3,3′-Diphenyl-1,1′-(butane-1,4-di­yl)dithio­urea

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

doi:10.1107/S1600536811033071

organic compounds

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Volume 67| Part 9| September 2011| Page o2380

doi:10.1107/S1600536811033071

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3,3′-Diphenyl-1,1′-(butane-1,4-diyl)dithiourea

Pramod 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 4 August 2011; accepted 15 August 2011; online 27 August 2011)

The asymmetric unit of the title compound, C₁₈H₂₂N₄S₂, contains one half-molecule, the complete molecule being generated by crystallographic inversion symmetry. The crystal structure features two intermolecular N—H⋯S hydrogen-bonding interactions, the first generating an infinite chain along the b axis and the second an infinite chain along the a axis, together forming an interlocking structure.

Related literature

Thiourea derivatives are conspicuous for their biological activity as they form strong hydrogen-bonding interactions and coordinate to metal ions, see: Wittkopp & Schreiner (2003 ); Li et al. (2008 ). For appliactions of thiourea, see Abdallah et al. (2006 ); Karamé et al. (2003 ); Nan et al. (2000 ); Breuzard et al. (2000 ); Tommasino et al., (2000 ); Reinoso García et al. (2004 ); Leung et al. (2008 ). For synthesis of the title compound, see: Lee et al. (1985 ).

Experimental

Crystal data

C₁₈H₂₂N₄S₂
M_r = 358.52
Monoclinic, P 2₁ /c
a = 9.6795 (3) Å
b = 7.8677 (3) Å
c = 12.3213 (4) Å
β = 105.816 (2)°
V = 902.81 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 173 K
0.46 × 0.45 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
9210 measured reflections
2192 independent reflections
1710 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.093
S = 1.06
2192 reflections
117 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1ⁱ	0.855 (18)	2.508 (18)	3.3465 (13)	167.1 (15)
N2—H2N⋯S1ⁱⁱ	0.806 (15)	2.713 (16)	3.3755 (14)	140.7 (13)
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus; 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/S1600536811033071/om2458sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033071/om2458Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033071/om2458Isup3.cml

checkCIF report

Comment top

Thiourea derivatives are conspicuous for their biological activity as they form strong hydrogen bonding interactions and coordinate metal ions (Wittkopp & Schreiner, 2003; Li et al., 2008). In recent years the use of thiourea groups as potential catalytic ligands has been extensively studied in reactions such as hydroformylation (Abdallah et al., 2006), hydrosilylation (Karamé et al., 2003), asymmetric reduction (Nan et al., 2000), cyclization (Breuzard et al., 2000) and hydrogenation (Tommasino et al., 2000). Other applications include their use as synthetic cation-anion ionophores (Reinoso García et al., 2004; Leung et al., 2008).

Here we report the crystal structure of the title compound (Lee et al., 1985) (Fig. 1). The structure shows two distinct intermolecular hydrogen bonding interactions. The first occurs between between N1–H1 and S1 2.508 (18) Å, that creates an infinite chain of molecules along the b axis. The second occurs between N2–H2 and S1 2.713 (16) Å, that generates an infinite chain along the a axis. Due to these interactions an interlocking molecular structure is formed (Fig. 2).

Related literature top

Thiourea derivatives are conspicuous for their biological activity as they form strong hydrogen-bonding interactions and coordinate metal ions, see: Wittkopp & Schreiner (2003); Li et al. (2008). For appliactions of thiourea, see Abdallah et al. (2006); Karamé et al. (2003); Nan et al. (2000); Breuzard et al. (2000); Tommasino et al., (2000); Reinoso García et al. (2004); Leung et al. (2008). For synthesis of the title compound, 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 stirred solution of anhydrous butane-1,4-diamine (8.81 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). The reaction mixture was maintained overnight at room temperature. Then the reaction mixture was acidified with conc. HCl up to pH 2.6. The solvents were evaporated under vacuum, the residue was suspended in hot water for 30 min and the resulting precipitate was filtered off. The product was washed with ice cold water and dried. The yield was 2.36 g (35%).

Crystals suitable for single-crystal X-ray diffraction were grown in methanol: methylene chloride (1:2) at room temperature. M.p. = 458 K.

¹H NMR (CDCl₃, 400 MHz) d (p.p.m.): 7.64 (br.s., 2H, NH—CS), 7.40- 7.46 (m, 4H, H-arom), 7.29–7.33 (t, 2H, H-arom), 7.19–7.21 (d, 4H, H-arom), 6.18 (br.s., 2H, –NH—CH₂), 3.65 (m, 4H, –CH₂–CH₂), 1.61 (m, 4H, –CH₂–CH₂).

