3-Methyl­quinoxaline-2-carb­oxy­lic acid 4-oxide monohydrate

Li, Y.; Zhou, W.; Wang, J.; Gao, H.; Zhou, Z.

doi:10.1107/S160053681002266X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1801

doi:10.1107/S160053681002266X

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3-Methylquinoxaline-2-carboxylic acid 4-oxide monohydrate

Yubo Li,^a Wenfeng Zhou,^a Jinli Wang,^a Haixiang Gao ^a ^* and Zhiqiang Zhou ^a ^*

^aDepartment of Applied Chemistry, China Agricultural University, Yuanmingyuan, West Road 2#, Haidian District, Beijing 100194, People's Republic of China
^*Correspondence e-mail: hxgao@cau.edu.cn, zqzhou@cau.edu.cn

(Received 26 May 2010; accepted 13 June 2010; online 26 June 2010)

In the crystal structure of the title compound, C₁₀H₈N₂O₃·H₂O, molecules are linked via intermolecular O—H⋯O and O—H⋯N hydrogen bonds into a two-dimensional network.

Related literature

For the synthesis of the starting material, see: Robertson & Kasublck (1973 ). For the synthesis of the title compound, see: Dirlam & McFarland (1977 ).

Experimental

Crystal data

C₁₀H₈N₂O₃·H₂O
M_r = 222.20
Monoclinic, P 2₁ /c
a = 6.0526 (13) Å
b = 18.068 (4) Å
c = 8.9195 (19) Å
β = 98.520 (15)°
V = 964.7 (4) Å³
Z = 4
Cu Kα radiation
μ = 1.02 mm⁻¹
T = 173 K
0.20 × 0.20 × 0.04 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1995 ) T_min = 0.822, T_max = 0.960
6140 measured reflections
1568 independent reflections
900 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.098
wR(F²) = 0.256
S = 1.10
1568 reflections
154 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O1ⁱ	0.85 (4)	1.97 (2)	2.794 (5)	164 (5)
O1W—H1WA⋯N2ⁱⁱ	0.86 (4)	2.14 (2)	2.968 (5)	163 (5)
O3—H3⋯O1W	0.84	1.76	2.574 (5)	162
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 2001 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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, global. DOI: 10.1107/S160053681002266X/lh5056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002266X/lh5056Isup2.hkl

checkCIF report

Comment top

The molecular structure of the title compound is shown in Fig. 1. In the crystal structure, molecules are linked via intermolecular O-H···O hydrogen bonds into a two-dimensional network.

Related literature top

For the synthesis of the starting material, see: Robertson & Kasublck (1973). For the synthesis of the title compound, see: Dirlam & McFarland (1977).

Experimental top

Following the procedure of Dirlam & McFarland (1977) ethyl-3-methyl-2-quinoxalinecarboxylate-1,4-dioxide (2.0 g, 8 mmol) (Robertson & Kasublck, 1973) was dissolved in 1-propanol (20 ml), trimethyl phosphate (2.0 g, 16 mmol) was added dropwise to the solution. The reaction mixture was heated under reflux for 2.5 h, and evaporated to dryness. The residue was recrystallized from ether-hexane (1:1) to yeild 1.6 g (80%) ethyl 2-methyl-3-quinoxalinecarboxylate-1-oxide. Ethyl 2-methyl-3-quinoxalinecarboxylate-1-oxide (5 g, 22 mmol) was suspended in aqueous 0.5M sodium hydroxide solution (50 mL), and stirred for 2 h. Then used concentrated hydrochloric acid to adjust the PH=2. The white solid was collected and recrystallized from water to give 4.0 g (80%) of the the title compound.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); 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. The molecular structure of the title compound, showing the labelling scheme. Displacement ellipsoids are drawn at the 30% probability level for all non-H atoms.
	Fig. 2. Part of the crystal structure of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines.

