Bis(4-amino-2-chloro­phen­yl) disulfide

Tang, J.-M.; Feng, Z.-Q.; Cheng, W.

doi:10.1107/S1600536811014425

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1197

doi:10.1107/S1600536811014425

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Bis(4-amino-2-chlorophenyl) disulfide

Jun-Mei Tang,^a ^* Zhi-Qiang Feng ^b and Wei Cheng ^a

^aDepartment of Biological and Chemical Engineering, Chien-shiung Institute of Technology, Taicang 215411, Suzhou, People's Republic of China, and ^bSchool of Materials Engineering, Jinling Institute of Technology, Nanjing 211169, People's Republic of China
^*Correspondence e-mail: Tangjm_83@126.com

(Received 10 March 2011; accepted 17 April 2011; online 22 April 2011)

The title compound, C₁₂H₁₀Cl₂N₂S₂, features an S—S bond [2.0671 (16) Å] that bridges two 4-amino-2-chlorophenyl rings with a C—S—S—C torsion angle of −84.2 (2)°. The two benzene rings are twisted with respect to each other at a dihedral angle of 39.9 (2)°. Intermolecular N—H⋯S hydrogen bonding is present in the crystal structure.

Related literature

For the application of the title compound, see: Crowley (1964 ). For S—S bond distances, see: Allen et al. (1991 ). For similar C—S—S—C torsion angles in disulfide compounds, see: Korp & Bernal (1984 ); Poveteva & Zvonkova (1975 ).

Experimental

Crystal data

C₁₂H₁₀Cl₂N₂S₂
M_r = 317.24
Monoclinic, C c
a = 6.6360 (13) Å
b = 14.907 (3) Å
c = 13.588 (3) Å
β = 95.09 (3)°
V = 1338.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.800, T_max = 0.940
2606 measured reflections
1331 independent reflections
1221 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.088
S = 1.00
1331 reflections
163 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ), 110 Friedel parirs
Flack parameter: 0.09 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.86	2.80	3.611 (5)	158
N2—H2A⋯S2ⁱⁱ	0.86	2.86	3.684 (5)	162
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014425/xu5174sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014425/xu5174Isup2.hkl

checkCIF report

Comment top

The title compound has been used as fungicide and mildew-proofing agent (Crowley, 1964). We herein report its crystal structure. The S-S distance, 2.0670 (13)Å, is normal and falls within the range of 2.018-2.099Å found for the acyclic disulfides in the Cambridge Structural Database (Allen et al., 1991). The torsion angle C-S-S-C of 84.2 (2)° is close to the 85.0° found in diphenyldisulfide (Korp & Bernal, 1984) and lower than the 101.7° found in 4-amino-4'-nitrodiphenyl disulfide (Poveteva & Zvonkova, 1975). The intermolecular N–H···S hydrogen bonds may be effective in the stabilization of the crystal structure.

Related literature top

For the application of the title compound, see: Crowley (1964). For S—S bond distances, see: Allen et al. (1991). For similar C—S—S—C torsion angles in disulfide compounds, see: Korp & Bernal (1984); Poveteva & Zvonkova (1975).

Experimental top

The aqueous solution (20 ml) of 3,4-dichloronitrobenzene (19.2 g, 0.1 mol) and sodium sulfhydrate (28.5 g, 0.22 mol) was refluxed for 16 h, and then filtered. The title compound was obtained from the filtrate. The single crystals were obtained by recrystallization from an ethanol solution after 5 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the molecule of (I). Displacement ellipsoids are drawn at the 50% probability level.

4-[(4-amino-2-chlorophenyl)disulfanyl]-3-chloroaniline top

Crystal data top

C₁₂H₁₀Cl₂N₂S₂	F(000) = 648
M_r = 317.24	D_x = 1.574 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 25 reflections
a = 6.6360 (13) Å	θ = 10–14°
b = 14.907 (3) Å	µ = 0.78 mm⁻¹
c = 13.588 (3) Å	T = 296 K
β = 95.09 (3)°	Block, yellow
V = 1338.9 (5) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1221 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.4°, θ_min = 2.7°
ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = −17→17
T_min = 0.800, T_max = 0.940	l = −16→16
2606 measured reflections	3 standard reflections every 200 reflections
1331 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.066P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1331 reflections	Δρ_max = 0.19 e Å⁻³
163 parameters	Δρ_min = −0.22 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 110 Friedel parirs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (11)

Crystal data top

C₁₂H₁₀Cl₂N₂S₂	V = 1338.9 (5) Å³
M_r = 317.24	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 6.6360 (13) Å	µ = 0.78 mm⁻¹
b = 14.907 (3) Å	T = 296 K
c = 13.588 (3) Å	0.30 × 0.20 × 0.10 mm
β = 95.09 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1221 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.026
T_min = 0.800, T_max = 0.940	3 standard reflections every 200 reflections
2606 measured reflections	intensity decay: 1%
1331 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.088	Δρ_max = 0.19 e Å⁻³
S = 1.00	Δρ_min = −0.22 e Å⁻³
1331 reflections	Absolute structure: Flack (1983), 110 Friedel parirs
163 parameters	Absolute structure parameter: 0.09 (11)
2 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.28662 (15)	0.23231 (7)	0.80302 (8)	0.0442 (3)
Cl1	−0.1503 (2)	0.18083 (8)	0.87818 (12)	0.0609 (4)
N1	−0.3017 (9)	0.5116 (3)	0.9000 (3)	0.0681 (14)
H1A	−0.2710	0.5674	0.8950	0.082*
H1B	−0.4135	0.4965	0.9229	0.082*
C1	−0.0811 (7)	0.2917 (3)	0.8603 (3)	0.0380 (9)
Cl2	−0.2000 (2)	0.26890 (7)	0.57856 (11)	0.0586 (4)
S2	0.26156 (17)	0.21357 (8)	0.65170 (9)	0.0441 (3)
N2	−0.3804 (7)	−0.0596 (3)	0.5629 (3)	0.0525 (10)
H2A	−0.3514	−0.1157	0.5684	0.063*
H2B	−0.5012	−0.0431	0.5426	0.063*
C2	−0.2194 (8)	0.3561 (3)	0.8835 (3)	0.0431 (10)
H2C	−0.3415	0.3397	0.9070	0.052*
C3	−0.1716 (8)	0.4459 (3)	0.8708 (3)	0.0453 (11)
C4	0.0098 (8)	0.4693 (3)	0.8332 (3)	0.0455 (11)
H4A	0.0401	0.5292	0.8226	0.055*
C5	0.1417 (8)	0.4043 (3)	0.8121 (3)	0.0425 (10)
H5A	0.2634	0.4208	0.7881	0.051*
C6	0.1012 (6)	0.3126 (3)	0.8252 (3)	0.0358 (9)
C7	0.0675 (7)	0.1343 (3)	0.6287 (3)	0.0364 (9)
C8	0.1075 (7)	0.0430 (3)	0.6402 (3)	0.0418 (10)
H8A	0.2376	0.0250	0.6627	0.050*
C9	−0.0379 (8)	−0.0212 (3)	0.6193 (3)	0.0464 (11)
H9A	−0.0047	−0.0815	0.6277	0.056*
C10	−0.2349 (7)	0.0029 (3)	0.5857 (3)	0.0379 (10)
C11	−0.2776 (7)	0.0940 (3)	0.5730 (3)	0.0371 (9)
H11A	−0.4068	0.1122	0.5490	0.044*
C12	−0.1295 (7)	0.1569 (3)	0.5957 (3)	0.0377 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0341 (6)	0.0425 (6)	0.0543 (6)	0.0054 (5)	−0.0052 (5)	−0.0064 (5)
Cl1	0.0460 (6)	0.0332 (5)	0.1040 (10)	−0.0052 (5)	0.0090 (6)	0.0041 (6)
N1	0.088 (4)	0.049 (2)	0.071 (3)	0.026 (3)	0.027 (3)	0.007 (2)
C1	0.036 (2)	0.031 (2)	0.046 (2)	0.0004 (18)	−0.0038 (19)	−0.0030 (17)
Cl2	0.0485 (7)	0.0276 (5)	0.0974 (10)	0.0017 (5)	−0.0065 (6)	0.0012 (6)
S2	0.0369 (6)	0.0427 (6)	0.0538 (6)	−0.0042 (5)	0.0115 (5)	−0.0047 (5)
N2	0.057 (2)	0.0300 (19)	0.069 (3)	−0.0092 (18)	−0.001 (2)	0.0023 (18)
C2	0.038 (2)	0.044 (2)	0.048 (2)	0.003 (2)	0.0039 (19)	0.003 (2)
C3	0.060 (3)	0.039 (2)	0.036 (2)	0.011 (2)	0.000 (2)	0.0018 (19)
C4	0.065 (3)	0.030 (2)	0.042 (2)	0.002 (2)	0.003 (2)	0.0003 (18)
C5	0.046 (3)	0.041 (2)	0.040 (2)	−0.007 (2)	0.003 (2)	0.0019 (18)
C6	0.030 (2)	0.033 (2)	0.043 (2)	0.0057 (17)	−0.0024 (17)	−0.0062 (16)
C7	0.037 (2)	0.035 (2)	0.038 (2)	0.0007 (18)	0.0072 (17)	−0.0044 (17)
C8	0.036 (2)	0.044 (2)	0.047 (2)	0.012 (2)	0.0091 (19)	0.0015 (19)
C9	0.060 (3)	0.028 (2)	0.051 (3)	0.005 (2)	0.006 (2)	−0.0003 (17)
C10	0.043 (3)	0.036 (2)	0.034 (2)	−0.0029 (18)	0.005 (2)	−0.0024 (17)
C11	0.035 (2)	0.034 (2)	0.042 (2)	−0.0049 (17)	0.0024 (18)	−0.0014 (17)
C12	0.048 (3)	0.0219 (19)	0.043 (2)	0.0055 (19)	0.0043 (19)	−0.0025 (16)

