Redetermination of 4-cyano­pyridine N-oxide

Moreno-Fuquen, R.; Arana, C.; De Simone, C.A.

doi:10.1107/S1600536812036690

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2805

doi:10.1107/S1600536812036690

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Redetermination of 4-cyanopyridine N-oxide

Rodolfo Moreno-Fuquen,^a ^* Carolina Arana ^a and Carlos A. De Simone ^b

^aDepartamento de Química - Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, and ^bInstituto de Física de São Carlos, IFSC, Universidade de São Paulo, USP, São Carlos, SP, Brazil
^*Correspondence e-mail: rodimo26@yahoo.es

(Received 21 August 2012; accepted 23 August 2012; online 31 August 2012)

In the title pyridine N-oxide derivative, C₆H₄N₂O, the 4-cyano substituent almost lies in the mean plane of the pyridine ring (r.m.s deviation of all non-H atoms = 0.004 Å). This redetermination results in a crystal structure with significantly higher precision [N—O bond length is 1.2997 (15) compared with 1.303 (5) Å in the original] than the original determination, which was recorded using the multiple-film technique and visually estimated intensities [Hardcastle et al. (1974 ). J. Cryst. Mol. Struct. 4, 305–311]. The crystal structure features weak C—H⋯O and C—H⋯N interactions, which lead to the formation of chains that intersect each other parallel to (001).

Related literature

For the synthesis of 4-cyanopyridine N-oxide with metal ions, see: Piovesana & Selbin (1969 ). For luminiscent properties of 4-cyanopyridine N-oxide lanthanide complexes, see: Eliseeva et al. (2006 , 2008 ). For the use of the title compound as a ligand to obtain metal-organic coordination polymers, see: Yang et al. (2009 ); Kapoor et al. (2012 ). For details concerning thermodynamic studies of the title compound, see: Ribeiro et al. (1998 ). For hydrogen bonding, see: Nardelli (1995 ). For the previous determination of the structure, see: Hardcastle et al. (1974).

Experimental

Crystal data

C₆H₄N₂O
M_r = 120.11
Monoclinic, P 2₁ /c
a = 7.8743 (8) Å
b = 6.0582 (6) Å
c = 11.6278 (10) Å
β = 91.973 (6)°
V = 554.36 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.37 × 0.32 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer
4336 measured reflections
1224 independent reflections
964 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.169
S = 1.10
1224 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.93	2.35	3.200 (2)	152
C5—H5⋯O1ⁱⁱ	0.93	2.43	3.323 (2)	161
C2—H2⋯N2ⁱⁱⁱ	0.93	2.68	3.530 (2)	153
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+2; (iii) -x+2, -y-1, -z+2.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812036690/hg5244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036690/hg5244Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812036690/hg5244Isup3.cml

checkCIF report

Comment top

The incorporation of 4-cyanopyridine N-oxide, (I) as ligand in the formation of diverse complexes with metal ions has been known for a long time (Piovesana & Selbin, 1969). This compound has also been used in the formation of dimeric lanthanide complexes showing luminiscent properties (Eliseeva et al., 2006 and Eliseeva et al., 2008). A series of metal-organic supramolecular co-ordinated polymers with the 4-cyanopyridine N-oxide as a ligand was also reported (Yang et al., 2009; Kapoor et al., 2012). Thermodynamic studies of diverse N-oxide components, including (I) compound, have also been reported (Ribeiro et al., 1998). As part of our studies on the substituent effects on the structures it was necessary to know the structural behavior of the 4-cyanopyridine N-oxide. The crystal and molecular structure of (I) had been determined before, but with low precision. Thus, the redetermination of the title compound (Fig. 1), results in a crystal structure with significantly higher precision than the original determination which was recorded using the multiple-film technique and visually estimated intensities (Hardcastle et al., (1974). Obtaining a more orthogonal cell compared with the original analysis, allows a more precise picture of the packing in the crystal structure. The pyridine ring is essentially planar (r.m.s. deviation of all non-hydrogen atoms = 0.004 Å) The plane formed by N2-C6-C3 atoms, which is part of the cyano group forms an angle of 2.7 (1) Å with the plane of pyridine. The pyridine ring bond lengths and bond angles of (I) are normal and are close to the values presented earlier for this same structure (Hardcastle et al., (1974). In the crystal, there are no classical hydrogen bonds. The crystal structure is stabilized by intermolecular C—H···O and C—H···N weak interactions, which lead to the formation of chains of molecules that intersect each other parallel to (001), (Table 1 and Fig. 2). Indeed, the chains of molecules are formed by weak C5—H5···O1 and C2—H2···N2 interactions (Nardelli, 1995). In turn, these chains are linked by C1—H1···O1 interactions.

