1,1′-Diphenyl-3,3′-(p-phenyl­enedicarbon­yl)dithio­urea

Hung, W.W.; Hassan, I.N.; Yamin, B.M.; Kassim, M.B.

doi:10.1107/S1600536809055834

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o314

https://doi.org/10.1107/S1600536809055834

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1,1′-Diphenyl-3,3′-(p-phenylenedicarbonyl)dithiourea

Wong W. Hung,^a Ibrahim N. Hassan,^a Bohari M. Yamin ^a and Mohammad B. Kassim ^a ^*

^aSchool of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 30 December 2009; accepted 30 December 2009; online 9 January 2010)

The molecule of the title compound, C₂₂H₁₈N₄O₂S₂, lies across a crystallographic inversion centre. The central benzene ring forms dihedral angles of 29.39 (9) and 79.11 (12)°, respectively, with the thiourea unit and the terminal phenyl ring. Intramolecular N—H⋯O hydrogen bonds generate two S(6) ring motifs. In the crystal, molecules are linked into chains along [1 $[\overline{1}]$ 0] by intermolecular N—H⋯S hydrogen bonds.

Related literature

For general background and crystal structures of thiourea derivatives, see: Dong et al. (2006 ); Hassan et al. (2008 ); Yamin & Hassan (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₂H₁₈N₄O₂S₂
M_r = 434.52
Triclinic, $[P \overline 1]$
a = 5.769 (2) Å
b = 7.919 (3) Å
c = 11.534 (4) Å
α = 75.961 (10)°
β = 87.000 (8)°
γ = 89.861 (8)°
V = 510.5 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 273 K
0.23 × 0.11 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.937, T_max = 0.986
5484 measured reflections
1809 independent reflections
1503 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.113
S = 1.13
1809 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86	1.94	2.644 (3)	138
N2—H2A⋯S1ⁱ	0.86	2.62	3.446 (3)	160
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809055834/ci5010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055834/ci5010Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound contains one-half of the molecule the other half being generated by the crystallographic inversion centre (Fig. 1). The thiourea fragment (S1/O1/N1/N2/C6/C7/C8) is planar, with atom C8 has the maximum deviation of 0.038 (2)Å from the mean plane. The dihedral angle between the central bridging benzene ring and the thiourea unit is 29.39 (9)° and that between the two benzene rings is 79.11 (12)°. The carbonyl and N-H groups are involved in intramolecular N—H···O hydrogen bonding resulting in the formation of two six-membered rings viz. C7/N2/C8/O1/H1A/N1 and C7A/N2A/C8A/O1A/H1AA/N1A. The C═O bond length of 1.220 (3) Å is longer than the average C═O bond length (1.200 Å). These features are similar to those observed in the structure of N-benzoyl-N'-(3-pyridyl)thiourea (Dong et al., 2006). Bond lengths are in normal ranges (Allen et al., 1987).

In the crystal structure, intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into a chain along the [110] (Fig 2).

Related literature top

For general background and crystal structures of thiourea derivatives, see: Dong et al. (2006); Hassan et al. (2008); Yamin & Hassan (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized according to a previously reported method (Hassan et al., 2008) with some modification. Terephthaloyl chloride (1.015 g, 0.5 mmol) was added to ammonium thiocyanate (0.770 g, 1 mmol) in tetrahydrofuran and the contents were stirred for 10 min. The precipitated ammonium chloride was removed by filtration and then aniline (1.0 ml, 1 mmol) in methanol was added dropwise. The mixture was refluxed for 5 h and the black coloured solution was dried using a evaporator before it was washed with cool methanol. Yellow crystals of the title compound were obtained by recrystallization from DMF.

Structure description top

In the crystal structure, intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into a chain along the [110] (Fig 2).

For general background and crystal structures of thiourea derivatives, see: Dong et al. (2006); Hassan et al. (2008); Yamin & Hassan (2004). For bond-length data, see: Allen et al. (1987).

