2,2′-[(2,2′-Bipyridine-3,3′-di­yl)bis­(nitrilo­methyl­idyne)]diphenol

Li, H.L.

doi:10.1107/S1600536809032346

organic compounds

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doi:10.1107/S1600536809032346

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2,2′-[(2,2′-Bipyridine-3,3′-diyl)bis(nitrilomethylidyne)]diphenol

Hong Liang Li ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: hongliangl1968@yahoo.com.cn

(Received 10 August 2009; accepted 15 August 2009; online 29 August 2009)

The title molecule, C₂₄H₁₈N₄O₂, lies on a twofold rotation axis with a dihedral angle of 73.7 (1)° between the mean planes of the symmetry-related pyridine rings. The dihedral angle between unique benzene and pyridine rings is 8.0 (1)°. An intramolecular O—H⋯N hydrogen bond may influence the molecular conformation. In the crystal structure, there are weak π–π stacking interactions with a centroid–centroid distance of 3.7838 (15) Å.

Related literature

For background to the use of 2,2-bipyridine derivatives in coordination chemistry, see: Stephenson & Hardie (2007 ); Hou et al. (2008a ,b ). For a related structure, see: Rice et al. (2002 ).

Experimental

Crystal data

C₂₄H₁₈N₄O₂
M_r = 394.42
Monoclinic, C 2/c
a = 21.017 (3) Å
b = 8.4485 (14) Å
c = 13.012 (2) Å
β = 121.980 (3)°
V = 1959.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.38 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.967, T_max = 0.986
5242 measured reflections
1913 independent reflections
1334 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.143
S = 1.02
1913 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.89	2.619 (2)	147

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536809032346/lh2878sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032346/lh2878Isup2.hkl

checkCIF report

Comment top

Derivatives of 2,2-bipyridine are useful ligands and play an important role in modern coordination chemistry (Stephenson & Hardie, 2007; Hou et al., 2008a,b). The title compound (I) was synthesized as a potential ligand and its crystal structure is reported herein. The molecular structure of (I) is shown in Fig. 1. The molecule lies on a twofold rotation axis with dihedral angle of 73.7 (1)° between the mean planes of the symmetry related pyridine rings. In the related crystal structure of 3,3'-diamino-2,2'-dipyridine which has already been reported (Rice et al. 2002) the molecule lies on an inversion center and the mean planes of the two pyridine are essentially co-planar. The large deviation from planarity in (I) can be expected in terms of steric relief with respect to the bulky 2-(methylimino)phenol substituents. An intramolecular O—H···N hydrogen bond may influence the molecular conformation. In the crystal structure, there is a weak π–π stacking interactions involving pyridine rings and symmetry-related benzene rings with the relevant geometry being Cg1···Cg2ⁱ = 3.7838 (15) Å, Cg1···Cg2ⁱ_perp = 3.353 Å and α = 7.97° [symmetry code: (i) -x, 1-y, -z; Cg1 and Cg2 are the centroids of the C8—C12/N2 ring and C1—C6 ring, respectively; Cg1···Cg2¹_perp is the perpendicular distance from ring Cg1 to ring Cg2ⁱ; α is the dihedral between ring plane Cg1 and ring plane Cg2ⁱ].

Related literature top

For background to the use of 2,2-bipyridine derivatives in coordination chemistry, see: Stephenson & Hardie (2007); Hou et al. (2008a,b). For a related structure, see: Rice et al. (2002).

Experimental top

A 35 ml methanol solution of 3,3'-diamino-2,2'-dipyridine (1.03 g, 5.53 mmol) was added to salicylaldehyde (1.40 g, 11.46 mmol) and the mixture was stirred and refluxed for 5 h. Yellow single crystals were obtained after the filtrate had been allowed to stand at room temperature for three weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 with displacement ellipsoids drawn at the 30% probability level. The dashed lines indicate hydrogen bonds and the unlabeled atoms are related by the symmetry code (-x, y, -z+1/2).

2,2'-[(2,2'-Bipyridine-3,3'-diyl)bis(nitrilomethylidyne)]diphenol top

Crystal data top

C₂₄H₁₈N₄O₂	F(000) = 824
M_r = 394.42	D_x = 1.337 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1047 reflections
a = 21.017 (3) Å	θ = 2.7–22.4°
b = 8.4485 (14) Å	µ = 0.09 mm⁻¹
c = 13.012 (2) Å	T = 298 K
β = 121.980 (3)°	Block, yellow
V = 1959.8 (5) Å³	0.38 × 0.20 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1913 independent reflections
Radiation source: fine-focus sealed tube	1334 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→25
T_min = 0.967, T_max = 0.986	k = −9→10
5242 measured reflections	l = −15→16

