2,2′-(2,6-Pyridinedi­yl)diquinoline

Garza Rodríguez, L. Á.; Bernès, S.; Elizondo Martínez, P.; Nájera Martínez, B.

doi:10.1107/S1600536810006033

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o666

doi:10.1107/S1600536810006033

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2,2′-(2,6-Pyridinediyl)diquinoline

Luis Ángel Garza Rodríguez,^a Sylvain Bernès,^b Perla Elizondo Martínez ^a and Blanca Nájera Martínez ^a ^*

^aLaboratorio de Química Industrial, CELAES, Facultad de Ciencias Químicas, UANL, Pedro de Alba S/N, 66451 San Nicolás de los Garza, N.L., Mexico, and ^bDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, N.L., Mexico
^*Correspondence e-mail: sylvain_bernes@Hotmail.com

(Received 3 February 2010; accepted 15 February 2010; online 20 February 2010)

The title molecule, C₂₃H₁₅N₃, is a terpyridine derivative resulting from the Friedländer annulation between 2,6-diacetylpyridine and N,N′-bis(2-aminobenzyl)ethylenediamine. The asymmetric unit contains one half-molecule, the complete molecule being generated by a mirror plane (one N atom and one C atom lie on the plane). The molecule, although aromatic, is deformed from planarity as a result of crystal packing forces: molecules are stacked along the short c axis, with a short separation of 3.605 (1) Å between the mean planes. The bent molecular shape is reflected in the dihedral angle of 16.10 (5)° between the essentially planar quinoline groups. In addition to π⋯π interactions, the crystal structure features weak inter-stack C—H⋯N contacts involving atoms of the central pyridine rings which lie in a common crystallographic m plane.

Related literature

For the synthesis and the coordination behavior of the title molecule, see: Bertrand et al. (2009 ); Harris et al. (1969 ); Klassen et al. (1975 ). For a terpyridine derivative closely related to the title molecule, see: Sasaki et al. (1998 ). For the Friedländer condensation as a tool for the preparation of quinolines, see: Da Costa et al. (2009 ); Sridharan et al. (2009 ).

Experimental

Crystal data

C₂₃H₁₅N₃
M_r = 333.38
Orthorhombic, P n m a
a = 11.960 (2) Å
b = 34.509 (6) Å
c = 3.9509 (5) Å
V = 1630.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.40 × 0.20 × 0.10 mm

Data collection

Siemens P4 diffractometer
5603 measured reflections
1469 independent reflections
1032 reflections with I > 2σ(I)
R_int = 0.031
2 standard reflections every 48 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.118
S = 1.02
1469 reflections
122 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N1ⁱ	0.93	2.72	3.641 (3)	169
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: XSCANS (Siemens, 1996 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL-Plus.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810006033/xu2726sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006033/xu2726Isup2.hkl

checkCIF report

Comment top

Thirty years after cisplatin was approved by the FDA for its use as a chemotherapy drug, studies regarding interactions between platinum-based complexes and basic sites in DNA remain actives. Recently, Bertrand et al. (2009) showed that Pt^II cationic complexes bearing 2,2':6',2"-terpyridine or a terpyridine derivative as ligand have the ability to platinate the human telomeric G-quadruplex. Interestingly, both the binding affinity and the platination activity seem to be determined by the extension of the aromatic surface of the terpyridine derivative. One of the ligands used in that work was 2,2'-(2,6-pyridinediyl)bis-quinoline, synthesized through the Friedländer condensation (Da Costa et al., 2009; Sridharan et al., 2009) between 2,6-diacetylpyridine and 2-nitrobenzaldehyde. We now report the crystal structure of this aromatic ligand.

The title terpyridine derivative was obtained as a by-product during the preparation of a macrocyclic ligand (see Experimental). More suitable synthesis are however available in the literature (Harris et al., 1969; Klassen et al., 1975; Bertrand et al., 2009). The molecule (Fig. 1) displays the crystallographic m symmetry, with atoms N1, C1 and H1A placed in the mirror planes normal to [010]. The molecular conformation observed in the solid-state is not suitable for coordination through the three N atoms: the quinoline N atoms are placed in a trans arrangement with respect to the central pyridine N atom, while a cis,cis conformation is required for the molecule to be a terdentate ligand. However, as invariably found in non-hindered terpyridine derivatives, aromatic fragments are free to rotate, for example about the C3—C4 bond in the case of the title molecule. Such a behavior has been reported, for example, for the coordination to Ru^II of a closely related terpyridine ligand, namely 2,6-bis(5,6,7,8-tetrahydroquinol-2-yl)pyridine (Sasaki et al., 1998).

