Crystal structure of (1E,1′E)-N,N′-(ethane-1,2-di­yl)bis­[(pyridin-2-yl)methanimine]

Abdoh, M.; Warad, I.; Naveen, S.; Lokanath, N.K.; Salghi, R.

doi:10.1107/S2056989015010087

organic compounds

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Crystal structure of (1E,1′E)-N,N′-(ethane-1,2-diyl)bis[(pyridin-2-yl)methanimine]

Muneer Abdoh,^a ^* Ismail Warad,^b S. Naveen,^c N. K. Lokanath ^d and Rachid Salghi ^e

^aDepartment of Physics, Science College, An-Najah National University, PO Box 7, Nablus, Palestinian Territories, ^bDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, Palestinian Territories, ^cInstitution of Excellence, University of Mysore, Manasagangotri, Mysore 570 006, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^eLaboratory of Environmental Engineering and Biotechnology, Science College, An-Najah National University, ENSA, Universite Ibn Zohr, PO Box 1136, 80000 Agadir, Morocco
^*Correspondence e-mail: muneer@najah.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 May 2015; accepted 24 May 2015; online 30 May 2015)

The whole molecule of the title compound, C₁₄H₁₄N₄, is generated by twofold rotation symmetry. The twofold axis bisects the central –CH₂-CH₂– bond and the planes of the pyridine rings are inclined to one another by 65.60 (7)°. In the crystal, there are no significant intermolecular interactions present.

Keywords: crystal structure; pyridinecarbaldehydes; 1,2-diaminopyridine; Schiff base; chelating ligands.

CCDC reference: 1402701

1. Related literature

For the use of Schiff bases, derived from pyridinecarbaldehydes, in synthetic chemistry, see: Marjani et al. (2009 ). For 1,2-diaminopyridine-derived Schiff bases as bidentate or polydentate chelating ligands and their possible medical applications, see: Warad et al. (2014 ).

2. Experimental

2.1. Crystal data

C₁₄H₁₄N₄
M_r = 238.29
Monoclinic, C 2/c
a = 19.347 (5) Å
b = 5.9339 (12) Å
c = 13.165 (2) Å
β = 122.266 (8)°
V = 1278.0 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.61 mm⁻¹
T = 296 K
0.30 × 0.27 × 0.25 mm

2.2. Data collection

Bruker X8 Proteum diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.837, T_max = 0.862
1539 measured reflections
933 independent reflections
881 reflections with I > 2σ(I)
R_int = 0.015

2.3. Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.120
S = 1.05
933 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.10 e Å⁻³

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1402701

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015010087/su5142sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015010087/su5142Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015010087/su5142Isup3.cml

checkCIF report

Structural commentary top

Schiff bases derived from pyridinecarbaldehydes have received considerable interest in synthetic chemistry (Marjani et al., 2009). 1,2-diamine-pyridine derived Schiff base bidentate or polydentate chelating ligand towards metal centers draw major attraction towards synthesis and medical application (Warad et al., 2014). It is still challenging to design and rationally synthesize ligands with unique structures and functions.

Synthesis and crystallization top

To a solution of pyridine-2-carbaldehyde (1 mmol) dissolved in 10 ml of absolute ethanol was added drop wise ethane-1,2-diamine (1 mmol) in 5 ml of absolute ethanol under constant stirring for 10 min. The mixture was refluxed for 4 h and then concentrated under reduced pressure. The title compound was precipitated by the addition of 50 ml of n-hexane. It was filtered off, washed three times with 80 ml of distilled water then with diethyl ether to give the title compound (yield: 86%). Single crystals suitable for X-ray analysis were obtained within two days by slow evaporation of a solution in dichloromethane.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were fixed geometrically (C—H = 0.93 – 0.97 Å) and allowed to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Related literature top

For the use of Schiff bases, derived from pyridinecarbaldehydes, in synthetic chemistry, see: Marjani et al. (2009). For 1,2-diaminopyridine-derived Schiff bases as bidentate or polydentate chelating ligands and their possible medical applications, see: Warad et al. (2014).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by twofold rotation symmetry (symmetry code: -x + 1, y, -z - 1/2).