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.063P)² + 0.6383P] where P = (F_o² + 2F_c²)/3
1913 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₄H₁₈N₄O₂	V = 1959.8 (5) Å³
M_r = 394.42	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.017 (3) Å	µ = 0.09 mm⁻¹
b = 8.4485 (14) Å	T = 298 K
c = 13.012 (2) Å	0.38 × 0.20 × 0.16 mm
β = 121.980 (3)°

Data collection top

Bruker SMART CCD diffractometer	1913 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1334 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.986	R_int = 0.025
5242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.02	Δρ_max = 0.17 e Å⁻³
1913 reflections	Δρ_min = −0.13 e Å⁻³
137 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	0.12783 (13)	0.8486 (3)	0.1341 (2)	0.0702 (6)
C2	0.18125 (15)	0.9514 (3)	0.1412 (3)	0.0917 (8)
H2	0.2263	0.9648	0.2147	0.110*
C3	0.16874 (18)	1.0339 (3)	0.0413 (3)	0.0928 (9)
H3	0.2052	1.1029	0.0480	0.111*
C4	0.10274 (19)	1.0156 (3)	−0.0687 (3)	0.0867 (8)
H4	0.0946	1.0706	−0.1366	0.104*
C5	0.04893 (14)	0.9146 (3)	−0.0766 (2)	0.0709 (6)
H5	0.0042	0.9023	−0.1507	0.085*
C6	0.05958 (12)	0.8302 (2)	0.02338 (19)	0.0567 (5)
C7	0.00038 (11)	0.7307 (2)	0.01146 (18)	0.0553 (5)
H7	−0.0435	0.7208	−0.0642	0.066*
C8	−0.05332 (10)	0.5646 (2)	0.09104 (17)	0.0513 (5)
C9	−0.12535 (12)	0.5543 (3)	−0.01036 (19)	0.0666 (6)
H9	−0.1379	0.6077	−0.0812	0.080*
C10	−0.17782 (13)	0.4647 (3)	−0.0050 (2)	0.0723 (6)
H10	−0.2263	0.4563	−0.0722	0.087*
C11	−0.15804 (12)	0.3878 (3)	0.1000 (2)	0.0681 (6)
H11	−0.1942	0.3269	0.1019	0.082*
C12	−0.03848 (11)	0.4816 (2)	0.19397 (17)	0.0516 (5)
N1	0.00610 (9)	0.65566 (19)	0.10122 (14)	0.0549 (4)
N2	−0.08982 (9)	0.3951 (2)	0.20004 (15)	0.0621 (5)
O1	0.14272 (9)	0.7671 (3)	0.23344 (14)	0.0978 (6)
H1	0.1053	0.7176	0.2190	0.147*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0733 (15)	0.0801 (15)	0.0708 (16)	−0.0074 (12)	0.0475 (13)	−0.0130 (12)
C2	0.0844 (19)	0.105 (2)	0.102 (2)	−0.0209 (15)	0.0600 (17)	−0.0259 (17)
C3	0.107 (2)	0.0738 (17)	0.142 (3)	−0.0137 (15)	0.097 (2)	−0.0202 (18)
C4	0.121 (2)	0.0668 (16)	0.119 (2)	0.0108 (15)	0.096 (2)	0.0133 (15)
C5	0.0889 (16)	0.0662 (14)	0.0815 (16)	0.0107 (12)	0.0614 (14)	0.0075 (12)
C6	0.0717 (14)	0.0539 (12)	0.0624 (13)	0.0046 (9)	0.0477 (12)	−0.0032 (10)
C7	0.0638 (12)	0.0581 (12)	0.0522 (12)	0.0057 (9)	0.0363 (10)	−0.0029 (9)
C8	0.0561 (12)	0.0530 (11)	0.0510 (12)	0.0017 (9)	0.0327 (10)	−0.0056 (9)
C9	0.0669 (14)	0.0753 (15)	0.0553 (13)	0.0011 (11)	0.0308 (11)	0.0047 (11)
C10	0.0587 (13)	0.0854 (16)	0.0628 (14)	−0.0059 (11)	0.0255 (11)	−0.0063 (12)
C11	0.0602 (13)	0.0752 (15)	0.0751 (15)	−0.0104 (11)	0.0401 (12)	−0.0098 (12)
C12	0.0569 (12)	0.0538 (11)	0.0544 (12)	0.0000 (9)	0.0364 (9)	−0.0069 (9)
N1	0.0613 (10)	0.0588 (10)	0.0524 (10)	0.0019 (8)	0.0353 (8)	0.0009 (8)
N2	0.0619 (11)	0.0686 (11)	0.0634 (11)	−0.0071 (9)	0.0385 (9)	−0.0041 (9)
O1	0.0857 (13)	0.1405 (17)	0.0616 (11)	−0.0203 (11)	0.0352 (9)	0.0015 (10)

