N,N′-Bis[(E)-1-(thio­phen-3-yl)ethyl­idene]ethane-1,2-diamine

Asiri, A.M.; Faidallah, H.M.; Khan, K.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812009798

organic compounds

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Volume 68| Part 4| April 2012| Page o1026

doi:10.1107/S1600536812009798

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N,N′-Bis[(E)-1-(thiophen-3-yl)ethylidene]ethane-1,2-diamine

Abdullah M. Asiri,^a,^b ‡ Hassan M. Faidallah,^a Khalid A. Khan,^a Seik Weng Ng ^c,^a and Edward R. T. Tiekink ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, ^bThe Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, PO Box 80203, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 5 March 2012; accepted 5 March 2012; online 10 March 2012)

The complete molecule of the title compound, C₁₄H₁₆N₂S₂, is generated by a crystallographic inversion centre. The thiophene residue is close to being coplanar with the imine group [C—C—C—N torsion angle = 6.5 (2)°], and the conformation about the imine C=N bond [1.281 (2) Å] is E. In the crystal, the three-dimensional architecture is consolidated by C—H⋯N, C—H⋯π and S⋯S [3.3932 (7) Å] interactions.

Related literature

For background to 2-substituted thiophenes, see: Kleemann et al. (2006 ). For related structures, see: Prasath et al. (2010a ,b ).

Experimental

Crystal data

C₁₄H₁₆N₂S₂
M_r = 276.41
Monoclinic, P 2₁ /c
a = 7.5231 (6) Å
b = 11.2338 (6) Å
c = 8.5967 (6) Å
β = 112.894 (9)°
V = 669.30 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.928, T_max = 0.963
2789 measured reflections
1542 independent reflections
1339 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.105
S = 1.06
1542 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1,C1–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N1ⁱ	0.95	2.51	3.454 (2)	172
C6—H6C⋯Cg1ⁱⁱ	0.98	2.74	3.624 (2)	150
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812009798/hb6669sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009798/hb6669Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009798/hb6669Isup3.cml

checkCIF report

Comment top

Thiophenes attract attention for their biological activity amongst other properties (Kleemann et al., 2006). In continuation of structural studies of thienyl derivatives (Prasath et al., 2010a; Prasath et al., 2010b), herein the title compound, bis[1-(thiophen-3-yl)ethylidene]ethane-1,2-diamine (I), is described.

The asymmetric unit in (I), Fig. 1, comprises half a molecule with the full molecule generated by a crystallographic centre of inversion. The thiophene residue is co-planar with the imine group as seen in the value of the C2—C3—C5—N1 torsion angle of 6.5 (2) °. In fact the entire molecule is planar with the r.m.s. deviation for the 18 non-hydrogen atoms being 0.068 Å; the maximum deviations are found for the S1 [0.092 (1) Å] and C2 [-0.099 (2) Å] atoms. The conformation about the imine N1—C5 bond [1.281 (2) Å] is E.

In the crystal packing the molecules associate via C—H···N, C—H···π, [Table 1] and S···S [S1···S1ⁱ = 3.3932 (7) Å for i: 2 - x, 1 - y, 2 - z] interactions to form a three-dimensional architecture, Fig. 2.

Related literature top

For background to 2-substituted thiophenes, see: Kleemann et al. (2006). For related structures, see: Prasath et al. (2010a,b).

Experimental top

A mixture of ethylenediamine (0.6 g, 0.01 M) and 2-acetyl thiophene (0.7 g, 0.01 M) in dry benzene (50 ml) was refluxed using a Dean-Stark trap until no more water was collected (2 h). The benzene was then removed under reduced pressure and the residue treated with methanol. The solid that separated out was recrystallized from ethanol as colourless prisms. Yield: 72%. M.pt: 405–407 K.

Structure description top

For background to 2-substituted thiophenes, see: Kleemann et al. (2006). For related structures, see: Prasath et al. (2010a,b).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level. The unlabelled atoms are related by the symmetry operation (1-x, 1-y, -z).
	Fig. 2. A view in projection down the c axis of the unit-cell contents of (I). The C—N···N, C—H···π and S···S interactions are shown as blue, purple and orange dashed lines, respectively.

N,N'-Bis[(E)-1-(thiophen-3-yl)ethylidene]ethane-1,2-diamine top

Crystal data top

C₁₄H₁₆N₂S₂	F(000) = 292
M_r = 276.41	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1637 reflections
a = 7.5231 (6) Å	θ = 2.6–27.5°
b = 11.2338 (6) Å	µ = 0.38 mm⁻¹
c = 8.5967 (6) Å	T = 100 K
β = 112.894 (9)°	Prism, colourless
V = 669.30 (8) Å³	0.20 × 0.15 × 0.10 mm
Z = 2

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1542 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1339 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.033
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.9°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −14→9
T_min = 0.928, T_max = 0.963	l = −11→7
2789 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0482P)² + 0.3751P] where P = (F_o² + 2F_c²)/3
1542 reflections	(Δ/σ)_max = 0.001
83 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₄H₁₆N₂S₂	V = 669.30 (8) Å³
M_r = 276.41	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5231 (6) Å	µ = 0.38 mm⁻¹
b = 11.2338 (6) Å	T = 100 K
c = 8.5967 (6) Å	0.20 × 0.15 × 0.10 mm
β = 112.894 (9)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1542 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1339 reflections with I > 2σ(I)
T_min = 0.928, T_max = 0.963	R_int = 0.033
2789 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	Δρ_max = 0.45 e Å⁻³
1542 reflections	Δρ_min = −0.41 e Å⁻³
83 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	0.88734 (7)	0.59544 (4)	0.83858 (6)	0.01735 (17)
N1	0.6122 (2)	0.51740 (13)	0.23310 (18)	0.0129 (3)
C1	0.7443 (3)	0.69397 (16)	0.6897 (2)	0.0161 (4)
H1	0.7138	0.7719	0.7143	0.019*
C2	0.6805 (3)	0.64614 (16)	0.5325 (2)	0.0138 (4)
H2	0.5985	0.6872	0.4342	0.017*
C3	0.7493 (2)	0.52741 (15)	0.5294 (2)	0.0127 (4)
C4	0.8632 (3)	0.48878 (16)	0.6889 (2)	0.0151 (4)
H4	0.9214	0.4123	0.7133	0.018*
C5	0.7023 (2)	0.45986 (15)	0.3700 (2)	0.0121 (4)
C6	0.7668 (3)	0.33137 (16)	0.3829 (2)	0.0156 (4)
H6A	0.6939	0.2903	0.2764	0.023*
H6B	0.7435	0.2923	0.4751	0.023*
H6C	0.9049	0.3283	0.4055	0.023*
C7	0.5591 (3)	0.45805 (16)	0.0702 (2)	0.0144 (4)
H7A	0.4831	0.3856	0.0675	0.017*
H7B	0.6771	0.4338	0.0537	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0200 (3)	0.0185 (3)	0.0112 (3)	0.00100 (18)	0.00349 (19)	−0.00088 (17)
N1	0.0144 (8)	0.0129 (7)	0.0110 (7)	−0.0001 (6)	0.0043 (6)	−0.0005 (6)
C1	0.0183 (9)	0.0150 (8)	0.0170 (9)	0.0011 (7)	0.0091 (7)	0.0012 (7)
C2	0.0147 (9)	0.0151 (9)	0.0128 (8)	0.0013 (7)	0.0065 (7)	0.0023 (7)
C3	0.0124 (8)	0.0129 (8)	0.0134 (9)	−0.0012 (7)	0.0057 (7)	0.0010 (7)
C4	0.0171 (9)	0.0137 (8)	0.0136 (9)	0.0003 (7)	0.0052 (7)	0.0001 (7)
C5	0.0101 (8)	0.0123 (8)	0.0146 (9)	−0.0011 (6)	0.0055 (7)	−0.0006 (7)
C6	0.0184 (9)	0.0125 (8)	0.0158 (9)	0.0020 (7)	0.0064 (7)	0.0004 (7)
C7	0.0177 (9)	0.0124 (8)	0.0121 (9)	0.0005 (7)	0.0047 (7)	−0.0024 (7)