Related literature top

For the synthesis of 4-cyanopyridine N-oxide with metallic ions, see: Piovesana & Selbin (1969). For luminiscent properties of 4-cyanopyridine N-oxide lanthanide complexes, see: Eliseeva et al. (2006, 2008). For the use of the title compound as a ligand to obtain metal-organic coordinated polymers, see: Yang et al. (2009); Kapoor et al. (2012). For details concerning thermodynamic studies of the title compound, see: Ribeiro et al. (1998). For hydrogen bonding, see: Nardelli (1995). For the previous low-precision determination of the structure, see: Hardcastle et al. (1974).

Experimental top

Commercial 4-cyanopyridine N-oxide [CAS-14906-59-3] (Aldrich) was recrystallized from acetonitrile.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular conformation and atom numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

Fig. 2. Part of the crystal structure of (I), showing the formation of chains which running parallel to (001). Symmetry code: (i) -x+1,+y-1/2,-z+3/2; (ii) -x+1,-y+1,-z+2; (iii) -x+2,-y-1,-z+2.

4-cyanopyridine N-oxide top

Crystal data top

C₆H₄N₂O	F(000) = 248
M_r = 120.11	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 496(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.8743 (8) Å	Cell parameters from 7553 reflections
b = 6.0582 (6) Å	θ = 2.6–27.5°
c = 11.6278 (10) Å	µ = 0.10 mm⁻¹
β = 91.973 (6)°	T = 295 K
V = 554.36 (9) Å³	Block, pale-green
Z = 4	0.37 × 0.32 × 0.30 mm

Data collection top

Nonius KappaCCD diffractometer	964 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
Graphite monochromator	θ_max = 27.6°, θ_min = 2.6°
CCD rotation images, thick slices scans	h = −9→10
4336 measured reflections	k = −7→7
1224 independent reflections	l = −15→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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.1003P)² + 0.0643P] where P = (F_o² + 2F_c²)/3
1224 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₆H₄N₂O	V = 554.36 (9) Å³
M_r = 120.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8743 (8) Å	µ = 0.10 mm⁻¹
b = 6.0582 (6) Å	T = 295 K
c = 11.6278 (10) Å	0.37 × 0.32 × 0.30 mm
β = 91.973 (6)°

