1,4-Bis(3-pyridylmethyl­eneamino­meth­yl)benzene

He, M.-Y.; Li, C.; Xu, H.; Hu, Z.-J.; Chen, Q.

doi:10.1107/S1600536809000658

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o285

doi:10.1107/S1600536809000658

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1,4-Bis(3-pyridylmethyleneaminomethyl)benzene

Ming-Yang He,^a Chao Li,^a Huan Xu,^a Zhao-Jian Hu ^a and Qun Chen ^a ^*

^aKey Laboratory of Fine Petrochemical Technology, Jiangsu Polytechnic University, Changzhou 213164, People's Republic of China
^*Correspondence e-mail: chenqunjpu@yahoo.com

(Received 1 December 2008; accepted 7 January 2009; online 10 January 2009)

The title compound, C₂₀H₁₈N₄, is a flexible 3,3′-bipyridyl-type ligand with a long spacer group between the two pyridyl functions. The molecule crystallizes around an inversion center, with one half-molecule in the asymmetric unit and a dihedral angle of 71.85 (8)° between the pyridine ring and the central benzene ring.

Related literature

For background information on bipyridyl-type Schiff base ligands, see: Cho et al. (2006 ); Haga et al. (1985 ); Mahmoudi et al. (2007 ); Wang et al. (2008 ). Haga et al. (1985) describe the synthesis of the title compound.

Experimental

Crystal data

C₂₀H₁₈N₄
M_r = 314.38
Monoclinic, P 2₁ /c
a = 6.0990 (11) Å
b = 14.589 (3) Å
c = 9.9481 (18) Å
β = 107.851 (3)°
V = 842.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 (2) K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.98, T_max = 0.98
6535 measured reflections
1661 independent reflections
1085 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.101
S = 1.01
1661 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000658/zl2166sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000658/zl2166Isup2.hkl

checkCIF report

Comment top

Bipyridyl-type bidentate Schiff base ligands have been utilized intensively to assemble various coordination polymers with interesting topologies and fascinating structural diversities (Cho et al., 2006; Mahmoudi et al., 2007; Wang et al., 2008). We report here the crystal structure of the title compound.

A perspective view of the title compound, including the atomic numbering scheme, is shown in Fig. 1. The title compound crystallizes around a crystallographic center with half a molecule in the asymmetric unit. The bond lengths and angles are within normal ranges. The terminal pyridyl groups are coplanar, and they form a dihedral angle of 71.85 (8)° with the central benzene ring. The molecular structure is stabilized by an intramolecular C9—H9···N2 bond (Table 1), but no classical intermolecular interactions have been found in the crystal packing of the title compound.

Related literature top

For background information on bipyridyl-type Schiff base ligands, see: Cho et al. (2006); Haga et al. (1985); Mahmoudi et al. (2007); Wang et al. (2008). Haga et al. (1985) describe the synthesis of the title compound.

Experimental top

The title compound was synthesized and purified according to the method described by by Haga et al. (1985), by the condensation reaction of pyridine-3-carboxaldehyde and 1,4-benzenedimethanamine (yield 83%). Colorless block single crystals (m.p. 397–397.2 K) suitable for X-ray analysis were obtained by slow evaporation of a methanol solution at room temperature. Analysis calclated for C₂₀H₁₈N₄: C 76.41, H 5.77, N 17.82%; found: C 76.53, H 5.74, N 17.75%. IR (KBr pellet, cm^-1): 3436 (b), 3060 (m), 3048 (m), 2942 (m), 2903 (m), 2849 (m), 1640 (s), 1586 (s), 1565 (s), 1469 (s), 1434 (s), 1359 (m), 1324 (m), 1150 (w), 1015 (m), 990 (m), 848 (s), 777 (s), 739 (m), 617 (w), 571 (m), 506 (m), 403 (w).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).

Figures top

Fig. 1. The molecular structure of the title compound (thermal ellipsoids are shown at 30% probability levels).

1,4-Bis(3-pyridylmethyleneaminomethyl)benzene top

Crystal data top

C₂₀H₁₈N₄	F(000) = 332
M_r = 314.38	D_x = 1.239 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2797 reflections
a = 6.0990 (11) Å	θ = 2.6–27.2°
b = 14.589 (3) Å	µ = 0.08 mm⁻¹
c = 9.9481 (18) Å	T = 291 K
β = 107.851 (3)°	Block, colorless
V = 842.5 (3) Å³	0.24 × 0.22 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1661 independent reflections
Radiation source: sealed tube	1085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
T_min = 0.98, T_max = 0.98	k = −17→17
6535 measured reflections	l = −11→12

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
1661 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₂₀H₁₈N₄	V = 842.5 (3) Å³
M_r = 314.38	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0990 (11) Å	µ = 0.08 mm⁻¹
b = 14.589 (3) Å	T = 291 K
c = 9.9481 (18) Å	0.24 × 0.22 × 0.20 mm
β = 107.851 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	1661 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1085 reflections with I > 2σ(I)
T_min = 0.98, T_max = 0.98	R_int = 0.045
6535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	Δρ_max = 0.13 e Å⁻³
1661 reflections	Δρ_min = −0.12 e Å⁻³
109 parameters