¹³C NMR (CDCl₃, 400 MHz): 26.12, 44.75, 125.45, 127.55, 130.34, 180.92

IR. (ν, cm^-1) 3155, 3005, 2933, 1591, 1518, 1492, 1294, 1254, 1178,1071.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus (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 with atomic numbering scheme. The H atoms have been omitted for clarity. Displacement ellipsoids are drawn at 40% probability. The 1,1'-(butane-1,4-diyl)bis(3-phenylthiourea) has inversion symmetry [symmetry code: (i): 1 - x, -y, 1-z].
	Fig. 2. The hydrogen bonding interactions of the title compound as viewed down the a axis. All H atoms except those involved in hydrogen bonding interactions have been omitted for clarity.

3-phenyl-1-{4-[(phenylcarbamothioyl)amino]butyl}thiourea top

Crystal data top

C₁₈H₂₂N₄S₂	F(000) = 380
M_r = 358.52	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3394 reflections
a = 9.6795 (3) Å	θ = 3.1–28.2°
b = 7.8677 (3) Å	µ = 0.30 mm⁻¹
c = 12.3213 (4) Å	T = 173 K
β = 105.816 (2)°	Plate, colourless
V = 902.81 (5) Å³	0.46 × 0.45 × 0.13 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1710 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 28.0°, θ_min = 2.2°
ϕ and ω scans	h = −12→12
9210 measured reflections	k = −10→10
2192 independent reflections	l = −16→16

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0513P)² + 0.0075P] where P = (F_o² + 2F_c²)/3
2192 reflections	(Δ/σ)_max = 0.005
117 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₈H₂₂N₄S₂	V = 902.81 (5) Å³
M_r = 358.52	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6795 (3) Å	µ = 0.30 mm⁻¹
b = 7.8677 (3) Å	T = 173 K
c = 12.3213 (4) Å	0.46 × 0.45 × 0.13 mm
β = 105.816 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1710 reflections with I > 2σ(I)
9210 measured reflections	R_int = 0.042
2192 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.45 e Å⁻³
2192 reflections	Δρ_min = −0.23 e Å⁻³
117 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	0.23226 (14)	−0.10682 (19)	0.10971 (12)	0.0250 (3)
C2	0.17043 (15)	−0.0394 (2)	0.19000 (13)	0.0314 (4)
H2	0.2223	0.0392	0.2445	0.038*
C3	0.03242 (16)	−0.0880 (2)	0.18976 (14)	0.0383 (4)
H3	−0.0092	−0.0449	0.2457	0.046*
C4	−0.04488 (16)	−0.1990 (2)	0.10837 (15)	0.0393 (4)
H4	−0.1387	−0.2333	0.1092	0.047*
C5	0.01453 (16)	−0.2598 (2)	0.02594 (14)	0.0366 (4)
H5	−0.0397	−0.3326	−0.0315	0.044*
C6	0.15346 (15)	−0.2145 (2)	0.02723 (12)	0.0296 (3)
H6	0.1947	−0.2578	−0.0289	0.036*
C7	0.49385 (14)	−0.05136 (17)	0.19228 (11)	0.0223 (3)
C8	0.60322 (15)	−0.0926 (2)	0.39648 (12)	0.0286 (3)
H8A	0.6645	0.0072	0.3938	0.034*
H8B	0.6631	−0.1961	0.4027	0.034*
C9	0.54395 (17)	−0.0793 (2)	0.49881 (12)	0.0316 (3)
H9A	0.4833	−0.1801	0.5004	0.038*
H9B	0.6253	−0.0821	0.5680	0.038*
N1	0.37258 (12)	−0.05795 (17)	0.10580 (10)	0.0265 (3)
N2	0.48550 (13)	−0.10013 (17)	0.29351 (10)	0.0261 (3)
S1	0.65024 (4)	0.01605 (5)	0.16882 (3)	0.02773 (13)
H1N	0.3820 (18)	−0.045 (2)	0.0393 (15)	0.036 (5)*
H2N	0.4173 (16)	−0.158 (2)	0.2950 (13)	0.028 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0203 (7)	0.0312 (8)	0.0236 (7)	0.0032 (6)	0.0058 (5)	0.0059 (6)
C2	0.0244 (7)	0.0448 (9)	0.0253 (8)	0.0052 (6)	0.0073 (6)	0.0008 (6)
C3	0.0274 (8)	0.0553 (11)	0.0354 (9)	0.0102 (7)	0.0140 (7)	0.0074 (8)
C4	0.0216 (7)	0.0464 (10)	0.0506 (10)	0.0014 (7)	0.0110 (7)	0.0127 (8)
C5	0.0254 (8)	0.0352 (9)	0.0450 (10)	−0.0020 (6)	0.0024 (7)	0.0003 (7)
C6	0.0260 (7)	0.0321 (8)	0.0301 (8)	0.0030 (6)	0.0062 (6)	0.0008 (6)
C7	0.0219 (7)	0.0238 (7)	0.0225 (7)	0.0013 (5)	0.0083 (5)	−0.0036 (5)
C8	0.0223 (7)	0.0392 (8)	0.0230 (7)	0.0017 (6)	0.0041 (6)	−0.0015 (6)
C9	0.0311 (8)	0.0392 (9)	0.0234 (7)	0.0028 (7)	0.0057 (6)	0.0023 (6)
N1	0.0221 (6)	0.0406 (7)	0.0181 (6)	−0.0017 (5)	0.0076 (5)	0.0001 (5)
N2	0.0204 (6)	0.0368 (7)	0.0215 (6)	−0.0068 (5)	0.0064 (5)	0.0008 (5)
S1	0.0215 (2)	0.0385 (2)	0.0256 (2)	−0.00221 (15)	0.01058 (15)	−0.00035 (15)

