1,1′-(Ethane-1,2-di­yl)bis­[3-(4-chloro­benzoyl)­thio­urea]

Abusaadiya, S.M.; Yamin, B.M.; Ngatiman, F.; Hasbullah, S.A.

doi:10.1107/S2414314616009275

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160927

doi:10.1107/S2414314616009275

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1,1′-(Ethane-1,2-diyl)bis[3-(4-chlorobenzoyl)thiourea]

Salima M. Abusaadiya,^a Bohari M. Yamin,^a Fadzlee Ngatiman ^a and Siti Aishah Hasbullah ^a ^*

^aSchool of Chemical sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor D.E., Malaysia
^*Correspondence e-mail: Aishah80@ukm.edu.my

Edited by J. Simpson, University of Otago, New Zealand (Received 19 May 2016; accepted 8 June 2016; online 17 June 2016)

The title compound, C₁₈H₁₆Cl₂N₄O₂S₂, consists of two benzoylthioureido groups connected by an ethylene group. The asymmetric unit consists of one half of the molecule which lies about an inversion center. Both thiourea moieties maintain their trans geometry. The structure is stabilized by intermolecular N—H⋯S hydrogen bonds that form chains along the b-axis direction.

Keywords: crystal structure; bisthiourea; ethylenediamine; benzoylthioureido; hydrogen bonds; one-dimensional chains.

CCDC reference: 1484012

Structure description

Multipodal thiourea compounds are expected to be useful for molecular recognition studies and as ionophores for sensor development due to the nucleophilic nature of the sulfur atoms. In addition, the biological properties of thiourea are well known (Korkmaz et al., 2015 ). 1,1′-(Ethane-1,2-diyl)bis(3-phenylthiourea) is one of the few reported bisthiourea structures with an ethylene group as linker (Pansuriya et al., 2011 ). The present compound is similar except that it is a benzoyl rather than a phenylthiourea derivative. The asymmetric unit consists of one half of the molecule as the molecule lies about a center of inversion located at the midpoint of the C9—C9A bond (Fig. 1). Both thiourea moieties adopt a trans geometry and the thiono groups are also in a trans orientation with respect to the chlorobenzoyl group. The thiourea fragments S1/N1/N2/C7/C8 are planar with a maximum deviation from the least-squares plane of 0.008 (1) Å for the N1 atom. The dihedral angle between this plane and that of the benzene ring is 34.48 (8)°, which is considerably smaller than that found in 1,1′-(ethane-1,2-diyl)bis(3-phenylthiourea), 52.9 (4)°. Other bond lengths and angles are comparable to those in the analog and lie in normal ranges. As with most carbonoylthiourea derivatives, the molecule forms intramolecular N2—H2A⋯O1 hydrogen bonds between the carbonyl oxygen and the thioamide hydrogen atoms, to form S(6) rings.

Figure 1
The molecular structure with displacement ellipsoids drawn at the 50% probability level. The dashed lines indicate intramolecular hydrogen bonds.

In the crystal packing, molecules are linked by inversion-related intermolecular N1—H1A⋯S1 hydrogen bonds (Table 1), forming chains along the b-axis direction (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.87 (2)	2.01 (3)	2.670 (2)	133 (2)
N1—H1A⋯S1ⁱ	0.86 (1)	2.73 (2)	3.5203 (14)	153 (1)
Symmetry code: (i) -x+1, -y+2, -z.

Figure 2
The crystal packing of the title compound viewed along the a axis. The dashed lines indicate hydrogen bonds.

Synthesis and crystallization

An acetonitrile solution (30 ml) of ethylenediamine (0.30 g, 0.005 mol) was added dropwise into a two-necked round-bottomed flask containing 4-chlorobenzoylisothiocyanate (1.96 g, 0.01 mol). The mixture was refluxed for about 4 h, filtered into a beaker and left for the solvent to evaporate at room temperature. The resulting yellow precipitate was washed with cold ethanol. Crystals suitable for X-ray study were obtained by recrystallization from DMSO.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₆Cl₂N₄O₂S₂
M_r	455.37
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	300
a, b, c (Å)	6.0099 (3), 8.7905 (4), 9.2603 (4)
α, β, γ (°)	91.030 (2), 91.835 (2), 94.878 (2)
V (Å³)	487.09 (4)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.57
Crystal size (mm)	0.50 × 0.47 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.763, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	20610, 2421, 1985
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.06
No. of reflections	2421
No. of parameters	135
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.40
Computer programs: SMART and SAINT (Bruker, 2000), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1484012

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616009275/sj4038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616009275/sj4038Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

