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Acta Cryst. (2009). E65, o1251    [ doi:10.1107/S1600536809016948 ]

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

G. Zhang, Y. Wang, S. Long and J. Yang

Abstract top

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].

Comment top

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.

Related literature top

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 top

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.

Refinement top

The H atoms bound to the N atom were found in a difference Fourier map and refined freely. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq (C).

Computing details top

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Unlabelled atoms are related to the labelled atoms by the symmetry operator (1-x, y, 1/2-z).
Bis[4-(4-aminophenylsulfanyl)phenyl) ketone top
Crystal data top
C25H20N2OS2F000 = 896
Mr = 428.55Dx = 1.282 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 31 reflections
a = 18.945 (3) Åθ = 4.3–9.4º
b = 6.025 (2) ŵ = 0.26 mm−1
c = 20.793 (5) ÅT = 292 K
β = 110.64 (4)ºBlock, yellow
V = 2221.1 (11) Å30.52 × 0.48 × 0.42 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.010
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.1º
T = 292 Kh = −22→21
ω–2θ scansk = 0→7
Absorption correction: for a sphere
(WinGX; Farrugia, 1999)		l = −18→24
Tmin = 0.877, Tmax = 0.8993 standard reflections
2261 measured reflections every 150 reflections
1990 independent reflections intensity decay: 2.4%
1441 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.146  w = 1/[σ2(Fo2) + (0.0979P)2 + 0.2492P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
1990 reflectionsΔρmax = 0.22 e Å−3
145 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C25H20N2OS2V = 2221.1 (11) Å3
Mr = 428.55Z = 4
Monoclinic, C2/cMo Kα
a = 18.945 (3) ŵ = 0.26 mm−1
b = 6.025 (2) ÅT = 292 K
c = 20.793 (5) Å0.52 × 0.48 × 0.42 mm
β = 110.64 (4)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		1441 reflections with I > 2σ(I)
Absorption correction: for a sphere
(WinGX; Farrugia, 1999)		Rint = 0.010
Tmin = 0.877, Tmax = 0.8993 standard reflections
2261 measured reflections every 150 reflections
1990 independent reflections intensity decay: 2.4%
Refinement top
R[F2 > 2σ(F2)] = 0.050145 parameters
wR(F2) = 0.146H atoms treated by a mixture of
independent and constrained refinement
S = 1.05Δρmax = 0.22 e Å−3
1990 reflectionsΔρmin = −0.30 e Å−3
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 > 2σ(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
xyzUiso*/Ueq
S10.59611 (4)0.88028 (12)0.52196 (3)0.0591 (3)
O10.50000.1894 (4)0.25000.0638 (7)
N10.8241 (2)0.3345 (7)0.73370 (17)0.0954 (11)
HN10.811 (2)0.224 (7)0.7515 (19)0.096 (13)*
HN20.8651 (18)0.371 (5)0.7407 (16)0.071 (11)*
C10.50000.3937 (5)0.25000.0397 (7)
C20.52388 (11)0.5146 (3)0.31641 (10)0.0364 (5)
C30.57458 (12)0.4134 (4)0.37505 (11)0.0427 (5)
H30.59330.27310.37140.051*
C40.59739 (12)0.5168 (4)0.43805 (11)0.0437 (5)
H40.63120.44660.47640.052*
C50.56977 (12)0.7271 (4)0.44448 (11)0.0409 (5)
C60.51783 (12)0.8281 (4)0.38664 (10)0.0396 (5)
H60.49790.96620.39070.048*
C70.49596 (11)0.7241 (3)0.32367 (10)0.0371 (5)
H70.46210.79440.28540.045*
C80.66367 (12)0.7082 (4)0.58244 (11)0.0484 (6)
C90.73981 (14)0.7565 (5)0.60170 (13)0.0606 (7)
H90.75550.87500.58140.073*
C100.79254 (14)0.6301 (5)0.65085 (14)0.0650 (8)
H100.84350.66440.66310.078*