Molecules are stacked along the short axis c, at a distance of 3.605 Å (separation between two mean planes passing through two neighboring molecules in the [001] direction, see Fig.2, inset). This short separation, although larger than that observed in graphite (ca. 3.36 Å), results in strong π···π interactions in the stacks, which, in turn, deform the molecules from planarity. The dihedral angle between the central pyridine ring and the quinoline substituent is 8.13 (8)°. The bent shape is also reflected in the dihedral angle between quinoline systems, 16.10 (5)° (Fig. 2, inset). Finally, the crystal structure is completed by weak intermolecular C—H···N contacts (Table 1 and Fig. 2), linking the stacks in the [100] direction.

Related literature top

For the synthesis and the coordination behavior of the title molecule, see: Bertrand et al. (2009); Harris et al. (1969); Klassen et al. (1975). For a terpyridine derivative closely related to the title molecule, see: Sasaki et al. (1998). For the Friedländer condensation as a tool for the preparation of quinolines, see: Da Costa et al. (2009); Sridharan et al. (2009).

Experimental top

A mixture of 305 mg of 2,6-diacetylpyridine and 823 mg of Ce(NO₃)₃.6H₂O in methanol (25 ml) was refluxed for 30 min, followed by slow addition of a dissolution of N,N'-bis(2-aminobenzyl)ethylenediamine (530 mg in 25 ml methanol). The mixture was kept under these conditions for 3.5 h, and then cooled to room temperature, giving a red precipitate. After 1.5 month, the resulting solid was filtered, washed with cold methanol, diethyl ether, and air dried. Suitable single crystals were picked off from the solid. m.p. 495–497 K (lit. 500–501 K: Klassen et al., 1975).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with displacement ellipsoids at the 30% probability level for non-H atoms. Non-labeled atoms are generated by symmetry code x, 1/2-y, z.
	Fig. 2. A part of the crystal structure, viewed down c axis. Dashed lines represent non-bonding intermolecular contacts. The inset shows a part of a stack along [001]. Two least-squares planes are represented (red), which were computed using all atoms in each selected molecule (Macrae et al., 2008).

2,2'-(2,6-Pyridinediyl)diquinoline top

Crystal data top

C₂₃H₁₅N₃	D_x = 1.358 Mg m⁻³
M_r = 333.38	Melting point = 495–497 K
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 100 reflections
a = 11.960 (2) Å	θ = 5.5–11.7°
b = 34.509 (6) Å	µ = 0.08 mm⁻¹
c = 3.9509 (5) Å	T = 298 K
V = 1630.7 (5) Å³	Plate, orange
Z = 4	0.40 × 0.20 × 0.10 mm
F(000) = 696

Data collection top

Siemens P4 diffractometer	R_int = 0.031
Radiation source: X-ray	θ_max = 25.1°, θ_min = 2.4°
Graphite monochromator	h = −14→14
ω scans	k = −41→41
5603 measured reflections	l = −4→4
1469 independent reflections	2 standard reflections every 48 reflections
1032 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0614P)² + 0.1644P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1469 reflections	Δρ_max = 0.16 e Å⁻³
122 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints	Extinction correction: SHELXTL-Plus, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0069 (16)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₃H₁₅N₃	V = 1630.7 (5) Å³
M_r = 333.38	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.960 (2) Å	µ = 0.08 mm⁻¹
b = 34.509 (6) Å	T = 298 K
c = 3.9509 (5) Å	0.40 × 0.20 × 0.10 mm

Data collection top

Siemens P4 diffractometer	R_int = 0.031
5603 measured reflections	2 standard reflections every 48 reflections
1469 independent reflections	intensity decay: 1%
1032 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
1469 reflections	Δρ_min = −0.11 e Å⁻³
122 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.05056 (13)	0.2500	0.0324 (4)	0.0465 (5)
C1	−0.15745 (18)	0.2500	−0.2714 (6)	0.0572 (6)
H1A	−0.2280	0.2500	−0.3703	0.069*
C2	−0.10509 (12)	0.28415 (5)	−0.1980 (4)	0.0539 (4)
H2A	−0.1388	0.3077	−0.2506	0.065*
C3	−0.00108 (11)	0.28327 (4)	−0.0443 (4)	0.0465 (4)
C4	0.05844 (12)	0.32017 (4)	0.0278 (4)	0.0468 (4)
N5	0.00977 (10)	0.35190 (4)	−0.0808 (3)	0.0522 (4)
C6	0.06408 (13)	0.38627 (4)	−0.0411 (4)	0.0522 (4)
C7	0.01369 (16)	0.42018 (5)	−0.1667 (5)	0.0667 (5)
H7A	−0.0563	0.4188	−0.2686	0.080*
C8	0.06583 (19)	0.45476 (5)	−0.1410 (5)	0.0752 (6)
H8A	0.0319	0.4769	−0.2279	0.090*
C9	0.17008 (19)	0.45757 (5)	0.0147 (5)	0.0762 (6)
H9A	0.2049	0.4816	0.0326	0.091*
C10	0.22110 (16)	0.42554 (5)	0.1402 (5)	0.0660 (5)
H10A	0.2907	0.4278	0.2437	0.079*
C11	0.16971 (13)	0.38897 (4)	0.1153 (4)	0.0528 (4)
C12	0.21698 (13)	0.35438 (4)	0.2379 (4)	0.0555 (4)
H12A	0.2859	0.3549	0.3468	0.067*
C13	0.16215 (12)	0.32044 (4)	0.1973 (4)	0.0511 (4)
H13A	0.1925	0.2975	0.2804	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0355 (9)	0.0555 (11)	0.0484 (10)	0.000	0.0022 (8)	0.000
C1	0.0364 (11)	0.0734 (16)	0.0619 (14)	0.000	−0.0071 (11)	0.000
C2	0.0404 (8)	0.0637 (10)	0.0576 (10)	0.0072 (7)	−0.0014 (7)	−0.0021 (8)
C3	0.0361 (7)	0.0586 (9)	0.0448 (8)	0.0043 (7)	0.0045 (6)	−0.0018 (7)
C4	0.0395 (8)	0.0554 (9)	0.0456 (8)	0.0054 (7)	0.0048 (7)	−0.0030 (7)
N5	0.0442 (7)	0.0569 (8)	0.0555 (8)	0.0078 (6)	0.0016 (6)	−0.0002 (7)
C6	0.0506 (9)	0.0563 (10)	0.0498 (9)	0.0089 (8)	0.0066 (7)	−0.0027 (8)
C7	0.0688 (11)	0.0654 (11)	0.0659 (11)	0.0147 (9)	0.0013 (9)	0.0016 (9)
C8	0.0985 (16)	0.0599 (12)	0.0672 (12)	0.0145 (11)	0.0066 (12)	0.0053 (10)
C9	0.0981 (16)	0.0617 (11)	0.0687 (13)	−0.0086 (11)	0.0121 (11)	−0.0025 (10)
C10	0.0672 (11)	0.0673 (11)	0.0635 (11)	−0.0064 (10)	0.0044 (9)	−0.0083 (9)
C11	0.0522 (9)	0.0561 (10)	0.0501 (9)	0.0020 (7)	0.0060 (8)	−0.0062 (8)
C12	0.0443 (8)	0.0648 (11)	0.0575 (10)	0.0031 (8)	−0.0032 (7)	−0.0078 (8)
C13	0.0426 (8)	0.0545 (9)	0.0561 (9)	0.0077 (7)	−0.0033 (7)	−0.0043 (7)

Geometric parameters (Å, º) top

N1—C3ⁱ	1.3383 (16)	C7—C8	1.350 (2)
N1—C3	1.3383 (16)	C7—H7A	0.9300
C1—C2	1.3658 (18)	C8—C9	1.394 (3)
C1—C2ⁱ	1.3658 (18)	C8—H8A	0.9300
C1—H1A	0.9300	C9—C10	1.357 (2)
C2—C3	1.385 (2)	C9—H9A	0.9300
C2—H2A	0.9300	C10—C11	1.407 (2)
C3—C4	1.486 (2)	C10—H10A	0.9300
C4—N5	1.3123 (18)	C11—C12	1.407 (2)
C4—C13	1.410 (2)	C12—C13	1.352 (2)
N5—C6	1.3615 (19)	C12—H12A	0.9300
C6—C7	1.407 (2)	C13—H13A	0.9300
C6—C11	1.410 (2)

