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

Ding, Y.-J.; Chang, X.-B.; Yang, X.-Q.; Dong, W.-K.

doi:10.1107/S1600536808004340

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o658

doi:10.1107/S1600536808004340

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

Yu-Jie Ding,^a Xi-Bin Chang,^b Xiao-Qing Yang ^c and Wen-Kui Dong ^c ^*

^aDepartment of Biochemical Engineering, Anhui University of Technology and Science, Wuhu 241000, People's Republic of China, ^bQinghai Saltlake Industry Group Limited Company, Technological Center of Chemical Engineering, Geermu 81600, People's Republic of China, and ^cSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: dongwk@mail.lzjtu.cn

(Received 1 February 2008; accepted 13 February 2008; online 5 March 2008)

In the centrosymmetric title compound, C₂₀H₂₂N₄O₂S₂, the carbonyl group forms an intramolecular hydrogen bond with the NH group attached to the butanediyl linker, resulting in a six-membered ring. There are also intermolecular C—H⋯S interactions in the crystal structure, and π–π interactions between phenyl groups [2.425 (3) Å].

Related literature

For related literature, see: Breuzard et al. (2000 ); Burrows et al. (1997 ); Dong et al. (2006 ); Foss et al. (2004 ); Huang et al., 2006 ; Nan et al. (2000 ); Teoh et al. (1999 ); Valdés-Martínez et al. (2004 ); Zhang et al. (2006 ).

Experimental

Crystal data

C₂₀H₂₂N₄O₂S₂
M_r = 414.54
Monoclinic, P 2₁ /c
a = 6.0405 (11) Å
b = 23.358 (2) Å
c = 7.2877 (13) Å
β = 104.018 (2)°
V = 997.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 (2) K
0.22 × 0.16 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.939, T_max = 0.980
4845 measured reflections
1735 independent reflections
1044 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.106
S = 1.02
1735 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.06	2.717 (3)	133
C2—H2A⋯S1	0.97	2.68	3.060 (3)	103
C2—H2B⋯S1ⁱ	0.97	2.72	3.468 (3)	134
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 5.1; Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004340/hg2377sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004340/hg2377Isup2.hkl

checkCIF report

Comment top

Acylthioureas have been the subject of extensive investigation because of their biological activity and their ability to coordinate strongly with metal ions (Teoh et al., 1999; Huang et al., 2006; Foss et al., 2004). Some thioureas are organic catalysts in the metal-catalyzed asymmetric reduction of carbonyl compounds and carbonylative cyclization of o-hydroxyarylacetylenes (Nan et al., 2000; Breuzard et al., 2000). In recent years, thiourea derivatives have been studied because they are excellent H bonding donors and acceptors (Zhang et al., 2006; Valdés-Martínez et al., 2004), and readily form an intramolecular hydrogen bonding between the benzoyl (CO) and the N—H group (Dong et al., 2006). They also easily form intermolecular hydrogen bonds, which can be applied in the design and synthesis of three-dimension supramolecular structure (Burrows et al., 1997). Here we report synthesis and crystal structure of N, N'-(1, 4-tetramethylene)bisbenzoylthiourea (I), C₂₀H₂₂N₄O₂S₂.

The crystal structure of (I) consists of discrete molecules. The carbonyl group forms an intramolecular hydrogen bond with the N2—H2 group, which forms a six-membered ring (C4/N1/C1/N2/H2/O1) structure, the H2···O1 bond length is 2.055 (3) Å. This is similar to the situation found in the structure of N-benzoyl-N'-(3-pyridyl)thiourea (Dong et al., 2006). There is intermolecular hydrogen bonding between N2—H2 and the C?S group of another molecule, the H2···S1(x + 1, y, z) bond length is 2.906 (3) Å. The C?O bond length of 1.223 (3) Å is longer than the average C?O bond length (1.200 Å), which is due to intramolecular hydrogen bonding. The torsion angles of C2—N2—C1—N1 and C2—N2—C1—S1 are 178.3 (2) and -0.9 (4)°. There are π–π interactions between phenyl groups in the crystal lattice.