3-Methylquinoxaline-2-carboxylic acid 4-oxide monohydrate top

Crystal data top

C₁₀H₈N₂O₃·H₂O	F(000) = 464
M_r = 222.20	D_x = 1.530 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54186 Å
Hall symbol: -P 2ybc	Cell parameters from 426 reflections
a = 6.0526 (13) Å	θ = 3.1–68.1°
b = 18.068 (4) Å	µ = 1.02 mm⁻¹
c = 8.9195 (19) Å	T = 173 K
β = 98.520 (15)°	Plate, yellow
V = 964.7 (4) Å³	0.20 × 0.20 × 0.04 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1568 independent reflections
Radiation source: fine-focus sealed tube	900 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ω scans at fixed χ = 45°	θ_max = 63.7°, θ_min = 4.9°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −7→7
T_min = 0.822, T_max = 0.960	k = −20→20
6140 measured reflections	l = −10→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.098	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.256	w = 1/[σ²(F_o²) + (0.1186P)² + 0.0706P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1568 reflections	Δρ_max = 0.38 e Å⁻³
154 parameters	Δρ_min = −0.31 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (2)

Crystal data top

C₁₀H₈N₂O₃·H₂O	V = 964.7 (4) Å³
M_r = 222.20	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 6.0526 (13) Å	µ = 1.02 mm⁻¹
b = 18.068 (4) Å	T = 173 K
c = 8.9195 (19) Å	0.20 × 0.20 × 0.04 mm
β = 98.520 (15)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1568 independent reflections
Absorption correction: numerical (ABSCOR; Higashi, 1995)	900 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.960	R_int = 0.077
6140 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.098	3 restraints
wR(F²) = 0.256	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.38 e Å⁻³
1568 reflections	Δρ_min = −0.31 e Å⁻³
154 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
O1W	0.2035 (6)	0.6094 (2)	0.4980 (5)	0.0458 (12)
O1	0.6172 (6)	0.2378 (2)	0.1107 (4)	0.0546 (12)
O2	0.3088 (6)	0.4949 (2)	0.2089 (5)	0.0614 (13)
O3	0.2260 (7)	0.4704 (2)	0.4389 (4)	0.0532 (12)
H3	0.2018	0.5162	0.4401	0.080*
N1	0.4745 (7)	0.2663 (3)	0.1891 (5)	0.0393 (12)
N2	0.1661 (7)	0.3286 (2)	0.3563 (5)	0.0389 (12)
C1	0.1772 (8)	0.2529 (3)	0.3378 (6)	0.0403 (14)
C2	0.0313 (9)	0.2070 (3)	0.4034 (6)	0.0461 (15)
H2	−0.0732	0.2280	0.4609	0.055*
C3	0.0398 (9)	0.1315 (3)	0.3845 (6)	0.0474 (16)
H3A	−0.0604	0.1004	0.4277	0.057*
C4	0.1961 (9)	0.1006 (3)	0.3014 (6)	0.0490 (16)
H4	0.2012	0.0483	0.2900	0.059*
C5	0.3405 (9)	0.1436 (3)	0.2369 (6)	0.0451 (16)
H5	0.4457	0.1219	0.1810	0.054*
C6	0.3311 (8)	0.2207 (3)	0.2547 (6)	0.0387 (14)
C7	0.4655 (9)	0.3408 (3)	0.2072 (6)	0.0402 (15)
C8	0.3058 (9)	0.3687 (3)	0.2920 (6)	0.0383 (14)
C9	0.6295 (9)	0.3835 (3)	0.1352 (6)	0.0482 (16)
H9B	0.7788	0.3625	0.1647	0.072*
H9C	0.6287	0.4352	0.1684	0.072*
H9A	0.5896	0.3812	0.0247	0.072*
C10	0.2818 (9)	0.4516 (3)	0.3070 (7)	0.0434 (15)
H1WB	0.261 (8)	0.643 (2)	0.450 (6)	0.065*
H1WA	0.080 (5)	0.626 (3)	0.522 (6)	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1W	0.041 (2)	0.044 (3)	0.056 (3)	−0.003 (2)	0.0210 (19)	−0.003 (2)
O1	0.049 (2)	0.054 (3)	0.065 (3)	0.007 (2)	0.021 (2)	−0.005 (2)
O2	0.081 (3)	0.050 (3)	0.059 (3)	0.009 (2)	0.030 (2)	0.008 (2)
O3	0.065 (3)	0.043 (3)	0.056 (3)	0.004 (2)	0.021 (2)	−0.002 (2)
N1	0.032 (2)	0.052 (3)	0.037 (3)	0.005 (2)	0.016 (2)	−0.004 (2)
N2	0.034 (2)	0.040 (3)	0.045 (3)	0.001 (2)	0.013 (2)	−0.006 (2)
C1	0.031 (3)	0.043 (4)	0.048 (3)	0.004 (3)	0.010 (3)	−0.004 (3)
C2	0.044 (3)	0.051 (4)	0.045 (3)	−0.005 (3)	0.010 (3)	−0.007 (3)
C3	0.045 (4)	0.046 (4)	0.056 (4)	−0.011 (3)	0.021 (3)	−0.008 (3)
C4	0.050 (4)	0.040 (4)	0.060 (4)	0.004 (3)	0.018 (3)	−0.003 (3)
C5	0.037 (3)	0.048 (4)	0.053 (4)	0.006 (3)	0.018 (3)	−0.004 (3)
C6	0.037 (3)	0.044 (4)	0.036 (3)	0.000 (3)	0.012 (3)	−0.002 (3)
C7	0.033 (3)	0.049 (4)	0.040 (3)	0.004 (3)	0.008 (2)	−0.003 (3)
C8	0.034 (3)	0.046 (4)	0.036 (3)	0.004 (3)	0.008 (2)	−0.002 (3)
C9	0.045 (4)	0.047 (4)	0.056 (4)	0.003 (3)	0.016 (3)	−0.002 (3)
C10	0.038 (3)	0.047 (4)	0.048 (4)	0.000 (3)	0.015 (3)	−0.006 (3)