Geometric parameters (Å, º) top

C1—C6	1.382 (2)	C7—N2	1.3283 (17)
C1—C2	1.393 (2)	C7—N1	1.3543 (18)
C1—N1	1.4250 (17)	C7—S1	1.7014 (14)
C2—C3	1.389 (2)	C8—N2	1.4572 (18)
C2—H2	0.9500	C8—C9	1.5246 (19)
C3—C4	1.385 (2)	C8—H8A	0.9900
C3—H3	0.9500	C8—H8B	0.9900
C4—C5	1.382 (2)	C9—C9ⁱ	1.516 (3)
C4—H4	0.9500	C9—H9A	0.9900
C5—C6	1.387 (2)	C9—H9B	0.9900
C5—H5	0.9500	N1—H1N	0.855 (18)
C6—H6	0.9500	N2—H2N	0.806 (15)

C6—C1—C2	119.85 (13)	N1—C7—S1	119.92 (10)
C6—C1—N1	118.73 (12)	N2—C8—C9	109.98 (11)
C2—C1—N1	121.28 (13)	N2—C8—H8A	109.7
C3—C2—C1	119.53 (15)	C9—C8—H8A	109.7
C3—C2—H2	120.2	N2—C8—H8B	109.7
C1—C2—H2	120.2	C9—C8—H8B	109.7
C4—C3—C2	120.30 (15)	H8A—C8—H8B	108.2
C4—C3—H3	119.9	C9ⁱ—C9—C8	114.35 (16)
C2—C3—H3	119.9	C9ⁱ—C9—H9A	108.7
C5—C4—C3	119.97 (14)	C8—C9—H9A	108.7
C5—C4—H4	120.0	C9ⁱ—C9—H9B	108.7
C3—C4—H4	120.0	C8—C9—H9B	108.7
C4—C5—C6	119.93 (15)	H9A—C9—H9B	107.6
C4—C5—H5	120.0	C7—N1—C1	127.84 (12)
C6—C5—H5	120.0	C7—N1—H1N	117.0 (12)
C1—C6—C5	120.33 (14)	C1—N1—H1N	114.6 (12)
C1—C6—H6	119.8	C7—N2—C8	124.94 (12)
C5—C6—H6	119.8	C7—N2—H2N	116.4 (11)
N2—C7—N1	117.79 (12)	C8—N2—H2N	117.0 (11)
N2—C7—S1	122.29 (11)

C6—C1—C2—C3	3.2 (2)	N2—C8—C9—C9ⁱ	−62.1 (2)
N1—C1—C2—C3	178.86 (14)	N2—C7—N1—C1	2.1 (2)
C1—C2—C3—C4	−1.8 (2)	S1—C7—N1—C1	−178.44 (12)
C2—C3—C4—C5	−1.0 (3)	C6—C1—N1—C7	−135.44 (15)
C3—C4—C5—C6	2.3 (3)	C2—C1—N1—C7	48.9 (2)
C2—C1—C6—C5	−1.9 (2)	N1—C7—N2—C8	−176.58 (13)
N1—C1—C6—C5	−177.63 (14)	S1—C7—N2—C8	4.0 (2)
C4—C5—C6—C1	−0.9 (2)	C9—C8—N2—C7	154.26 (15)

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	0.855 (18)	2.508 (18)	3.3465 (13)	167.1 (15)
N2—H2N···S1ⁱⁱⁱ	0.806 (15)	2.713 (16)	3.3755 (14)	140.7 (13)

Symmetry codes: (ii) −x+1, −y, −z; (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₂N₄S₂
M_r	358.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.6795 (3), 7.8677 (3), 12.3213 (4)
β (°)	105.816 (2)
V (Å³)	902.81 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.46 × 0.45 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9210, 2192, 1710
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.093, 1.06
No. of reflections	2192
No. of parameters	117
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.23

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (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	0.855 (18)	2.508 (18)	3.3465 (13)	167.1 (15)
N2—H2N···S1ⁱⁱ	0.806 (15)	2.713 (16)	3.3755 (14)	140.7 (13)

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, y−1/2, −z+1/2.

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 c*change for financial support.

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