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

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ISSN: 2056-9890

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

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 ππ 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[Stephenson, M. D. & Hardie, M. J. (2007). CrystEngComm, 9, 496-502.]); Hou et al. (2008a[Hou, C., Shi, J. M., Shi, W., Cheng, P. & Liu, L. D. (2008a). Dalton Trans. pp. 5970-5976.],b[Hou, C., Shi, J. M., Shi, W., Cheng, P. & Liu, L. D. (2008b). Dalton Trans. pp. 5970-5976.]). For a related structure, see: Rice et al. (2002[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.]).

[Scheme 1]

Experimental

Crystal data
  • C24H18N4O2

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.967, Tmax = 0.986

  • 5242 measured reflections

  • 1913 independent reflections

  • 1334 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 0.143

  • S = 1.02

  • 1913 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

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

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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 ππ stacking interactions involving pyridine rings and symmetry-related benzene rings with the relevant geometry being Cg1···Cg2i = 3.7838 (15) Å, Cg1···Cg2iperp = 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···Cg21perp 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.

Refinement top

All H atoms were placed in in calculated positions and refined as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O).

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
[Figure 1] 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
C24H18N4O2F(000) = 824
Mr = 394.42Dx = 1.337 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1047 reflections
a = 21.017 (3) Åθ = 2.7–22.4°
b = 8.4485 (14) ŵ = 0.09 mm1
c = 13.012 (2) ÅT = 298 K
β = 121.980 (3)°Block, yellow
V = 1959.8 (5) Å30.38 × 0.20 × 0.16 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer
1913 independent reflections
Radiation source: fine-focus sealed tube1334 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ϕ and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2125
Tmin = 0.967, Tmax = 0.986k = 910
5242 measured reflectionsl = 1516
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.063P)2 + 0.6383P]
where P = (Fo2 + 2Fc2)/3
1913 reflections(Δ/σ)max < 0.001
137 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C24H18N4O2V = 1959.8 (5) Å3
Mr = 394.42Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.017 (3) ŵ = 0.09 mm1
b = 8.4485 (14) ÅT = 298 K
c = 13.012 (2) Å0.38 × 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)
Tmin = 0.967, Tmax = 0.986Rint = 0.025
5242 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.02Δρmax = 0.17 e Å3
1913 reflectionsΔρmin = 0.13 e Å3
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
xyzUiso*/Ueq
C10.12783 (13)0.8486 (3)0.1341 (2)0.0702 (6)
C20.18125 (15)0.9514 (3)0.1412 (3)0.0917 (8)
H20.22630.96480.21470.110*
C30.16874 (18)1.0339 (3)0.0413 (3)0.0928 (9)
H30.20521.10290.04800.111*
C40.10274 (19)1.0156 (3)0.0687 (3)0.0867 (8)
H40.09461.07060.13660.104*
C50.04893 (14)0.9146 (3)0.0766 (2)0.0709 (6)
H50.00420.90230.15070.085*
C60.05958 (12)0.8302 (2)0.02338 (19)0.0567 (5)
C70.00038 (11)0.7307 (2)0.01146 (18)0.0553 (5)
H70.04350.72080.06420.066*
C80.05332 (10)0.5646 (2)0.09104 (17)0.0513 (5)
C90.12535 (12)0.5543 (3)0.01036 (19)0.0666 (6)
H90.13790.60770.08120.080*
C100.17782 (13)0.4647 (3)0.0050 (2)0.0723 (6)
H100.22630.45630.07220.087*
C110.15804 (12)0.3878 (3)0.1000 (2)0.0681 (6)
H110.19420.32690.10190.082*
C120.03848 (11)0.4816 (2)0.19397 (17)0.0516 (5)
N10.00610 (9)0.65566 (19)0.10122 (14)0.0549 (4)
N20.08982 (9)0.3951 (2)0.20004 (15)0.0621 (5)
O10.14272 (9)0.7671 (3)0.23344 (14)0.0978 (6)
H10.10530.71760.21900.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0733 (15)0.0801 (15)0.0708 (16)0.0074 (12)0.0475 (13)0.0130 (12)
C20.0844 (19)0.105 (2)0.102 (2)0.0209 (15)0.0600 (17)0.0259 (17)
C30.107 (2)0.0738 (17)0.142 (3)0.0137 (15)0.097 (2)0.0202 (18)
C40.121 (2)0.0668 (16)0.119 (2)0.0108 (15)0.096 (2)0.0133 (15)
C50.0889 (16)0.0662 (14)0.0815 (16)0.0107 (12)0.0614 (14)0.0075 (12)
C60.0717 (14)0.0539 (12)0.0624 (13)0.0046 (9)0.0477 (12)0.0032 (10)
C70.0638 (12)0.0581 (12)0.0522 (12)0.0057 (9)0.0363 (10)0.0029 (9)
C80.0561 (12)0.0530 (11)0.0510 (12)0.0017 (9)0.0327 (10)0.0056 (9)
C90.0669 (14)0.0753 (15)0.0553 (13)0.0011 (11)0.0308 (11)0.0047 (11)
C100.0587 (13)0.0854 (16)0.0628 (14)0.0059 (11)0.0255 (11)0.0063 (12)
C110.0602 (13)0.0752 (15)0.0751 (15)0.0104 (11)0.0401 (12)0.0098 (12)
C120.0569 (12)0.0538 (11)0.0544 (12)0.0000 (9)0.0364 (9)0.0069 (9)
N10.0613 (10)0.0588 (10)0.0524 (10)0.0019 (8)0.0353 (8)0.0009 (8)
N20.0619 (11)0.0686 (11)0.0634 (11)0.0071 (9)0.0385 (9)0.0041 (9)
O10.0857 (13)0.1405 (17)0.0616 (11)0.0203 (11)0.0352 (9)0.0015 (10)
Geometric parameters (Å, º) top
C1—O11.347 (3)C7—H70.9300
C1—C21.383 (3)C8—C91.387 (3)
C1—C61.403 (3)C8—C121.393 (3)
C2—C31.372 (4)C8—N11.412 (2)
C2—H20.9300C9—C101.369 (3)
C3—C41.376 (4)C9—H90.9300
C3—H30.9300C10—C111.364 (3)
C4—C51.377 (3)C10—H100.9300
C4—H40.9300C11—N21.333 (3)
C5—C61.393 (3)C11—H110.9300
C5—H50.9300C12—N21.340 (2)
C6—C71.440 (3)C12—C12i1.498 (4)
C7—N11.278 (2)O1—H10.8200
O1—C1—C2119.3 (2)C6—C7—H7118.9
O1—C1—C6121.3 (2)C9—C8—C12117.31 (18)
C2—C1—C6119.4 (2)C9—C8—N1126.07 (18)
C3—C2—C1120.9 (3)C12—C8—N1116.59 (17)
C3—C2—H2119.5C10—C9—C8119.3 (2)
C1—C2—H2119.5C10—C9—H9120.4
C2—C3—C4120.7 (3)C8—C9—H9120.4
C2—C3—H3119.7C11—C10—C9119.2 (2)
C4—C3—H3119.7C11—C10—H10120.4
C3—C4—C5118.9 (3)C9—C10—H10120.4
C3—C4—H4120.6N2—C11—C10123.8 (2)
C5—C4—H4120.6N2—C11—H11118.1
C4—C5—C6121.9 (2)C10—C11—H11118.1
C4—C5—H5119.1N2—C12—C8123.65 (18)
C6—C5—H5119.1N2—C12—C12i115.52 (18)
C5—C6—C1118.2 (2)C8—C12—C12i120.82 (18)
C5—C6—C7119.7 (2)C7—N1—C8122.31 (17)
C1—C6—C7122.05 (19)C11—N2—C12116.79 (18)
N1—C7—C6122.25 (19)C1—O1—H1109.5
N1—C7—H7118.9
O1—C1—C2—C3178.6 (2)N1—C8—C9—C10177.84 (18)
C6—C1—C2—C30.8 (4)C8—C9—C10—C110.1 (3)
C1—C2—C3—C40.3 (4)C9—C10—C11—N20.5 (3)
C2—C3—C4—C50.8 (4)C9—C8—C12—N20.7 (3)
C3—C4—C5—C60.2 (3)N1—C8—C12—N2177.33 (16)
C4—C5—C6—C10.9 (3)C9—C8—C12—C12i177.85 (16)
C4—C5—C6—C7177.60 (19)N1—C8—C12—C12i4.1 (2)
O1—C1—C6—C5178.0 (2)C6—C7—N1—C8176.66 (16)
C2—C1—C6—C51.4 (3)C9—C8—N1—C75.5 (3)
O1—C1—C6—C73.5 (3)C12—C8—N1—C7176.58 (17)
C2—C1—C6—C7177.06 (19)C10—C11—N2—C121.1 (3)
C5—C6—C7—N1177.25 (18)C8—C12—N2—C111.3 (3)
C1—C6—C7—N11.2 (3)C12i—C12—N2—C11177.40 (16)
C12—C8—C9—C100.0 (3)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.892.619 (2)147

Experimental details

Crystal data
Chemical formulaC24H18N4O2
Mr394.42
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)21.017 (3), 8.4485 (14), 13.012 (2)
β (°) 121.980 (3)
V3)1959.8 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.38 × 0.20 × 0.16
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.967, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
5242, 1913, 1334
Rint0.025
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.143, 1.02
No. of reflections1913
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.13

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.892.619 (2)147.0
 

References

First citationBruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHou, C., Shi, J. M., Shi, W., Cheng, P. & Liu, L. D. (2008a). Dalton Trans. pp. 5970–5976.  Web of Science CSD CrossRef Google Scholar
First citationHou, C., Shi, J. M., Shi, W., Cheng, P. & Liu, L. D. (2008b). Dalton Trans. pp. 5970–5976.  Web of Science CSD CrossRef Google Scholar
First citationRice, 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
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStephenson, M. D. & Hardie, M. J. (2007). CrystEngComm, 9, 496–502.  Web of Science CSD CrossRef CAS Google Scholar

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