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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2883.
Published online 2010 October 23. doi:  10.1107/S160053681004167X
PMCID: PMC3009004

N,N′-Bis[(E)-(5-chloro-2-thienyl)methyl­idene]ethane-1,2-diamine

Abstract

The full mol­ecule of the title compound, C12H10Cl2N2S2, is generated by the application of a centre of inversion. The thio­phene and imine residues are co-planar [the N—C—C—S torsion angle is −2.5 (4)°] and the conformation about the imine bond [1.268 (4) Å] is E. Supra­molecular arrays are formed in the bc plane via C—Cl(...)π inter­actions and these stack along the a axis.

Related literature

For background to 2-substituted thio­phenes, see: Campaigne (1984 [triangle]); Kleemann et al. (2006 [triangle]). For related structures, see: Wang et al. (2007 [triangle]); Wardell et al. (2010 [triangle]); Prasath et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2883-scheme1.jpg

Experimental

Crystal data

  • C12H10Cl2N2S2
  • M r = 317.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2883-efi1.jpg
  • a = 14.682 (2) Å
  • b = 4.7016 (7) Å
  • c = 10.6607 (15) Å
  • β = 109.439 (2)°
  • V = 693.92 (17) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.75 mm−1
  • T = 100 K
  • 0.25 × 0.15 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.835, T max = 0.963
  • 5721 measured reflections
  • 1576 independent reflections
  • 1270 reflections with I > 2σ(I)
  • R int = 0.058

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.117
  • S = 1.01
  • 1576 reflections
  • 82 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.48 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681004167X/hg2729sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004167X/hg2729Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

PB acknowledges the Department of Science and Technology (DST), India, for a research grant (SR/FTP/CS-57/2007). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

Interest in their putative biological activity (Wardell et al., 2010) motivates studies of 2-substituted thiophene rings (Campaigne, 1984; Kleemann et al., 2006), including on-going crystallographic investigations (Wardell et al. 2010; Prasath et al., 2010).

The asymmetric unit of (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 N1—C2—C3—S1 torsion angle of -2.5 (4) °. The conformation about the imine N1—C2 [1.268 (4) Å] bond is E. The observed conformation matches closely those found for related compounds (Wang et al., 2007; Prasath et al., 2010).

The most prominent contacts in the crystal packing are of the type C—Cl···π, Table 1. These serve to connect molecules into a 2-D array in the bc plane, Fig. 2, which stack along the a axis, Fig. 3, with the chlorido atoms facing each other. Concerning the latter, the closest interlayer Cl···Cl contact is 3.3831 (11) Å [symmetry operation: 2 - x, -1/2 + y, 3/2 - z].

Experimental

A mixture of 5-chloro-2-thiophenecarboxaldehyde (0.43 ml, 0.004 M) and ethylenediamine (0.13 ml, 0.002 M) was stirred in dichloromethane for 3 h at room temperature. The solvent from the reaction mixture was removed under reduced pressure. The resulting solid was dried and purified by column chromatography using a 1:3 mixture of ethyl acetate and hexane. Recrystallization was by slow evaporation of a dichloromethane solution of (I) which yielded colourless needles (yield: 73%). M. pt. 353–355 K.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Uequiv(C). In the final refinement a low angle reflection evidently effected by the beam stop was omitted, i.e. (100).

Figures

Fig. 1.
Molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Symmetry operation i: 1 - x, 1 - y, 1 - z.
Fig. 2.
A view of the supramolecular 2-D array in the bc plane mediated by C—Cl···π interactions (purple dashed lines).
Fig. 3.
Stacking of layers along the a axis in the crystal structure of (I). The C—Cl···π interactions are shown as purple dashed lines.