(1E,1'E)-N,N'-(Ethane-1,2-diyl)bis[(pyridin-2-yl)methanimine] top

Crystal data top

C₁₄H₁₄N₄	F(000) = 504
M_r = 238.29	D_x = 1.238 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 881 reflections
a = 19.347 (5) Å	θ = 5.4–63.8°
b = 5.9339 (12) Å	µ = 0.61 mm⁻¹
c = 13.165 (2) Å	T = 296 K
β = 122.266 (8)°	Block, colourless
V = 1278.0 (5) Å³	0.30 × 0.27 × 0.25 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	933 independent reflections
Radiation source: Rotating Anode	881 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Detector resolution: 18.4 pixels mm^-1	θ_max = 63.8°, θ_min = 5.4°
ϕ and ω scans	h = −8→21
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −6→5
T_min = 0.837, T_max = 0.862	l = −15→12
1539 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0763P)² + 0.2763P] where P = (F_o² + 2F_c²)/3
933 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.10 e Å⁻³
0 restraints	Δρ_min = −0.10 e Å⁻³

Crystal data top

C₁₄H₁₄N₄	V = 1278.0 (5) Å³
M_r = 238.29	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 19.347 (5) Å	µ = 0.61 mm⁻¹
b = 5.9339 (12) Å	T = 296 K
c = 13.165 (2) Å	0.30 × 0.27 × 0.25 mm
β = 122.266 (8)°

Data collection top

Bruker X8 Proteum diffractometer	933 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	881 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.862	R_int = 0.015
1539 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.10 e Å⁻³
933 reflections	Δρ_min = −0.10 e Å⁻³
82 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
N3	0.69126 (7)	0.50665 (18)	0.02615 (10)	0.0576 (4)
N6	0.55349 (7)	0.05345 (19)	−0.11311 (9)	0.0542 (4)
C1	0.67191 (10)	0.7085 (3)	0.16610 (14)	0.0703 (6)
C2	0.70819 (9)	0.6792 (2)	0.10143 (14)	0.0634 (5)
C4	0.63482 (8)	0.3583 (2)	0.01373 (11)	0.0478 (4)
C5	0.61592 (8)	0.1747 (2)	−0.07264 (11)	0.0495 (4)
C7	0.54261 (9)	−0.1287 (2)	−0.19397 (13)	0.0585 (5)
C8	0.59615 (9)	0.3750 (2)	0.07686 (12)	0.0591 (5)
C9	0.61501 (11)	0.5541 (3)	0.15343 (14)	0.0728 (6)
H1	0.68570	0.83080	0.21760	0.0840*
H2	0.55830	0.26720	0.06750	0.0710*
H4	0.74660	0.78490	0.11040	0.0760*
H5	0.65170	0.14760	−0.09810	0.0590*
H7	0.58250	−0.11360	−0.21680	0.0700*
H8	0.55230	−0.27160	−0.15260	0.0700*
H9	0.58950	0.57050	0.19620	0.0870*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0509 (8)	0.0571 (7)	0.0602 (7)	0.0007 (5)	0.0265 (6)	0.0064 (5)
N6	0.0501 (8)	0.0609 (7)	0.0466 (6)	0.0031 (5)	0.0225 (5)	0.0005 (5)
C1	0.0714 (11)	0.0636 (9)	0.0601 (9)	−0.0011 (7)	0.0246 (8)	−0.0102 (7)
C2	0.0554 (10)	0.0564 (9)	0.0628 (9)	−0.0038 (6)	0.0212 (7)	0.0035 (6)
C4	0.0410 (8)	0.0514 (7)	0.0430 (7)	0.0068 (5)	0.0171 (6)	0.0090 (5)
C5	0.0463 (8)	0.0551 (8)	0.0473 (7)	0.0085 (6)	0.0251 (6)	0.0079 (5)
C7	0.0600 (9)	0.0532 (8)	0.0540 (8)	0.0048 (6)	0.0249 (7)	−0.0001 (6)
C8	0.0561 (9)	0.0674 (9)	0.0542 (8)	−0.0052 (7)	0.0298 (7)	−0.0034 (6)
C9	0.0743 (12)	0.0866 (11)	0.0628 (9)	−0.0047 (8)	0.0401 (9)	−0.0136 (8)

Geometric parameters (Å, º) top

N3—C2	1.3384 (18)	C8—C9	1.373 (2)
N3—C4	1.343 (2)	C1—H1	0.9300
N6—C5	1.254 (2)	C2—H4	0.9300
N6—C7	1.4514 (18)	C5—H5	0.9300
C1—C2	1.373 (3)	C7—H7	0.9700
C1—C9	1.372 (3)	C7—H8	0.9700
C4—C5	1.4730 (18)	C8—H2	0.9300
C4—C8	1.387 (2)	C9—H9	0.9300
C7—C7ⁱ	1.516 (2)

C2—N3—C4	116.96 (15)	N3—C2—H4	118.00
C5—N6—C7	117.93 (15)	C1—C2—H4	118.00
C2—C1—C9	118.85 (16)	N6—C5—H5	119.00
N3—C2—C1	123.50 (16)	C4—C5—H5	119.00
N3—C4—C5	115.43 (14)	N6—C7—H7	109.00
N3—C4—C8	122.94 (12)	N6—C7—H8	109.00
C5—C4—C8	121.62 (13)	H7—C7—H8	108.00
N6—C5—C4	122.55 (15)	C7ⁱ—C7—H7	109.00
N6—C7—C7ⁱ	111.74 (13)	C7ⁱ—C7—H8	109.00
C4—C8—C9	118.56 (16)	C4—C8—H2	121.00
C1—C9—C8	119.17 (19)	C9—C8—H2	121.00
C2—C1—H1	121.00	C1—C9—H9	120.00
C9—C1—H1	121.00	C8—C9—H9	120.00

C2—N3—C4—C5	178.17 (12)	N3—C4—C5—N6	−164.26 (12)
C2—N3—C4—C8	−1.6 (2)	C5—C4—C8—C9	−178.16 (14)
C4—N3—C2—C1	0.9 (2)	C8—C4—C5—N6	15.5 (2)
C7—N6—C5—C4	−177.50 (11)	N3—C4—C8—C9	1.6 (2)
C5—N6—C7—C7ⁱ	−131.18 (14)	N6—C7—C7ⁱ—N6ⁱ	73.41 (17)
C9—C1—C2—N3	−0.2 (3)	C4—C8—C9—C1	−0.8 (2)
C2—C1—C9—C8	0.1 (3)

Symmetry code: (i) −x+1, y, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄
M_r	238.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	19.347 (5), 5.9339 (12), 13.165 (2)
β (°)	122.266 (8)
V (Å³)	1278.0 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.30 × 0.27 × 0.25

Data collection
Diffractometer	Bruker X8 Proteum diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2013)
T_min, T_max	0.837, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	1539, 933, 881
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.582

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.120, 1.05
No. of reflections	933
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.10

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors are thankful to IOE, Vijnana Bhavana, University of Mysore, Mysore, for providing the single-crystal X-ray diffraction facility. IW is grateful to An-Najah National University and Zamala (fellowship program for the development of university education) for financial support.

References

Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Marjani, K., Asgarian, J., Mousavi, M. & Amani, V. (2009). Z. Anorg. Allg. Chem. 635, 1633–1637. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Warad, I., Khan, A., Azam, M., Al-Resayes, S. I. & Haddad, S. (2014). J. Mol. Struct. 1062, 167–173. CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 6| June 2015| Page o431

doi:10.1107/S2056989015010087

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (1E,1′E)-N,N′-(ethane-1,2-di­yl)bis­­[(pyridin-2-yl)methanimine]

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (1E,1′E)-N,N′-(ethane-1,2-diyl)bis[(pyridin-2-yl)methanimine]