Geometric parameters (Å, º) top

C1—O1	1.347 (3)	C7—H7	0.9300
C1—C2	1.383 (3)	C8—C9	1.387 (3)
C1—C6	1.403 (3)	C8—C12	1.393 (3)
C2—C3	1.372 (4)	C8—N1	1.412 (2)
C2—H2	0.9300	C9—C10	1.369 (3)
C3—C4	1.376 (4)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.364 (3)
C4—C5	1.377 (3)	C10—H10	0.9300
C4—H4	0.9300	C11—N2	1.333 (3)
C5—C6	1.393 (3)	C11—H11	0.9300
C5—H5	0.9300	C12—N2	1.340 (2)
C6—C7	1.440 (3)	C12—C12ⁱ	1.498 (4)
C7—N1	1.278 (2)	O1—H1	0.8200

O1—C1—C2	119.3 (2)	C6—C7—H7	118.9
O1—C1—C6	121.3 (2)	C9—C8—C12	117.31 (18)
C2—C1—C6	119.4 (2)	C9—C8—N1	126.07 (18)
C3—C2—C1	120.9 (3)	C12—C8—N1	116.59 (17)
C3—C2—H2	119.5	C10—C9—C8	119.3 (2)
C1—C2—H2	119.5	C10—C9—H9	120.4
C2—C3—C4	120.7 (3)	C8—C9—H9	120.4
C2—C3—H3	119.7	C11—C10—C9	119.2 (2)
C4—C3—H3	119.7	C11—C10—H10	120.4
C3—C4—C5	118.9 (3)	C9—C10—H10	120.4
C3—C4—H4	120.6	N2—C11—C10	123.8 (2)
C5—C4—H4	120.6	N2—C11—H11	118.1
C4—C5—C6	121.9 (2)	C10—C11—H11	118.1
C4—C5—H5	119.1	N2—C12—C8	123.65 (18)
C6—C5—H5	119.1	N2—C12—C12ⁱ	115.52 (18)
C5—C6—C1	118.2 (2)	C8—C12—C12ⁱ	120.82 (18)
C5—C6—C7	119.7 (2)	C7—N1—C8	122.31 (17)
C1—C6—C7	122.05 (19)	C11—N2—C12	116.79 (18)
N1—C7—C6	122.25 (19)	C1—O1—H1	109.5
N1—C7—H7	118.9

O1—C1—C2—C3	178.6 (2)	N1—C8—C9—C10	−177.84 (18)
C6—C1—C2—C3	−0.8 (4)	C8—C9—C10—C11	0.1 (3)
C1—C2—C3—C4	−0.3 (4)	C9—C10—C11—N2	0.5 (3)
C2—C3—C4—C5	0.8 (4)	C9—C8—C12—N2	−0.7 (3)
C3—C4—C5—C6	−0.2 (3)	N1—C8—C12—N2	177.33 (16)
C4—C5—C6—C1	−0.9 (3)	C9—C8—C12—C12ⁱ	177.85 (16)
C4—C5—C6—C7	177.60 (19)	N1—C8—C12—C12ⁱ	−4.1 (2)
O1—C1—C6—C5	−178.0 (2)	C6—C7—N1—C8	176.66 (16)
C2—C1—C6—C5	1.4 (3)	C9—C8—N1—C7	−5.5 (3)
O1—C1—C6—C7	3.5 (3)	C12—C8—N1—C7	176.58 (17)
C2—C1—C6—C7	−177.06 (19)	C10—C11—N2—C12	−1.1 (3)
C5—C6—C7—N1	−177.25 (18)	C8—C12—N2—C11	1.3 (3)
C1—C6—C7—N1	1.2 (3)	C12ⁱ—C12—N2—C11	−177.40 (16)
C12—C8—C9—C10	0.0 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.89	2.619 (2)	147

Experimental details

Crystal data
Chemical formula	C₂₄H₁₈N₄O₂
M_r	394.42
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	21.017 (3), 8.4485 (14), 13.012 (2)
β (°)	121.980 (3)
V (Å³)	1959.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.38 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.967, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	5242, 1913, 1334
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.143, 1.02
No. of reflections	1913
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.89	2.619 (2)	147.0

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hou, C., Shi, J. M., Shi, W., Cheng, P. & Liu, L. D. (2008a). Dalton Trans. pp. 5970–5976. Web of Science CSD CrossRef Google Scholar
Hou, C., Shi, J. M., Shi, W., Cheng, P. & Liu, L. D. (2008b). Dalton Trans. pp. 5970–5976. Web of Science CSD CrossRef Google Scholar
Rice, C. R., Onions, S., Vidal, N., Wallis, J. D., Senna, M.-C., Pilkington, M. & Stoeckli-Evans, H. (2002). Eur. J. Inorg. Chem. pp. 1985–1997. CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stephenson, M. D. & Hardie, M. J. (2007). CrystEngComm, 9, 496–502. Web of Science CSD CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2290

doi:10.1107/S1600536809032346

Open

access