Crystal data

C12H10Cl2N2S2F(000) = 324
Mr = 317.24Dx = 1.518 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2363 reflections
a = 14.682 (2) Åθ = 3.0–28.0°
b = 4.7016 (7) ŵ = 0.75 mm1
c = 10.6607 (15) ÅT = 100 K
β = 109.439 (2)°Prism, colourless
V = 693.92 (17) Å30.25 × 0.15 × 0.05 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer1576 independent reflections
Radiation source: fine-focus sealed tube1270 reflections with I > 2σ(I)
graphiteRint = 0.058
ω scansθmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −18→18
Tmin = 0.835, Tmax = 0.963k = −6→6
5721 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0662P)2 + 0.3727P] where P = (Fo2 + 2Fc2)/3
1576 reflections(Δ/σ)max = 0.001
82 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = −0.48 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.94014 (5)1.46904 (14)0.80609 (6)0.0258 (2)
S10.76180 (5)1.12742 (14)0.69149 (6)0.0220 (2)
N10.58522 (16)0.7601 (5)0.6104 (2)0.0286 (5)
C10.4988 (2)0.5840 (6)0.5603 (3)0.0333 (7)
H1A0.44060.70620.53550.040*
H1B0.49550.45140.63080.040*
C20.63515 (19)0.7367 (6)0.7325 (3)0.0267 (6)
H20.61510.60770.78680.032*
C30.72211 (19)0.9026 (5)0.7907 (3)0.0238 (6)
C40.7822 (2)0.9074 (6)0.9193 (3)0.0282 (6)
H40.77160.79700.98790.034*
C50.8620 (2)1.0934 (6)0.9411 (3)0.0271 (6)
H50.91091.12201.02470.033*
C60.85924 (19)1.2254 (6)0.8263 (2)0.0220 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0284 (4)0.0242 (4)0.0285 (3)−0.0067 (2)0.0141 (3)−0.0066 (2)
S10.0249 (4)0.0199 (4)0.0230 (3)−0.0031 (2)0.0104 (3)−0.0007 (2)
N10.0241 (12)0.0212 (12)0.0432 (14)−0.0047 (9)0.0149 (10)−0.0032 (10)
C10.0288 (15)0.0285 (15)0.0463 (18)−0.0089 (12)0.0173 (13)−0.0043 (13)
C20.0302 (14)0.0184 (13)0.0402 (16)−0.0028 (11)0.0232 (12)−0.0029 (11)
C30.0287 (14)0.0169 (13)0.0323 (14)−0.0025 (10)0.0187 (12)−0.0013 (10)
C40.0416 (17)0.0220 (14)0.0274 (13)−0.0028 (12)0.0202 (12)0.0001 (10)
C50.0353 (15)0.0261 (15)0.0219 (12)−0.0025 (11)0.0122 (11)−0.0033 (10)
C60.0259 (13)0.0188 (13)0.0241 (12)−0.0002 (10)0.0122 (10)−0.0050 (9)

Geometric parameters (Å, °)

Cl1—C61.714 (3)C2—C31.448 (4)
S1—C61.719 (3)C2—H20.9500
S1—C31.728 (3)C3—C41.362 (4)
N1—C21.268 (4)C4—C51.419 (4)
N1—C11.459 (3)C4—H40.9500
C1—C1i1.519 (6)C5—C61.361 (4)
C1—H1A0.9900C5—H50.9500
C1—H1B0.9900
C6—S1—C390.50 (13)C4—C3—S1111.7 (2)
C2—N1—C1117.5 (2)C2—C3—S1119.7 (2)
N1—C1—C1i110.1 (3)C3—C4—C5113.4 (2)
N1—C1—H1A109.6C3—C4—H4123.3
C1i—C1—H1A109.6C5—C4—H4123.3
N1—C1—H1B109.6C6—C5—C4111.0 (3)
C1i—C1—H1B109.6C6—C5—H5124.5
H1A—C1—H1B108.2C4—C5—H5124.5
N1—C2—C3121.3 (2)C5—C6—Cl1127.1 (2)
N1—C2—H2119.4C5—C6—S1113.4 (2)
C3—C2—H2119.4Cl1—C6—S1119.53 (15)
C4—C3—C2128.6 (2)
C2—N1—C1—C1i−126.6 (3)S1—C3—C4—C50.0 (3)
C1—N1—C2—C3179.9 (2)C3—C4—C5—C60.2 (4)
N1—C2—C3—C4178.4 (3)C4—C5—C6—Cl1179.4 (2)
N1—C2—C3—S1−2.5 (4)C4—C5—C6—S1−0.3 (3)
C6—S1—C3—C4−0.1 (2)C3—S1—C6—C50.3 (2)
C6—S1—C3—C2−179.4 (2)C3—S1—C6—Cl1−179.49 (17)
C2—C3—C4—C5179.1 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S3,C3–C6 ring.
D—H···AD—HH···AD···AD—H···A
C6—Cl1···Cg1ii1.714 (3)3.5182 (14)3.994 (3)93.01 (10)

Symmetry codes: (ii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2729).

References

  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Campaigne, E. (1984). Comprehensive Heterocyclic Chemistry, Vol. 4, edited by A. R. Katritzky & C. W. Rees, pp. 863–934. Oxford: Pergamon.
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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography