1,1′-(Ethane-1,2-di­yl)bis­(3-phenyl­thio­urea)

Pansuriya, P.B.; Friedrich, H.B.; Maguire, G.E.M.

doi:10.1107/S1600536811039936

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2819

doi:10.1107/S1600536811039936

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1,1′-(Ethane-1,2-diyl)bis(3-phenylthiourea)

Pramod B. Pansuriya,^a Holger B. Friedrich ^a and Glenn E. M. Maguire ^a ^*

^aSchool of Chemistry, University of KwaZulu-Natal, Durban 4000, South Africa
^*Correspondence e-mail: maguireg@ukzn.ac.za

(Received 20 September 2011; accepted 28 September 2011; online 5 October 2011)

The complete molecule of the title compound, C₁₆H₁₈N₄S₂, is generated by crystallographic inversion symmetry. The dihedral angle between the phenyl ring and the thiourea group is 52.9 (4)°. The crystal structure displays intermolecular N—H⋯S hydrogen bonding, which generates sheets in the ab plane.

Related literature

Bisthiourea and urea derivatives with alkane bridges can adopt two general shapes, bent (Pansuriya et al., 2011a ) or straight alkyl chains (Pansuriya et al., 2011b ; Koevoets et al., 2005 ). For the synthesis see: Lee et al. (1985 ).

Experimental

Crystal data

C₁₆H₁₈N₄S₂
M_r = 330.46
Orthorhombic, P b c a
a = 10.5823 (4) Å
b = 9.1053 (3) Å
c = 16.4163 (6) Å
V = 1581.79 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 173 K
0.53 × 0.26 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
22438 measured reflections
1902 independent reflections
1523 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.135
S = 1.13
1902 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1ⁱ	0.88	2.57	3.379 (2)	153
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811039936/pk2349sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039936/pk2349Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811039936/pk2349Isup3.cml

checkCIF report

Comment top

Thiourea and urea functionalized ligands play key roles in a wide range of catalytic reactions. Here we report the crystal structure of such a compound (Lee et al., 1985) (Fig. 1). We recently reported a similar thiourea structure, where the molecules were bent (Pansuriya et al., 2011a). Bisthiourea and urea derivatives with alkane bridges can adopt two general shapes, bent (Pansuriya et al., 2011a) or straight alkyl chains (Pansuriya et al., 2011b; Koevoets et al., 2005). The spacer length between the two terminal thiourea or urea groups does not appear to influence the shape the bridging atoms take. The closest structure to the title compound 1,1'-(butane-1,4-diyl)bis(3-phenylthiourea) (Pansuriya et al., 2011a) has also a transoid arrangement of the two thiourea groups. The asymmetric unit of the title compound is a half molecule and the complete molecule is generated by inversion symmetry (i): 1 - x, -y, 1 - z. The structure shows intermolecular hydrogen bonding interactions between N1–H1···S1, 3.379 (2) Å, that creates sheets in the ab plane(Fig. 2). The dihedral angle between the phenyl ring and the thiourea group is 52.9 (4)°.

Related literature top

Bisthiourea and urea derivatives with alkane bridges can adopt two general shapes, bent (Pansuriya et al., 2011a) or straight alkyl chains (Pansuriya et al., 2011b; Koevoets et al., 2005). For the synthesis see: Lee et al. (1985).

Experimental top

A solution of phenyl isothiocyanate (6.75 g, 50 mmol) in diethyl ether (15 ml) was added dropwise at 15 °C to a vigorously stirring solution of anhydrous ethane-1,2-diamine (6.01 g, 100 mmol) in isopropyl alcohol (100 ml) over a period of 30 min. The reaction mixture was stirred for 2 hrs at room temperature and quenched with water (200 ml). This reaction mixture was then maintained overnight at room temperature. Then the reaction mixture was acidified with conc. HCl up to pH 2.6. The solvents were evaporated under reduced pressure, the residue was suspended in hot water for 30 min. The resulting precipitate was filtered by vacuum. The product was washed with ice cold water and dried. The yield was 2.90 g (35%).

