1-Benzoyl-3-(4-chloro­phen­yl)thio­urea dichloro­methane hemisolvate

N Selvakumaran; M Mary Sheeba; R Karvembu; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812045588

. 2012 Nov 10;68(Pt 12):o3313. doi: 10.1107/S1600536812045588

1-Benzoyl-3-(4-chlorophenyl)thiourea dichloromethane hemisolvate

N Selvakumaran ^a, M Mary Sheeba ^a, R Karvembu ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3588922 PMID: 23476158

Abstract

In the title hemisolvate, C₁₄H₁₁ClN₂OS·0.5CH₂Cl₂, an anti disposition is found for the thione and ketone atoms, as well as the N—H H atoms; the dichloromethane C atom lies on a twofold axis. The central chromophore (including the two adjacent ipso C atoms) is planar (r.m.s. deviation = 0.021 Å) owing to the presence of an intramolecular N—H⋯O hydrogen bond, which closes an S(6) loop. Significant twists are evident in the molecule, the dihedral angles between the central moiety and the phenyl and benzene rings being 29.52 (7) and 40.02 (7)°, respectively. In the crystal, eight-membered {⋯HNC= S}₂ synthons with twofold symmetry form via N—H⋯S hydrogen bonds. The dimers are connected into a supramolecular chain along [111] by C—H⋯O interactions. The chains stack along the c axis, forming columns which define channels in which the occluded dichloromethane molecules reside.

Related literature

For complexation of N-benzoyl-N′-arylthiourea derivatives to transition metals, see: Selvakumaran et al. (2011 ▶). For related structures, see: Khawar Rauf et al. (2006 ▶); Selvakumaran et al. (2012 ▶). graphic file with name e-68-o3313-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₁ClN₂OS·0.5CH₂Cl₂
M _r = 333.23
Monoclinic,
a = 20.0800 (4) Å
b = 16.0136 (2) Å
c = 10.3752 (2) Å
β = 117.690 (3)°
V = 2954.10 (9) Å³
Z = 8
Cu Kα radiation
μ = 5.26 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.619, T _max = 1.000
5766 measured reflections
2937 independent reflections
2802 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.090
S = 1.05
2937 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶), DIAMOND (Brandenburg, 2006 ▶) and Qmol (Gans & Shalloway, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(18.2KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812045588/hg5268sup1.cif

e-68-o3313-sup1.cif^{(18.2KB, cif)}

Click here for additional data file.^{(144.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045588/hg5268Isup2.hkl

e-68-o3313-Isup2.hkl^{(144.2KB, hkl)}

Click here for additional data file.^{(5.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812045588/hg5268Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯O1	0.90 (2)	1.85 (2)	2.6034 (17)	140.6 (18)
N1—H1n⋯S1ⁱ	0.87 (2)	2.59 (2)	3.4368 (15)	167 (2)
C12—H12⋯O1ⁱⁱ	0.95	2.47	3.3743 (19)	160

Open in a new tab

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

Acknowledgments

NS thanks NITT for a Fellowship. The authors also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

supplementary crystallographic information

Comment

As part of continuing studies of N-benzoyl-N'-arylthiourea derivatives (Selvakumaran et al., 2012) and their coordination to transition metals such as Pd^II (Selvakumaran et al., 2011), the title compound (I) was investigated as its dichloromethane hemi-solvate. The structure of the unsolvated form is available for comparison (Khawar Rauf et al., 2006).

In (I), Fig. 1, anti dispositions are found for the thione and ketone atoms, and for the N—H H-atoms. The central chromophore (including the two adjacent ipso C atoms) is planar with a r.m.s. deviation of 0.021 Å [maximum deviations of 0.033 (1) Å for N1, and -0.023 (1) Å for S1] owing to the presence of an intramolecular N—H···O hydrogen bond which closes an S(6) loop, Table 1. The observed disposition of atoms is the same as for the unsolvated form (Khawar Rauf et al., 2006).

A significant twist is evident in (I) as seen in the dihedral angles of 29.52 (7) and 40.02 (7)° formed between the central moiety and the C1-phenyl and C9-benzene rings, respectively. The dihedral angle between the six-membered rings is 11.11 (9)°. This pattern of dihedral angles contrasts the situation for the unsolvated form where the comparable dihedral angles are 41.42 (8), 2.77 (8) and 43.93 (10)°, respectively, indicating a significantly greater twist in the molecule as highlighted in the overlay diagram, Fig. 2.

Eight-membered {···HNC═S}₂ synthons (2-fold symmetry) feature in the crystal packing which arise via N—H···S hydrogen bonds and these are connected into a supramolecular chain along [111] by C—H···O interactions which stabilize centrosymmetric 18-membered {···OCNCNC₃H}₂ synthons., Fig. 3 and Table 1. Chains stack along the c axis to form columns which define channels in which the occluded dichloromethane molecules (with 2-fold axis symmetry) reside. There are no specific interactions between the chains nor with the solvent molecules, Fig. 4.

Experimental

A solution of benzoyl chloride (0.005 mol, 0.7029 g) in acetone (30 ml) was added drop wise to a suspension of potassium thiocyanate (0.005 mol, 0.4859 g) in anhydrous acetone (30 ml). The reaction mixture was heated under reflux for 45 minutes and then cooled to room temperature. A solution of '4-chloroaniline (0.005 mol, 0.6379 g) in acetone (30 ml) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and resulting solid was filtered, washed with water and dried in vacuo. The resulting solid product (78% yield) was recrystallized as colourless blocks from its ethanol/dichloromethane (1:2 ratio) solution. Characterization (dried sample): M.pt: 411 K, Anal. Calcd. For C₁₄H₁₁ClN₂O₂S (%): C, 57.8; H, 3.81; N, 9.63; Found: C, 57.5; H, 4.0; N, 9.8. ¹H NMR: δ (400 MHz, CDCl₃, p.p.m.): 7.35–7.88 (m, 9H); 9.14 (s, 1H, thiourea NH); 12.58 (s, 1H, amide NH). ¹³C NMR: δ (400 MHz, CDCl₃, p.p.m.): 125.3; 127.5; 129.0; 129.2; 131.4; 132.1; 133.8; 136.1; 167.0; 178.4. IR (KBr, cm^-1): 3230 ν(amide N–H), 3028 ν(thiourea N–H), 1688 ν(C=O), 1262 ν(C=S).