Data collection top

Nonius KappaCCD diffractometer	964 reflections with I > 2σ(I)
4336 measured reflections	R_int = 0.037
1224 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.10	Δρ_max = 0.25 e Å⁻³
1224 reflections	Δρ_min = −0.21 e Å⁻³
82 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 > 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
N1	0.62819 (15)	0.2012 (2)	0.91581 (10)	0.0456 (4)
O1	0.54449 (17)	0.3499 (2)	0.85653 (10)	0.0671 (5)
C4	0.7599 (2)	0.0848 (3)	1.09136 (14)	0.0500 (4)
H4	0.7885	0.1123	1.1683	0.060*
C6	0.90575 (19)	−0.2718 (2)	1.10517 (13)	0.0482 (4)
N2	0.9834 (2)	−0.4015 (2)	1.15568 (14)	0.0656 (5)
C3	0.80898 (17)	−0.1108 (2)	1.04066 (12)	0.0427 (4)
C2	0.7643 (2)	−0.1471 (3)	0.92614 (13)	0.0500 (4)
H2	0.7958	−0.2775	0.8905	0.060*
C5	0.6695 (2)	0.2377 (3)	1.02802 (13)	0.0504 (4)
H5	0.6360	0.3683	1.0626	0.061*
C1	0.6735 (2)	0.0094 (2)	0.86553 (13)	0.0523 (5)
H1	0.6426	−0.0162	0.7888	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0492 (7)	0.0422 (7)	0.0449 (7)	0.0025 (5)	−0.0066 (5)	0.0031 (5)
O1	0.0830 (9)	0.0573 (8)	0.0596 (7)	0.0187 (6)	−0.0172 (6)	0.0103 (6)
C4	0.0580 (9)	0.0493 (9)	0.0422 (8)	0.0037 (7)	−0.0078 (7)	−0.0040 (6)
C6	0.0508 (8)	0.0445 (8)	0.0489 (8)	0.0025 (6)	−0.0047 (7)	0.0019 (7)
N2	0.0726 (10)	0.0572 (9)	0.0660 (10)	0.0104 (7)	−0.0116 (7)	0.0040 (7)
C3	0.0415 (7)	0.0410 (8)	0.0454 (8)	−0.0015 (5)	−0.0019 (6)	0.0038 (6)
C2	0.0576 (9)	0.0429 (8)	0.0491 (9)	0.0032 (6)	−0.0029 (7)	−0.0055 (6)
C5	0.0607 (9)	0.0435 (8)	0.0465 (8)	0.0057 (7)	−0.0071 (7)	−0.0057 (6)
C1	0.0643 (10)	0.0504 (9)	0.0417 (8)	0.0030 (7)	−0.0079 (7)	−0.0044 (7)

Geometric parameters (Å, º) top

N1—O1	1.2997 (15)	C6—C3	1.4336 (19)
N1—C5	1.3520 (19)	C3—C2	1.383 (2)
N1—C1	1.354 (2)	C2—C1	1.368 (2)
C4—C5	1.368 (2)	C2—H2	0.9300
C4—C3	1.385 (2)	C5—H5	0.9300
C4—H4	0.9300	C1—H1	0.9300
C6—N2	1.1453 (19)

O1—N1—C5	119.96 (13)	C1—C2—C3	119.79 (14)
O1—N1—C1	120.14 (13)	C1—C2—H2	120.1
C5—N1—C1	119.90 (13)	C3—C2—H2	120.1
C5—C4—C3	119.86 (14)	N1—C5—C4	120.84 (14)
C5—C4—H4	120.1	N1—C5—H5	119.6
C3—C4—H4	120.1	C4—C5—H5	119.6
N2—C6—C3	179.31 (16)	N1—C1—C2	120.87 (14)
C2—C3—C4	118.71 (14)	N1—C1—H1	119.6
C2—C3—C6	120.58 (13)	C2—C1—H1	119.6
C4—C3—C6	120.71 (13)

C5—C4—C3—C2	−0.2 (2)	C1—N1—C5—C4	1.4 (2)
C5—C4—C3—C6	179.17 (14)	C3—C4—C5—N1	−0.5 (3)
N2—C6—C3—C4	−167 (14)	O1—N1—C1—C2	178.83 (15)
C4—C3—C2—C1	0.1 (2)	C5—N1—C1—C2	−1.4 (2)
C6—C3—C2—C1	−179.26 (14)	C3—C2—C1—N1	0.7 (2)
O1—N1—C5—C4	−178.92 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.35	3.200 (2)	152
C5—H5···O1ⁱⁱ	0.93	2.43	3.323 (2)	161
C2—H2···N2ⁱⁱⁱ	0.93	2.68	3.530 (2)	153

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) −x+2, −y−1, −z+2.

Experimental details

Crystal data
Chemical formula	C₆H₄N₂O
M_r	120.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.8743 (8), 6.0582 (6), 11.6278 (10)
β (°)	91.973 (6)
V (Å³)	554.36 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.37 × 0.32 × 0.30

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4336, 1224, 964
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.169, 1.10
No. of reflections	1224
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.35	3.200 (2)	152.3
C5—H5···O1ⁱⁱ	0.93	2.43	3.323 (2)	160.6
C2—H2···N2ⁱⁱⁱ	0.93	2.68	3.530 (2)	153.1

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) −x+2, −y−1, −z+2.

Acknowledgements

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database and also thanks the Universidad del Valle, Colombia, for partial financial support.

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