C3ⁱ—N1—C3	118.13 (17)	C6—C7—H7A	119.6
C2—C1—C2ⁱ	119.3 (2)	C7—C8—C9	120.52 (18)
C2—C1—H1A	120.3	C7—C8—H8A	119.7
C2ⁱ—C1—H1A	120.3	C9—C8—H8A	119.7
C1—C2—C3	119.07 (15)	C10—C9—C8	120.48 (18)
C1—C2—H2A	120.5	C10—C9—H9A	119.8
C3—C2—H2A	120.5	C8—C9—H9A	119.8
N1—C3—C2	122.20 (14)	C9—C10—C11	120.57 (18)
N1—C3—C4	118.07 (13)	C9—C10—H10A	119.7
C2—C3—C4	119.69 (13)	C11—C10—H10A	119.7
N5—C4—C13	122.69 (14)	C12—C11—C10	124.15 (16)
N5—C4—C3	116.09 (13)	C12—C11—C6	117.07 (14)
C13—C4—C3	121.21 (13)	C10—C11—C6	118.78 (15)
C4—N5—C6	118.54 (13)	C13—C12—C11	119.96 (14)
N5—C6—C7	118.67 (15)	C13—C12—H12A	120.0
N5—C6—C11	122.39 (14)	C11—C12—H12A	120.0
C7—C6—C11	118.92 (15)	C12—C13—C4	119.27 (14)
C8—C7—C6	120.72 (18)	C12—C13—H13A	120.4
C8—C7—H7A	119.6	C4—C13—H13A	120.4

C2ⁱ—C1—C2—C3	−1.4 (3)	C6—C7—C8—C9	−0.8 (3)
C3ⁱ—N1—C3—C2	0.1 (3)	C7—C8—C9—C10	0.5 (3)
C3ⁱ—N1—C3—C4	−177.46 (10)	C8—C9—C10—C11	0.0 (3)
C1—C2—C3—N1	0.6 (3)	C9—C10—C11—C12	179.83 (16)
C1—C2—C3—C4	178.17 (16)	C9—C10—C11—C6	−0.3 (3)
N1—C3—C4—N5	173.63 (14)	N5—C6—C11—C12	−1.3 (2)
C2—C3—C4—N5	−4.0 (2)	C7—C6—C11—C12	179.88 (15)
N1—C3—C4—C13	−5.2 (2)	N5—C6—C11—C10	178.75 (14)
C2—C3—C4—C13	177.17 (14)	C7—C6—C11—C10	0.0 (2)
C13—C4—N5—C6	3.0 (2)	C10—C11—C12—C13	−178.88 (16)
C3—C4—N5—C6	−175.81 (13)	C6—C11—C12—C13	1.2 (2)
C4—N5—C6—C7	178.05 (14)	C11—C12—C13—C4	0.8 (2)
C4—N5—C6—C11	−0.7 (2)	N5—C4—C13—C12	−3.1 (2)
N5—C6—C7—C8	−178.24 (16)	C3—C4—C13—C12	175.65 (14)
C11—C6—C7—C8	0.6 (2)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N1ⁱⁱ	0.93	2.72	3.641 (3)	169

Symmetry code: (ii) x−1/2, −y+1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₁₅N₃
M_r	333.38
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	11.960 (2), 34.509 (6), 3.9509 (5)
V (Å³)	1630.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5603, 1469, 1032
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.02
No. of reflections	1469
No. of parameters	122
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.11

Computer programs: XSCANS (Siemens, 1996), SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N1ⁱ	0.93	2.72	3.641 (3)	168.8

Symmetry code: (i) x−1/2, −y+1/2, −z−1/2.

Acknowledgements

The authors thank FCQ-UANL (Project No. 03-6375-QMT-08-006) and PAICYT-UANL (Project No. CA-1260-06) for supporting this work.

References

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