Geometric parameters (Å, º) top

S1—C6	1.762 (4)	C3—C4	1.393 (7)
S1—S2	2.0671 (16)	C4—C5	1.354 (7)
Cl1—C1	1.738 (4)	C4—H4A	0.9300
N1—C3	1.387 (6)	C5—C6	1.407 (6)
N1—H1A	0.8601	C5—H5A	0.9300
N1—H1B	0.8599	C7—C12	1.385 (7)
C1—C6	1.375 (7)	C7—C8	1.393 (6)
C1—C2	1.384 (6)	C8—C9	1.371 (7)
Cl2—C12	1.744 (4)	C8—H8A	0.9300
S2—C7	1.755 (4)	C9—C10	1.393 (7)
N2—C10	1.357 (6)	C9—H9A	0.9300
N2—H2A	0.8599	C10—C11	1.396 (6)
N2—H2B	0.8600	C11—C12	1.374 (7)
C2—C3	1.390 (6)	C11—H11A	0.9300
C2—H2C	0.9300

C6—S1—S2	105.43 (14)	C6—C5—H5A	118.9
C3—N1—H1A	120.2	C1—C6—C5	116.6 (4)
C3—N1—H1B	119.8	C1—C6—S1	123.7 (3)
H1A—N1—H1B	120.0	C5—C6—S1	119.6 (4)
C6—C1—C2	122.9 (4)	C12—C7—C8	116.0 (4)
C6—C1—Cl1	121.0 (3)	C12—C7—S2	123.4 (3)
C2—C1—Cl1	116.1 (4)	C8—C7—S2	120.5 (4)
C7—S2—S1	105.13 (15)	C9—C8—C7	122.4 (4)
C10—N2—H2A	119.9	C9—C8—H8A	118.8
C10—N2—H2B	120.1	C7—C8—H8A	118.8
H2A—N2—H2B	120.0	C8—C9—C10	120.7 (4)
C1—C2—C3	118.5 (5)	C8—C9—H9A	119.7
C1—C2—H2C	120.8	C10—C9—H9A	119.7
C3—C2—H2C	120.8	N2—C10—C9	121.7 (4)
N1—C3—C2	119.4 (5)	N2—C10—C11	120.5 (4)
N1—C3—C4	120.6 (4)	C9—C10—C11	117.8 (4)
C2—C3—C4	120.0 (4)	C12—C11—C10	120.2 (4)
C5—C4—C3	119.7 (4)	C12—C11—H11A	119.9
C5—C4—H4A	120.2	C10—C11—H11A	119.9
C3—C4—H4A	120.2	C11—C12—C7	122.9 (4)
C4—C5—C6	122.3 (5)	C11—C12—Cl2	116.4 (4)
C4—C5—H5A	118.9	C7—C12—Cl2	120.7 (3)

C6—S1—S2—C7	−84.2 (2)	S1—S2—C7—C12	99.7 (4)
C6—C1—C2—C3	−0.1 (7)	S1—S2—C7—C8	−82.5 (3)
Cl1—C1—C2—C3	179.9 (4)	C12—C7—C8—C9	0.6 (6)
C1—C2—C3—N1	−175.6 (4)	S2—C7—C8—C9	−177.4 (3)
C1—C2—C3—C4	1.6 (7)	C7—C8—C9—C10	−0.2 (6)
N1—C3—C4—C5	175.0 (4)	C8—C9—C10—N2	178.8 (4)
C2—C3—C4—C5	−2.1 (7)	C8—C9—C10—C11	0.8 (6)
C3—C4—C5—C6	1.1 (6)	N2—C10—C11—C12	−179.7 (4)
C2—C1—C6—C5	−0.8 (6)	C9—C10—C11—C12	−1.7 (6)
Cl1—C1—C6—C5	179.2 (3)	C10—C11—C12—C7	2.1 (6)
C2—C1—C6—S1	175.6 (3)	C10—C11—C12—Cl2	−179.2 (3)
Cl1—C1—C6—S1	−4.4 (5)	C8—C7—C12—C11	−1.5 (6)
C4—C5—C6—C1	0.3 (6)	S2—C7—C12—C11	176.4 (3)
C4—C5—C6—S1	−176.3 (3)	C8—C7—C12—Cl2	179.8 (3)
S2—S1—C6—C1	102.4 (3)	S2—C7—C12—Cl2	−2.2 (5)
S2—S1—C6—C5	−81.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.80	3.611 (5)	158
N2—H2A···S2ⁱⁱ	0.86	2.86	3.684 (5)	162

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀Cl₂N₂S₂
M_r	317.24
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	6.6360 (13), 14.907 (3), 13.588 (3)
β (°)	95.09 (3)
V (Å³)	1338.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.800, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	2606, 1331, 1221
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.088, 1.00
No. of reflections	1331
No. of parameters	163
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22
Absolute structure	Flack (1983), 110 Friedel parirs
Absolute structure parameter	0.09 (11)

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.80	3.611 (5)	158
N2—H2A···S2ⁱⁱ	0.86	2.86	3.684 (5)	162

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x−1/2, y−1/2, z.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for data collection.

References

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