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

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

doi:10.1107/S1600536809016948

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1251

doi:10.1107/S1600536809016948

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

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

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, ^bAnalysis & Testing Centre, Sichuan University, Chengdu 610064, People's Republic of China, and ^cInstitute of Materials Science & Technology, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: ppsf@scu.edu.cn

(Received 9 April 2009; accepted 5 May 2009; online 14 May 2009)

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, C 2/c
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[F² > 2σ(F²)] = 0.050
wR(F²) = 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

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)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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.

Supporting information

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

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

checkCIF report

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.

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

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

C₂₅H₂₀N₂OS₂	F(000) = 896
M_r = 428.55	D_x = 1.282 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 31 reflections
a = 18.945 (3) Å	θ = 4.3–9.4°
b = 6.025 (2) Å	µ = 0.26 mm⁻¹
c = 20.793 (5) Å	T = 292 K
β = 110.64 (4)°	Block, yellow
V = 2221.1 (11) Å³	0.52 × 0.48 × 0.42 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1441 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.010
Graphite monochromator	θ_max = 25.5°, θ_min = 2.1°
ω–2θ scans	h = −22→21
Absorption correction: for a sphere (WinGX; Farrugia, 1999)	k = 0→7
T_min = 0.877, T_max = 0.899	l = −18→24
2261 measured reflections	3 standard reflections every 150 reflections
1990 independent reflections	intensity decay: 2.4%

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)] = 0.050	Hydrogen site location: mixed
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0979P)² + 0.2492P] where P = (F_o² + 2F_c²)/3
1990 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₂₅H₂₀N₂OS₂	V = 2221.1 (11) Å³
M_r = 428.55	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.945 (3) Å	µ = 0.26 mm⁻¹
b = 6.025 (2) Å	T = 292 K
c = 20.793 (5) Å	0.52 × 0.48 × 0.42 mm
β = 110.64 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1441 reflections with I > 2σ(I)
Absorption correction: for a sphere (WinGX; Farrugia, 1999)	R_int = 0.010
T_min = 0.877, T_max = 0.899	3 standard reflections every 150 reflections
2261 measured reflections	intensity decay: 2.4%
1990 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.22 e Å⁻³
1990 reflections	Δρ_min = −0.30 e Å⁻³
145 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 > 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

	x	y	z	U_iso*/U_eq
S1	0.59611 (4)	0.88028 (12)	0.52196 (3)	0.0591 (3)
O1	0.5000	0.1894 (4)	0.2500	0.0638 (7)
N1	0.8241 (2)	0.3345 (7)	0.73370 (17)	0.0954 (11)
HN1	0.811 (2)	0.224 (7)	0.7515 (19)	0.096 (13)*
HN2	0.8651 (18)	0.371 (5)	0.7407 (16)	0.071 (11)*
C1	0.5000	0.3937 (5)	0.2500	0.0397 (7)
C2	0.52388 (11)	0.5146 (3)	0.31641 (10)	0.0364 (5)
C3	0.57458 (12)	0.4134 (4)	0.37505 (11)	0.0427 (5)
H3	0.5933	0.2731	0.3714	0.051*
C4	0.59739 (12)	0.5168 (4)	0.43805 (11)	0.0437 (5)
H4	0.6312	0.4466	0.4764	0.052*
C5	0.56977 (12)	0.7271 (4)	0.44448 (11)	0.0409 (5)
C6	0.51783 (12)	0.8281 (4)	0.38664 (10)	0.0396 (5)
H6	0.4979	0.9662	0.3907	0.048*
C7	0.49596 (11)	0.7241 (3)	0.32367 (10)	0.0371 (5)
H7	0.4621	0.7944	0.2854	0.045*
C8	0.66367 (12)	0.7082 (4)	0.58244 (11)	0.0484 (6)
C9	0.73981 (14)	0.7565 (5)	0.60170 (13)	0.0606 (7)
H9	0.7555	0.8750	0.5814	0.073*
C10	0.79254 (14)	0.6301 (5)	0.65085 (14)	0.0650 (8)
H10	0.8435	0.6644	0.6631	0.078*
C11	0.77125 (14)	0.4541 (5)	0.68221 (12)	0.0580 (7)
C12	0.69484 (15)	0.4026 (5)	0.66200 (13)	0.0634 (7)
H12	0.6794	0.2819	0.6816	0.076*
C13	0.64197 (13)	0.5290 (5)	0.61320 (12)	0.0567 (7)
H13	0.5911	0.4940	0.6007	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0615 (5)	0.0678 (5)	0.0395 (4)	0.0091 (3)	0.0073 (3)	−0.0110 (3)
O1	0.0882 (19)	0.0344 (13)	0.0499 (14)	0.000	0.0009 (13)	0.000
N1	0.0612 (19)	0.134 (3)	0.084 (2)	0.0128 (19)	0.0163 (16)	0.042 (2)
C1	0.0395 (16)	0.0318 (16)	0.0397 (16)	0.000	0.0038 (13)	0.000
C2	0.0376 (11)	0.0363 (11)	0.0336 (10)	−0.0016 (9)	0.0103 (8)	0.0045 (8)
C3	0.0456 (12)	0.0357 (12)	0.0413 (12)	0.0045 (9)	0.0084 (10)	0.0046 (9)
C4	0.0408 (12)	0.0475 (13)	0.0364 (11)	0.0030 (10)	0.0058 (9)	0.0049 (10)
C5	0.0375 (11)	0.0475 (13)	0.0379 (11)	−0.0045 (10)	0.0137 (9)	−0.0013 (9)
C6	0.0395 (11)	0.0413 (12)	0.0401 (11)	0.0021 (9)	0.0166 (10)	0.0012 (9)
C7	0.0350 (10)	0.0383 (11)	0.0366 (11)	0.0017 (9)	0.0109 (9)	0.0039 (9)
C8	0.0412 (13)	0.0668 (16)	0.0348 (11)	−0.0065 (11)	0.0102 (10)	−0.0071 (11)
C9	0.0500 (14)	0.0760 (18)	0.0540 (15)	−0.0172 (13)	0.0164 (12)	0.0067 (13)
C10	0.0364 (13)	0.092 (2)	0.0602 (16)	−0.0089 (13)	0.0092 (12)	0.0043 (15)
C11	0.0501 (15)	0.0776 (17)	0.0433 (13)	0.0015 (13)	0.0126 (11)	0.0023 (12)
C12	0.0585 (16)	0.079 (2)	0.0537 (15)	−0.0130 (14)	0.0206 (13)	0.0093 (13)
C13	0.0380 (12)	0.0843 (19)	0.0454 (13)	−0.0144 (12)	0.0115 (10)	−0.0014 (13)

