4,4′-[Ethylenebis(nitrilomethylidyne)]dibenzonitrile

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

doi:10.1107/S1600536809007284

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o682-o683

doi:10.1107/S1600536809007284

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4,4′-[Ethylenebis(nitrilomethylidyne)]dibenzonitrile

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 26 February 2009; accepted 27 February 2009; online 6 March 2009)

The molecule of the title Schiff base compound, C₁₈H₁₄N₄, lies across a crystallographic inversion centre and adopts an E configuration with respect to the azomethine (C=N) bonds. The imino groups are coplanar with the aromatic rings with a maximum deviation of 0.1574 (12) Å for the N atom. Within the molecule, the planar units are parallel, but extend in opposite directions from the dimethylene bridge. In the crystal structure, pairs of intermolecular C—H⋯N hydrogen bonds link neighbouring molecules into centrosymmetric dimers with R²₂(10) ring motifs. An interesting feature of the crystal structure is the short intermolecular C⋯C interaction with a distance of 3.3821 (13) Å, which is shorter than the sum of the van der Waals radius of a carbon atom.

Related literature

For bond-length data, see Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures see, for example: Fun & Kia (2008 ): 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 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₈H₁₄N₄
M_r = 286.33
Triclinic, $[P \overline 1]$
a = 4.6843 (2) Å
b = 6.9872 (3) Å
c = 11.6208 (5) Å
α = 78.147 (3)°
β = 87.462 (3)°
γ = 74.081 (2)°
V = 357.94 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.45 × 0.29 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.964, T_max = 0.995
7927 measured reflections
2551 independent reflections
2034 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.146
S = 1.08
2551 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.44 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
C4—H4A⋯N2ⁱ	0.93	2.60	3.4702 (12)	156
Symmetry code: (i) -x+3, -y+1, -z+1.

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, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007284/at2733sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007284/at2733Isup2.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 application in the 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 a crystallographic inversion centre and adopts an E configuration with respect to the azomethine (C═N) bond. The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable with the values found in related structures (Fun & Kia 2008; Fun, Kargar & Kia 2008; Fun, Kia & Kargar 2008). The two planar units are parallel but extend in opposite directions from the dimethylene bridge. The interesting feature of the crystal structure is the short intermolecular C3···C6 interactions [symmetry code: 1 + x, y, z] with a distance of 3.3821 (13) Å, which is shorter than the sum of the van der Waals radius of carbon atom. In the crystal structure, pairs of intermolecular C—H···N hydrogen bonds link neighbouring molecules into dimer with R²₂(10) ring motif (Bernstein et al., 1995) (Table 1, Fig. 2).

Related literature top

For bond-length data, see Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures see, for example: Fun & Kia (2008): 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). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

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, 2009).

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 + 1, -y, -z].
	Fig. 2. The crystal packing of (I), viewed approximately down the a-axis, showing dimer formation by R²₂(10) ring motif. Intermolecular interactions are shown as dashed lines.

4,4'-[Ethylenebis(nitrilomethylidyne)]dibenzonitrile top

Crystal data top

C₁₈H₁₄N₄	Z = 1
M_r = 286.33	F(000) = 150
Triclinic, P1	D_x = 1.328 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.6843 (2) Å	Cell parameters from 3276 reflections
b = 6.9872 (3) Å	θ = 3.1–36.3°
c = 11.6208 (5) Å	µ = 0.08 mm⁻¹
α = 78.147 (3)°	T = 100 K
β = 87.462 (3)°	Plate, colourless
γ = 74.081 (2)°	0.45 × 0.29 × 0.06 mm
V = 357.94 (3) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2551 independent reflections
Radiation source: fine-focus sealed tube	2034 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 32.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→7
T_min = 0.964, T_max = 0.995	k = −10→10
7927 measured reflections	l = −17→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0885P)² + 0.0252P] where P = (F_o² + 2F_c²)/3
2551 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₈H₁₄N₄	γ = 74.081 (2)°
M_r = 286.33	V = 357.94 (3) Å³
Triclinic, P1	Z = 1
a = 4.6843 (2) Å	Mo Kα radiation
b = 6.9872 (3) Å	µ = 0.08 mm⁻¹
c = 11.6208 (5) Å	T = 100 K
α = 78.147 (3)°	0.45 × 0.29 × 0.06 mm
β = 87.462 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2551 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2034 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.995	R_int = 0.023
7927 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.08	Δρ_max = 0.44 e Å⁻³
2551 reflections	Δρ_min = −0.25 e Å⁻³
100 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
N1	0.59056 (17)	0.17735 (11)	0.08275 (6)	0.01615 (18)
N2	1.42099 (19)	0.74379 (12)	0.37951 (7)	0.0216 (2)
C1	0.8714 (2)	0.45474 (13)	0.15338 (7)	0.01522 (19)
H1A	0.7912	0.4927	0.0776	0.018*
C2	1.0275 (2)	0.57187 (13)	0.19178 (8)	0.01621 (19)
H2A	1.0552	0.6873	0.1416	0.019*
C3	1.14366 (19)	0.51580 (13)	0.30666 (7)	0.01489 (19)
C4	1.1063 (2)	0.34172 (13)	0.38257 (7)	0.01654 (19)
H4A	1.1845	0.3047	0.4586	0.020*
C5	0.9504 (2)	0.22467 (13)	0.34268 (8)	0.01632 (19)
H5A	0.9235	0.1088	0.3927	0.020*
C6	0.83369 (19)	0.27878 (13)	0.22843 (7)	0.01374 (18)
C7	0.67371 (19)	0.14854 (13)	0.18937 (7)	0.01451 (18)
H7A	0.6322	0.0424	0.2440	0.017*
C8	0.4324 (2)	0.03967 (13)	0.05429 (7)	0.01563 (19)
H8A	0.2243	0.1108	0.0394	0.019*
H8B	0.4460	−0.0732	0.1202	0.019*
C9	1.2999 (2)	0.64058 (13)	0.34745 (7)	0.01641 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0164 (4)	0.0181 (3)	0.0170 (3)	−0.0075 (3)	−0.0010 (3)	−0.0063 (3)
N2	0.0229 (4)	0.0232 (4)	0.0216 (4)	−0.0100 (3)	−0.0030 (3)	−0.0054 (3)
C1	0.0149 (4)	0.0185 (4)	0.0139 (4)	−0.0058 (3)	−0.0021 (3)	−0.0047 (3)
C2	0.0167 (4)	0.0168 (4)	0.0169 (4)	−0.0068 (3)	−0.0011 (3)	−0.0040 (3)
C3	0.0127 (4)	0.0173 (4)	0.0168 (4)	−0.0051 (3)	−0.0004 (3)	−0.0067 (3)
C4	0.0169 (4)	0.0191 (4)	0.0151 (4)	−0.0059 (3)	−0.0028 (3)	−0.0047 (3)
C5	0.0175 (4)	0.0166 (4)	0.0159 (4)	−0.0063 (3)	−0.0015 (3)	−0.0029 (3)
C6	0.0120 (4)	0.0157 (4)	0.0149 (4)	−0.0040 (3)	−0.0001 (3)	−0.0056 (3)
C7	0.0142 (4)	0.0159 (4)	0.0153 (4)	−0.0059 (3)	0.0003 (3)	−0.0050 (3)
C8	0.0159 (4)	0.0183 (4)	0.0162 (4)	−0.0085 (3)	−0.0008 (3)	−0.0058 (3)
C9	0.0158 (4)	0.0182 (4)	0.0159 (4)	−0.0047 (3)	−0.0012 (3)	−0.0046 (3)

Geometric parameters (Å, º) top

N1—C7	1.2745 (11)	C4—C5	1.3893 (12)
N1—C8	1.4585 (11)	C4—H4A	0.9300
N2—C9	1.1551 (11)	C5—C6	1.3962 (12)
C1—C2	1.3821 (11)	C5—H5A	0.9300
C1—C6	1.4031 (12)	C6—C7	1.4730 (11)
C1—H1A	0.9300	C7—H7A	0.9300
C2—C3	1.4017 (12)	C8—C8ⁱ	1.5246 (16)
C2—H2A	0.9300	C8—H8A	0.9700
C3—C4	1.3966 (12)	C8—H8B	0.9700
C3—C9	1.4389 (11)

C7—N1—C8	117.00 (7)	C6—C5—H5A	119.6
C2—C1—C6	120.14 (8)	C5—C6—C1	119.61 (8)
C2—C1—H1A	119.9	C5—C6—C7	118.94 (7)
C6—C1—H1A	119.9	C1—C6—C7	121.45 (8)
C1—C2—C3	119.68 (8)	N1—C7—C6	121.78 (8)
C1—C2—H2A	120.2	N1—C7—H7A	119.1
C3—C2—H2A	120.2	C6—C7—H7A	119.1
C4—C3—C2	120.80 (8)	N1—C8—C8ⁱ	109.60 (9)
C4—C3—C9	119.58 (8)	N1—C8—H8A	109.8
C2—C3—C9	119.61 (7)	C8ⁱ—C8—H8A	109.8
C5—C4—C3	118.95 (8)	N1—C8—H8B	109.8
C5—C4—H4A	120.5	C8ⁱ—C8—H8B	109.8
C3—C4—H4A	120.5	H8A—C8—H8B	108.2
C4—C5—C6	120.81 (8)	N2—C9—C3	178.76 (9)
C4—C5—H5A	119.6

C6—C1—C2—C3	−1.03 (13)	C4—C5—C6—C7	179.13 (7)
C1—C2—C3—C4	0.65 (13)	C2—C1—C6—C5	1.07 (13)
C1—C2—C3—C9	−178.50 (7)	C2—C1—C6—C7	−178.76 (7)
C2—C3—C4—C5	−0.28 (13)	C8—N1—C7—C6	−179.67 (7)
C9—C3—C4—C5	178.86 (7)	C5—C6—C7—N1	−172.24 (8)
C3—C4—C5—C6	0.32 (14)	C1—C6—C7—N1	7.59 (14)
C4—C5—C6—C1	−0.71 (14)	C7—N1—C8—C8ⁱ	−131.42 (10)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N2ⁱⁱ	0.93	2.60	3.4702 (12)	156

Symmetry code: (ii) −x+3, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₄
M_r	286.33
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	4.6843 (2), 6.9872 (3), 11.6208 (5)
α, β, γ (°)	78.147 (3), 87.462 (3), 74.081 (2)
V (Å³)	357.94 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.45 × 0.29 × 0.06

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.964, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	7927, 2551, 2034
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.146, 1.08
No. of reflections	2551
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.25

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N2ⁱ	0.9300	2.6000	3.4702 (12)	156.00

Symmetry code: (i) −x+3, −y+1, −z+1.

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 post-doctoral research fellowship. HK thanks PNU for financial support. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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