Crystals suitable for single-crystal X-ray diffraction analysis were grown in methanol: methylene chloride (1:2) at room temperature. M.p. = 462 K.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level. The 1,1'-(ethane-1,2-diyl)bis(3-phenylthiourea) has inversion symmetry, so that unlabelled atoms are related by (1 - x, -y, 1 - z.
	Fig. 2. The crystal packing structure in the ab plane. All hydrogen atoms except those involved in hydrogen bonding interactions have been omitted for clarity.

1,1'-(Ethane-1,2-diyl)bis(3-phenylthiourea) top

Crystal data top

C₁₆H₁₈N₄S₂	D_x = 1.388 Mg m⁻³
M_r = 330.46	Melting point: 462 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8682 reflections
a = 10.5823 (4) Å	θ = 2.5–28.3°
b = 9.1053 (3) Å	µ = 0.34 mm⁻¹
c = 16.4163 (6) Å	T = 173 K
V = 1581.79 (10) Å³	Plate, colourless
Z = 4	0.53 × 0.26 × 0.12 mm
F(000) = 696

Data collection top

Bruker APEXII CCD diffractometer	1523 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.078
Graphite monochromator	θ_max = 28.0°, θ_min = 2.5°
ϕ and ω scans	h = −13→13
22438 measured reflections	k = −12→12
1902 independent reflections	l = −21→21

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0373P)² + 3.3624P] where P = (F_o² + 2F_c²)/3
1902 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₆H₁₈N₄S₂	V = 1581.79 (10) Å³
M_r = 330.46	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 10.5823 (4) Å	µ = 0.34 mm⁻¹
b = 9.1053 (3) Å	T = 173 K
c = 16.4163 (6) Å	0.53 × 0.26 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	1523 reflections with I > 2σ(I)
22438 measured reflections	R_int = 0.078
1902 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.13	Δρ_max = 0.55 e Å⁻³
1902 reflections	Δρ_min = −0.38 e Å⁻³
100 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
C1	0.4907 (2)	0.4345 (3)	0.35565 (15)	0.0229 (5)
C2	0.4488 (3)	0.3631 (3)	0.28604 (17)	0.0281 (6)
H2	0.4897	0.2763	0.2678	0.034*
C3	0.3463 (3)	0.4196 (3)	0.24308 (18)	0.0329 (6)
H3	0.3161	0.3700	0.1961	0.039*
C4	0.2885 (3)	0.5468 (3)	0.26835 (18)	0.0339 (6)
H4	0.2185	0.5848	0.2389	0.041*
C5	0.3321 (3)	0.6195 (3)	0.33647 (18)	0.0321 (6)
H5	0.2932	0.7086	0.3530	0.039*
C6	0.4330 (3)	0.5630 (3)	0.38118 (17)	0.0280 (6)
H6	0.4619	0.6121	0.4287	0.034*
C7	0.6127 (2)	0.2403 (3)	0.42665 (15)	0.0226 (5)
C8	0.5090 (3)	0.0019 (3)	0.45415 (16)	0.0263 (5)
H8A	0.5891	−0.0479	0.4398	0.032*
H8B	0.4389	−0.0520	0.4276	0.032*
N1	0.5975 (2)	0.3795 (2)	0.39925 (14)	0.0246 (5)
H1N	0.6591	0.4418	0.4092	0.030*
N2	0.5118 (2)	0.1523 (2)	0.42399 (14)	0.0258 (5)
H2N	0.4421	0.1877	0.4025	0.031*
S1	0.75428 (6)	0.18711 (7)	0.46353 (4)	0.0273 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0182 (11)	0.0206 (12)	0.0298 (12)	−0.0016 (9)	−0.0006 (10)	0.0067 (10)
C2	0.0263 (13)	0.0241 (13)	0.0338 (13)	0.0016 (11)	0.0008 (11)	0.0000 (11)
C3	0.0346 (15)	0.0306 (14)	0.0335 (14)	−0.0042 (12)	−0.0079 (12)	0.0026 (12)
C4	0.0268 (14)	0.0340 (15)	0.0407 (15)	−0.0005 (12)	−0.0072 (12)	0.0107 (12)
C5	0.0238 (13)	0.0281 (14)	0.0445 (16)	0.0071 (11)	0.0010 (12)	0.0039 (12)
C6	0.0265 (13)	0.0266 (13)	0.0309 (13)	0.0009 (11)	−0.0005 (10)	−0.0005 (11)
C7	0.0170 (11)	0.0230 (12)	0.0279 (12)	0.0013 (9)	0.0023 (10)	0.0006 (10)
C8	0.0229 (12)	0.0184 (11)	0.0376 (14)	−0.0016 (9)	−0.0004 (11)	0.0030 (10)
N1	0.0164 (10)	0.0196 (10)	0.0378 (12)	−0.0019 (8)	−0.0033 (9)	0.0024 (9)
N2	0.0152 (10)	0.0219 (11)	0.0403 (12)	−0.0003 (8)	−0.0024 (9)	0.0084 (9)
S1	0.0150 (3)	0.0218 (3)	0.0450 (4)	0.0017 (2)	−0.0026 (3)	0.0001 (3)

