1,4-Bis[(2-pyridyl­eth­yl)imino­meth­yl]benzene

Chiririwa, H.; Moss, J.R.; Su, H.; Hendricks, D.; Meijboom, R.

doi:10.1107/S1600536811009809

organic compounds

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Volume 67| Part 4| April 2011| Page o921

doi:10.1107/S1600536811009809

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1,4-Bis[(2-pyridylethyl)iminomethyl]benzene

Haleden Chiririwa,^a John R. Moss,^a Hong Su,^a ^* Denver Hendricks ^b and Reinout Meijboom ^c

^aDepartment of Chemistry, University of Cape Town, Private Bag, Rondebosch 7707, South Africa, ^bDivision of Medical Biochemistry, Faculty of Health Sciences, Private Bag X3, Observatory 7935, South Africa, and ^cDepartment of Chemistry University of Johannesburg, PO Box 524, Auckland Park, Johannesburg 2006, South Africa.
^*Correspondence e-mail: harrychiririwa@yahoo.com

(Received 23 February 2011; accepted 15 March 2011; online 19 March 2011)

In the title compound, C₂₂H₂₂N₄, the centroid of the benzene ring is located on an inversion centre. The dihedral angle between the benzene and pyridine rings is 10.94 (5)°. The crystal structure displays weak intermolecular C—H⋯N hydrogen bonding and C—H⋯π interactions.

Related literature

For related compounds, see: Chakraborty et al. (1999 ); Haga et al. (1985 ).

Experimental

Crystal data

C₂₂H₂₂N₄
M_r = 342.44
Monoclinic, P 2₁ /n
a = 6.0078 (6) Å
b = 26.023 (3) Å
c = 6.1319 (7) Å
β = 106.009 (2)°
V = 921.47 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.26 × 0.24 × 0.17 mm

Data collection

Bruker Kappa DUO APEXII diffractometer
11941 measured reflections
2288 independent reflections
1945 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.06
2288 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C5/N1 and C9–C11/C9′–C11′ rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.95	2.74	3.544 (3)	143 (3)
C4—H4⋯N2ⁱ	0.95	2.69	3.593 (2)	159 (4)
C7—H7A⋯N1ⁱⁱ	0.99	2.87	3.847 (2)	171 (5)
C2—H2⋯Cg1ⁱⁱⁱ	0.95	2.88	3.826 (4)	172 (5)
C6—H6A⋯Cg2^iv	0.99	2.90	3.508 (3)	120 (2)
Symmetry codes: (i) x, y, z+1; (ii) x-1, y, z; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x+1, y, z+1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009809/go2006sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009809/go2006Isup2.hkl

checkCIF report

Comment top

This work originates from our interest in developing a new class of tetradentate ligands. To the best of our knowledge, this work demonstrates the first example of neutral pyridinyldimine-based bridging ligand. The title compound might be expected to behave as a tetradentate chelating agent, in which both of the N atoms from the imine might coordinate, along with the two pyridinyl N atoms. Chakraborty et al. (1999) reported coordination of similar ligands to ruthenium whilst Haga and Koizumi (1985) reported their coordination to molybdenum. The structure of the title compound crystallized in space group P2₁/n with Z = 2. The molecule, shown in Fig. 1, has a center of inversion at the centroid of the benzene ring and was located in special positions at Wyckoff positon a. The conformation of the molecule is best described by the dihedral angle of the central ring and pyridyl ring of 10.94 (5)°. The structure is stabilized by weak hydrogen bonds of the type C—H···N and C—H···π, the metrics of which are given in Table 1. The C—H···N intermolecular interactions, as well as C6—H6A···Ring 1 (of C10—C9—C11—C10'-C9'-C11'), connect the parallel neighbouring molecules into 2-dimentional layers. And these layers are then linked along the b axis into 3-dimentional herringbone packing via C2—H2···Ring 2 (of C1—C2—C3—C4—C5—N1) interactions, as shown in Fig.2.

Related literature top

For related ligands, see: Chakraborty et al. (1999); Haga et al. (1985).

