N-(2-Thienylmethyl­ene)-2-(2-{[2-(2-thienylmethyl­eneamino)phen­yl]sulfan­yl}ethyl­sulfan­yl)aniline

Kakanejadifard, A.; Amani, V.

doi:10.1107/S1600536809024404

organic compounds

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doi:10.1107/S1600536809024404

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N-(2-Thienylmethylene)-2-(2-{[2-(2-thienylmethyleneamino)phenyl]sulfanyl}ethylsulfanyl)aniline

Ali Kakanejadifard ^a ^* and Vahid Amani ^b

^aDepartment of Chemistry, Faculty of Science, Lorestan University, Khorramabad, Iran, and ^bDepartment of Chemistry, Islamic Azad University, Shahr-e-Rey Branch, Tehran, Iran
^*Correspondence e-mail: alikakanejadifard@yahoo.com

(Received 18 June 2009; accepted 24 June 2009; online 27 June 2009)

The asymmetric unit of the title compound, C₂₄H₂₀N₂S₄, contains one half-molecule: a crystallographic centre of inversion is located at the mid-point of the two central C atoms. The thiophene ring is oriented at a dihedral angle of 60.64 (3)° with respect to the benzene ring. In the crystal structure, π–π contacts between thiophene rings [centroid–centroid distance = 3.581 (1) Å] may stabilize the structure. A weak C—H⋯π interaction is also present.

Related literature

For related structures, see: Dharaa et al. (2005 ); Gok & Demirbas (1989 ); Kakanejadifard et al. (2007 ); Kakanejadifard & Amani (2008 ); Morshedi et al. (2009 ); Rajsekhar et al. (2002 , 2004 ); Taylor et al. (2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₄H₂₀N₂S₄
M_r = 464.66
Monoclinic, P 2₁ /c
a = 11.179 (5) Å
b = 7.730 (4) Å
c = 12.608 (6) Å
β = 91.899 (12)°
V = 1088.9 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.895, T_max = 0.930
12880 measured reflections
2899 independent reflections
2569 reflections with I > 2/s(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.079
S = 1.00
2899 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯Cg1ⁱ	0.95	2.80	3.740 (3)	171
Symmetry code: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg1 is centroid of the ring C2–C7 ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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/S1600536809024404/hk2716sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024404/hk2716Isup2.hkl

checkCIF report

Comment top

There are several examples of N₂S₂ Schiff bases type of adducts which exist as anti configuration. For 2-[2-(2-aminophenylthio)benzeneamine] adduct see: (Gok & Demirbas, 1989; Dharaa et al., 2005; Kakanejadifard et al., 2007; Kakanejadifard & Amani, 2008). For N₂S₂ Schiff bases adduct see: (Rajsekhar et al., 2002; Taylor et al., 2008; Morshedi et al., 2009). For N₂O₂S₂ Schiff bases adduct see: (Rajsekhar et al., 2004). We report herein the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains one-half molecule. A crystallographic centre of inversion is located at the midpoint between the two central C atoms. The bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C2-C7) and B (S2/C9-C12) are, of course, planar and they are oriented at a dihedral angle of 60.64 (3)°.

In the crystal structure, the π–π contact between the thiophene rings, Cg2—Cg2ⁱ, [symmetry code: (i) -x, -y, 1 - z, where Cg2 is centroid of the ring B (S2/C9-C12)] may stabilize the structure, with centroid-centroid distance of 3.581 (1) Å. There also exits a weak C—H···π interaction (Table 1).

Related literature top

For related structures, see: Dharaa et al. (2005); Gok & Demirbas (1989); Kakanejadifard et al. (2007); Kakanejadifard & Amani (2008); Morshedi et al. (2009); Rajsekhar et al. (2002, 2004); Taylor et al. (2008). For bond-length data, see: Allen et al. (1987). Cg1 is centroid of the ring C2–C7 ring.

Experimental top

For the preparation of the title compound, a solution of thiophencarbaldehyde (20 mmol) was added dropwise to a solution of 2-[2-(2-aminophenylthio)benzeneamine] (2.76 g, 10 mmol) in absolute ethanol (25 ml) with stirring in 10 min at room temperature. The mixture was stirred and heated to reflux for 5 h. The product was filtered and crystallized from CH₃CN (yield; 45%, m.p. 398-399 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (a) 1 - x, -y, 2 -z].
	Fig. 2. A partial packing diagram.

