presence of S, N and O electron donors, the versalitility and interesting behavior of acylthioureas as building blocks in polydentate ligands for metal ions have become a topic of interest in the last few years.It has been reported that substituted acylthiourea ligands might act as monodentate sulfur donors, bidentate oxygen and nitrogen donors. As a part of our continuing interest in biologically active thiourea derivatives and their transition metal complexes, we are reporting a route for synthesis of these compounds by using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC) to augment the yield of products. In view of the above and in continuation of our research program concerned with structural modification of certain biologically active thiourea derivatives and their transition metal complexes with the purpose of enhancing their biological activity, we aimed to incorporate the aliphatic and aromatic moieties in the substituted phenyl nucleus with thiourea functionality to obtain new functions in an attempt to improve the antimicrobial profile of compounds. The compound, N-(morpholine-4-carbothioyl)-4-nitro-benzamide, crystallizes in a triclinic primitive space group, P -1 (#2). Like its other analogue, the molecule is not planar. The nitro group, N1/O1/O2, is slightly twisted (6.58 (11)°) from the benzene ring plane of C1—C6. The thioureido group is also twisted. The amide group C4/C7/O3/N2 is making a dihedral angle of 25.68 (5)° with the benzene ring plane and 65.10 (6)° with the thiourea group, N2/C8/S1/N3. The morpholine ring is in the chair form.

Inter-molecular N2—H2N···O4 H-bond interactions link the molecules to form 1-dimensional chains in the [110] plane in the crystal lattice Table 1. π–π interactions help to stack the chains into 3-D network. The centroid-to-centroid distance of the ring C1—C6 and (C1—C6)ⁱ (ⁱ symmetry code: -x, 1-y, 1-z) 3.8301 (11) and the perpendicular distance between the centriod of C1—C6 and mean plane of (C1—C6)ⁱ is 3.449 Å. C—H···π interactions are also obseved with the distance between H2ⁱⁱ and centroid of C1—C6 3.454Å (ⁱⁱ symmetry code: -x, 2-y, 1-z) Table 1.

Experimental

All the chemicals used for the preparation were of reagent grade quality. The ammonium thiocyanate was dried by heating at 100°C and the acetone using potassium carbonate. A solution of 4-nitrobenzoyl chloride (0.01 mol) in anhydrous acetone (80 ml) and 3% tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC) in anhydrous acetone was added dropwise to a suspension of dry ammonium thiocyanate (0.01 mol) in acetone (50 ml) and the reaction mixture was refluxed for 45 min. After cooling to room temperature, a solution of morpholine (0.01 mol) in anhydrous acetone (25 ml) was added dropwise and the resulting mixture refluxed for 3 h. Hydrochloric acid (0.1 M, 400 ml) was added, and the solution was filtered. The solid product was washed with water and purified by re-crystallization from an ethanol-dichloromethane mixture (1:2).