Related literature top

For related literature, see: Breuzard et al. (2000); Burrows et al. (1997); Dong et al. (2006); Foss et al. (2004); Huang et al., 2006; Nan et al. (2000); Teoh et al. (1999); Valdés-Martínez et al. (2004); Zhang et al. (2006).

Experimental top

Benzoyl chloride (1.41 g, 10 mmol) was reacted with ammonium thiocyanate (1.14 g, 15 mmol) in CH₂Cl₂ (25 ml) solution under solid–liquid phase transfer catalysis, using polyethylene glycol-400 (0.18 g) as the catalyst, to give the corresponding benzoyl isothiocyanate. Then a solution of 1,4-butylenediamine (0.40 g, 4.5 mmol) in CH₂Cl₂ (15 ml) was added dropwise to benzoyl isothiocyanate, to give the title compound. Yield, 81.8%. m.p. 196–198 °C. Anal. Calc. for C₂₀H₂₂N₄O₂S₂ (%): C, 57.97; H, 5.31; N, 13.53. Found: C, 57.90; H, 5.45; N, 13.35. Selected IR data (cm^-1, KBr pellet): 3416, 3222 (ν NH), 1672 (ν C?O), 1146 (ν C?S). ¹H NMR (200 MHz, DMSO-d6, δ, p.p.m.): 1.71 (t, 4H, CH2); 3.69 (t, 4H, CH2); 7.48–7.93 (m, 10H, C6H5); 10.95 (s, 1H, NH); 11.06 (s, 1H, NH). A DMF solution of the title compound was placed in a diethyl ether atmosphere, after several days, along with diffusion of diethyl ether into the DMF solution of the title compound, colorless block-shaped single crystals suitable for X-ray crystallographic analysis were obtained.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 5.1; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 5.1; Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I)

3,3'-Dibenzoyl-1,1'-(butane-1,4-diyl)dithiourea top

Crystal data top

C₂₀H₂₂N₄O₂S₂	F(000) = 436
M_r = 414.54	D_x = 1.380 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 469–471 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.0405 (11) Å	Cell parameters from 1545 reflections
b = 23.358 (2) Å	θ = 2.9–27.5°
c = 7.2877 (13) Å	µ = 0.29 mm⁻¹
β = 104.018 (2)°	T = 298 K
V = 997.6 (3) Å³	Block, colourless
Z = 2	0.22 × 0.16 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1735 independent reflections
Radiation source: fine-focus sealed tube	1044 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.939, T_max = 0.980	k = −27→21
4845 measured reflections	l = −8→7