Geometric parameters (Å, º) top

C1—C6	1.385 (4)	C6—H6	0.9500
C1—C2	1.387 (4)	C7—N2	1.336 (3)
C1—N1	1.428 (3)	C7—N1	1.354 (3)
C2—C3	1.393 (4)	C7—S1	1.687 (2)
C2—H2	0.9500	C8—N2	1.456 (3)
C3—C4	1.373 (4)	C8—C8ⁱ	1.518 (5)
C3—H3	0.9500	C8—H8A	0.9900
C4—C5	1.379 (4)	C8—H8B	0.9900
C4—H4	0.9500	N1—H1N	0.8800
C5—C6	1.394 (4)	N2—H2N	0.8800
C5—H5	0.9500

C6—C1—C2	120.3 (2)	C5—C6—H6	120.3
C6—C1—N1	119.6 (2)	N2—C7—N1	117.1 (2)
C2—C1—N1	120.1 (2)	N2—C7—S1	123.3 (2)
C1—C2—C3	119.5 (3)	N1—C7—S1	119.59 (19)
C1—C2—H2	120.2	N2—C8—C8ⁱ	111.2 (3)
C3—C2—H2	120.2	N2—C8—H8A	109.4
C4—C3—C2	120.4 (3)	C8ⁱ—C8—H8A	109.4
C4—C3—H3	119.8	N2—C8—H8B	109.4
C2—C3—H3	119.8	C8ⁱ—C8—H8B	109.4
C3—C4—C5	120.0 (3)	H8A—C8—H8B	108.0
C3—C4—H4	120.0	C7—N1—C1	126.1 (2)
C5—C4—H4	120.0	C7—N1—H1N	117.0
C4—C5—C6	120.4 (3)	C1—N1—H1N	117.0
C4—C5—H5	119.8	C7—N2—C8	124.7 (2)
C6—C5—H5	119.8	C7—N2—H2N	117.6
C1—C6—C5	119.4 (3)	C8—N2—H2N	117.6
C1—C6—H6	120.3

C6—C1—C2—C3	−1.5 (4)	N2—C7—N1—C1	−11.0 (4)
N1—C1—C2—C3	−178.6 (2)	S1—C7—N1—C1	170.1 (2)
C1—C2—C3—C4	1.3 (4)	C6—C1—N1—C7	130.0 (3)
C2—C3—C4—C5	0.1 (4)	C2—C1—N1—C7	−52.9 (4)
C3—C4—C5—C6	−1.4 (4)	N1—C7—N2—C8	−177.1 (2)
C2—C1—C6—C5	0.3 (4)	S1—C7—N2—C8	1.8 (4)
N1—C1—C6—C5	177.4 (2)	C8ⁱ—C8—N2—C7	80.6 (4)
C4—C5—C6—C1	1.2 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱⁱ	0.88	2.57	3.379 (2)	153

Symmetry code: (ii) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₄S₂
M_r	330.46
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	10.5823 (4), 9.1053 (3), 16.4163 (6)
V (Å³)	1581.79 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.53 × 0.26 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	22438, 1902, 1523
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.135, 1.13
No. of reflections	1902
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.38

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.88	2.57	3.379 (2)	153

Symmetry code: (i) −x+3/2, y+1/2, z.

Acknowledgements

The authors wish to thank Dr Manuel Fernandes from the Chemistry Department of the University of the Witwatersrand for his assistance with the data collection and the DST–National Research Foundation, c*change for financial support.

References

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