Methyl isonicotinate 1-oxide

Li, H.; Zheng, W.-N.

doi:10.1107/S1600536810004629

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o584

doi:10.1107/S1600536810004629

Open

access

Methyl isonicotinate 1-oxide

Hui Li ^a ^* and Wen-Ni Zheng ^a

^aCollege of Chemistry and Chemical, Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 28 January 2010; accepted 5 February 2010; online 10 February 2010)

In the title compound, C₇H₇NO₃, the benzene ring and the methyl ester group are nearly coplanar, forming a dihedral of 3.09 (9)°. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen bonds, forming layers parallel to (101).

Related literature

For the application of carboxylate derivatives in microelectronics and as memory storage devices, see: Fu et al. (2007 , 2008 ); Fu & Xiong (2008 ).

Experimental

Crystal data

C₇H₇NO₃
M_r = 153.14
Monoclinic, P 2₁ /c
a = 7.2429 (14) Å
b = 10.347 (2) Å
c = 9.898 (2) Å
β = 105.09 (3)°
V = 716.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.96, T_max = 1.00
7070 measured reflections
1640 independent reflections
972 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.180
S = 1.02
1640 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O2ⁱ	0.93	2.44	3.204 (3)	139
C4—H4A⋯O3ⁱⁱ	0.93	2.42	3.263 (3)	150
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810004629/rz2415sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004629/rz2415Isup2.hkl

checkCIF report

Comment top

Carboxylate derivatives attracted more attention as pharmaceutical and phase transition dielectric materials for their application in micro-electronics and as memory storage devices (Fu et al., 2007; Fu & Xiong 2008; Fu et al., 2008). With the purpose of obtaining phase transition crystals of carboxylate compounds, the interaction of methyl isonicotinate with hydrogen peroxide has been studied and we have elaborated a series of new materials including these organic molecules. In this paper, we describe the crystal structure of the title compound, Methyl isonicotinate 1-oxide.

In the title compound (Fig. 1), the benzene ring and the methyl ester group are nearly coplanar, the dihedral angle they form being 3.09 (9)°). The N1—O3 bond length of the nitrile group (1.292 (2)Å) is within the normal range. The crystal structure is stabilized by intermolecular C—H···O hydrogen bonds (Table 1) linking the molecules to form layers parallel to the (101) plane.

Related literature top

For the application of carboxylate derivatives in micro-electronics and as memory storage devices, see: Fu et al. (2007, 2008); Fu & Xiong (2008).

Experimental top

Methyl isonicotinate 1-oxide (3 mmol, 0.46 g) was dissolved in methanol. The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound suitable for X-ray analysis. Permittivity measurements show that there is no phase transition within the temperature range (from 100 K to 400 K), and the permittivity is 6.5 at 1 MHz at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

methyl isonicotinate 1-oxide top

Crystal data top

C₇H₇NO₃	F(000) = 320
M_r = 153.14	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1640 reflections
a = 7.2429 (14) Å	θ = 3.5–27.5°
b = 10.347 (2) Å	µ = 0.11 mm⁻¹
c = 9.898 (2) Å	T = 298 K
β = 105.09 (3)°	Block, colourless
V = 716.2 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1640 independent reflections
Radiation source: fine-focus sealed tube	972 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
CCD profile fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.96, T_max = 1.00	l = −12→12
7070 measured reflections

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0868P)² + 0.0635P] where P = (F_o² + 2F_c²)/3
1640 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₇H₇NO₃	V = 716.2 (3) Å³
M_r = 153.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2429 (14) Å	µ = 0.11 mm⁻¹
b = 10.347 (2) Å	T = 298 K
c = 9.898 (2) Å	0.30 × 0.25 × 0.20 mm
β = 105.09 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1640 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	972 reflections with I > 2σ(I)
T_min = 0.96, T_max = 1.00	R_int = 0.053
7070 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.180	H-atom parameters constrained
S = 1.02	Δρ_max = 0.18 e Å⁻³
1640 reflections	Δρ_min = −0.16 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 > 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	0.3267 (3)	0.76927 (18)	0.0785 (2)	0.0666 (5)
C5	0.2388 (3)	1.02039 (19)	−0.0124 (2)	0.0542 (5)
C6	0.1852 (3)	1.1517 (2)	−0.0654 (2)	0.0642 (6)
C4	0.3492 (3)	0.99507 (19)	0.1224 (2)	0.0582 (6)
H4A	0.3944	1.0628	0.1838	0.070*
O3	0.3658 (3)	0.65171 (15)	0.1201 (2)	0.0955 (6)
O1	0.2579 (2)	1.24307 (15)	0.02709 (18)	0.0782 (6)
O2	0.0834 (3)	1.17357 (17)	−0.18032 (17)	0.0934 (7)
C3	0.3912 (3)	0.8701 (2)	0.1644 (2)	0.0650 (6)
H3A	0.4662	0.8542	0.2545	0.078*
C2	0.2201 (3)	0.7926 (2)	−0.0537 (2)	0.0686 (6)
H2A	0.1772	0.7237	−0.1140	0.082*
C1	0.1753 (3)	0.9152 (2)	−0.0993 (2)	0.0642 (6)
H1A	0.1010	0.9290	−0.1900	0.077*
C7	0.2062 (4)	1.3747 (3)	−0.0153 (4)	0.1006 (9)
H7A	0.2665	1.4325	0.0590	0.151*
H7B	0.0699	1.3843	−0.0356	0.151*
H7C	0.2479	1.3946	−0.0974	0.151*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0654 (11)	0.0577 (11)	0.0714 (12)	0.0002 (9)	0.0082 (9)	0.0014 (9)
C5	0.0466 (11)	0.0622 (13)	0.0524 (11)	0.0009 (9)	0.0105 (8)	0.0025 (9)
C6	0.0579 (13)	0.0722 (15)	0.0616 (13)	0.0056 (11)	0.0138 (10)	0.0080 (11)
C4	0.0558 (12)	0.0581 (12)	0.0557 (12)	−0.0056 (9)	0.0057 (9)	−0.0022 (9)
O3	0.1118 (15)	0.0544 (10)	0.1071 (14)	0.0042 (9)	0.0045 (11)	0.0097 (9)
O1	0.0841 (11)	0.0557 (10)	0.0839 (12)	0.0033 (8)	0.0022 (9)	0.0055 (8)
O2	0.1046 (14)	0.0930 (14)	0.0680 (11)	0.0193 (10)	−0.0035 (10)	0.0157 (9)
C3	0.0644 (13)	0.0637 (13)	0.0577 (12)	−0.0054 (10)	−0.0003 (9)	0.0027 (10)
C2	0.0688 (14)	0.0720 (15)	0.0601 (14)	−0.0032 (11)	0.0081 (11)	−0.0125 (11)
C1	0.0621 (12)	0.0753 (15)	0.0498 (11)	0.0024 (11)	0.0047 (9)	−0.0021 (10)
C7	0.108 (2)	0.0577 (15)	0.126 (2)	0.0122 (14)	0.0125 (18)	0.0178 (15)

