2-(Thio­phen-2-yl)-N-(4-{(E)-[2-(thio­phen-2-yl)eth­yl]imino­meth­yl}benzyl­idene)ethanamine

Chiririwa, H.; Meijboom, R.; Omondi, B.

doi:10.1107/S1600536811009810

organic compounds

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doi:10.1107/S1600536811009810

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2-(Thiophen-2-yl)-N-(4-{(E)-[2-(thiophen-2-yl)ethyl]iminomethyl}benzylidene)ethanamine

Haleden Chiririwa,^a ^* Reinout Meijboom ^b and Bernard Omondi ^b

^aDepartment of Chemistry, University of Cape Town, Private Bag, Rondebosch 7707, South Africa, and ^bResearch Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg, PO Box 524 Auckland Park, Johannesburg 2006, South Africa
^*Correspondence e-mail: harrychiririwa@yahoo.com

(Received 3 March 2011; accepted 15 March 2011; online 19 March 2011)

In the crystal of the centrosymmetric title compound, C₂₀H₂₀N₂S₂, molecules are linked by head-to-tail C—H⋯N hydrogen bonds, resulting in chains extending along the a axis. Three additional C—H⋯π intermolecular interactions give rise to a herringbone packing motif which extends along the c axis. The C—H⋯N interactions provide links between the sheets.

Related literature

For related literature on bidendate Schiff base ligands, see: Chakraborty et al. (1999 ); Haga & Koizumi (1985 ).

Experimental

Crystal data

C₂₀H₂₀N₂S₂
M_r = 352.52
Monoclinic, C 2/c
a = 9.8592 (10) Å
b = 7.1533 (6) Å
c = 25.678 (2) Å
β = 96.646 (5)°
V = 1798.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 173 K
0.22 × 0.2 × 0.04 mm

Data collection

Nonius Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.925, T_max = 0.988
16248 measured reflections
2230 independent reflections
1679 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.181
S = 1.08
2230 reflections
109 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 andCg2 are the centroids of the thiophene and benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N8ⁱ	0.95	2.61	3.514 (3)	159
C2—H2⋯Cg1ⁱⁱ	0.95	2.79	3.702 (3)	161
C6—H6A⋯Cg2ⁱⁱⁱ	0.99	2.72	3.515 (3)	137
C6—H6A⋯Cg2^iv	0.99	2.72	3.515 (3)	137
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009810/go2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009810/go2007Isup2.hkl

checkCIF report

Comment top

The title compound belongs to a class of tetradentate ligands. To the best of our knowledge, this is the first example of a neutral thiophenyldimine-based bridging ligand. This compound is a potential tetra-coordinate ligand but on complexation the compound will probably behave as a bidentate ligand as the sulfur, on the thiophene, has weak donor capacity towards co-ordination for majority of metal ions. Besides its use as a ligand, it is interesting from the crystal engineering point of view for the analysis of the packing mode of (I).

Compound (I) crystallizes with half a molecule in the asymmetric unit, with the other half generated through symmetry located in the center of the phenyl ring (Fig. 1). The phenyl ring together with the atoms C7—N8—C9 and the thiophene ring together with the atom C6 are planar with N8 and C5 deviating the most from the planes by 0.018 (2) Å and 0.010 (2) Å respectively. The two planes are close to parallel, the angle between them being 9.3 (1)°. Bond distances and angles in (I) are as expected from the chemical bonding.

The crystal structure of (I) is composed of head-to-tail C—H···N hydrogen bonded chains (Table 1) that extend in the crystallographic a axis (Fig. 2). Additionally, the phenyl and thiophen rings are involved in C—H···π intermolecular interactions that result in a herringbone motif that spreads along the crystallographic c axis (Fig. 3). The C—H···N interactions are found to connect these herringbone sheets along the a axis.,

Related literature top

For related literature [on what subject(s)?], see: Chakraborty et al. (1999); Haga & Koizumi (1985).