1,1'-(Ethane-1,2-diyl)bis[3-(4-chlorobenzoyl)thiourea] top

Crystal data top

C₁₈H₁₆Cl₂N₄O₂S₂	Z = 1
M_r = 455.37	F(000) = 234
Triclinic, P1	D_x = 1.552 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0099 (3) Å	Cell parameters from 20610 reflections
b = 8.7905 (4) Å	θ = 3.1–28.5°
c = 9.2603 (4) Å	µ = 0.57 mm⁻¹
α = 91.030 (2)°	T = 300 K
β = 91.835 (2)°	Block, colourless
γ = 94.878 (2)°	0.50 × 0.47 × 0.10 mm
V = 487.09 (4) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2421 independent reflections
Radiation source: fine-focus sealed tube	1985 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 83.66 pixels mm^-1	θ_max = 28.5°, θ_min = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −11→11
T_min = 0.763, T_max = 0.945	l = −12→12
20610 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0389P)² + 0.2974P] where P = (F_o² + 2F_c²)/3
2421 reflections	(Δ/σ)_max = 0.001
135 parameters	Δρ_max = 0.22 e Å⁻³
2 restraints	Δρ_min = −0.40 e Å⁻³

Special details top

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.35967 (9)	1.43588 (6)	0.67959 (5)	0.04843 (16)
S1	0.41800 (7)	0.75184 (5)	−0.05845 (5)	0.03377 (14)
O1	−0.1332 (2)	0.92654 (15)	0.20898 (15)	0.0379 (3)
N1	0.2191 (2)	0.92314 (16)	0.12526 (16)	0.0310 (3)
H1A	0.342 (2)	0.981 (2)	0.120 (2)	0.035 (5)*
N2	0.0029 (2)	0.71056 (16)	0.03437 (17)	0.0306 (3)
H2A	−0.107 (3)	0.743 (3)	0.081 (3)	0.059 (8)*
C1	−0.0034 (3)	1.1925 (2)	0.3763 (2)	0.0350 (4)
H1	−0.1497	1.1852	0.3394	0.042*
C2	0.0614 (3)	1.2974 (2)	0.4854 (2)	0.0377 (4)
H2	−0.0401	1.3614	0.5215	0.045*
C3	0.2780 (3)	1.3064 (2)	0.54035 (18)	0.0315 (4)
C4	0.4312 (3)	1.2145 (2)	0.4867 (2)	0.0353 (4)
H4	0.5772	1.2221	0.5243	0.042*
C5	0.3664 (3)	1.1105 (2)	0.37613 (19)	0.0320 (4)
H5	0.4696	1.0488	0.3386	0.038*
C6	0.1481 (3)	1.09795 (18)	0.32110 (17)	0.0264 (3)
C7	0.0619 (3)	0.97689 (18)	0.21382 (18)	0.0272 (3)
C8	0.1979 (3)	0.79277 (18)	0.03623 (18)	0.0263 (3)
C9	−0.0421 (3)	0.56512 (18)	−0.0434 (2)	0.0311 (4)
H9A	0.0307	0.5703	−0.1354	0.037*
H9B	−0.2016	0.5455	−0.0626	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0560 (3)	0.0468 (3)	0.0394 (3)	−0.0113 (2)	0.0062 (2)	−0.0203 (2)
S1	0.0291 (2)	0.0325 (2)	0.0389 (3)	−0.00209 (17)	0.00894 (17)	−0.01205 (18)
O1	0.0314 (7)	0.0346 (7)	0.0465 (8)	−0.0026 (5)	0.0073 (5)	−0.0130 (6)
N1	0.0312 (8)	0.0248 (7)	0.0352 (8)	−0.0084 (6)	0.0113 (6)	−0.0112 (6)
N2	0.0280 (7)	0.0213 (7)	0.0419 (8)	−0.0017 (5)	0.0087 (6)	−0.0104 (6)
C1	0.0296 (9)	0.0348 (9)	0.0406 (10)	0.0045 (7)	0.0017 (7)	−0.0106 (8)
C2	0.0380 (10)	0.0327 (9)	0.0426 (10)	0.0054 (8)	0.0077 (8)	−0.0136 (8)
C3	0.0392 (9)	0.0271 (8)	0.0270 (8)	−0.0044 (7)	0.0065 (7)	−0.0070 (6)
C4	0.0309 (9)	0.0407 (10)	0.0334 (9)	0.0005 (7)	0.0003 (7)	−0.0059 (7)
C5	0.0322 (9)	0.0318 (9)	0.0324 (9)	0.0048 (7)	0.0048 (7)	−0.0055 (7)
C6	0.0330 (9)	0.0210 (7)	0.0250 (8)	0.0004 (6)	0.0056 (6)	−0.0027 (6)
C7	0.0329 (9)	0.0209 (7)	0.0275 (8)	−0.0002 (6)	0.0051 (6)	−0.0029 (6)
C8	0.0302 (8)	0.0199 (7)	0.0285 (8)	−0.0006 (6)	0.0034 (6)	−0.0035 (6)
C9	0.0293 (8)	0.0223 (8)	0.0403 (10)	−0.0034 (6)	0.0013 (7)	−0.0111 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.7354 (17)	C2—C3	1.378 (3)
S1—C8	1.6709 (17)	C2—H2	0.9300
O1—C7	1.217 (2)	C3—C4	1.374 (3)
N1—C7	1.378 (2)	C4—C5	1.384 (3)
N1—C8	1.394 (2)	C4—H4	0.9300
N1—H1A	0.862 (9)	C5—C6	1.386 (3)
N2—C8	1.323 (2)	C5—H5	0.9300
N2—C9	1.456 (2)	C6—C7	1.491 (2)
N2—H2A	0.865 (10)	C9—C9ⁱ	1.522 (4)
C1—C2	1.380 (3)	C9—H9A	0.9700
C1—C6	1.387 (2)	C9—H9B	0.9700
C1—H1	0.9300