Geometric parameters (Å, º) top

S1—C5	1.769 (2)	C5—C6	1.397 (3)
S1—C8	1.777 (3)	C6—C7	1.377 (3)
O1—C1	1.231 (3)	C6—H6	0.9300
N1—C11	1.383 (4)	C7—H7	0.9300
N1—HN1	0.84 (4)	C8—C9	1.385 (3)
N1—HN2	0.77 (3)	C8—C13	1.389 (4)
C1—C2	1.484 (2)	C9—C10	1.380 (4)
C1—C2ⁱ	1.484 (2)	C9—H9	0.9300
C2—C7	1.397 (3)	C10—C11	1.377 (4)
C2—C3	1.398 (3)	C10—H10	0.9300
C3—C4	1.375 (3)	C11—C12	1.393 (4)
C3—H3	0.9300	C12—C13	1.377 (4)
C4—C5	1.395 (3)	C12—H12	0.9300
C4—H4	0.9300	C13—H13	0.9300

C5—S1—C8	103.99 (12)	C6—C7—C2	121.02 (19)
C11—N1—HN1	121 (2)	C6—C7—H7	119.5
C11—N1—HN2	114 (2)	C2—C7—H7	119.5
HN1—N1—HN2	125 (3)	C9—C8—C13	118.5 (2)
O1—C1—C2	119.39 (12)	C9—C8—S1	119.9 (2)
O1—C1—C2ⁱ	119.39 (12)	C13—C8—S1	121.52 (17)
C2—C1—C2ⁱ	121.2 (2)	C10—C9—C8	120.4 (2)
C7—C2—C3	118.00 (18)	C10—C9—H9	119.8
C7—C2—C1	122.75 (18)	C8—C9—H9	119.8
C3—C2—C1	119.21 (19)	C11—C10—C9	121.3 (2)
C4—C3—C2	121.4 (2)	C11—C10—H10	119.4
C4—C3—H3	119.3	C9—C10—H10	119.4
C2—C3—H3	119.3	C10—C11—N1	120.9 (3)
C3—C4—C5	120.0 (2)	C10—C11—C12	118.4 (2)
C3—C4—H4	120.0	N1—C11—C12	120.7 (3)
C5—C4—H4	120.0	C13—C12—C11	120.5 (3)
C4—C5—C6	119.15 (19)	C13—C12—H12	119.7
C4—C5—S1	124.48 (16)	C11—C12—H12	119.7
C6—C5—S1	116.37 (17)	C12—C13—C8	120.8 (2)
C7—C6—C5	120.3 (2)	C12—C13—H13	119.6
C7—C6—H6	119.8	C8—C13—H13	119.6
C5—C6—H6	119.8

O1—C1—C2—C7	−150.51 (15)	C3—C2—C7—C6	0.2 (3)
C2ⁱ—C1—C2—C7	29.49 (15)	C1—C2—C7—C6	178.04 (18)
O1—C1—C2—C3	27.3 (2)	C5—S1—C8—C9	102.6 (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—C10	177.1 (2)
C2—C3—C4—C5	0.1 (3)	C8—C9—C10—C11	−0.3 (4)
C3—C4—C5—C6	1.3 (3)	C9—C10—C11—N1	−177.0 (3)
C3—C4—C5—S1	−178.56 (17)	C9—C10—C11—C12	1.5 (4)
C8—S1—C5—C4	1.7 (2)	C10—C11—C12—C13	−1.8 (4)
C8—S1—C5—C6	−178.18 (16)	N1—C11—C12—C13	176.7 (3)
C4—C5—C6—C7	−2.0 (3)	C11—C12—C13—C8	0.9 (4)
S1—C5—C6—C7	177.89 (16)	C9—C8—C13—C12	0.3 (4)
C5—C6—C7—C2	1.3 (3)	S1—C8—C13—C12	−177.4 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN2···O1ⁱⁱ	0.77 (3)	2.52 (3)	3.231 (4)	154 (3)

Symmetry code: (ii) −x+3/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀N₂OS₂
M_r	428.55
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	292
a, b, c (Å)	18.945 (3), 6.025 (2), 20.793 (5)
β (°)	110.64 (4)
V (Å³)	2221.1 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.52 × 0.48 × 0.42

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	For a sphere (WinGX; Farrugia, 1999)
T_min, T_max	0.877, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	2261, 1990, 1441
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.146, 1.05
No. of reflections	1990
No. of parameters	145
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.30

Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (i) −x+3/2, −y+1/2, −z+1.

Acknowledgements

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

References

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