N,N′-Bis-(2,4-dichloro­benzyl­idene)-2,2-dimethyl­propane-1,3-diamine

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

doi:10.1107/S1600536808035745

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2285

doi:10.1107/S1600536808035745

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N,N′-Bis-(2,4-dichlorobenzylidene)-2,2-dimethylpropane-1,3-diamine

Reza Kia,^a Hoong-Kun Fun ^a ^* and Hadi Kargar ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran
^*Correspondence e-mail: hkfun@usm.my

(Received 28 October 2008; accepted 31 October 2008; online 8 November 2008)

The molecule of the title Schiff base compound, C₁₉H₁₈Cl₄N₂, has crystallographic twofold rotation symmetry, with one C atom lying on the rotation axis. The dihedral angle between the two symmetry-related benzene rings is 84.70 (2)°. The plane of the –C=N—C– group is twisted away from the benzene ring by 7.5 (1)°. In the crystal structure, weak intermolecular Cl⋯Cl [3.4851 (3) Å] contacts link neighbouring molecules into a two-dimensional network parallel to the bc plane.

Related literature

For bond-length data, see: Allen et al. (1987 ). For related structures, see: Li et al. (2005 ); Bomfim et al. (2005 ); Glidewell et al. (2005 , 2006 ); Sun et al. (2004 ); Fun et al. (2008 ).

Experimental

Crystal data

C₁₉H₁₈Cl₄N₂
M_r = 416.15
Orthorhombic, P c c a
a = 30.7633 (4) Å
b = 5.4012 (1) Å
c = 11.4532 (1) Å
V = 1903.05 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 100.0 (1) K
0.43 × 0.25 × 0.23 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.774, T_max = 0.872
86683 measured reflections
6565 independent reflections
5678 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.099
S = 1.19
4992 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.30 e Å⁻³

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/S1600536808035745/ci2702sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035745/ci2702Isup2.hkl

checkCIF report

Comment top

Schiff bases are one of most prevalent mixed-donor ligands in the field of coordination chemistry. They play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism, and supramolecular architectures. Crystal structures of Schiff bases derived from substituted benzaldehydes and closely related to the title compound have been reported earlier (Li et al., 2005; Bomfim et al., 2005; Glidewell et al., 2005, 2006; Sun et al., 2004; Fun et al., 2008).

The molecule of the title Schiff base compound has crystallographic twofold rotation symmetry (Fig. 1). Bond lengths are within normal ranges (Allen et al., 1987). The plane of the –C═N—C– group is twisted away from the benzene ring by 7.5 (1)°.

In the crystal structure, weak intermolecular Cl···Cl contacts [Cl1···Cl2(x,1 - y,-1/2 + z) = 3.4851 (3) Å] link neighbouring molecules into a two-dimensional network parallel to the bc plane (Fig.2).

Related literature top

For bond-length data, see: Allen et al. (1987). For related structures, see: Li et al. (2005); Bomfim et al. (2005); Glidewell et al. (2005, 2006); Sun et al. (2004); Fun et al. (2008).

Experimental top

The synthetic method has been described earlier (Fun et al., 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: APEX2 (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 the title compound, with atom labels and 50% probability ellipsoids for non-H atoms. Atoms labelled with the suffix A are generated by the symmetry operation (1/2 - x, 2 - y, z).
	Fig. 2. Part of the crystal structure of the title compound, viewed down the b-axis. Dashed lines indicate intermolecular Cl···Cl interactions.

N,N'-Bis-(2,4-dichlorobenzylidene)-2,2-dimethylpropane-1,3-diamine top

Crystal data top

C₁₉H₁₈Cl₄N₂	F(000) = 856
M_r = 416.15	D_x = 1.452 Mg m⁻³
Orthorhombic, Pcca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ac	Cell parameters from 9929 reflections
a = 30.7633 (4) Å	θ = 3.6–41.1°
b = 5.4012 (1) Å	µ = 0.63 mm⁻¹
c = 11.4532 (1) Å	T = 100 K
V = 1903.05 (5) Å³	Block, colourless
Z = 4	0.43 × 0.25 × 0.23 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	6565 independent reflections
Radiation source: fine-focus sealed tube	5678 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 42.5°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −52→57
T_min = 0.774, T_max = 0.872	k = −9→10
86683 measured reflections	l = −20→20