N-(2-Thienylmethylene)-2-(2-{[2-(2- thienylmethyleneamino)phenyl]sulfanyl}ethylsulfanyl)aniline top

Crystal data top

C₂₄H₂₀N₂S₄	F(000) = 484
M_r = 464.66	D_x = 1.417 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 887 reflections
a = 11.179 (5) Å	θ = 3–30°
b = 7.730 (4) Å	µ = 0.45 mm⁻¹
c = 12.608 (6) Å	T = 100 K
β = 91.899 (12)°	Prism, yellow
V = 1088.9 (9) Å³	0.30 × 0.20 × 0.15 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	2899 independent reflections
Radiation source: fine-focus sealed tube	2569 reflections with I > 2/s(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 29.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→15
T_min = 0.895, T_max = 0.930	k = −10→10
12880 measured reflections	l = −17→17

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0441P)² + 0.43P] where P = (F_o² + 2F_c²)/3
2899 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₄H₂₀N₂S₄	V = 1088.9 (9) Å³
M_r = 464.66	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.179 (5) Å	µ = 0.45 mm⁻¹
b = 7.730 (4) Å	T = 100 K
c = 12.608 (6) Å	0.30 × 0.20 × 0.15 mm
β = 91.899 (12)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2899 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2569 reflections with I > 2/s(I)
T_min = 0.895, T_max = 0.930	R_int = 0.029
12880 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.00	Δρ_max = 0.34 e Å⁻³
2899 reflections	Δρ_min = −0.26 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	0.63766 (3)	−0.06436 (4)	0.88963 (2)	0.01981 (9)
S2	0.96427 (3)	0.15452 (4)	0.67870 (2)	0.01990 (9)
N1	0.79244 (9)	−0.14058 (14)	0.72259 (8)	0.0188 (2)
C1	0.51924 (11)	−0.09011 (16)	0.98300 (10)	0.0199 (2)
H1A	0.4507	−0.1525	0.9492	0.024*
H1B	0.5485	−0.1574	1.0454	0.024*
C2	0.64682 (11)	−0.27273 (16)	0.83345 (10)	0.0178 (2)
C3	0.58160 (11)	−0.41715 (17)	0.86395 (10)	0.0212 (3)
H3A	0.5258	−0.4071	0.9188	0.025*
C4	0.59782 (12)	−0.57566 (17)	0.81445 (11)	0.0232 (3)
H4A	0.5528	−0.6732	0.8357	0.028*
C5	0.67894 (12)	−0.59283 (18)	0.73454 (11)	0.0238 (3)
H5A	0.6912	−0.7024	0.7025	0.029*
C6	0.74233 (12)	−0.44926 (17)	0.70128 (10)	0.0216 (3)
H6A	0.7970	−0.4605	0.6456	0.026*
C7	0.72613 (10)	−0.28888 (16)	0.74913 (9)	0.0180 (2)
C8	0.79459 (11)	−0.09360 (17)	0.62510 (10)	0.0196 (2)
H8A	0.7488	−0.1565	0.5733	0.024*
C9	0.86458 (11)	0.05200 (17)	0.59218 (10)	0.0188 (2)
C10	0.86686 (12)	0.12347 (18)	0.49235 (10)	0.0213 (3)
H10A	0.8185	0.0843	0.4338	0.026*
C11	0.94924 (12)	0.26160 (18)	0.48653 (10)	0.0234 (3)
H11A	0.9619	0.3261	0.4237	0.028*
C12	1.00852 (12)	0.29220 (17)	0.58100 (10)	0.0223 (3)
H12B	1.0675	0.3797	0.5914	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01936 (16)	0.01889 (16)	0.02154 (16)	−0.00077 (11)	0.00610 (11)	−0.00011 (11)
S2	0.02172 (16)	0.02322 (17)	0.01469 (15)	−0.00207 (11)	−0.00047 (11)	−0.00144 (11)
N1	0.0163 (5)	0.0226 (5)	0.0174 (5)	−0.0002 (4)	0.0025 (4)	−0.0003 (4)
C1	0.0180 (6)	0.0221 (6)	0.0199 (6)	0.0015 (5)	0.0049 (4)	0.0027 (5)
C2	0.0168 (5)	0.0188 (6)	0.0178 (5)	0.0017 (4)	−0.0008 (4)	0.0010 (4)
C3	0.0190 (6)	0.0226 (6)	0.0221 (6)	−0.0004 (5)	0.0013 (5)	0.0045 (5)
C4	0.0226 (6)	0.0196 (6)	0.0270 (6)	−0.0027 (5)	−0.0036 (5)	0.0044 (5)
C5	0.0239 (6)	0.0210 (6)	0.0261 (6)	0.0016 (5)	−0.0053 (5)	−0.0026 (5)
C6	0.0196 (6)	0.0251 (6)	0.0200 (6)	0.0021 (5)	−0.0005 (5)	−0.0024 (5)
C7	0.0160 (5)	0.0210 (6)	0.0170 (5)	−0.0001 (4)	−0.0013 (4)	0.0014 (4)
C8	0.0173 (5)	0.0240 (6)	0.0176 (6)	0.0002 (5)	0.0007 (4)	−0.0011 (5)
C9	0.0173 (5)	0.0229 (6)	0.0163 (5)	0.0004 (4)	0.0001 (4)	−0.0020 (5)
C10	0.0220 (6)	0.0259 (6)	0.0159 (6)	0.0006 (5)	−0.0010 (4)	0.0000 (5)
C11	0.0277 (6)	0.0230 (6)	0.0198 (6)	0.0008 (5)	0.0034 (5)	0.0037 (5)
C12	0.0247 (6)	0.0193 (6)	0.0232 (6)	−0.0022 (5)	0.0032 (5)	0.0002 (5)