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).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Atoms labelled with the suffix A are generated by the symmetry operation (2-x, -y, 1-z).
	Fig. 2. Crystal packing of of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

1,1'-Diphenyl-3,3'-(p-phenylenedicarbonyl)dithiourea top

Crystal data top

C₂₂H₁₈N₄O₂S₂	Z = 1
M_r = 434.52	F(000) = 226
Triclinic, P1	D_x = 1.413 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.769 (2) Å	Cell parameters from 1272 reflections
b = 7.919 (3) Å	θ = 1.8–25.0°
c = 11.534 (4) Å	µ = 0.29 mm⁻¹
α = 75.961 (10)°	T = 273 K
β = 87.000 (8)°	Plate, yellow
γ = 89.861 (8)°	0.23 × 0.11 × 0.05 mm
V = 510.5 (3) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1809 independent reflections
Radiation source: fine-focus sealed tube	1503 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scan	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→6
T_min = 0.937, T_max = 0.986	k = −9→9
5484 measured reflections	l = −13→13

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0449P)² + 0.1485P] where P = (F_o² + 2F_c²)/3
1809 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₂H₁₈N₄O₂S₂	γ = 89.861 (8)°
M_r = 434.52	V = 510.5 (3) Å³
Triclinic, P1	Z = 1
a = 5.769 (2) Å	Mo Kα radiation
b = 7.919 (3) Å	µ = 0.29 mm⁻¹
c = 11.534 (4) Å	T = 273 K
α = 75.961 (10)°	0.23 × 0.11 × 0.05 mm
β = 87.000 (8)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1809 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1503 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.986	R_int = 0.030
5484 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.13	Δρ_max = 0.25 e Å⁻³
1809 reflections	Δρ_min = −0.16 e Å⁻³
136 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
S1	0.32753 (13)	0.52539 (9)	0.65718 (6)	0.0563 (3)
N1	0.2814 (3)	0.2027 (3)	0.79479 (17)	0.0451 (5)
H1A	0.3202	0.0953	0.8057	0.054*
N2	0.5449 (3)	0.2421 (2)	0.63257 (16)	0.0402 (5)
H2A	0.6037	0.3126	0.5690	0.048*
O1	0.5453 (3)	−0.0411 (2)	0.73721 (17)	0.0647 (6)
C1	0.1594 (5)	0.1854 (3)	1.0006 (2)	0.0506 (7)
H1B	0.2946	0.1251	1.0236	0.061*
C2	−0.0015 (5)	0.2172 (4)	1.0865 (2)	0.0580 (8)
H2B	0.0274	0.1796	1.1672	0.070*
C3	−0.2010 (5)	0.3030 (4)	1.0531 (3)	0.0570 (8)
H3A	−0.3086	0.3232	1.1111	0.068*
C4	−0.2439 (5)	0.3599 (4)	0.9342 (3)	0.0582 (8)
H4A	−0.3807	0.4184	0.9119	0.070*
C5	−0.0854 (4)	0.3310 (3)	0.8470 (2)	0.0504 (7)
H5A	−0.1148	0.3696	0.7664	0.060*
C6	0.1173 (4)	0.2439 (3)	0.8812 (2)	0.0413 (6)
C7	0.3798 (4)	0.3128 (3)	0.6997 (2)	0.0392 (6)
C8	0.6254 (4)	0.0747 (3)	0.6550 (2)	0.0416 (6)
C9	0.8197 (4)	0.0410 (3)	0.5729 (2)	0.0366 (5)
C10	0.9840 (4)	0.1665 (3)	0.5176 (2)	0.0424 (6)
H10A	0.9741	0.2781	0.5300	0.051*
C11	1.1621 (4)	0.1265 (3)	0.4442 (2)	0.0420 (6)
H11A	1.2700	0.2117	0.4063	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0734 (5)	0.0418 (4)	0.0480 (4)	0.0108 (3)	0.0225 (3)	−0.0049 (3)
N1	0.0520 (13)	0.0393 (11)	0.0402 (12)	0.0059 (9)	0.0153 (10)	−0.0063 (9)
N2	0.0425 (11)	0.0406 (11)	0.0337 (11)	0.0043 (9)	0.0123 (9)	−0.0046 (9)
O1	0.0729 (13)	0.0485 (11)	0.0597 (12)	0.0131 (9)	0.0335 (10)	0.0042 (10)
C1	0.0528 (16)	0.0529 (16)	0.0418 (15)	0.0031 (13)	0.0062 (12)	−0.0049 (12)
C2	0.0677 (19)	0.0633 (19)	0.0397 (15)	−0.0032 (15)	0.0129 (13)	−0.0097 (13)
C3	0.0584 (18)	0.0592 (18)	0.0540 (18)	−0.0055 (14)	0.0247 (14)	−0.0205 (14)
C4	0.0433 (16)	0.0655 (19)	0.067 (2)	0.0032 (13)	0.0102 (14)	−0.0221 (15)
C5	0.0451 (15)	0.0641 (18)	0.0419 (15)	0.0022 (13)	0.0032 (12)	−0.0137 (13)
C6	0.0410 (14)	0.0391 (14)	0.0430 (14)	−0.0015 (11)	0.0105 (11)	−0.0110 (11)
C7	0.0384 (13)	0.0445 (14)	0.0346 (13)	0.0039 (11)	0.0027 (10)	−0.0106 (11)
C8	0.0419 (14)	0.0419 (14)	0.0386 (14)	0.0050 (11)	0.0056 (11)	−0.0070 (12)
C9	0.0368 (13)	0.0406 (13)	0.0318 (12)	0.0052 (10)	−0.0009 (10)	−0.0079 (10)
C10	0.0437 (14)	0.0376 (14)	0.0462 (15)	0.0032 (11)	0.0040 (11)	−0.0124 (11)
C11	0.0391 (13)	0.0401 (14)	0.0439 (14)	−0.0001 (10)	0.0086 (11)	−0.0068 (11)