C7—N1—C8	127.96 (14)	C4—C5—C6	120.32 (16)
C7—N1—H1A	115.7 (14)	C4—C5—H5	119.8
C8—N1—H1A	116.2 (14)	C6—C5—H5	119.8
C8—N2—C9	123.80 (14)	C5—C6—C1	119.30 (16)
C8—N2—H2A	119.6 (18)	C5—C6—C7	122.74 (15)
C9—N2—H2A	116.6 (18)	C1—C6—C7	117.72 (16)
C2—C1—C6	120.52 (17)	O1—C7—N1	122.85 (15)
C2—C1—H1	119.7	O1—C7—C6	121.59 (15)
C6—C1—H1	119.7	N1—C7—C6	115.52 (14)
C3—C2—C1	119.29 (17)	N2—C8—N1	116.65 (14)
C3—C2—H2	120.4	N2—C8—S1	125.18 (12)
C1—C2—H2	120.4	N1—C8—S1	118.17 (12)
C4—C3—C2	121.17 (16)	N2—C9—C9ⁱ	111.15 (18)
C4—C3—Cl1	119.23 (14)	N2—C9—H9A	109.4
C2—C3—Cl1	119.60 (14)	C9ⁱ—C9—H9A	109.4
C3—C4—C5	119.38 (17)	N2—C9—H9B	109.4
C3—C4—H4	120.3	C9ⁱ—C9—H9B	109.4
C5—C4—H4	120.3	H9A—C9—H9B	108.0

C6—C1—C2—C3	−0.6 (3)	C8—N1—C7—C6	166.43 (17)
C1—C2—C3—C4	1.1 (3)	C5—C6—C7—O1	149.94 (18)
C1—C2—C3—Cl1	−179.00 (15)	C1—C6—C7—O1	−24.4 (3)
C2—C3—C4—C5	−0.4 (3)	C5—C6—C7—N1	−27.9 (2)
Cl1—C3—C4—C5	179.68 (14)	C1—C6—C7—N1	157.85 (16)
C3—C4—C5—C6	−0.7 (3)	C9—N2—C8—N1	−174.95 (16)
C4—C5—C6—C1	1.1 (3)	C9—N2—C8—S1	4.8 (3)
C4—C5—C6—C7	−173.06 (17)	C7—N1—C8—N2	0.8 (3)
C2—C1—C6—C5	−0.5 (3)	C7—N1—C8—S1	−178.87 (15)
C2—C1—C6—C7	174.04 (17)	C8—N2—C9—C9ⁱ	81.7 (2)
C8—N1—C7—O1	−11.3 (3)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.87 (2)	2.01 (3)	2.670 (2)	133 (2)
C9—H9A···S1	0.97	2.77	3.1017 (18)	101
N1—H1A···S1ⁱⁱ	0.86 (1)	2.73 (2)	3.5203 (14)	153 (1)

Symmetry code: (ii) −x+1, −y+2, −z.

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia and Universiti Kebangsaan Malaysia for the research grant FRGS 1/2015/ST01/UKM/02/2 and DIP-UKM-2014–16 for the X-ray facility. SMA would like to thank the Ministry of Higher Education of Libya for a scholarship.

References

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