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0375P)² + 0.093P] where P = (F_o² + 2F_c²)/3
1735 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₀H₂₂N₄O₂S₂	V = 997.6 (3) Å³
M_r = 414.54	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0405 (11) Å	µ = 0.29 mm⁻¹
b = 23.358 (2) Å	T = 298 K
c = 7.2877 (13) Å	0.22 × 0.16 × 0.07 mm
β = 104.018 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1735 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1044 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.980	R_int = 0.058
4845 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
1735 reflections	Δρ_min = −0.21 e Å⁻³
127 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
N1	0.6333 (4)	0.33193 (10)	0.2464 (3)	0.0436 (7)
H1	0.4996	0.3174	0.2342	0.052*
N2	0.8393 (4)	0.41571 (9)	0.2530 (3)	0.0378 (6)
H2	0.9588	0.3944	0.2747	0.045*
O1	1.0080 (4)	0.30751 (8)	0.3060 (3)	0.0556 (7)
S1	0.39076 (13)	0.42652 (4)	0.19513 (14)	0.0579 (3)
C1	0.6387 (5)	0.39150 (12)	0.2345 (4)	0.0367 (7)
C2	0.8669 (5)	0.47772 (12)	0.2383 (4)	0.0403 (8)
H2A	0.7351	0.4931	0.1482	0.048*
H2B	1.0004	0.4853	0.1902	0.048*
C3	0.8930 (4)	0.50817 (12)	0.4263 (4)	0.0415 (8)
H3A	0.8946	0.5491	0.4051	0.050*
H3B	0.7612	0.4996	0.4755	0.050*
C4	0.8082 (5)	0.29268 (13)	0.2746 (4)	0.0395 (8)
C5	0.7380 (5)	0.23119 (12)	0.2626 (4)	0.0383 (8)
C6	0.5157 (6)	0.21226 (13)	0.1896 (5)	0.0530 (9)
H6	0.3997	0.2387	0.1462	0.064*
C7	0.4663 (6)	0.15458 (15)	0.1811 (5)	0.0617 (10)
H7	0.3171	0.1425	0.1316	0.074*
C8	0.6341 (6)	0.11496 (14)	0.2445 (5)	0.0557 (10)
H8	0.5993	0.0761	0.2394	0.067*
C9	0.8531 (6)	0.13299 (14)	0.3154 (5)	0.0555 (9)
H9	0.9681	0.1062	0.3581	0.067*
C10	0.9057 (5)	0.19086 (13)	0.3241 (4)	0.0462 (9)
H10	1.0558	0.2026	0.3720	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0352 (14)	0.0346 (15)	0.060 (2)	−0.0048 (12)	0.0101 (13)	−0.0022 (13)
N2	0.0309 (14)	0.0340 (14)	0.0476 (17)	0.0051 (11)	0.0077 (12)	−0.0024 (12)
O1	0.0374 (13)	0.0408 (13)	0.0810 (18)	−0.0008 (10)	−0.0005 (12)	0.0001 (12)
S1	0.0363 (5)	0.0507 (5)	0.0883 (8)	0.0062 (4)	0.0181 (5)	0.0070 (5)
C1	0.0325 (17)	0.0413 (18)	0.036 (2)	0.0030 (14)	0.0078 (14)	0.0004 (15)
C2	0.0375 (17)	0.0373 (18)	0.047 (2)	0.0039 (14)	0.0125 (15)	0.0036 (16)
C3	0.0386 (17)	0.0299 (17)	0.055 (2)	0.0042 (13)	0.0102 (16)	0.0017 (16)
C4	0.043 (2)	0.0399 (19)	0.033 (2)	0.0048 (15)	0.0035 (16)	−0.0001 (15)
C5	0.0455 (19)	0.0358 (18)	0.034 (2)	0.0012 (15)	0.0108 (16)	−0.0009 (15)
C6	0.047 (2)	0.042 (2)	0.065 (3)	0.0019 (16)	0.0047 (18)	0.0009 (19)
C7	0.056 (2)	0.049 (2)	0.075 (3)	−0.0142 (18)	0.007 (2)	−0.005 (2)
C8	0.074 (3)	0.039 (2)	0.057 (3)	−0.0035 (19)	0.021 (2)	0.0001 (18)
C9	0.071 (3)	0.043 (2)	0.054 (3)	0.0150 (19)	0.018 (2)	0.0049 (18)
C10	0.044 (2)	0.044 (2)	0.048 (2)	0.0045 (16)	0.0070 (17)	−0.0015 (17)

Geometric parameters (Å, º) top

N1—C4	1.376 (3)	C3—H3B	0.9700
N1—C1	1.395 (3)	C4—C5	1.494 (4)
N1—H1	0.8600	C5—C10	1.376 (4)
N2—C1	1.314 (3)	C5—C6	1.391 (4)
N2—C2	1.465 (3)	C6—C7	1.378 (4)
N2—H2	0.8600	C6—H6	0.9300
O1—C4	1.223 (3)	C7—C8	1.368 (4)
S1—C1	1.669 (3)	C7—H7	0.9300
C2—C3	1.518 (4)	C8—C9	1.365 (4)
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700	C9—C10	1.387 (4)
C3—C3ⁱ	1.516 (5)	C9—H9	0.9300
C3—H3A	0.9700	C10—H10	0.9300

