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

Qiang, H.; Zhang, F.; Wang, Z.

doi:10.1107/S1600536810033957

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2632

doi:10.1107/S1600536810033957

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

Hong Qiang,^a ^* Fan Zhang ^a and Zi-jia Wang ^a

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: qiang-hong@163.com

(Received 25 July 2010; accepted 23 August 2010; online 25 September 2010)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.058
wR(F²) = 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810033957/jj2048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810033957/jj2048Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker 2007); cell refinement: APEX2 and SAINT (Bruker 2007); data reduction: SAINT (Bruker 2007); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	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.

2,5-pyridinediylbis(2-pyridinyl)methanone top

Crystal data top

C₁₇H₁₁N₃O₂	Z = 1
M_r = 289.30	F(000) = 150
Triclinic, P1	D_x = 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 top

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

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.177	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.096P)² + 0.0878P] where P = (F_o² + 2F_c²)/3
1623 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₇H₁₁N₃O₂	γ = 99.772 (6)°
M_r = 289.30	V = 333.29 (19) Å³
Triclinic, P1	Z = 1
a = 3.8453 (13) Å	Mo Kα radiation
b = 8.447 (3) Å	µ = 0.10 mm⁻¹
c = 11.202 (3) Å	T = 293 K
α = 108.672 (6)°	0.60 × 0.50 × 0.29 mm
β = 97.251 (6)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1623 independent reflections
Absorption correction: multi-scan SADABS (Bruker, 2007)	1198 reflections with I > 2σ(I)
T_min = 0.622, T_max = 1.000	R_int = 0.016
2301 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.07	Δρ_max = 0.31 e Å⁻³
1623 reflections	Δρ_min = −0.26 e Å⁻³
100 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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, º) top

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 code: (i) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₁N₃O₂
M_r	289.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	3.8453 (13), 8.447 (3), 11.202 (3)
α, β, γ (°)	108.672 (6), 97.251 (6), 99.772 (6)
V (Å³)	333.29 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.60 × 0.50 × 0.29

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan SADABS (Bruker, 2007)
T_min, T_max	0.622, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2301, 1623, 1198
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.177, 1.07
No. of reflections	1623
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.26

Computer programs: APEX2 (Bruker 2007), APEX2 and SAINT (Bruker 2007), SAINT (Bruker 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors are grateful for financial support from the Science and Technology program, Beijing Municipal Education Commission.

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