Special details top

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
C1	0.0338 (3)	0.59733 (9)	0.90988 (16)	0.0402 (4)
C2	0.2284 (3)	0.63315 (11)	1.00966 (18)	0.0512 (4)
H2	0.3749	0.6142	1.0117	0.061*
C3	0.2005 (3)	0.69698 (11)	1.1050 (2)	0.0592 (5)
H3	0.3278	0.7216	1.1728	0.071*
C4	−0.0183 (4)	0.72359 (11)	1.0983 (2)	0.0627 (5)
H4	−0.0346	0.7673	1.1625	0.075*
C5	−0.1780 (3)	0.62821 (11)	0.91503 (19)	0.0522 (4)
H5	−0.3091	0.6036	0.8506	0.063*
C6	0.0482 (3)	0.53005 (10)	0.80278 (16)	0.0418 (4)
H6	−0.0874	0.5064	0.7416	0.050*
C7	0.2348 (3)	0.43652 (11)	0.68220 (17)	0.0475 (4)
H7A	0.0771	0.4255	0.6247	0.057*
H7B	0.2981	0.3791	0.7264	0.057*
C8	0.3738 (3)	0.46922 (10)	0.58876 (15)	0.0390 (4)
C9	0.3934 (3)	0.56235 (10)	0.56217 (16)	0.0430 (4)
H9	0.3223	0.6050	0.6044	0.052*
C10	0.5155 (3)	0.59265 (10)	0.47492 (17)	0.0424 (4)
H10	0.5239	0.6551	0.4585	0.051*
N1	−0.2079 (3)	0.69096 (10)	1.00596 (19)	0.0667 (5)
N2	0.2369 (2)	0.50359 (9)	0.79117 (15)	0.0489 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0437 (9)	0.0402 (7)	0.0394 (9)	−0.0009 (6)	0.0165 (7)	0.0070 (6)
C2	0.0458 (10)	0.0571 (10)	0.0500 (10)	0.0002 (8)	0.0134 (8)	−0.0032 (8)
C3	0.0643 (12)	0.0516 (10)	0.0579 (12)	−0.0079 (8)	0.0134 (9)	−0.0118 (8)
C4	0.0786 (14)	0.0431 (9)	0.0738 (13)	−0.0012 (9)	0.0345 (11)	−0.0131 (9)
C5	0.0470 (9)	0.0501 (9)	0.0600 (11)	0.0011 (8)	0.0169 (8)	−0.0034 (8)
C6	0.0425 (9)	0.0458 (8)	0.0374 (9)	−0.0011 (6)	0.0127 (7)	0.0029 (6)
C7	0.0467 (9)	0.0508 (8)	0.0462 (9)	0.0005 (7)	0.0161 (7)	−0.0041 (7)
C8	0.0379 (8)	0.0423 (7)	0.0333 (9)	0.0013 (6)	0.0055 (6)	−0.0063 (6)
C9	0.0464 (9)	0.0423 (7)	0.0414 (9)	0.0065 (7)	0.0149 (7)	−0.0081 (7)
C10	0.0477 (9)	0.0346 (7)	0.0442 (9)	0.0017 (6)	0.0129 (7)	−0.0025 (6)
N1	0.0609 (10)	0.0550 (9)	0.0887 (13)	0.0041 (8)	0.0297 (9)	−0.0173 (8)
N2	0.0478 (8)	0.0624 (9)	0.0393 (8)	0.0002 (6)	0.0175 (6)	−0.0074 (6)

Geometric parameters (Å, º) top

C1—C5	1.384 (2)	C6—H6	0.9300
C1—C2	1.395 (2)	C7—N2	1.458 (2)
C1—C6	1.471 (2)	C7—C8	1.514 (2)
C2—C3	1.376 (2)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C4	1.372 (3)	C8—C10ⁱ	1.391 (2)
C3—H3	0.9300	C8—C9	1.396 (2)
C4—N1	1.325 (3)	C9—C10	1.378 (2)
C4—H4	0.9300	C9—H9	0.9300
C5—N1	1.338 (2)	C10—C8ⁱ	1.391 (2)
C5—H5	0.9300	C10—H10	0.9300
C6—N2	1.253 (2)

C5—C1—C2	116.88 (15)	N2—C7—C8	111.49 (13)
C5—C1—C6	120.51 (15)	N2—C7—H7A	109.3
C2—C1—C6	122.61 (14)	C8—C7—H7A	109.3
C3—C2—C1	119.09 (16)	N2—C7—H7B	109.3
C3—C2—H2	120.5	C8—C7—H7B	109.3
C1—C2—H2	120.5	H7A—C7—H7B	108.0
C4—C3—C2	118.78 (18)	C10ⁱ—C8—C9	117.60 (13)
C4—C3—H3	120.6	C10ⁱ—C8—C7	121.10 (13)
C2—C3—H3	120.6	C9—C8—C7	121.30 (12)
N1—C4—C3	124.15 (17)	C10—C9—C8	121.72 (13)
N1—C4—H4	117.9	C10—C9—H9	119.1
C3—C4—H4	117.9	C8—C9—H9	119.1
N1—C5—C1	124.74 (18)	C9—C10—C8ⁱ	120.68 (13)
N1—C5—H5	117.6	C9—C10—H10	119.7
C1—C5—H5	117.6	C8ⁱ—C10—H10	119.7
N2—C6—C1	122.21 (15)	C4—N1—C5	116.34 (16)
N2—C6—H6	118.9	C6—N2—C7	118.48 (14)
C1—C6—H6	118.9

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N2	0.93	2.55	2.858 (2)	100

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₄
M_r	314.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	6.0990 (11), 14.589 (3), 9.9481 (18)
β (°)	107.851 (3)
V (Å³)	842.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.98, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	6535, 1661, 1085
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.101, 1.01
No. of reflections	1661
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N2	0.9300	2.5500	2.858 (2)	100.00

Acknowledgements

The authors thank the Center for Testing and Analysis at Yangzhou University for support.

References

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