C4—N1—C1	130.2 (2)	O1—C4—N1	121.8 (3)
C4—N1—H1	114.9	O1—C4—C5	122.4 (3)
C1—N1—H1	114.9	N1—C4—C5	115.8 (3)
C1—N2—C2	122.4 (2)	C10—C5—C6	118.2 (3)
C1—N2—H2	118.8	C10—C5—C4	117.6 (3)
C2—N2—H2	118.8	C6—C5—C4	124.2 (3)
N2—C1—N1	117.2 (2)	C7—C6—C5	120.4 (3)
N2—C1—S1	125.0 (2)	C7—C6—H6	119.8
N1—C1—S1	117.8 (2)	C5—C6—H6	119.8
N2—C2—C3	112.7 (2)	C8—C7—C6	120.8 (3)
N2—C2—H2A	109.1	C8—C7—H7	119.6
C3—C2—H2A	109.1	C6—C7—H7	119.6
N2—C2—H2B	109.1	C9—C8—C7	119.3 (3)
C3—C2—H2B	109.1	C9—C8—H8	120.3
H2A—C2—H2B	107.8	C7—C8—H8	120.3
C3ⁱ—C3—C2	114.0 (3)	C8—C9—C10	120.6 (3)
C3ⁱ—C3—H3A	108.8	C8—C9—H9	119.7
C2—C3—H3A	108.8	C10—C9—H9	119.7
C3ⁱ—C3—H3B	108.8	C5—C10—C9	120.7 (3)
C2—C3—H3B	108.8	C5—C10—H10	119.7
H3A—C3—H3B	107.7	C9—C10—H10	119.7

C2—N2—C1—N1	178.3 (2)	O1—C4—C5—C6	−166.1 (3)
C2—N2—C1—S1	−0.9 (4)	N1—C4—C5—C6	13.4 (4)
C4—N1—C1—N2	−0.3 (4)	C10—C5—C6—C7	0.5 (5)
C4—N1—C1—S1	179.0 (2)	C4—C5—C6—C7	179.0 (3)
C1—N2—C2—C3	88.5 (3)	C5—C6—C7—C8	0.2 (5)
N2—C2—C3—C3ⁱ	64.4 (4)	C6—C7—C8—C9	−0.6 (5)
C1—N1—C4—O1	4.7 (5)	C7—C8—C9—C10	0.3 (5)
C1—N1—C4—C5	−174.8 (3)	C6—C5—C10—C9	−0.8 (5)
O1—C4—C5—C10	12.4 (4)	C4—C5—C10—C9	−179.4 (3)
N1—C4—C5—C10	−168.1 (3)	C8—C9—C10—C5	0.4 (5)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.06	2.717 (3)	133
C2—H2A···S1	0.97	2.68	3.060 (3)	103
C2—H2B···S1ⁱⁱ	0.97	2.72	3.468 (3)	134

Symmetry code: (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₂N₄O₂S₂
M_r	414.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.0405 (11), 23.358 (2), 7.2877 (13)
β (°)	104.018 (2)
V (Å³)	997.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.22 × 0.16 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.939, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	4845, 1735, 1044
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.106, 1.02
No. of reflections	1735
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Version 5.1; Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.8600	2.0600	2.717 (3)	133.00
C2—H2A···S1	0.9700	2.6800	3.060 (3)	103.00
C2—H2B···S1ⁱ	0.9700	2.7200	3.468 (3)	134.00

Symmetry code: (i) x+1, y, z.

Acknowledgements

This work was supported by the Foundation of the Education Department of Gansu Province (grant No. 0604-01) and the Qing Lan Talent Engineering Fund of Lanzhou Jiaotong University (grant No. QL-03-01A), which are gratefully acknowledged.

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