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

Fun, H.-K.; Kia, R.

doi:10.1107/S1600536808033588

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2131

doi:10.1107/S1600536808033588

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

Hoong-Kun Fun ^a ^* and Reza Kia ^a ‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 6 September 2008; accepted 15 October 2008; online 18 October 2008)

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

Experimental

Crystal data

C₁₆H₁₂Cl₄N₂
M_r = 374.08
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.06
4162 reflections
124 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl2ⁱ	0.962 (14)	2.830 (16)	3.6479 (9)	143.5 (13)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 and PLATON (Spek, 2003 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

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) and PLATON (Spek, 2003).

Figures top

	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.

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

Crystal data top

C₁₆H₁₂Cl₄N₂	F(000) = 380
M_r = 374.08	D_x = 1.567 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9889 reflections
a = 8.0539 (3) Å	θ = 2.7–39.9°
b = 14.0170 (4) Å	µ = 0.74 mm⁻¹
c = 7.5015 (3) Å	T = 100 K
β = 110.612 (1)°	Block, colourless
V = 792.64 (5) Å³	0.52 × 0.25 × 0.13 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4162 independent reflections
Radiation source: fine-focus sealed tube	3485 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
CCD rotation images, thin slices scans	θ_max = 37.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
T_min = 0.699, T_max = 0.908	k = −23→24
34536 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: refall
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0543P)² + 0.1408P] where P = (F_o² + 2F_c²)/3
4162 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₁₂Cl₄N₂	V = 792.64 (5) Å³
M_r = 374.08	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0539 (3) Å	µ = 0.74 mm⁻¹
b = 14.0170 (4) Å	T = 100 K
c = 7.5015 (3) Å	0.52 × 0.25 × 0.13 mm
β = 110.612 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4162 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3485 reflections with I > 2σ(I)
T_min = 0.699, T_max = 0.908	R_int = 0.035
34536 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.70 e Å⁻³
4162 reflections	Δρ_min = −0.25 e Å⁻³
124 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.28013 (3)	0.291680 (16)	−0.02974 (3)	0.02218 (6)
Cl2	0.72672 (3)	0.547370 (15)	0.42924 (4)	0.02557 (7)
N1	0.83741 (10)	0.09945 (5)	0.45102 (12)	0.01963 (14)
C1	0.58794 (11)	0.24294 (6)	0.24399 (13)	0.01689 (14)
C2	0.47672 (11)	0.31735 (6)	0.15494 (13)	0.01727 (14)
C3	0.51579 (12)	0.41204 (6)	0.20925 (13)	0.01900 (15)
C4	0.67376 (12)	0.43026 (6)	0.35795 (13)	0.01858 (14)
C5	0.78922 (11)	0.35774 (6)	0.45130 (13)	0.01811 (14)
C6	0.74533 (11)	0.26360 (6)	0.39426 (12)	0.01621 (13)
C7	0.86553 (11)	0.18627 (6)	0.49751 (12)	0.01690 (14)
C8	0.96808 (13)	0.03109 (6)	0.56502 (14)	0.02076 (16)
H1	0.558 (2)	0.1783 (10)	0.202 (2)	0.025 (4)*
H3	0.447 (2)	0.4639 (12)	0.150 (2)	0.034 (4)*
H5	0.8978 (18)	0.3723 (10)	0.5610 (19)	0.019 (3)*
H7	0.956 (2)	0.2083 (11)	0.602 (2)	0.027 (4)*
H8A	0.9095 (19)	−0.0120 (10)	0.641 (2)	0.019 (3)*
H8B	1.071 (2)	0.0617 (11)	0.660 (2)	0.022 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01762 (9)	0.02168 (10)	0.02490 (11)	0.00313 (6)	0.00456 (8)	0.00146 (7)
Cl2	0.02981 (12)	0.01319 (9)	0.03115 (12)	0.00056 (7)	0.00756 (9)	−0.00046 (7)
N1	0.0189 (3)	0.0151 (3)	0.0234 (3)	0.0039 (2)	0.0056 (3)	0.0025 (2)
C1	0.0164 (3)	0.0142 (3)	0.0213 (3)	0.0015 (2)	0.0082 (3)	0.0015 (2)
C2	0.0160 (3)	0.0164 (3)	0.0203 (3)	0.0021 (2)	0.0075 (3)	0.0019 (3)
C3	0.0200 (3)	0.0151 (3)	0.0234 (4)	0.0038 (3)	0.0096 (3)	0.0030 (3)
C4	0.0211 (3)	0.0127 (3)	0.0234 (4)	0.0011 (3)	0.0098 (3)	0.0010 (3)
C5	0.0192 (3)	0.0148 (3)	0.0209 (3)	0.0013 (2)	0.0078 (3)	0.0011 (2)
C6	0.0167 (3)	0.0134 (3)	0.0200 (3)	0.0021 (2)	0.0083 (3)	0.0025 (2)
C7	0.0156 (3)	0.0160 (3)	0.0193 (3)	0.0031 (2)	0.0064 (3)	0.0018 (2)
C8	0.0218 (4)	0.0162 (3)	0.0227 (4)	0.0051 (3)	0.0058 (3)	0.0030 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.7353 (9)	C3—H3	0.929 (17)
Cl2—C4	1.7326 (9)	C4—C5	1.3893 (12)
N1—C7	1.2643 (11)	C5—C6	1.3939 (12)
N1—C8	1.4571 (11)	C5—H5	0.988 (13)
C1—C2	1.3839 (11)	C6—C7	1.4778 (11)
C1—C6	1.3983 (12)	C7—H7	0.916 (16)
C1—H1	0.962 (14)	C8—C8ⁱ	1.526 (2)
C2—C3	1.3916 (12)	C8—H8A	1.050 (15)
C3—C4	1.3888 (13)	C8—H8B	0.979 (15)

C7—N1—C8	116.67 (8)	C4—C5—H5	120.5 (8)
C2—C1—C6	118.82 (8)	C6—C5—H5	120.4 (8)
C2—C1—H1	120.4 (9)	C5—C6—C1	120.23 (7)
C6—C1—H1	120.8 (9)	C5—C6—C7	119.01 (7)
C1—C2—C3	122.43 (8)	C1—C6—C7	120.75 (7)
C1—C2—Cl1	118.86 (7)	N1—C7—C6	122.74 (8)
C3—C2—Cl1	118.70 (6)	N1—C7—H7	124.9 (10)
C4—C3—C2	117.34 (8)	C6—C7—H7	112.3 (10)
C4—C3—H3	117.8 (11)	N1—C8—C8ⁱ	109.68 (10)
C2—C3—H3	124.8 (11)	N1—C8—H8A	109.1 (8)
C3—C4—C5	122.12 (8)	C8ⁱ—C8—H8A	109.6 (8)
C3—C4—Cl2	118.59 (6)	N1—C8—H8B	112.8 (9)
C5—C4—Cl2	119.29 (7)	C8ⁱ—C8—H8B	109.2 (9)
C4—C5—C6	119.05 (8)	H8A—C8—H8B	106.4 (12)

C6—C1—C2—C3	0.08 (14)	C4—C5—C6—C1	0.58 (14)
C6—C1—C2—Cl1	−179.26 (7)	C4—C5—C6—C7	−178.13 (8)
C1—C2—C3—C4	0.42 (14)	C2—C1—C6—C5	−0.59 (14)
Cl1—C2—C3—C4	179.76 (7)	C2—C1—C6—C7	178.10 (8)
C2—C3—C4—C5	−0.43 (14)	C8—N1—C7—C6	179.56 (8)
C2—C3—C4—Cl2	179.97 (7)	C5—C6—C7—N1	−177.99 (9)
C3—C4—C5—C6	−0.06 (14)	C1—C6—C7—N1	3.30 (14)
Cl2—C4—C5—C6	179.54 (7)	C7—N1—C8—C8ⁱ	−127.06 (11)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl2ⁱⁱ	0.962 (14)	2.830 (16)	3.6479 (9)	143.5 (13)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₄N₂
M_r	374.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.0539 (3), 14.0170 (4), 7.5015 (3)
β (°)	110.612 (1)
V (Å³)	792.64 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.52 × 0.25 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.699, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	34536, 4162, 3485
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.857

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.06
No. of reflections	4162
No. of parameters	124
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.25

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl2ⁱ	0.962 (14)	2.830 (16)	3.6479 (9)	143.5 (13)

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

Footnotes

‡Additional correspondence author, e-mail: zsrkk@yahoo.com.

Acknowledgements

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.

References

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