Experimental top

A solution of benzene 1,4-dicarboxaldehyde (0.50 g, 3.73 mmol) in methanol (10 ml) was added dropwise to a stirred solution of 2-thiophenylethylamine (0.95 g, 7.42 mmol) in methanol (10 ml). The mixture was stirred at room temperature for ca 16 h. The precipitate was filtered off and washed with diethylether and dried under vacuum for 4 h affording a fine shiny white powder in 80% yield. M.p.: 240–242 °C. Recrystallization was done by slow diffusion of Et₂O into a concentrated CH₂Cl₂ solution of the white powder to give colorless crystals fo (I).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of (I) (50% probability displacement ellipsoids) with H atoms presented as small spheres of arbitrary radii.
	Fig. 2. C—H···N hydrogen bond interactions in the crystal structure of (I). [Symmetry operators: (i) = -1/2 + x, 1/2 + y, z]
	Fig. 3. Sheets of C—H···π intermolecular interactions between molecules alligned along the bc face.

2-(Thiophen-2-yl)-N-(4-{(E)-[2-(thiophen-2- yl)ethyl]iminomethyl}benzylidene)ethanamine top

Crystal data top

C₂₀H₂₀N₂S₂	F(000) = 744
M_r = 352.52	D_x = 1.302 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 34223 reflections
a = 9.8592 (10) Å	θ = 3.2–28.3°
b = 7.1533 (6) Å	µ = 0.30 mm⁻¹
c = 25.678 (2) Å	T = 173 K
β = 96.646 (5)°	Plate, colourless
V = 1798.8 (3) Å³	0.22 × 0.2 × 0.04 mm
Z = 4

Data collection top

Nonius Kappa CCD diffractometer	R_int = 0.045
Graphite monochromator	θ_max = 28.3°, θ_min = 3.2°
1.0° ω scans, 60s	h = −13→13
16248 measured reflections	k = −9→9
2230 independent reflections	l = −34→34
1679 reflections with I > 2σ(I)

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0971P)² + 3.1807P] where P = (F_o² + 2F_c²)/3
2230 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.80 e Å⁻³
14 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₂₀H₂₀N₂S₂	V = 1798.8 (3) Å³
M_r = 352.52	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 9.8592 (10) Å	µ = 0.30 mm⁻¹
b = 7.1533 (6) Å	T = 173 K
c = 25.678 (2) Å	0.22 × 0.2 × 0.04 mm
β = 96.646 (5)°

Data collection top

Nonius Kappa CCD diffractometer	1679 reflections with I > 2σ(I)
16248 measured reflections	R_int = 0.045
2230 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	14 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.08	Δρ_max = 0.80 e Å⁻³
2230 reflections	Δρ_min = −0.42 e Å⁻³
109 parameters

Special details top

Experimental. The intensity data was collected on a Nonius Kappa CCD diffractometer using an exposure time of 60 sec/per frame. Analytical data: IR (KBr): 1613?cm-1 (C=N, imine); 1H NMR: (CDCl3) δ H 8.23 (d, 2H) 7.76 (s, 2H) 7.13 (dd, 2H) 6.92 (dd, 2H) 6.84 (dd, 4H) 3.91 (dt, 4H) 3.25 (t, 4H); Anal. calcd. for C20H20N2S2: C, 68.14%; H, 5.72%; N, 7.95%; S, 18.19; Found: C, 68.19%; H, 5.52%; N, 7.72%; S, 18.44; EI—MS: m/z 351.76 [M]+;

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	0.62222 (7)	−0.24504 (10)	0.31079 (3)	0.0357 (3)
C2	0.7356 (3)	−0.3763 (4)	0.28220 (10)	0.0400 (7)
H2	0.711	−0.4684	0.2562	0.048*
C3	0.8651 (3)	−0.3341 (4)	0.30095 (10)	0.0355 (6)
H3	0.9419	−0.3955	0.2896	0.043*
C4	0.8766 (2)	−0.1915 (3)	0.33866 (8)	0.0194 (4)
H4	0.9607	−0.1441	0.3552	0.023*
C5	0.7453 (2)	−0.1270 (3)	0.34886 (9)	0.0230 (5)
C6	0.7117 (3)	0.0246 (3)	0.38573 (10)	0.0286 (5)
H6A	0.7616	0.0005	0.4208	0.034*
H6B	0.6128	0.0204	0.3891	0.034*
C7	0.7483 (3)	0.2186 (3)	0.36770 (10)	0.0266 (5)
H7A	0.8479	0.2266	0.366	0.032*
H7B	0.701	0.2431	0.3322	0.032*
N8	0.7077 (2)	0.3574 (3)	0.40432 (8)	0.0257 (5)
C9	0.8002 (2)	0.4632 (3)	0.42630 (9)	0.0232 (5)
H9	0.891	0.4474	0.4181	0.028*
C10	0.7729 (2)	0.6096 (3)	0.46404 (9)	0.0220 (5)
C11	0.6408 (2)	0.6450 (3)	0.47609 (9)	0.0235 (5)
H11	0.5661	0.5741	0.4598	0.028*
C12	0.8813 (2)	0.7162 (3)	0.48807 (9)	0.0234 (5)
H12	0.9713	0.6935	0.4798	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0339 (4)	0.0352 (4)	0.0373 (4)	−0.0022 (3)	0.0007 (3)	−0.0044 (3)
C2	0.073 (2)	0.0227 (13)	0.0245 (12)	−0.0002 (13)	0.0045 (13)	−0.0058 (10)
C3	0.0487 (16)	0.0284 (13)	0.0314 (13)	0.0127 (12)	0.0133 (12)	−0.0009 (9)
C4	0.0167 (9)	0.0190 (10)	0.0217 (10)	0.0007 (8)	−0.0012 (8)	0.0046 (7)
C5	0.0288 (11)	0.0183 (11)	0.0230 (11)	0.0037 (9)	0.0073 (9)	0.0019 (9)
C6	0.0396 (14)	0.0218 (12)	0.0262 (12)	0.0020 (10)	0.0118 (10)	−0.0013 (9)
C7	0.0309 (13)	0.0223 (12)	0.0282 (12)	−0.0010 (9)	0.0096 (10)	−0.0063 (9)
N8	0.0293 (11)	0.0214 (10)	0.0269 (10)	0.0010 (8)	0.0055 (8)	−0.0061 (8)
C9	0.0260 (11)	0.0207 (11)	0.0238 (11)	0.0007 (9)	0.0073 (9)	−0.0010 (9)
C10	0.0269 (12)	0.0181 (11)	0.0211 (10)	−0.0002 (9)	0.0028 (8)	−0.0003 (9)
C11	0.0236 (11)	0.0220 (11)	0.0248 (11)	−0.0024 (9)	0.0026 (9)	−0.0030 (9)
C12	0.0200 (11)	0.0245 (12)	0.0263 (11)	0.0009 (9)	0.0048 (9)	−0.0015 (9)

Geometric parameters (Å, º) top

S1—C2	1.691 (3)	C7—N8	1.455 (3)
S1—C5	1.693 (2)	C7—H7A	0.99
C2—C3	1.345 (4)	C7—H7B	0.99
C2—H2	0.95	N8—C9	1.266 (3)
C3—C4	1.402 (4)	C9—C10	1.472 (3)
C3—H3	0.95	C9—H9	0.95
C4—C5	1.427 (3)	C10—C11	1.397 (3)
C4—H4	0.95	C10—C12	1.397 (3)
C5—C6	1.501 (3)	C11—C12ⁱ	1.388 (3)
C6—C7	1.520 (3)	C11—H11	0.95
C6—H6A	0.99	C12—C11ⁱ	1.388 (3)
C6—H6B	0.99	C12—H12	0.95

C2—S1—C5	93.55 (13)	N8—C7—C6	109.48 (19)
C3—C2—S1	111.6 (2)	N8—C7—H7A	109.8
C3—C2—H2	124.2	C6—C7—H7A	109.8
S1—C2—H2	124.2	N8—C7—H7B	109.8
C2—C3—C4	114.1 (2)	C6—C7—H7B	109.8
C2—C3—H3	122.9	H7A—C7—H7B	108.2
C4—C3—H3	122.9	C9—N8—C7	117.3 (2)
C3—C4—C5	111.0 (2)	N8—C9—C10	122.8 (2)
C3—C4—H4	124.5	N8—C9—H9	118.6
C5—C4—H4	124.5	C10—C9—H9	118.6
C4—C5—C6	128.3 (2)	C11—C10—C12	119.2 (2)
C4—C5—S1	109.73 (17)	C11—C10—C9	121.4 (2)
C6—C5—S1	121.93 (18)	C12—C10—C9	119.4 (2)
C5—C6—C7	113.0 (2)	C12ⁱ—C11—C10	119.9 (2)
C5—C6—H6A	109	C12ⁱ—C11—H11	120
C7—C6—H6A	109	C10—C11—H11	120
C5—C6—H6B	109	C11ⁱ—C12—C10	120.8 (2)
C7—C6—H6B	109	C11ⁱ—C12—H12	119.6
H6A—C6—H6B	107.8	C10—C12—H12	119.6

C5—S1—C2—C3	0.4 (2)	C5—C6—C7—N8	177.7 (2)
S1—C2—C3—C4	−0.9 (3)	C6—C7—N8—C9	121.8 (2)
C2—C3—C4—C5	1.1 (3)	C7—N8—C9—C10	179.9 (2)
C3—C4—C5—C6	−179.2 (2)	N8—C9—C10—C11	−2.7 (4)
C3—C4—C5—S1	−0.8 (2)	N8—C9—C10—C12	177.7 (2)
C2—S1—C5—C4	0.25 (18)	C12—C10—C11—C12ⁱ	−0.5 (4)
C2—S1—C5—C6	178.7 (2)	C9—C10—C11—C12ⁱ	179.9 (2)
C4—C5—C6—C7	69.3 (3)	C11—C10—C12—C11ⁱ	0.6 (4)
S1—C5—C6—C7	−108.9 (2)	C9—C10—C12—C11ⁱ	−179.9 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg1 andCg2 are the centroids of the thiophene and benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N8ⁱⁱ	0.95	2.61	3.514 (3)	159
C2—H2···Cg1ⁱⁱⁱ	0.95	2.79	3.702 (3)	161
C6—H6A···Cg2^iv	0.99	2.72	3.515 (3)	137
C6—H6A···Cg2^v	0.99	2.72	3.515 (3)	137

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₂S₂
M_r	352.52
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	9.8592 (10), 7.1533 (6), 25.678 (2)
β (°)	96.646 (5)
V (Å³)	1798.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.22 × 0.2 × 0.04

Data collection
Diffractometer	Nonius Kappa CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16248, 2230, 1679
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.181, 1.08
No. of reflections	2230
No. of parameters	109
No. of restraints	14
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.42

Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005) and ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg1 andCg2 are the centroids of the thiophene and benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N8ⁱ	0.95	2.61	3.514 (3)	159
C2—H2···Cg1ⁱⁱ	0.95	2.79	3.702 (3)	161
C6—H6A···Cg2ⁱⁱⁱ	0.99	2.72	3.515 (3)	137
C6—H6A···Cg2^iv	0.99	2.72	3.515 (3)	137

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

Acknowledgements

We gratefully acknowledge Mintek and Project AuTEK for funding this project.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chakraborty, S., Munshi, P. & Lahiri, G. K. (1999). Polyhedron, 18, 1437–1444. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Haga, M. & Koizumi, K. (1985). Inorg. Chim. Acta, 104, 47–50. CrossRef CAS Web of Science Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft. The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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2-(Thio­phen-2-yl)-N-(4-{(E)-[2-(thio­phen-2-yl)eth­yl]imino­meth­yl}benzyl­­idene)ethanamine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-(Thiophen-2-yl)-N-(4-{(E)-[2-(thiophen-2-yl)ethyl]iminomethyl}benzylidene)ethanamine