C110.77125 (14)0.4541 (5)0.68221 (12)0.0580 (7)
C120.69484 (15)0.4026 (5)0.66200 (13)0.0634 (7)
H120.67940.28190.68160.076*
C130.64197 (13)0.5290 (5)0.61320 (12)0.0567 (7)
H130.59110.49400.60070.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0615 (5)0.0678 (5)0.0395 (4)0.0091 (3)0.0073 (3)−0.0110 (3)
O10.0882 (19)0.0344 (13)0.0499 (14)0.0000.0009 (13)0.000
N10.0612 (19)0.134 (3)0.084 (2)0.0128 (19)0.0163 (16)0.042 (2)
C10.0395 (16)0.0318 (16)0.0397 (16)0.0000.0038 (13)0.000
C20.0376 (11)0.0363 (11)0.0336 (10)−0.0016 (9)0.0103 (8)0.0045 (8)
C30.0456 (12)0.0357 (12)0.0413 (12)0.0045 (9)0.0084 (10)0.0046 (9)
C40.0408 (12)0.0475 (13)0.0364 (11)0.0030 (10)0.0058 (9)0.0049 (10)
C50.0375 (11)0.0475 (13)0.0379 (11)−0.0045 (10)0.0137 (9)−0.0013 (9)
C60.0395 (11)0.0413 (12)0.0401 (11)0.0021 (9)0.0166 (10)0.0012 (9)
C70.0350 (10)0.0383 (11)0.0366 (11)0.0017 (9)0.0109 (9)0.0039 (9)
C80.0412 (13)0.0668 (16)0.0348 (11)−0.0065 (11)0.0102 (10)−0.0071 (11)
C90.0500 (14)0.0760 (18)0.0540 (15)−0.0172 (13)0.0164 (12)0.0067 (13)
C100.0364 (13)0.092 (2)0.0602 (16)−0.0089 (13)0.0092 (12)0.0043 (15)
C110.0501 (15)0.0776 (17)0.0433 (13)0.0015 (13)0.0126 (11)0.0023 (12)
C120.0585 (16)0.079 (2)0.0537 (15)−0.0130 (14)0.0206 (13)0.0093 (13)
C130.0380 (12)0.0843 (19)0.0454 (13)−0.0144 (12)0.0115 (10)−0.0014 (13)
Geometric parameters (Å, °) top
S1—C51.769 (2)C5—C61.397 (3)
S1—C81.777 (3)C6—C71.377 (3)
O1—C11.231 (3)C6—H60.9300
N1—C111.383 (4)C7—H70.9300
N1—HN10.84 (4)C8—C91.385 (3)
N1—HN20.77 (3)C8—C131.389 (4)
C1—C21.484 (2)C9—C101.380 (4)
C1—C2i1.484 (2)C9—H90.9300
C2—C71.397 (3)C10—C111.377 (4)
C2—C31.398 (3)C10—H100.9300
C3—C41.375 (3)C11—C121.393 (4)
C3—H30.9300C12—C131.377 (4)
C4—C51.395 (3)C12—H120.9300
C4—H40.9300C13—H130.9300
C5—S1—C8103.99 (12)C6—C7—C2121.02 (19)
C11—N1—HN1121 (2)C6—C7—H7119.5
C11—N1—HN2114 (2)C2—C7—H7119.5
HN1—N1—HN2125 (3)C9—C8—C13118.5 (2)
O1—C1—C2119.39 (12)C9—C8—S1119.9 (2)
O1—C1—C2i119.39 (12)C13—C8—S1121.52 (17)
C2—C1—C2i121.2 (2)C10—C9—C8120.4 (2)
C7—C2—C3118.00 (18)C10—C9—H9119.8
C7—C2—C1122.75 (18)C8—C9—H9119.8
C3—C2—C1119.21 (19)C11—C10—C9121.3 (2)
C4—C3—C2121.4 (2)C11—C10—H10119.4
C4—C3—H3119.3C9—C10—H10119.4
C2—C3—H3119.3C10—C11—N1120.9 (3)
C3—C4—C5120.0 (2)C10—C11—C12118.4 (2)
C3—C4—H4120.0N1—C11—C12120.7 (3)
C5—C4—H4120.0C13—C12—C11120.5 (3)
C4—C5—C6119.15 (19)C13—C12—H12119.7
C4—C5—S1124.48 (16)C11—C12—H12119.7
C6—C5—S1116.37 (17)C12—C13—C8120.8 (2)
C7—C6—C5120.3 (2)C12—C13—H13119.6
C7—C6—H6119.8C8—C13—H13119.6
C5—C6—H6119.8
O1—C1—C2—C7−150.51 (15)C3—C2—C7—C60.2 (3)
C2i—C1—C2—C729.49 (15)C1—C2—C7—C6178.04 (18)
O1—C1—C2—C327.3 (2)C5—S1—C8—C9102.6 (2)
C2i—C1—C2—C3−152.7 (2)C5—S1—C8—C13−79.8 (2)
C7—C2—C3—C4−0.8 (3)C13—C8—C9—C10−0.6 (4)
C1—C2—C3—C4−178.80 (18)S1—C8—C9—C10177.1 (2)
C2—C3—C4—C50.1 (3)C8—C9—C10—C11−0.3 (4)
C3—C4—C5—C61.3 (3)C9—C10—C11—N1−177.0 (3)
C3—C4—C5—S1−178.56 (17)C9—C10—C11—C121.5 (4)
C8—S1—C5—C41.7 (2)C10—C11—C12—C13−1.8 (4)
C8—S1—C5—C6−178.18 (16)N1—C11—C12—C13176.7 (3)
C4—C5—C6—C7−2.0 (3)C11—C12—C13—C80.9 (4)
S1—C5—C6—C7177.89 (16)C9—C8—C13—C120.3 (4)
C5—C6—C7—C21.3 (3)S1—C8—C13—C12−177.4 (2)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—HN2···O1ii0.77 (3)2.52 (3)3.231 (4)154 (3)
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—HN2···O1i0.77 (3)2.52 (3)3.231 (4)154 (3)
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1.
Acknowledgements top

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

references
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