Geometric parameters (Å, º) top

S1—C7	1.667 (2)	C3—C4	1.372 (4)
N1—C7	1.327 (3)	C3—H3A	0.93
N1—C6	1.433 (3)	C4—C5	1.383 (3)
N1—H1A	0.86	C4—H4A	0.93
N2—C8	1.373 (3)	C5—C6	1.383 (3)
N2—C7	1.396 (3)	C5—H5A	0.93
N2—H2A	0.86	C8—C9	1.495 (3)
O1—C8	1.220 (3)	C9—C10	1.388 (3)
C1—C6	1.376 (4)	C9—C11ⁱ	1.390 (3)
C1—C2	1.389 (4)	C10—C11	1.382 (3)
C1—H1B	0.93	C10—H10A	0.93
C2—C3	1.361 (4)	C11—C9ⁱ	1.390 (3)
C2—H2B	0.93	C11—H11A	0.93

C7—N1—C6	126.8 (2)	C4—C5—H5A	120.4
C7—N1—H1A	116.6	C1—C6—C5	120.3 (2)
C6—N1—H1A	116.6	C1—C6—N1	118.3 (2)
C8—N2—C7	128.3 (2)	C5—C6—N1	121.3 (2)
C8—N2—H2A	115.8	N1—C7—N2	115.9 (2)
C7—N2—H2A	115.8	N1—C7—S1	125.62 (18)
C6—C1—C2	119.5 (3)	N2—C7—S1	118.42 (17)
C6—C1—H1B	120.2	O1—C8—N2	122.6 (2)
C2—C1—H1B	120.2	O1—C8—C9	121.2 (2)
C3—C2—C1	120.4 (3)	N2—C8—C9	116.2 (2)
C3—C2—H2B	119.8	C10—C9—C11ⁱ	119.5 (2)
C1—C2—H2B	119.8	C10—C9—C8	123.1 (2)
C2—C3—C4	120.1 (2)	C11ⁱ—C9—C8	117.4 (2)
C2—C3—H3A	119.9	C11—C10—C9	120.3 (2)
C4—C3—H3A	119.9	C11—C10—H10A	119.8
C3—C4—C5	120.6 (3)	C9—C10—H10A	119.8
C3—C4—H4A	119.7	C10—C11—C9ⁱ	120.1 (2)
C5—C4—H4A	119.7	C10—C11—H11A	119.9
C6—C5—C4	119.2 (3)	C9ⁱ—C11—H11A	119.9
C6—C5—H5A	120.4

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	1.94	2.644 (3)	138
N2—H2A···S1ⁱⁱ	0.86	2.62	3.446 (3)	160

Symmetry code: (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₈N₄O₂S₂
M_r	434.52
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	5.769 (2), 7.919 (3), 11.534 (4)
α, β, γ (°)	75.961 (10), 87.000 (8), 89.861 (8)
V (Å³)	510.5 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.23 × 0.11 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.937, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	5484, 1809, 1503
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.113, 1.13
No. of reflections	1809
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	1.94	2.644 (3)	138
N2—H2A···S1ⁱ	0.86	2.62	3.446 (3)	160

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia for providing facilities and the Ministry of Science, Technology and Innovation for the research fund (grant Nos. UKM-ST-01-FRGS-0016–2006 and UKM-OUP-TK-16–73/2009).

References

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