Geometric parameters (Å, º) top

N1—O3	1.292 (2)	C4—H4A	0.9300
N1—C3	1.350 (3)	O1—C7	1.445 (3)
N1—C2	1.357 (3)	C3—H3A	0.9300
C5—C1	1.389 (3)	C2—C1	1.357 (3)
C5—C4	1.390 (3)	C2—H2A	0.9300
C5—C6	1.472 (3)	C1—H1A	0.9300
C6—O2	1.205 (3)	C7—H7A	0.9600
C6—O1	1.326 (3)	C7—H7B	0.9600
C4—C3	1.368 (3)	C7—H7C	0.9600

O3—N1—C3	121.0 (2)	N1—C3—H3A	119.1
O3—N1—C2	119.8 (2)	C4—C3—H3A	119.1
C3—N1—C2	119.1 (2)	N1—C2—C1	120.9 (2)
C1—C5—C4	117.49 (19)	N1—C2—H2A	119.5
C1—C5—C6	119.2 (2)	C1—C2—H2A	119.5
C4—C5—C6	123.3 (2)	C2—C1—C5	121.0 (2)
O2—C6—O1	123.6 (2)	C2—C1—H1A	119.5
O2—C6—C5	123.3 (2)	C5—C1—H1A	119.5
O1—C6—C5	113.05 (19)	O1—C7—H7A	109.5
C3—C4—C5	119.77 (19)	O1—C7—H7B	109.5
C3—C4—H4A	120.1	H7A—C7—H7B	109.5
C5—C4—H4A	120.1	O1—C7—H7C	109.5
C6—O1—C7	116.4 (2)	H7A—C7—H7C	109.5
N1—C3—C4	121.7 (2)	H7B—C7—H7C	109.5

C1—C5—C6—O2	2.1 (3)	O3—N1—C3—C4	−179.25 (19)
C4—C5—C6—O2	−177.0 (2)	C2—N1—C3—C4	1.1 (3)
C1—C5—C6—O1	−178.87 (17)	C5—C4—C3—N1	−0.6 (3)
C4—C5—C6—O1	2.0 (3)	O3—N1—C2—C1	179.22 (18)
C1—C5—C4—C3	0.1 (3)	C3—N1—C2—C1	−1.2 (3)
C6—C5—C4—C3	179.26 (17)	N1—C2—C1—C5	0.7 (3)
O2—C6—O1—C7	1.1 (3)	C4—C5—C1—C2	−0.1 (3)
C5—C6—O1—C7	−177.87 (18)	C6—C5—C1—C2	−179.32 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱ	0.93	2.44	3.204 (3)	139
C4—H4A···O3ⁱⁱ	0.93	2.42	3.263 (3)	150

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

Experimental details

Crystal data
Chemical formula	C₇H₇NO₃
M_r	153.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.2429 (14), 10.347 (2), 9.898 (2)
β (°)	105.09 (3)
V (Å³)	716.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.96, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	7070, 1640, 972
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.180, 1.02
No. of reflections	1640
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱ	0.93	2.44	3.204 (3)	139
C4—H4A···O3ⁱⁱ	0.93	2.42	3.263 (3)	150

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

Acknowledgements

This work was supported by the Innovative Dissertation Fund of Southeast University.

References

Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H., Huang, S.-P. & -, D. (2007). J. Am. Chem. Soc. 129, 5346–5347. Web of Science CSD CrossRef PubMed CAS Google Scholar
Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946–3948. Web of Science CSD CrossRef Google Scholar
Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar