(2-Pyrid­yl)[5-(2-pyridyl­carbon­yl)-2-pyrid­yl]methanone

Abstract

In the centrosymmetric title compound, C₁₇H₁₁N₃O₂, the dihedral angle between the central and pendant pyridyl rings is 50.29 (9)°. In the crystal, mol­ecules stack along the a axis by π–π inter­actions between the pyridine rings with centroid–centroid distances of 3.845 (2) Å. The N atom and one of the C atoms of the central ring are disordered by symmetry.

Related literature

For studies on other pyridinyl-based methanone species, see: Papaefstathiou & Perlepes (2002 ▶); Dendrinou-Samara et al. (2003 ▶); Crowder et al. (2004 ▶); Chen et al. (2005 ▶); Wan et al. (2008 ▶).

Experimental

Crystal data

• C₁₇H₁₁N₃O₂

• M _r = 289.30

• Triclinic,

• a = 3.8453 (13) Å

• b = 8.447 (3) Å

• c = 11.202 (3) Å

• α = 108.672 (6)°

• β = 97.251 (6)°

• γ = 99.772 (6)°

• V = 333.29 (19) ų

• Z = 1

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 293 K

• 0.60 × 0.50 × 0.29 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.622, T _max = 1.000

• 2301 measured reflections

• 1623 independent reflections

• 1198 reflections with I > 2σ(I)

• R _int = 0.016

Refinement

• R[F ² > 2σ(F ²)] = 0.058

• wR(F ²) = 0.177

• S = 1.07

• 1623 reflections

• 100 parameters

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Di-2-pyridylmethanone has attracted great interest in recent years as it can exist in various forms in stabilizing its metal complexes, including its neat ketone form, singly and doubly deprotonated gem-diol forms, as well as the monoanion of its hemiacetal form (Papaefstathiou et al., 2002; Dendrinou-Samara et al., 2003; Crowder et al., 2004). Therefore, homolog compounds such as 2,6-pyridinediylbis(2-pyridyl)methanone (Chen et al., 2005) and 2,6-pyridinediylbis(3-pyridyl)methanone (Wan et al., 2008) were also synthesized and characterized.

In the present study, a new member of this family, namely 2,5-pyridinediylbis(2-pyridyl)methanone (C₁₇H₁₁N₃O₂), is reported. X-ray diffraction analysis shows that the N2 and C9 atoms of the 2,5-pyridinediyl ring have an equal occupancy at the same site. Thus the molecule is centrosymmetric with two 2-pyridyl methanone groups bonding to the 2,5-pyridinediyl ring at the 2 and 5 positions, respectively. The 2-pyridyl and the center 2,5-pyridinediyl rings exhibit a dihedral angle of 50.29 (9)° (Fig. 1). Along the a axis, the packing between the molecules is provided by weak un-covalent interaction only: /p-electron···/p-electron ring interaction. The distance between the centroids of the proximate pyridyl rings equals 3.845 (2) Å, as shown in Fig. 2.

Experimental

The preparation of the title compound followed the procedure previously developed for 2,6-pyridinediylbis(3-pyridyl)methanone (Wan et al., 2008).The crude product was extracted with chloroform, and the combined organic extract was dried over anhydrous sodium sulfate and finally concentrated in vacuo to give a brown oil. Further purification by chromatography on silica gel (R_f= 0.44, eluent: ether acetate/dichloromethane = 1:6, v/v), giving 2.96 g of light yellow powder of 2,5-pyridinediylbis(2-pyridyl)methanone in 41% yield; m.p. 108-110°C; The yellow crystals of the title compound having a average 0.40 × 0.30 × 0.20 mm dimension were obtained by slow evaporation from its solution of dichloromethane/N,N-dimethylformamide 1/1 (v/v).

Refinement

The hydrogen atoms were placed in idealized positions and allowed to ride on the relevant carbon atoms, with C—H = 0.93 Å and Uĩso~(H) = 1.2U~eq~(C).

Figures

Fig. 1.

The atom-numbering scheme of the title compound C17H11N3O2. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as sticks of arbitrary radii. Symmetry code: i -x + 2, -y + 2, -z.

Fig. 2.

The packing illustration of the title compound, C17H11N3O2. The red-dashed lines indicate weak π···π stacking interactions.

Crystal data

C17H11N3O2	Z = 1
Mr = 289.30	F(000) = 150
Triclinic, P1	Dx = 1.441 Mg m−3
Hall symbol: -P 1	Melting point: 401 K
a = 3.8453 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.447 (3) Å	Cell parameters from 230 reflections
c = 11.202 (3) Å	θ = 1.9–28.1°
α = 108.672 (6)°	µ = 0.10 mm−1
β = 97.251 (6)°	T = 293 K
γ = 99.772 (6)°	Block, yellow
V = 333.29 (19) Å3	0.60 × 0.50 × 0.29 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1623 independent reflections
Radiation source: fine-focus sealed tube	1198 reflections with I > 2σ(I)
graphite	Rint = 0.016
ω–scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan SADABS (Bruker, 2007)	h = −5→4
Tmin = 0.622, Tmax = 1.000	k = −11→11
2301 measured reflections	l = −12→14

Refinement

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.096P)2 + 0.0878P] where P = (Fo2 + 2Fc2)/3
1623 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.3180 (5)	1.09147 (19)	0.33644 (14)	0.0620 (6)
N1	0.7459 (5)	0.6838 (2)	0.16816 (16)	0.0402 (4)
N2	0.9591 (5)	1.1260 (2)	0.10902 (16)	0.0377 (4)	0.50
C9	0.9591 (5)	1.1260 (2)	0.10902 (16)	0.0377 (4)	0.50
H9A	0.9331	1.2127	0.1798	0.045*	0.50
C1	0.9713 (5)	0.8073 (2)	0.26845 (17)	0.0339 (4)
C2	1.0530 (6)	0.7939 (3)	0.38842 (19)	0.0435 (5)
H2A	1.2108	0.8826	0.4556	0.052*
C3	0.8934 (7)	0.6452 (3)	0.4057 (2)	0.0517 (6)
H3A	0.9378	0.6331	0.4855	0.062*
C4	0.6689 (7)	0.5157 (3)	0.3033 (2)	0.0524 (6)
H4A	0.5633	0.4134	0.3120	0.063*
C5	0.6028 (6)	0.5402 (3)	0.1870 (2)	0.0485 (6)
H5A	0.4502	0.4519	0.1181	0.058*
C6	1.1320 (5)	0.9691 (2)	0.24786 (17)	0.0372 (5)
C7	1.0544 (5)	0.9809 (2)	0.11607 (17)	0.0333 (4)
C8	1.0969 (5)	0.8553 (2)	0.00732 (18)	0.0369 (5)
H8A	1.1642	0.7573	0.0141	0.044*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0862 (13)	0.0422 (8)	0.0381 (8)	−0.0157 (8)	−0.0097 (8)	0.0113 (7)
N1	0.0422 (10)	0.0355 (8)	0.0394 (9)	−0.0001 (7)	0.0059 (7)	0.0136 (7)
N2	0.0467 (11)	0.0295 (8)	0.0341 (9)	0.0035 (7)	0.0096 (7)	0.0092 (7)
C9	0.0467 (11)	0.0295 (8)	0.0341 (9)	0.0035 (7)	0.0096 (7)	0.0092 (7)
C1	0.0360 (10)	0.0330 (9)	0.0334 (9)	0.0065 (7)	0.0077 (7)	0.0128 (7)
C2	0.0538 (13)	0.0404 (10)	0.0373 (10)	0.0106 (9)	0.0065 (9)	0.0157 (8)
C3	0.0712 (16)	0.0510 (12)	0.0471 (12)	0.0209 (11)	0.0180 (11)	0.0299 (10)
C4	0.0632 (15)	0.0379 (10)	0.0671 (15)	0.0110 (10)	0.0239 (12)	0.0291 (10)
C5	0.0511 (13)	0.0355 (10)	0.0534 (13)	−0.0015 (9)	0.0097 (10)	0.0140 (9)
C6	0.0421 (11)	0.0328 (9)	0.0326 (9)	0.0012 (8)	0.0041 (8)	0.0108 (7)
C7	0.0333 (10)	0.0298 (8)	0.0335 (9)	−0.0016 (7)	0.0047 (7)	0.0116 (7)
C8	0.0418 (11)	0.0302 (8)	0.0380 (10)	0.0041 (7)	0.0075 (8)	0.0132 (7)

Geometric parameters (Å, °)

O1—C6	1.216 (2)	C3—C4	1.372 (3)
N1—C5	1.336 (3)	C3—H3A	0.9300
N1—C1	1.341 (2)	C4—C5	1.383 (3)
N2—C8i	1.358 (2)	C4—H4A	0.9300
N2—C7	1.360 (3)	C5—H5A	0.9300
N2—H9A	0.9207	C6—C7	1.507 (2)
C1—C2	1.386 (3)	C7—C8	1.385 (3)
C1—C6	1.501 (3)	C8—C9i	1.358 (2)
C2—C3	1.385 (3)	C8—N2i	1.358 (2)
C2—H2A	0.9300	C8—H8A	0.9300
C5—N1—C1	116.84 (17)	C5—C4—H4A	120.6
C8i—N2—C7	118.59 (16)	N1—C5—C4	123.62 (19)
C8i—N2—H9A	118.5	N1—C5—H5A	118.2
C7—N2—H9A	123.0	C4—C5—H5A	118.2
N1—C1—C2	123.47 (17)	O1—C6—C1	120.89 (17)
N1—C1—C6	117.03 (16)	O1—C6—C7	119.68 (16)
C2—C1—C6	119.48 (17)	C1—C6—C7	119.42 (15)
C3—C2—C1	118.27 (19)	N2—C7—C8	120.92 (17)
C3—C2—H2A	120.9	N2—C7—C6	116.89 (16)
C1—C2—H2A	120.9	C8—C7—C6	122.09 (16)
C4—C3—C2	119.06 (19)	C9i—C8—C7	120.49 (17)
C4—C3—H3A	120.5	N2i—C8—C7	120.49 (17)
C2—C3—H3A	120.5	C9i—C8—H8A	119.8
C3—C4—C5	118.71 (18)	N2i—C8—H8A	119.8
C3—C4—H4A	120.6	C7—C8—H8A	119.8
C5—N1—C1—C2	−1.5 (3)	C2—C1—C6—C7	177.66 (17)
C5—N1—C1—C6	−179.82 (19)	C8i—N2—C7—C8	0.5 (3)
N1—C1—C2—C3	0.0 (3)	C8i—N2—C7—C6	177.03 (17)
C6—C1—C2—C3	178.27 (19)	O1—C6—C7—N2	−45.2 (3)
C1—C2—C3—C4	1.6 (3)	C1—C6—C7—N2	133.4 (2)
C2—C3—C4—C5	−1.6 (4)	O1—C6—C7—C8	131.2 (2)
C1—N1—C5—C4	1.5 (3)	C1—C6—C7—C8	−50.2 (3)
C3—C4—C5—N1	0.0 (4)	N2—C7—C8—C9i	−0.5 (3)
N1—C1—C6—O1	174.7 (2)	C6—C7—C8—C9i	−176.85 (17)
C2—C1—C6—O1	−3.7 (3)	N2—C7—C8—N2i	−0.5 (3)
N1—C1—C6—C7	−4.0 (3)	C6—C7—C8—N2i	−176.85 (17)

Symmetry codes: (i) −x+2, −y+2, −z.