Bis[4-(4-amino­phenyl­sulfanyl)phenyl] ketone

Gang Zhang; Yan-lun Wang; Sheng-ru Long; Jie Yang

doi:10.1107/S1600536809016948

. 2009 May 14;65(Pt 6):o1251. doi: 10.1107/S1600536809016948

Bis[4-(4-aminophenylsulfanyl)phenyl] ketone

Gang Zhang ^a, Yan-lun Wang ^b, Sheng-ru Long ^c, Jie Yang ^c,^*

PMCID: PMC2969735 PMID: 21583116

Abstract

The molecule of the title compound, C₂₅H₂₀N₂OS₂, has imposed twofold rotation symmetry. The dihedral angle formed by the two crystallographically independent phenyl rings is 79.23 (7)°. In the crystal packing, the molecules are linked by intermolecular N—H⋯O hydrogen bonds, forming chains running parallel to [102].

Related literature

For the properties and applications of the title compound and related derivatives, see: Wang et al. (2006a ▶,b ▶); Jiang et al. (2006 ▶); Aritomi & Terauchi (1985 ▶); Aritomi & Fujiwara (1986 ▶). For the synthesis of the title compound, see: Yang et al. (2007 ▶); Chen et al. (2009 ▶).

Experimental

Crystal data

C₂₅H₂₀N₂OS₂
M _r = 428.55
Monoclinic,
a = 18.945 (3) Å
b = 6.025 (2) Å
c = 20.793 (5) Å
β = 110.64 (4)°
V = 2221.1 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 292 K
0.52 × 0.48 × 0.42 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: spherical (WinGX; Farrugia, 1999 ▶) T _min = 0.877, T _max = 0.899
2261 measured reflections
1990 independent reflections
1441 reflections with I > 2σ(I)
R _int = 0.010
3 standard reflections every 150 reflections intensity decay: 2.4%

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.146
S = 1.05
1990 reflections
145 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: DIFRAC (Gabe et al., 1993 ▶); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016948/rz2311sup1.cif

e-65-o1251-sup1.cif^{(16.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016948/rz2311Isup2.hkl

e-65-o1251-Isup2.hkl^{(98KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—HN2⋯O1ⁱ	0.77 (3)	2.52 (3)	3.231 (4)	154 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Mr Zhi-Hua Mao of Sichuan University for the X-ray data collection.

supplementary crystallographic information

Comment

The title compound is a major active photo-initiator used in coatings, optics and microelectronic materials (Wang et al., 2006a,b; Jiang et al., 2006) and can be used as monomer in the synthesis of high performance polyamide. Moreover, as photo initiator it has showed superior to the natural compound 4,4'-difluorobenzophenone (Wang et al., 2006a). Besides their properties as photo-initiators, some derivatives of the title compound have also been reported to possess good thermostability and chemical resistance (Aritomi & Terauchi, 1985; Aritomi & Fujiwara, 1986). The synthetic procedure of the title compound have been reported elsewhere (Yang et al., 2007; Chen et al., 2009).

The molecule of the title compound (Fig. 1) has crystallographically imposed twofold rotation symmetry. In the asymmetric unit, the phenyl rings form a dihedral angle of 79.23 (7)°. The C2–C1–C2ⁱ–C7ⁱ torsion angle is 29.49 (15)° (symmetry code: i = 1-x, y, 1/2-z). In the crystal packing, intermolecular N—H···O hydrogen bonding interactions (Table 1) link the molecules into chains running parallel to the [102] direction.

Experimental

A mixture of 4,4'-difluorobenzophenone (21.8 g, 0.1 mol), 4-aminothiophenol (25 g, 0.2 mol), K₂CO₃ (14.0 g, 0.101 mol) and dimethyl acetamide (120 ml) were charged into a three-necked round-bottomed flask fitted with a mechanical stirrer, a thermometer and a nitrogen inlet. The mixture was stirred vigorously at 120°C for 3 h, then the mixture was heated to 166°C and kept for 5 h under nitrogen atmosphere. After the reactor was cooled to room temperature, the reaction solution was poured into water. The resulting solid was filtered, washed with hot water and methanol, dried and recrystallized from a mixture of dimethyl formamide and water (3:1 v/v) to get a yellow powder. Light yellow crystals suitable for X-ray analysis were obtained by slow evaporation of a formamide/water (3:1 v/v) solution at 60°C.