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0454P)² + 0.5965P] where P = (F_o² + 2F_c²)/3
4992 reflections	(Δ/σ)_max = 0.001
115 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₉H₁₈Cl₄N₂	V = 1903.05 (5) Å³
M_r = 416.15	Z = 4
Orthorhombic, Pcca	Mo Kα radiation
a = 30.7633 (4) Å	µ = 0.63 mm⁻¹
b = 5.4012 (1) Å	T = 100 K
c = 11.4532 (1) Å	0.43 × 0.25 × 0.23 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	6565 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5678 reflections with I > 2σ(I)
T_min = 0.774, T_max = 0.872	R_int = 0.028
86683 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.19	Δρ_max = 0.51 e Å⁻³
4992 reflections	Δρ_min = −0.30 e Å⁻³
115 parameters

Special details top

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

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
Cl1	0.053693 (7)	1.12278 (4)	0.346996 (17)	0.01671 (5)
Cl2	0.046757 (8)	0.37440 (4)	0.653936 (18)	0.02040 (6)
N1	0.19231 (2)	0.96758 (14)	0.31674 (6)	0.01660 (12)
C1	0.08049 (2)	0.88739 (14)	0.42126 (6)	0.01301 (12)
C2	0.05625 (3)	0.74765 (14)	0.49989 (6)	0.01467 (12)
H2A	0.0270	0.7822	0.5127	0.018*
C3	0.07667 (3)	0.55568 (15)	0.55865 (7)	0.01504 (12)
C4	0.12041 (3)	0.50138 (16)	0.54095 (7)	0.01807 (13)
H4A	0.1336	0.3713	0.5807	0.022*
C5	0.14395 (3)	0.64492 (16)	0.46298 (8)	0.01748 (13)
H5A	0.1732	0.6098	0.4510	0.021*
C6	0.12480 (2)	0.84188 (14)	0.40166 (7)	0.01397 (12)
C7	0.15133 (2)	0.99635 (15)	0.32244 (7)	0.01527 (12)
H7A	0.1379	1.1157	0.2763	0.018*
C8	0.21668 (3)	1.13674 (14)	0.24238 (7)	0.01553 (13)
H8A	0.2317	1.2566	0.2909	0.019*
H8B	0.1966	1.2262	0.1925	0.019*
C9	0.2500	1.0000	0.16598 (9)	0.01351 (16)
C18	0.22667 (3)	0.81059 (16)	0.08866 (7)	0.01774 (13)
H18A	0.2044	0.8922	0.0443	0.027*
H18B	0.2138	0.6850	0.1368	0.027*
H18C	0.2472	0.7358	0.0364	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01438 (9)	0.01789 (9)	0.01786 (9)	0.00404 (6)	0.00073 (5)	0.00121 (5)
Cl2	0.02045 (10)	0.02338 (10)	0.01738 (9)	−0.00623 (7)	0.00240 (6)	0.00349 (6)
N1	0.0117 (3)	0.0205 (3)	0.0176 (3)	−0.0015 (2)	0.0016 (2)	0.0025 (2)
C1	0.0116 (3)	0.0143 (3)	0.0131 (3)	0.0006 (2)	0.0001 (2)	−0.0008 (2)
C2	0.0117 (3)	0.0175 (3)	0.0149 (3)	−0.0002 (2)	0.0016 (2)	−0.0010 (2)
C3	0.0143 (3)	0.0170 (3)	0.0139 (3)	−0.0031 (2)	0.0004 (2)	0.0006 (2)
C4	0.0136 (3)	0.0197 (3)	0.0209 (3)	−0.0004 (2)	−0.0016 (2)	0.0046 (3)
C5	0.0108 (3)	0.0207 (3)	0.0209 (3)	0.0005 (2)	−0.0002 (2)	0.0044 (3)
C6	0.0102 (3)	0.0168 (3)	0.0149 (3)	−0.0004 (2)	0.0005 (2)	0.0009 (2)
C7	0.0120 (3)	0.0178 (3)	0.0160 (3)	−0.0004 (2)	0.0010 (2)	0.0015 (2)
C8	0.0120 (3)	0.0163 (3)	0.0183 (3)	−0.0012 (2)	0.0021 (2)	0.0009 (2)
C9	0.0113 (4)	0.0144 (4)	0.0148 (4)	−0.0023 (3)	0.000	0.000
C18	0.0169 (3)	0.0176 (3)	0.0187 (3)	−0.0033 (3)	−0.0036 (2)	−0.0008 (2)