Geometric parameters (Å, º) top

S1—C2	1.7639 (15)	C4—H4A	0.9500
S1—C1	1.8114 (14)	C5—C6	1.389 (2)
S2—C12	1.7132 (15)	C5—H5A	0.9500
S2—C9	1.7261 (14)	C6—C7	1.3932 (19)
N1—C8	1.2827 (17)	C6—H6A	0.9500
N1—C7	1.4114 (17)	C8—C9	1.4396 (18)
C1—C1ⁱ	1.524 (3)	C8—H8A	0.9500
C1—H1A	0.9900	C9—C10	1.3757 (18)
C1—H1B	0.9900	C10—C11	1.414 (2)
C2—C3	1.3944 (18)	C10—H10A	0.9500
C2—C7	1.4122 (17)	C11—C12	1.3644 (19)
C3—C4	1.3897 (19)	C11—H11A	0.9500
C3—H3A	0.9500	C12—H12B	0.9500
C4—C5	1.384 (2)

C2—S1—C1	102.36 (6)	C5—C6—C7	120.35 (12)
C12—S2—C9	91.53 (7)	C5—C6—H6A	119.8
C8—N1—C7	118.94 (11)	C7—C6—H6A	119.8
C1ⁱ—C1—S1	107.55 (11)	C6—C7—N1	122.90 (11)
C1ⁱ—C1—H1A	110.2	C6—C7—C2	119.91 (12)
S1—C1—H1A	110.2	N1—C7—C2	117.03 (11)
C1ⁱ—C1—H1B	110.2	N1—C8—C9	121.68 (12)
S1—C1—H1B	110.2	N1—C8—H8A	119.2
H1A—C1—H1B	108.5	C9—C8—H8A	119.2
C3—C2—C7	118.94 (12)	C10—C9—C8	127.19 (12)
C3—C2—S1	125.63 (10)	C10—C9—S2	111.26 (10)
C7—C2—S1	115.42 (9)	C8—C9—S2	121.50 (10)
C4—C3—C2	120.32 (12)	C9—C10—C11	112.50 (12)
C4—C3—H3A	119.8	C9—C10—H10A	123.7
C2—C3—H3A	119.8	C11—C10—H10A	123.7
C5—C4—C3	120.66 (12)	C12—C11—C10	112.59 (12)
C5—C4—H4A	119.7	C12—C11—H11A	123.7
C3—C4—H4A	119.7	C10—C11—H11A	123.7
C4—C5—C6	119.75 (13)	C11—C12—S2	112.12 (10)
C4—C5—H5A	120.1	C11—C12—H12B	123.9
C6—C5—H5A	120.1	S2—C12—H12B	123.9

C2—S1—C1—C1ⁱ	−166.07 (12)	S1—C2—C7—C6	178.23 (9)
C1—S1—C2—C3	−4.13 (13)	C3—C2—C7—N1	−178.52 (11)
C1—S1—C2—C7	174.52 (9)	S1—C2—C7—N1	2.73 (14)
C7—C2—C3—C4	2.25 (19)	C7—N1—C8—C9	−177.31 (11)
S1—C2—C3—C4	−179.14 (10)	N1—C8—C9—C10	−174.31 (13)
C2—C3—C4—C5	0.2 (2)	N1—C8—C9—S2	8.43 (18)
C3—C4—C5—C6	−1.9 (2)	C12—S2—C9—C10	−0.04 (10)
C4—C5—C6—C7	1.1 (2)	C12—S2—C9—C8	177.62 (11)
C5—C6—C7—N1	176.60 (12)	C8—C9—C10—C11	−177.69 (12)
C5—C6—C7—C2	1.38 (19)	S2—C9—C10—C11	−0.20 (15)
C8—N1—C7—C6	53.92 (17)	C9—C10—C11—C12	0.42 (17)
C8—N1—C7—C2	−130.73 (13)	C10—C11—C12—S2	−0.44 (15)
C3—C2—C7—C6	−3.02 (18)	C9—S2—C12—C11	0.28 (11)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···Cg1ⁱⁱ	0.95	2.80	3.740 (3)	171

Symmetry code: (ii) x, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₀N₂S₄
M_r	464.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.179 (5), 7.730 (4), 12.608 (6)
β (°)	91.899 (12)
V (Å³)	1088.9 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.895, 0.930
No. of measured, independent and observed [I > 2/s(I)] reflections	12880, 2899, 2569
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.079, 1.00
No. of reflections	2899
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.26

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···Cg1ⁱ	0.95	2.80	3.740 (3)	171

Symmetry code: (i) x, −y−1/2, z−1/2.

Acknowledgements

We are grateful to the Research Grant Council of Lorestan University for financial support.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N-(2-Thienylmethyl­ene)-2-(2-{[2-(2-thienylmethyl­ene­amino)phen­yl]sulfan­yl}ethyl­sulfan­yl)aniline

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

N-(2-Thienylmethylene)-2-(2-{[2-(2-thienylmethyleneamino)phenyl]sulfanyl}ethylsulfanyl)aniline