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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2131.
Published online 2008 October 18. doi:  10.1107/S1600536808033588
PMCID: PMC2959545

N,N′-Bis(3,5-dichloro­benzyl­idene)­ethane-1,2-diamine

Abstract

The mol­ecule of the title Schiff base compound, C16H12Cl4N2, lies across an inversion centre and adopts an E configuration with respect to the azomethine C=N bond. The imine groups are coplanar with the aromatic rings. Within the mol­ecule, the planar units are parallel but extend in opposite directions from the dimethyl­ene bridge. In the crystal structure, mol­ecules are linked together by inter­molecular C—H(...)Cl hydrogen bonds along the a axis.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]). For related structures, see, for example: Fun & Kia (2008a [triangle],b [triangle],c [triangle]); Fun, Kargar & Kia (2008 [triangle]); Fun, Kia & Kargar (2008 [triangle]). For information on Schiff base complexes and their applications, see, for example: Pal et al. (2005 [triangle]); Calligaris & Randaccio (1987 [triangle]); Hou et al. (2001 [triangle]); Ren et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2131-scheme1.jpg

Experimental

Crystal data

  • C16H12Cl4N2
  • M r = 374.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2131-efi1.jpg
  • a = 8.0539 (3) Å
  • b = 14.0170 (4) Å
  • c = 7.5015 (3) Å
  • β = 110.612 (1)°
  • V = 792.64 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.74 mm−1
  • T = 100.0 (1) K
  • 0.52 × 0.25 × 0.13 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.699, T max = 0.908
  • 34536 measured reflections
  • 4162 independent reflections
  • 3485 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.097
  • S = 1.06
  • 4162 reflections
  • 124 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.70 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033588/bg2206sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033588/bg2206Isup2.hkl

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

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for the award of a postdoctoral research fellowship.

supplementary crystallographic information

Comment

Schiff bases are among the most prevalent mixed-donor ligands in the field of coordination chemistry in which there has been growing interest, mainly because of their wide applications in areas such as biochemistry, synthesis, and catalysis (Pal et al., 2005; Hou et al., 2001; Ren et al., 2002). Many Schiff base complexes have been structurally characterized, but only a relatively small number of free Schiff bases have had their X-ray structures reported (Calligaris & Randaccio, 1987). As an extension of our work (Fun, Kargar & Kia 2008; Fun, Kia & Kargar 2008) on the structural characterization of Schiff base ligands, the title compound (I), is reported here.

The molecule of the title compound (Fig. 1), lies across an inversion centre and adopts an E configuration with respect to the azomethine C═N bond. The bond lengths and angles are within normal ranges (Allen et al., 1987) and are comparable with the values found in related structures (Fun & Kia (2008a,b,c); Fun, Kargar & Kia 2008; Fun, Kia & Kargar 2008). The two planar units are parallel but extend in opposite directions from the dimethylene bridge. In the crystal structure, molecules are linked together by intermolecular C—H···Cl hydrogen bonds along the a-axis.

Experimental

The synthetic method has been described earlier (Fun, Kargar, & Kia, 2008). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution at room temperature.

Refinement

All of the hydrogen atoms were located from the difference Fourier map and refined freely. The highest peak is located 0.63 Å from C7 and the deepest hole is located 0.55 Å from Cl2.

Figures

Fig. 1.
The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms. The suffix A corresponds to symmetry code (-x + 2, -y, -z + 1).
Fig. 2.
The crystal packing of (I), viewed down the c-axis, showing the linking of the molecules by intermolecular C—H···Cl hydrogen bonds along the a-axis. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C16H12Cl4N2F(000) = 380
Mr = 374.08Dx = 1.567 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9889 reflections
a = 8.0539 (3) Åθ = 2.7–39.9°
b = 14.0170 (4) ŵ = 0.74 mm1
c = 7.5015 (3) ÅT = 100 K
β = 110.612 (1)°Block, colourless
V = 792.64 (5) Å30.52 × 0.25 × 0.13 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer4162 independent reflections
Radiation source: fine-focus sealed tube3485 reflections with I > 2σ(I)
graphiteRint = 0.035
CCD rotation images, thin slices scansθmax = 37.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −13→13
Tmin = 0.699, Tmax = 0.908k = −23→24
34536 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: refall
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0543P)2 + 0.1408P] where P = (Fo2 + 2Fc2)/3
4162 reflections(Δ/σ)max = 0.001
124 parametersΔρmax = 0.70 e Å3
0 restraintsΔρmin = −0.25 e Å3

Special details

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.
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)

xyzUiso*/Ueq
Cl10.28013 (3)0.291680 (16)−0.02974 (3)0.02218 (6)
Cl20.72672 (3)0.547370 (15)0.42924 (4)0.02557 (7)
N10.83741 (10)0.09945 (5)0.45102 (12)0.01963 (14)
C10.58794 (11)0.24294 (6)0.24399 (13)0.01689 (14)
C20.47672 (11)0.31735 (6)0.15494 (13)0.01727 (14)
C30.51579 (12)0.41204 (6)0.20925 (13)0.01900 (15)
C40.67376 (12)0.43026 (6)0.35795 (13)0.01858 (14)
C50.78922 (11)0.35774 (6)0.45130 (13)0.01811 (14)
C60.74533 (11)0.26360 (6)0.39426 (12)0.01621 (13)
C70.86553 (11)0.18627 (6)0.49751 (12)0.01690 (14)
C80.96808 (13)0.03109 (6)0.56502 (14)0.02076 (16)
H10.558 (2)0.1783 (10)0.202 (2)0.025 (4)*
H30.447 (2)0.4639 (12)0.150 (2)0.034 (4)*
H50.8978 (18)0.3723 (10)0.5610 (19)0.019 (3)*
H70.956 (2)0.2083 (11)0.602 (2)0.027 (4)*
H8A0.9095 (19)−0.0120 (10)0.641 (2)0.019 (3)*
H8B1.071 (2)0.0617 (11)0.660 (2)0.022 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.01762 (9)0.02168 (10)0.02490 (11)0.00313 (6)0.00456 (8)0.00146 (7)
Cl20.02981 (12)0.01319 (9)0.03115 (12)0.00056 (7)0.00756 (9)−0.00046 (7)
N10.0189 (3)0.0151 (3)0.0234 (3)0.0039 (2)0.0056 (3)0.0025 (2)
C10.0164 (3)0.0142 (3)0.0213 (3)0.0015 (2)0.0082 (3)0.0015 (2)
C20.0160 (3)0.0164 (3)0.0203 (3)0.0021 (2)0.0075 (3)0.0019 (3)
C30.0200 (3)0.0151 (3)0.0234 (4)0.0038 (3)0.0096 (3)0.0030 (3)
C40.0211 (3)0.0127 (3)0.0234 (4)0.0011 (3)0.0098 (3)0.0010 (3)
C50.0192 (3)0.0148 (3)0.0209 (3)0.0013 (2)0.0078 (3)0.0011 (2)
C60.0167 (3)0.0134 (3)0.0200 (3)0.0021 (2)0.0083 (3)0.0025 (2)
C70.0156 (3)0.0160 (3)0.0193 (3)0.0031 (2)0.0064 (3)0.0018 (2)
C80.0218 (4)0.0162 (3)0.0227 (4)0.0051 (3)0.0058 (3)0.0030 (3)

Geometric parameters (Å, °)

Cl1—C21.7353 (9)C3—H30.929 (17)
Cl2—C41.7326 (9)C4—C51.3893 (12)
N1—C71.2643 (11)C5—C61.3939 (12)
N1—C81.4571 (11)C5—H50.988 (13)
C1—C21.3839 (11)C6—C71.4778 (11)
C1—C61.3983 (12)C7—H70.916 (16)
C1—H10.962 (14)C8—C8i1.526 (2)
C2—C31.3916 (12)C8—H8A1.050 (15)
C3—C41.3888 (13)C8—H8B0.979 (15)
C7—N1—C8116.67 (8)C4—C5—H5120.5 (8)
C2—C1—C6118.82 (8)C6—C5—H5120.4 (8)
C2—C1—H1120.4 (9)C5—C6—C1120.23 (7)
C6—C1—H1120.8 (9)C5—C6—C7119.01 (7)
C1—C2—C3122.43 (8)C1—C6—C7120.75 (7)
C1—C2—Cl1118.86 (7)N1—C7—C6122.74 (8)
C3—C2—Cl1118.70 (6)N1—C7—H7124.9 (10)
C4—C3—C2117.34 (8)C6—C7—H7112.3 (10)
C4—C3—H3117.8 (11)N1—C8—C8i109.68 (10)
C2—C3—H3124.8 (11)N1—C8—H8A109.1 (8)
C3—C4—C5122.12 (8)C8i—C8—H8A109.6 (8)
C3—C4—Cl2118.59 (6)N1—C8—H8B112.8 (9)
C5—C4—Cl2119.29 (7)C8i—C8—H8B109.2 (9)
C4—C5—C6119.05 (8)H8A—C8—H8B106.4 (12)
C6—C1—C2—C30.08 (14)C4—C5—C6—C10.58 (14)
C6—C1—C2—Cl1−179.26 (7)C4—C5—C6—C7−178.13 (8)
C1—C2—C3—C40.42 (14)C2—C1—C6—C5−0.59 (14)
Cl1—C2—C3—C4179.76 (7)C2—C1—C6—C7178.10 (8)
C2—C3—C4—C5−0.43 (14)C8—N1—C7—C6179.56 (8)
C2—C3—C4—Cl2179.97 (7)C5—C6—C7—N1−177.99 (9)
C3—C4—C5—C6−0.06 (14)C1—C6—C7—N13.30 (14)
Cl2—C4—C5—C6179.54 (7)C7—N1—C8—C8i−127.06 (11)

Symmetry codes: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···Cl2ii0.962 (14)2.830 (16)3.6479 (9)143.5 (13)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2206).

References

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