1-[6-(6-Acetyl­pyridin-2-yl)pyridin-2-yl]ethanone

Dogan, H.Z.; Sengul, A.; Coles, S.J.

doi:10.1107/S160053681101556X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1295

doi:10.1107/S160053681101556X

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1-[6-(6-Acetylpyridin-2-yl)pyridin-2-yl]ethanone

Huseyin Zekeriya Dogan,^a Abdurrahman Sengul ^a ^* and Simon John Coles ^b

^aDepartment of Chemistry, Faculty of Arts and Sciences, Zonguldak Karaelmas University, TR-67100 Zonguldak, Turkey, and ^bSchool of Chemistry, University of Southampton, University Road, Highfield, Southampton SO17 1BJ, England
^*Correspondence e-mail: sengul@karaelmas.edu.tr

(Received 8 March 2011; accepted 25 April 2011; online 7 May 2011)

In the title compound, C₁₄H₁₂N₂O₂, the asymmetric unit comprises one half-molecule with an inversion center between the pyridine rings. The rings are trans coplanar with the acetyl groups deviating slightly from the mean planes, making a dihedral angle of 4.63 (4)°. In the crystal, molecules are linked by weak intermolecular C—H⋯O hydrogen bonds, forming a supramolecular sheet parallel to (100).

Related literature

The compound is of interest with respect to supramolecular chemistry as a precursor for polypyridyl bridging ligands. For related structures, see: Parks et al. (1973 ); Potts et al. (1993 ); Zong et al. (2006 ); Şengül et al. (1998); Agac et al. (2010 ); Iyoda et al. (1990 ); Janiak et al. (1999 ); O'Donnell & Steel (2010 ); Kochel (2005 ). For applications of related structures, see: Parks et al. (1973); Iyoda et al. (1990); Şengül et al. (2009 ); Agac et al. (2010).

Experimental

Crystal data

C₁₄H₁₂N₂O₂
M_r = 240.26
Monoclinic, P 2₁ /c
a = 3.9338 (2) Å
b = 13.8005 (8) Å
c = 10.8728 (6) Å
β = 94.437 (4)°
V = 588.50 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 120 K
0.50 × 0.20 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer with APEXII area detector
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.955, T_max = 0.982
10564 measured reflections
1336 independent reflections
1220 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.105
S = 1.10
1336 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.95	2.56	3.2992 (16)	135
Symmetry code: (i) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101556X/bq2286sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101556X/bq2286Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681101556X/bq2286Isup3.cml

checkCIF report

Comment top

The principles of supramolecular chemistry provide guidelines for the construction of quite complex molecules or constructs from relatively simple components. In this respect, 6,6'-diacetyl-2,2'-bipyridine, acting as a diketone has been widely used as a precursor or building block for the construction of polypyridine bridging ligands [Şengül et al., 2009; Agac et al., 2010; Potts et al., 1993; Zong et al., 2006]. The well established coordination ability of 2,2'-bipyridine suggests that ligands containing multiple pyridine rings joined through their 2,6-positions would be ideal for the self-assembly of mono-, double-, or triple-stranded helicates containing one or more transition-metal cations and producing a variety of coordination geometries and architectures. This area is therefore of interest with respect to supramolecular chemistry as a precursor for polypyridyl bridging ligands (Janiak et al., 1999; Potts et al., 1993; Zong et al., 2006) and derivatives are important materials for the preparation of oximes or other funcionalities (Iyoda et al., 1990; Parks et al., 1973; Agac et al., 2010).

As a continuation of work on the structures of such compounds (Şengül et al., 1998) the title compound derived from the coupling of 6-bromo-2-acetylpyridine is reported herein. The molecule of the title compound (Fig. 1.) possesses a twofold symmetry where each of the pyridyl rings are trans to each other, forming an essentially planar structure. The bond lengths have normal values (Şengül et al., 1998), and are comparable to those observed in similar compounds (Janiak et al., 1999; O'Donnell & Steel, 2010; Kochel, 2005; Şengül et al. 2009).

In the crystal, molecules are linked through intermolecular C-H···O H-bonds (Table 1) to form a supramolecular network parallel to (100) (Fig. 1).