Geometric parameters (Å, º) top

Cl1—C1	1.7376 (8)	C5—H5A	0.93
Cl2—C3	1.7311 (8)	C6—C7	1.4783 (11)
N1—C7	1.2720 (10)	C7—H7A	0.93
N1—C8	1.4566 (10)	C8—C9	1.5369 (10)
C1—C2	1.3917 (11)	C8—H8A	0.97
C1—C6	1.4033 (11)	C8—H8B	0.97
C2—C3	1.3866 (11)	C9—C18	1.5316 (10)
C2—H2A	0.93	C9—C18ⁱ	1.5316 (10)
C3—C4	1.3917 (11)	C9—C8ⁱ	1.5369 (10)
C4—C5	1.3869 (12)	C18—H18A	0.96
C4—H4A	0.93	C18—H18B	0.96
C5—C6	1.4043 (11)	C18—H18C	0.96

C7—N1—C8	117.61 (7)	N1—C7—H7A	119.7
C2—C1—C6	121.94 (7)	C6—C7—H7A	119.7
C2—C1—Cl1	117.35 (6)	N1—C8—C9	112.00 (6)
C6—C1—Cl1	120.71 (6)	N1—C8—H8A	109.2
C3—C2—C1	118.49 (7)	C9—C8—H8A	109.2
C3—C2—H2A	120.8	N1—C8—H8B	109.2
C1—C2—H2A	120.8	C9—C8—H8B	109.2
C2—C3—C4	121.66 (7)	H8A—C8—H8B	107.9
C2—C3—Cl2	119.21 (6)	C18—C9—C18ⁱ	109.36 (9)
C4—C3—Cl2	119.12 (6)	C18—C9—C8ⁱ	108.71 (4)
C5—C4—C3	118.74 (8)	C18ⁱ—C9—C8ⁱ	109.73 (4)
C5—C4—H4A	120.6	C18—C9—C8	109.73 (4)
C3—C4—H4A	120.6	C18ⁱ—C9—C8	108.71 (4)
C4—C5—C6	121.76 (7)	C8ⁱ—C9—C8	110.59 (9)
C4—C5—H5A	119.1	C9—C18—H18A	109.5
C6—C5—H5A	119.1	C9—C18—H18B	109.5
C1—C6—C5	117.40 (7)	H18A—C18—H18B	109.5
C1—C6—C7	122.39 (7)	C9—C18—H18C	109.5
C5—C6—C7	120.19 (7)	H18A—C18—H18C	109.5
N1—C7—C6	120.65 (7)	H18B—C18—H18C	109.5

C6—C1—C2—C3	−1.08 (11)	Cl1—C1—C6—C7	2.99 (11)
Cl1—C1—C2—C3	178.81 (6)	C4—C5—C6—C1	−0.64 (13)
C1—C2—C3—C4	0.20 (12)	C4—C5—C6—C7	177.81 (8)
C1—C2—C3—Cl2	−178.30 (6)	C8—N1—C7—C6	−176.18 (7)
C2—C3—C4—C5	0.42 (13)	C1—C6—C7—N1	172.02 (8)
Cl2—C3—C4—C5	178.92 (7)	C5—C6—C7—N1	−6.36 (12)
C3—C4—C5—C6	−0.19 (13)	C7—N1—C8—C9	−134.46 (8)
C2—C1—C6—C5	1.29 (11)	N1—C8—C9—C18	59.07 (9)
Cl1—C1—C6—C5	−178.59 (6)	N1—C8—C9—C18ⁱ	178.63 (7)
C2—C1—C6—C7	−177.13 (7)	N1—C8—C9—C8ⁱ	−60.85 (5)

Symmetry code: (i) −x+1/2, −y+2, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈Cl₄N₂
M_r	416.15
Crystal system, space group	Orthorhombic, Pcca
Temperature (K)	100
a, b, c (Å)	30.7633 (4), 5.4012 (1), 11.4532 (1)
V (Å³)	1903.05 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.43 × 0.25 × 0.23

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.774, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	86683, 6565, 5678
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.950

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.099, 1.19
No. of reflections	4992
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.30

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

Acknowledgements

HKF and RK thanks the Malaysian Government and Universiti sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK thanks PNU for financial support.

References

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