Experimental top

The title compound was synthesized as follows: a solution of benzene 1,4-dicarboxaldehyde (0.50 g, 3.73 mmol) in methanol (10 ml) was added dropwise to a stirred solution of 2-(pyridin-2-yl)ethanamine(0.91 g, 7.42 mmol) in methanol (10 ml). The mixture was stirred at room temperature for ca 16 h. The precipitate was filtered off and washed with diethylether and dried under vacuum for 4 h affording a fine shiny white powder in 85% yield. M.p.: does not melt below 260 °C. Recrystallization by slow diffusion of Et₂O into a concentrated CH₂Cl₂ of the solution gave colorless crystals suitable for X-ray structure analysis.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of titled compound showing the atomic numbering scheme. All non-hydrogen atoms were presented with ellipsoidal model with probability level 40%. Half of the molecule without atomic labels was generated via centre of symmetry (symmetry code: -x, -y, -z).
	Fig. 2. Projection viewed along [100] showing 3-D herringbone packing. Only the hydrogen atoms that invloved in C—H···N and C—H···π intermolecular interactions (see the list in Table 1) are shown and labelled. The red dotted lines represent the weak interactions.

1,4-Bis[(2-pyridylethyl)iminomethyl]benzene top

Crystal data top

C₂₂H₂₂N₄	F(000) = 364
M_r = 342.44	D_x = 1.234 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11941 reflections
a = 6.0078 (6) Å	θ = 3.1–28.3°
b = 26.023 (3) Å	µ = 0.08 mm⁻¹
c = 6.1319 (7) Å	T = 173 K
β = 106.009 (2)°	Plate, colourless
V = 921.47 (17) Å³	0.26 × 0.24 × 0.17 mm
Z = 2

Data collection top

Bruker Kappa DUO APEXII diffractometer	1945 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.3°, θ_min = 3.1°
0.5° ϕ scans and ω	h = −8→8
11941 measured reflections	k = −34→33
2288 independent reflections	l = −8→8

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0506P)² + 0.2363P] where P = (F_o² + 2F_c²)/3
2288 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₂H₂₂N₄	V = 921.47 (17) Å³
M_r = 342.44	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.0078 (6) Å	µ = 0.08 mm⁻¹
b = 26.023 (3) Å	T = 173 K
c = 6.1319 (7) Å	0.26 × 0.24 × 0.17 mm
β = 106.009 (2)°

Data collection top

Bruker Kappa DUO APEXII diffractometer	1945 reflections with I > 2σ(I)
11941 measured reflections	R_int = 0.024
2288 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	Δρ_max = 0.28 e Å⁻³
2288 reflections	Δρ_min = −0.20 e Å⁻³
118 parameters

Special details top

Experimental. Data for (I):

IR (KBr): 1610 cm^-1 (C=N, imine) ¹HNMR:(CDCl₃) δ_H 8.55(ddd, 2H, J =0.8 Hz, J = 1.7 Hz, J = 4.8 Hz) 8.21 (t, 2H, J = 1.3 Hz) 7.69 (s, 2H) 7.55 (dt, 2H, J = 1.9 Hz, J = 7.7 Hz) 7.11 (m, 2H) 4.03 (dt, 8H, J = 1.2 Hz, J = 7.2 Hz) 3.19(t, 4H, J = 7.2 Hz); ¹³CNMR: (400 MHz, CDCl₃) δ 161.05, 159.45, 149.37, 138.88, 136.13, 128.21, 123.67, 121.24, 61.18, 39.61; Analysis calculated for C₂₂H₂₂N₄:C, 77.16%; H, 6.48%; N, 16.36%; Found: C, 77.19%; H, 6.22%; N, 16.52%; EI—MS: m/z 249.90[M – C₇H₆N]⁺.

Half sphere of data collected using SAINT strategy (Bruker, 2006). Crystal to detector distance = 50 mm; combination of ϕ and ω scans of 0.5°, 40 s per °, 2 iterations.