Related literature top

The compound is of interest with respect to supramolecular chemistry as a precursor for polypyridyl bridging ligands. For related structures, see: Parks et al. (1973); Potts et al. (1993); Zong et al. (2006); Şengül et al. (1998); Agac et al. (2010); Iyoda et al. (1990); Janiak et al. (1999); O'Donnell & Steel (2010); Kochel (2005). For applications of related structures, see: Parks et al. (1973); Iyoda et al. (1990); Şengül et al. (2009); Agac et al. (2010).

Experimental top

The title compound was synthesized by the reported method of homocoupling of aryl halides using Ni(II) complex and zinc in the presence of triphenylphosphine by Janiak et al. (1999). The spectroscopic and analytical data are in good agreement with the reported values in literature by Zong et al., 2006; Potts et al., 1993; Agac et al., 2010 and Parks et al., 1973. The solid was crystallized from dichloromethane to afford colourless needless suitable for X-ray diffraction. Mp.: 178.5–179.5 °C. ¹H-NMR (dmso-d₆, δ_p.p.m.): 8.81(d, 2H, J_3,4 = 8 Hz, H3,3'), 8.23(d, 2H, J_5,4 = 7 Hz, H5,5'), 8.07(dd, 2H, J_4,3 = 8.2 Hz, J_4,5 = 1 Hz, H4,4'), 2.79(s, 6H, 2xCH₃). Calc. for C₁₄H₁₂N₂O₂: C, 69,99; H, 5,03; N, 11,66 Found: C,62,54; H, 4,54; N, 11,68%. IR (ATR, ν cm^-1): 3056 (CH_ar), 2990 (CH_al), 1590 (C=O), 1487 and 1437 (C=N and C=C), 1311, 1182, 1120, 1094, 1071, 995, 861, 748, 720. UV-Vis (MeCN, λ_max/nm): 286, 258, 219.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) -x, -y, -z
	Fig. 2. Intermolecular C=O···H contacts forming a supramolecular sheet along the a axis

1-[6-(6-Acetylpyridin-2-yl)pyridin-2-yl]ethanone top

Crystal data top

C₁₄H₁₂N₂O₂	F(000) = 252
M_r = 240.26	D_x = 1.356 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 452 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 3.9338 (2) Å	Cell parameters from 10564 reflections
b = 13.8005 (8) Å	θ = 2.9–27.5°
c = 10.8728 (6) Å	µ = 0.09 mm⁻¹
β = 94.437 (4)°	T = 120 K
V = 588.50 (6) Å³	Rod, colourless
Z = 2	0.50 × 0.20 × 0.20 mm

Data collection top

Bruker–Nonius Kappa CCD diffractometer with APEXII area detector	1336 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1220 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −5→4
T_min = 0.955, T_max = 0.982	k = −17→17
10564 measured reflections	l = −14→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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0431P)² + 0.237P] where P = (F_o² + 2F_c²)/3
1336 reflections	(Δ/σ)_max = 0.001
83 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₁₂N₂O₂	V = 588.50 (6) Å³
M_r = 240.26	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9338 (2) Å	µ = 0.09 mm⁻¹
b = 13.8005 (8) Å	T = 120 K
c = 10.8728 (6) Å	0.50 × 0.20 × 0.20 mm
β = 94.437 (4)°

Data collection top

Bruker–Nonius Kappa CCD diffractometer with APEXII area detector	1336 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	1220 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.982	R_int = 0.034
10564 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.10	Δρ_max = 0.26 e Å⁻³
1336 reflections	Δρ_min = −0.19 e Å⁻³
83 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.4161 (3)	0.54168 (8)	0.46613 (10)	0.0185 (3)
C2	0.4431 (3)	0.63598 (9)	0.51269 (11)	0.0234 (3)
H2	0.5670	0.6485	0.5895	0.028*
C3	0.2863 (3)	0.71096 (9)	0.44508 (12)	0.0277 (3)
H3	0.3018	0.7757	0.4748	0.033*
C4	0.1063 (3)	0.69010 (9)	0.33338 (12)	0.0248 (3)
H4	−0.0011	0.7402	0.2846	0.030*
C5	0.0871 (3)	0.59397 (8)	0.29474 (10)	0.0197 (3)
C6	−0.1175 (3)	0.56675 (9)	0.17703 (11)	0.0216 (3)
C7	−0.1483 (3)	0.46102 (9)	0.14615 (11)	0.0247 (3)
H7A	−0.2969	0.4528	0.0703	0.037*
H7B	−0.2460	0.4266	0.2139	0.037*
H7C	0.0780	0.4346	0.1341	0.037*
N1	0.2396 (2)	0.52066 (7)	0.35884 (9)	0.0190 (2)
O1	−0.2556 (3)	0.62953 (7)	0.11205 (8)	0.0315 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0184 (5)	0.0192 (6)	0.0174 (5)	−0.0012 (4)	−0.0011 (4)	0.0013 (4)
C2	0.0270 (6)	0.0206 (6)	0.0215 (6)	−0.0012 (5)	−0.0047 (5)	−0.0012 (4)
C3	0.0333 (7)	0.0185 (6)	0.0297 (7)	0.0004 (5)	−0.0073 (5)	−0.0017 (5)
C4	0.0275 (6)	0.0199 (6)	0.0259 (6)	0.0018 (5)	−0.0053 (5)	0.0032 (5)
C5	0.0199 (6)	0.0200 (6)	0.0189 (5)	0.0005 (4)	−0.0012 (4)	0.0018 (4)
C6	0.0210 (6)	0.0234 (6)	0.0199 (6)	0.0019 (4)	−0.0019 (4)	0.0016 (4)
C7	0.0258 (6)	0.0245 (6)	0.0225 (6)	0.0006 (5)	−0.0063 (5)	−0.0017 (5)
N1	0.0191 (5)	0.0197 (5)	0.0178 (5)	0.0000 (4)	−0.0014 (4)	0.0016 (4)
O1	0.0384 (6)	0.0282 (5)	0.0259 (5)	0.0068 (4)	−0.0104 (4)	0.0033 (4)

Geometric parameters (Å, º) top

C1—N1	1.3423 (15)	C4—H4	0.9500
C1—C2	1.3975 (16)	C5—N1	1.3433 (14)
C1—C1ⁱ	1.492 (2)	C5—C6	1.5058 (16)
C2—C3	1.3861 (17)	C6—O1	1.2189 (15)
C2—H2	0.9500	C6—C7	1.5000 (17)
C3—C4	1.3878 (17)	C7—H7A	0.9800
C3—H3	0.9500	C7—H7B	0.9800
C4—C5	1.3919 (17)	C7—H7C	0.9800

N1—C1—C2	122.39 (11)	N1—C5—C6	116.16 (10)
N1—C1—C1ⁱ	116.22 (12)	C4—C5—C6	120.48 (10)
C2—C1—C1ⁱ	121.39 (13)	O1—C6—C7	122.48 (11)
C3—C2—C1	119.01 (11)	O1—C6—C5	120.02 (11)
C3—C2—H2	120.5	C7—C6—C5	117.49 (10)
C1—C2—H2	120.5	C6—C7—H7A	109.5
C2—C3—C4	119.03 (11)	C6—C7—H7B	109.5
C2—C3—H3	120.5	H7A—C7—H7B	109.5
C4—C3—H3	120.5	C6—C7—H7C	109.5
C3—C4—C5	118.28 (11)	H7A—C7—H7C	109.5
C3—C4—H4	120.9	H7B—C7—H7C	109.5
C5—C4—H4	120.9	C1—N1—C5	117.92 (10)
N1—C5—C4	123.35 (11)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱⁱ	0.95	2.56	3.2992 (16)	135

Symmetry code: (ii) x+1, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₂
M_r	240.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	3.9338 (2), 13.8005 (8), 10.8728 (6)
β (°)	94.437 (4)
V (Å³)	588.50 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.20 × 0.20

Data collection
Diffractometer	Bruker–Nonius Kappa CCD diffractometer with APEXII area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.955, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	10564, 1336, 1220
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.105, 1.10
No. of reflections	1336
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.19

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.95	2.56	3.2992 (16)	134.8

Symmetry code: (i) x+1, −y+3/2, z+1/2.

Acknowledgements

This work was supported by the research project fund of Zonguldak Karaelmas University (grant No. 2010–13–02–04) and the UK Engineering and Physical Sciences Research Council.

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