Geometric parameters (Å, º) top

S1—C4	1.7154 (18)	C3—C5	1.484 (2)
S1—C1	1.7174 (19)	C4—H4	0.9500
N1—C5	1.281 (2)	C5—C6	1.513 (2)
N1—C7	1.460 (2)	C6—H6A	0.9800
C1—C2	1.357 (2)	C6—H6B	0.9800
C1—H1	0.9500	C6—H6C	0.9800
C2—C3	1.435 (2)	C7—C7ⁱ	1.517 (3)
C2—H2	0.9500	C7—H7A	0.9900
C3—C4	1.374 (2)	C7—H7B	0.9900

C4—S1—C1	92.19 (9)	N1—C5—C6	126.06 (15)
C5—N1—C7	120.01 (15)	C3—C5—C6	117.77 (15)
C2—C1—S1	111.31 (14)	C5—C6—H6A	109.5
C2—C1—H1	124.3	C5—C6—H6B	109.5
S1—C1—H1	124.3	H6A—C6—H6B	109.5
C1—C2—C3	113.35 (16)	C5—C6—H6C	109.5
C1—C2—H2	123.3	H6A—C6—H6C	109.5
C3—C2—H2	123.3	H6B—C6—H6C	109.5
C4—C3—C2	111.37 (16)	N1—C7—C7ⁱ	109.65 (18)
C4—C3—C5	126.30 (16)	N1—C7—H7A	109.7
C2—C3—C5	122.32 (15)	C7ⁱ—C7—H7A	109.7
C3—C4—S1	111.78 (14)	N1—C7—H7B	109.7
C3—C4—H4	124.1	C7ⁱ—C7—H7B	109.7
S1—C4—H4	124.1	H7A—C7—H7B	108.2
N1—C5—C3	116.16 (15)

C4—S1—C1—C2	0.34 (14)	C7—N1—C5—C3	−179.72 (15)
S1—C1—C2—C3	−0.7 (2)	C7—N1—C5—C6	1.3 (3)
C1—C2—C3—C4	0.8 (2)	C4—C3—C5—N1	−172.11 (17)
C1—C2—C3—C5	−177.97 (16)	C2—C3—C5—N1	6.5 (2)
C2—C3—C4—S1	−0.6 (2)	C4—C3—C5—C6	7.0 (3)
C5—C3—C4—S1	178.19 (14)	C2—C3—C5—C6	−174.39 (15)
C1—S1—C4—C3	0.13 (15)	C5—N1—C7—C7ⁱ	175.58 (18)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S1,C1–C4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1ⁱⁱ	0.95	2.51	3.454 (2)	172
C6—H6C···Cg1ⁱⁱⁱ	0.98	2.74	3.624 (2)	150

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂S₂
M_r	276.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.5231 (6), 11.2338 (6), 8.5967 (6)
β (°)	112.894 (9)
V (Å³)	669.30 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.928, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	2789, 1542, 1339
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.06
No. of reflections	1542
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.41

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S1,C1–C4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1ⁱ	0.95	2.51	3.454 (2)	172
C6—H6C···Cg1ⁱⁱ	0.98	2.74	3.624 (2)	150

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

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors are grateful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing the research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kleemann, A., Engel, J. B., Kutscher, B. & Reichert, D. (2006). In Pharmaceutical Substances. New York, Stuttgart: Georg Thieme Verlag. Google Scholar
Prasath, R., Bhavana, P., Ng, S. W. & Tiekink, E. R. T. (2010a). Acta Cryst. E66, o2883. Web of Science CSD CrossRef IUCr Journals Google Scholar
Prasath, R., Bhavana, P., Ng, S. W. & Tiekink, E. R. T. (2010b). Acta Cryst. E66, o2883. Web of Science CSD CrossRef IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1026

doi:10.1107/S1600536812009798

Open

access