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
N1	1.01974 (18)	0.16910 (4)	0.82099 (17)	0.0365 (3)
C1	1.1434 (2)	0.20288 (5)	0.9711 (2)	0.0431 (3)
H1	1.2675	0.2201	0.9339	0.052*
N2	0.40565 (16)	0.09448 (4)	0.35620 (15)	0.0282 (2)
C2	1.1022 (2)	0.21422 (5)	1.1750 (2)	0.0406 (3)
H2	1.1936	0.2389	1.2748	0.049*
C3	0.9248 (2)	0.18885 (5)	1.2306 (2)	0.0381 (3)
H3	0.8928	0.1952	1.3715	0.046*
C4	0.7937 (2)	0.15394 (4)	1.07884 (19)	0.0312 (3)
H4	0.6689	0.1363	1.1130	0.037*
C5	0.84667 (18)	0.14496 (4)	0.87569 (18)	0.0252 (2)
C6	0.7121 (2)	0.10708 (4)	0.7047 (2)	0.0327 (3)
H6A	0.6662	0.0778	0.7860	0.039*
H6B	0.8134	0.0936	0.6152	0.039*
C7	0.49617 (19)	0.13015 (4)	0.54368 (19)	0.0283 (2)
H7A	0.3778	0.1365	0.6254	0.034*
H7B	0.5346	0.1634	0.4844	0.034*
C8	0.21489 (18)	0.07288 (4)	0.34628 (17)	0.0251 (2)
H8	0.1384	0.0810	0.4584	0.030*
C9	0.10603 (17)	0.03556 (4)	0.16772 (17)	0.0231 (2)
C10	−0.10072 (18)	0.01157 (4)	0.17194 (18)	0.0259 (2)
H10	−0.1702	0.0196	0.2894	0.031*
C11	0.20546 (18)	0.02380 (4)	−0.00674 (18)	0.0254 (2)
H11	0.3453	0.0401	−0.0122	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0364 (6)	0.0409 (6)	0.0340 (5)	−0.0050 (4)	0.0129 (4)	0.0008 (4)
C1	0.0345 (6)	0.0402 (7)	0.0532 (8)	−0.0114 (5)	0.0095 (6)	0.0025 (6)
N2	0.0260 (5)	0.0295 (5)	0.0272 (5)	−0.0033 (4)	0.0044 (4)	−0.0064 (4)
C2	0.0428 (7)	0.0273 (6)	0.0400 (7)	−0.0030 (5)	−0.0081 (5)	−0.0037 (5)
C3	0.0552 (8)	0.0312 (6)	0.0266 (6)	0.0043 (5)	0.0089 (5)	−0.0037 (5)
C4	0.0354 (6)	0.0288 (5)	0.0317 (6)	−0.0010 (5)	0.0131 (5)	−0.0008 (4)
C5	0.0249 (5)	0.0240 (5)	0.0242 (5)	0.0031 (4)	0.0025 (4)	0.0002 (4)
C6	0.0342 (6)	0.0275 (6)	0.0311 (6)	0.0025 (5)	0.0000 (5)	−0.0061 (4)
C7	0.0257 (5)	0.0278 (5)	0.0296 (5)	−0.0019 (4)	0.0045 (4)	−0.0074 (4)
C8	0.0244 (5)	0.0252 (5)	0.0250 (5)	0.0007 (4)	0.0056 (4)	−0.0027 (4)
C9	0.0219 (5)	0.0217 (5)	0.0239 (5)	0.0004 (4)	0.0034 (4)	−0.0009 (4)
C10	0.0252 (5)	0.0284 (5)	0.0252 (5)	−0.0010 (4)	0.0088 (4)	−0.0026 (4)
C11	0.0214 (5)	0.0262 (5)	0.0289 (5)	−0.0030 (4)	0.0073 (4)	−0.0014 (4)

Geometric parameters (Å, º) top

N1—C5	1.3344 (15)	C6—C7	1.5204 (16)
N1—C1	1.3395 (17)	C6—H6A	0.9900
C1—C2	1.372 (2)	C6—H6B	0.9900
C1—H1	0.9500	C7—H7A	0.9900
N2—C8	1.2628 (14)	C7—H7B	0.9900
N2—C7	1.4609 (13)	C8—C9	1.4748 (14)
C2—C3	1.3739 (19)	C8—H8	0.9500
C2—H2	0.9500	C9—C11	1.3954 (14)
C3—C4	1.3811 (17)	C9—C10	1.3968 (14)
C3—H3	0.9500	C10—C11ⁱ	1.3848 (14)
C4—C5	1.3880 (15)	C10—H10	0.9500
C4—H4	0.9500	C11—C10ⁱ	1.3848 (14)
C5—C6	1.5023 (15)	C11—H11	0.9500

C5—N1—C1	117.33 (10)	C7—C6—H6B	109.0
N1—C1—C2	124.19 (12)	H6A—C6—H6B	107.8
N1—C1—H1	117.9	N2—C7—C6	109.03 (9)
C2—C1—H1	117.9	N2—C7—H7A	109.9
C8—N2—C7	117.17 (9)	C6—C7—H7A	109.9
C1—C2—C3	118.02 (11)	N2—C7—H7B	109.9
C1—C2—H2	121.0	C6—C7—H7B	109.9
C3—C2—H2	121.0	H7A—C7—H7B	108.3
C2—C3—C4	119.10 (11)	N2—C8—C9	122.66 (9)
C2—C3—H3	120.4	N2—C8—H8	118.7
C4—C3—H3	120.4	C9—C8—H8	118.7
C3—C4—C5	119.07 (11)	C11—C9—C10	119.15 (9)
C3—C4—H4	120.5	C11—C9—C8	121.17 (9)
C5—C4—H4	120.5	C10—C9—C8	119.68 (9)
N1—C5—C4	122.27 (10)	C11ⁱ—C10—C9	120.70 (9)
N1—C5—C6	116.12 (10)	C11ⁱ—C10—H10	119.6
C4—C5—C6	121.60 (10)	C9—C10—H10	119.6
C5—C6—C7	113.13 (9)	C10ⁱ—C11—C9	120.15 (9)
C5—C6—H6A	109.0	C10ⁱ—C11—H11	119.9
C7—C6—H6A	109.0	C9—C11—H11	119.9
C5—C6—H6B	109.0

C5—N1—C1—C2	−0.4 (2)	C8—N2—C7—C6	111.41 (11)
N1—C1—C2—C3	0.9 (2)	C5—C6—C7—N2	167.84 (9)
C1—C2—C3—C4	−1.10 (19)	C7—N2—C8—C9	−179.14 (9)
C2—C3—C4—C5	0.83 (18)	N2—C8—C9—C11	−2.76 (16)
C1—N1—C5—C4	0.06 (17)	N2—C8—C9—C10	177.48 (10)
C1—N1—C5—C6	−179.64 (10)	C11—C9—C10—C11ⁱ	0.57 (17)
C3—C4—C5—N1	−0.30 (17)	C8—C9—C10—C11ⁱ	−179.67 (9)
C3—C4—C5—C6	179.39 (10)	C10—C9—C11—C10ⁱ	−0.57 (17)
N1—C5—C6—C7	−94.33 (12)	C8—C9—C11—C10ⁱ	179.68 (9)
C4—C5—C6—C7	85.97 (13)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C5/N1 and C9–C11/C9'–C11' rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱⁱ	0.95	2.74	3.544 (3)	143 (3)
C4—H4···N2ⁱⁱ	0.95	2.69	3.593 (2)	159 (4)
C7—H7A···N1ⁱⁱⁱ	0.99	2.87	3.847 (2)	171 (5)
C2—H2···Cg1^iv	0.95	2.88	3.826 (4)	172 (5)
C6—H6A···Cg2^v	0.99	2.90	3.508 (3)	120 (2)

Symmetry codes: (ii) x, y, z+1; (iii) x−1, y, z; (iv) x+1/2, −y+1/2, z+1/2; (v) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂N₄
M_r	342.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	6.0078 (6), 26.023 (3), 6.1319 (7)
β (°)	106.009 (2)
V (Å³)	921.47 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.26 × 0.24 × 0.17

Data collection
Diffractometer	Bruker Kappa DUO APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11941, 2288, 1945
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.06
No. of reflections	2288
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.20

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C5/N1 and C9–C11/C9'–C11' rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.74	3.544 (3)	143 (3)
C4—H4···N2ⁱ	0.95	2.69	3.593 (2)	159 (4)
C7—H7A···N1ⁱⁱ	0.99	2.87	3.847 (2)	171 (5)
C2—H2···Cg1ⁱⁱⁱ	0.95	2.88	3.826 (4)	172 (5)
C6—H6A···Cg2^iv	0.99	2.90	3.508 (3)	120 (2)

Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z; (iii) x+1/2, −y+1/2, z+1/2; (iv) x+1, y, z+1.

Acknowledgements

We gratefully acknowledge Mintek and Project AuTEK for funding this project.

References

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