Geometric parameters (Å, º) top

O1W—H1WB	0.85 (4)	C2—H2	0.9500
O1W—H1WA	0.86 (4)	C3—C4	1.401 (7)
O1—N1	1.296 (5)	C3—H3A	0.9500
O2—C10	1.202 (6)	C4—C5	1.359 (7)
O3—C10	1.316 (6)	C4—H4	0.9500
O3—H3	0.8400	C5—C6	1.404 (7)
N1—C7	1.357 (7)	C5—H5	0.9500
N1—C6	1.388 (6)	C7—C8	1.406 (7)
N2—C8	1.309 (6)	C7—C9	1.477 (7)
N2—C1	1.380 (6)	C8—C10	1.514 (8)
C1—C6	1.401 (6)	C9—H9B	0.9800
C1—C2	1.401 (7)	C9—H9C	0.9800
C2—C3	1.377 (6)	C9—H9A	0.9800

H1WB—O1W—H1WA	108 (4)	C6—C5—H5	120.6
C10—O3—H3	109.5	N1—C6—C1	118.8 (5)
O1—N1—C7	120.0 (5)	N1—C6—C5	120.3 (5)
O1—N1—C6	120.0 (5)	C1—C6—C5	120.9 (5)
C7—N1—C6	120.1 (4)	N1—C7—C8	117.5 (5)
C8—N2—C1	116.8 (4)	N1—C7—C9	115.2 (5)
N2—C1—C6	121.6 (5)	C8—C7—C9	127.3 (5)
N2—C1—C2	119.4 (5)	N2—C8—C7	125.2 (5)
C6—C1—C2	119.0 (5)	N2—C8—C10	115.6 (5)
C3—C2—C1	119.9 (5)	C7—C8—C10	119.0 (5)
C3—C2—H2	120.1	C7—C9—H9B	109.5
C1—C2—H2	120.1	C7—C9—H9C	109.5
C2—C3—C4	120.0 (5)	H9B—C9—H9C	109.5
C2—C3—H3A	120.0	C7—C9—H9A	109.5
C4—C3—H3A	120.0	H9B—C9—H9A	109.5
C5—C4—C3	121.5 (5)	H9C—C9—H9A	109.5
C5—C4—H4	119.3	O2—C10—O3	124.3 (6)
C3—C4—H4	119.3	O2—C10—C8	123.7 (5)
C4—C5—C6	118.7 (5)	O3—C10—C8	112.0 (5)
C4—C5—H5	120.6

C8—N2—C1—C6	0.2 (7)	C4—C5—C6—C1	0.4 (8)
C8—N2—C1—C2	−179.8 (5)	O1—N1—C7—C8	179.4 (4)
N2—C1—C2—C3	179.4 (4)	C6—N1—C7—C8	−0.7 (7)
C6—C1—C2—C3	−0.6 (8)	O1—N1—C7—C9	−1.3 (7)
C1—C2—C3—C4	0.9 (8)	C6—N1—C7—C9	178.7 (4)
C2—C3—C4—C5	−0.6 (8)	C1—N2—C8—C7	−0.4 (8)
C3—C4—C5—C6	0.0 (8)	C1—N2—C8—C10	176.9 (4)
O1—N1—C6—C1	−179.5 (4)	N1—C7—C8—N2	0.6 (8)
C7—N1—C6—C1	0.6 (7)	C9—C7—C8—N2	−178.7 (5)
O1—N1—C6—C5	0.2 (7)	N1—C7—C8—C10	−176.5 (4)
C7—N1—C6—C5	−179.7 (4)	C9—C7—C8—C10	4.2 (8)
N2—C1—C6—N1	−0.3 (7)	N2—C8—C10—O2	−143.8 (5)
C2—C1—C6—N1	179.6 (5)	C7—C8—C10—O2	33.6 (8)
N2—C1—C6—C5	180.0 (5)	N2—C8—C10—O3	35.6 (6)
C2—C1—C6—C5	−0.1 (8)	C7—C8—C10—O3	−147.0 (5)
C4—C5—C6—N1	−179.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O1ⁱ	0.85 (4)	1.97 (2)	2.794 (5)	164 (5)
O1W—H1WA···N2ⁱⁱ	0.86 (4)	2.14 (2)	2.968 (5)	163 (5)
O3—H3···O1W	0.84	1.76	2.574 (5)	162

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂O₃·H₂O
M_r	222.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.0526 (13), 18.068 (4), 8.9195 (19)
β (°)	98.520 (15)
V (Å³)	964.7 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.20 × 0.20 × 0.04

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Numerical (ABSCOR; Higashi, 1995)
T_min, T_max	0.822, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	6140, 1568, 900
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.581

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.098, 0.256, 1.10
No. of reflections	1568
No. of parameters	154
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.31

Computer programs: RAPID-AUTO (Rigaku, 2001), 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
O1W—H1WB···O1ⁱ	0.85 (4)	1.97 (2)	2.794 (5)	164 (5)
O1W—H1WA···N2ⁱⁱ	0.86 (4)	2.14 (2)	2.968 (5)	163 (5)
O3—H3···O1W	0.84	1.76	2.574 (5)	162.0

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

Acknowledgements

This work was supported by the 973 Fund and the Ministry of Science and Technology, China (grant No. 2009CB118801). We acknowledge Dr Liang Tongling for collecting the data at the Analysis and Testing Center, Institute of Chemistry, Academy of Science, Beijing.

References

Dirlam, J. P. & McFarland, J. W. (1977). J. Org. Chem. 42, 1360–1364. CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2001). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Robertson, R. L. & Kasublck, A. V. (1973). US Patent No. 3 767 657. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar