5,6-Dimethyl­pyrazine-2,3-dicarb­oxy­lic acid

Liu, F.-H.

doi:10.1107/S1600536811052366

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o132

doi:10.1107/S1600536811052366

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5,6-Dimethylpyrazine-2,3-dicarboxylic acid

Fu-Hong Liu ^a ^*

^aBasis Department, Jilin Business and Technology College, Hao Yue Road No. 1606, Changchun, Jilin, People's Republic of China
^*Correspondence e-mail: liufuhong123@gmail.com

(Received 13 November 2011; accepted 5 December 2011; online 14 December 2011)

The asymmetric unit of the title compound, C₈H₈N₂O₄, consists of one complete molecule and a second molecule generated by the application of twofold axis. The mean planes of the two carboxyl groups attached to the pyrazine ring at neighboring positions are twisted by 10.8 (1) and 87.9 (1)° in the complete molecule and 43.0 (1)° in the symmetry-generated molecule. The crystal packing features O—H⋯N hydrogen bonds, which link the molecules into layers along [101].

Related literature

For the synthesis of the title compound, see Tsuda & Fujishima (1981 ). For the structure of the hydrate of the title compound, see Vishweshwar et al. (2001 , 2004 ). For a related compound containing pyrazine-2,3-dicarboxylic acid, see: Alborés & Rentschler (2009 ).

Experimental

Crystal data

C₈H₈N₂O₄
M_r = 196.16
Monoclinic, C 2/c
a = 15.873 (3) Å
b = 14.057 (3) Å
c = 11.991 (2) Å
β = 109.21 (3)°
V = 2526.6 (9) Å³
Z = 12
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCX-mini diffractometer
10832 measured reflections
2230 independent reflections
1937 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.133
S = 1.07
2230 reflections
196 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.82 (1)	2.04	2.845 (2)	167
O3—H3⋯N3ⁱⁱ	0.82 (1)	2.00	2.803 (2)	165
O5—H5⋯N1ⁱⁱⁱ	0.82 (1)	2.06	2.874 (2)	169
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y, z-1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052366/jj2111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052366/jj2111Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052366/jj2111Isup3.cml

checkCIF report

Comment top

2,3-dicarboxypyrazine-based ligands are well suited for the building of large clusters. With two carboxyl groups available for binding and a non-binding site opposite, selective interactions with metal ions are common. For example, a Co36 cluster using a pyrazine-2,3-dicarboxylic acid ligand similar to the title compound has been reported (Alborés & Rentschler, 2009) Similarly, the crystal structure of the title compound containing one water molecule in the unit cell has also been reported (Vishweshwar et al., 2001; Vishweshwar et al., 2004), In view of the importance of compounds containing this ligand we report herin the crystal structure of the title compound, (I).

The asymmetric unit of the title compound, C₈H₈N₂O₄, consists of one molecule and a second complete molecule generated by the application of a centre of inversion (Fig. 1). For each molecule, the mean planes of the two carboxyl groups attached to the pyrazine ring at neighboring positionsare twisted by 10.8 (1)° and 87.9 (3)°. Crystal packing is stabilized by O—H···N hydrogen bonds which link the molecules into layers along [101] (Fig. 2).

Related literature top

For the synthesis of the title compound, see Tsuda & Fujishima (1981). For the structure of the hydrate of the title compound, see Vishweshwar et al. (2001, 2004). For a related compound containing a similar pyrazine-2,3-dicarboxylic acid ligand, see: Alborés & Rentschler (2009).

Experimental top

The compound was synthesized by a reported reaction (Tsuda & Fujishima, 1981) and crystallized by a solvent-thermal reaction as follows: 196.16 mg (1 mmol) C₈H₈N₂O₄ and 10 mlN, N-dimethylformamide (DMF) was added to a 20 ml Teflon vessel. The vessel was sealed and placed inside a stainless steel autoclave, which was kept at 130°C for 72 h. Crystals suitable for single-crystal analysis were formed upon standing.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing view of (I). (a) View of layers in (I) along the b axis. (b) View of the title compound along the a axis. Dashed lines indicate O—H···N hydrogen bonds. H atoms not involved in hydrogen bonds have been deleted for clarity.

5,6-Dimethylpyrazine-2,3-dicarboxylic acid top

Crystal data top

C₈H₈N₂O₄	F(000) = 1224
M_r = 196.16	D_x = 1.547 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10631 reflections
a = 15.873 (3) Å	θ = 3.4–27.8°
b = 14.057 (3) Å	µ = 0.13 mm⁻¹
c = 11.991 (2) Å	T = 293 K
β = 109.21 (3)°	Block, colourless
V = 2526.6 (9) Å³	0.30 × 0.25 × 0.20 mm
Z = 12

Data collection top

Rigaku SCX-mini diffractometer	1937 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 25.0°, θ_min = 3.4°
ω scans	h = −18→18
10832 measured reflections	k = −16→16
2230 independent 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0617P)² + 3.0039P] where P = (F_o² + 2F_c²)/3
2230 reflections	(Δ/σ)_max < 0.001
196 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₈H₈N₂O₄	V = 2526.6 (9) Å³
M_r = 196.16	Z = 12
Monoclinic, C2/c	Mo Kα radiation
a = 15.873 (3) Å	µ = 0.13 mm⁻¹
b = 14.057 (3) Å	T = 293 K
c = 11.991 (2) Å	0.30 × 0.25 × 0.20 mm
β = 109.21 (3)°

Data collection top

Rigaku SCX-mini diffractometer	1937 reflections with I > 2σ(I)
10832 measured reflections	R_int = 0.043
2230 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.07	Δρ_max = 0.63 e Å⁻³
2230 reflections	Δρ_min = −0.39 e Å⁻³
196 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
O1	0.28005 (14)	0.38972 (11)	0.78999 (16)	0.0595 (6)
H1	0.2587	0.3468	0.7428	0.089*
O2	0.17345 (15)	0.47314 (13)	0.66739 (18)	0.0745 (7)
O3	0.20112 (11)	0.67092 (14)	0.57803 (14)	0.0482 (5)
H3	0.1591	0.6847	0.5190	0.072*
O4	0.09881 (12)	0.67291 (15)	0.66709 (16)	0.0567 (5)
O5	0.40546 (13)	0.35937 (12)	0.02848 (13)	0.0474 (5)
H5	0.3815	0.4101	0.0026	0.071*
O6	0.40159 (11)	0.41517 (11)	0.20060 (15)	0.0439 (4)
N1	0.34098 (12)	0.54156 (12)	0.92729 (14)	0.0318 (4)
N2	0.28289 (12)	0.72021 (12)	0.84036 (15)	0.0325 (4)
N3	0.43566 (12)	0.18493 (12)	0.14017 (14)	0.0311 (4)
C1	0.23855 (16)	0.46795 (15)	0.75119 (19)	0.0362 (5)
C2	0.27656 (14)	0.55308 (14)	0.82342 (17)	0.0291 (5)
C3	0.37616 (14)	0.61868 (15)	0.98780 (18)	0.0325 (5)
C4	0.44770 (18)	0.60708 (18)	1.1037 (2)	0.0491 (7)
H4A	0.4231	0.6160	1.1662	0.074*
H4B	0.4936	0.6534	1.1110	0.074*
H4C	0.4726	0.5444	1.1090	0.074*
C5	0.17291 (15)	0.66150 (14)	0.66717 (19)	0.0324 (5)
C6	0.24752 (13)	0.64193 (14)	0.78045 (17)	0.0276 (5)
C7	0.34688 (14)	0.70945 (15)	0.94401 (18)	0.0315 (5)
C8	0.38542 (18)	0.79617 (17)	1.0119 (2)	0.0489 (7)
H8A	0.4458	0.8040	1.0132	0.073*
H8B	0.3846	0.7900	1.0913	0.073*
H8C	0.3508	0.8506	0.9752	0.073*
C9	0.42126 (14)	0.35590 (15)	0.14246 (18)	0.0316 (5)
C10	0.46645 (14)	0.26613 (14)	0.19620 (17)	0.0286 (5)
C11	0.46841 (15)	0.10400 (15)	0.19300 (18)	0.0315 (5)
C12	0.43794 (18)	0.01403 (16)	0.1277 (2)	0.0462 (6)
H12A	0.3870	0.0264	0.0593	0.069*
H12B	0.4220	−0.0306	0.1780	0.069*
H12C	0.4851	−0.0120	0.1036	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0717 (13)	0.0232 (8)	0.0508 (11)	0.0069 (8)	−0.0244 (9)	−0.0016 (7)
O2	0.0871 (15)	0.0368 (10)	0.0546 (12)	0.0090 (10)	−0.0375 (11)	−0.0110 (9)
O3	0.0448 (10)	0.0646 (12)	0.0236 (8)	0.0094 (9)	−0.0042 (7)	0.0075 (8)
O4	0.0354 (10)	0.0753 (14)	0.0467 (11)	0.0054 (9)	−0.0037 (8)	0.0138 (9)
O5	0.0688 (12)	0.0361 (9)	0.0240 (8)	0.0145 (9)	−0.0028 (8)	0.0065 (7)
O6	0.0525 (11)	0.0343 (9)	0.0447 (10)	0.0100 (8)	0.0157 (8)	0.0008 (7)
N1	0.0353 (10)	0.0277 (9)	0.0221 (9)	−0.0014 (8)	−0.0044 (8)	0.0045 (7)
N2	0.0346 (10)	0.0269 (9)	0.0257 (9)	−0.0005 (8)	−0.0040 (8)	0.0010 (7)
N3	0.0375 (10)	0.0278 (9)	0.0201 (9)	−0.0013 (8)	−0.0014 (7)	−0.0005 (7)
C1	0.0447 (13)	0.0259 (11)	0.0258 (11)	−0.0001 (10)	−0.0049 (10)	0.0017 (9)
C2	0.0313 (11)	0.0263 (11)	0.0223 (10)	−0.0008 (9)	−0.0011 (8)	0.0021 (8)
C3	0.0344 (12)	0.0310 (11)	0.0232 (11)	−0.0061 (9)	−0.0027 (9)	0.0032 (8)
C4	0.0528 (16)	0.0414 (13)	0.0319 (13)	−0.0110 (12)	−0.0148 (11)	0.0073 (10)
C5	0.0341 (13)	0.0226 (11)	0.0295 (12)	0.0000 (9)	−0.0042 (9)	0.0024 (8)
C6	0.0291 (11)	0.0241 (10)	0.0226 (10)	−0.0021 (9)	−0.0011 (8)	−0.0004 (8)
C7	0.0340 (12)	0.0298 (11)	0.0229 (11)	−0.0052 (9)	−0.0012 (9)	0.0002 (8)
C8	0.0577 (16)	0.0324 (13)	0.0369 (14)	−0.0090 (11)	−0.0111 (12)	−0.0027 (10)
C9	0.0312 (11)	0.0287 (11)	0.0275 (11)	−0.0012 (9)	−0.0006 (9)	0.0019 (9)
C10	0.0339 (11)	0.0263 (11)	0.0210 (10)	−0.0003 (9)	0.0026 (8)	−0.0011 (8)
C11	0.0392 (12)	0.0260 (11)	0.0239 (11)	−0.0021 (9)	0.0027 (9)	−0.0010 (8)
C12	0.0618 (16)	0.0295 (12)	0.0338 (13)	−0.0040 (11)	−0.0025 (11)	−0.0054 (10)

Geometric parameters (Å, º) top

O1—C1	1.288 (3)	C3—C7	1.400 (3)
O1—H1	0.8200	C3—C4	1.487 (3)
O2—C1	1.183 (3)	C4—H4A	0.9600
O3—C5	1.294 (3)	C4—H4B	0.9600
O3—H3	0.8200	C4—H4C	0.9600
O4—C5	1.187 (3)	C5—C6	1.505 (3)
O5—C9	1.307 (3)	C7—C8	1.482 (3)
O5—H5	0.8200	C8—H8A	0.9600
O6—C9	1.192 (3)	C8—H8B	0.9600
N1—C3	1.322 (3)	C8—H8C	0.9600
N1—C2	1.336 (3)	C9—C10	1.489 (3)
N2—C7	1.330 (3)	C10—C10ⁱ	1.377 (4)
N2—C6	1.333 (3)	C11—C11ⁱ	1.405 (4)
N3—C11	1.323 (3)	C11—C12	1.482 (3)
N3—C10	1.333 (3)	C12—H12A	0.9600
C1—C2	1.484 (3)	C12—H12B	0.9600
C2—C6	1.372 (3)	C12—H12C	0.9600

C1—O1—H1	109.5	C2—C6—C5	124.95 (18)
C5—O3—H3	109.5	N2—C7—C3	120.76 (18)
C9—O5—H5	109.5	N2—C7—C8	118.06 (19)
C3—N1—C2	117.91 (17)	C3—C7—C8	121.17 (19)
C7—N2—C6	117.82 (18)	C7—C8—H8A	109.5
C11—N3—C10	118.29 (17)	C7—C8—H8B	109.5
O2—C1—O1	124.0 (2)	H8A—C8—H8B	109.5
O2—C1—C2	121.3 (2)	C7—C8—H8C	109.5
O1—C1—C2	114.60 (18)	H8A—C8—H8C	109.5
N1—C2—C6	121.33 (18)	H8B—C8—H8C	109.5
N1—C2—C1	119.07 (18)	O6—C9—O5	126.0 (2)
C6—C2—C1	119.54 (18)	O6—C9—C10	121.38 (19)
N1—C3—C7	120.89 (18)	O5—C9—C10	112.56 (19)
N1—C3—C4	118.57 (19)	N3—C10—C10ⁱ	120.98 (11)
C7—C3—C4	120.54 (19)	N3—C10—C9	117.57 (18)
C3—C4—H4A	109.5	C10ⁱ—C10—C9	121.30 (11)
C3—C4—H4B	109.5	N3—C11—C11ⁱ	120.57 (11)
H4A—C4—H4B	109.5	N3—C11—C12	118.19 (19)
C3—C4—H4C	109.5	C11ⁱ—C11—C12	121.23 (13)
H4A—C4—H4C	109.5	C11—C12—H12A	109.5
H4B—C4—H4C	109.5	C11—C12—H12B	109.5
O4—C5—O3	126.7 (2)	H12A—C12—H12B	109.5
O4—C5—C6	120.7 (2)	C11—C12—H12C	109.5
O3—C5—C6	112.4 (2)	H12A—C12—H12C	109.5
N2—C6—C2	121.28 (18)	H12B—C12—H12C	109.5
N2—C6—C5	113.73 (17)

C3—N1—C2—C6	0.0 (3)	O4—C5—C6—C2	93.3 (3)
C3—N1—C2—C1	177.4 (2)	O3—C5—C6—C2	−91.5 (3)
O2—C1—C2—N1	169.2 (3)	C6—N2—C7—C3	0.4 (3)
O1—C1—C2—N1	−8.3 (3)	C6—N2—C7—C8	−179.0 (2)
O2—C1—C2—C6	−13.3 (4)	N1—C3—C7—N2	0.0 (3)
O1—C1—C2—C6	169.1 (2)	C4—C3—C7—N2	−180.0 (2)
C2—N1—C3—C7	−0.2 (3)	N1—C3—C7—C8	179.4 (2)
C2—N1—C3—C4	179.8 (2)	C4—C3—C7—C8	−0.6 (4)
C7—N2—C6—C2	−0.6 (3)	C11—N3—C10—C10ⁱ	3.0 (4)
C7—N2—C6—C5	177.3 (2)	C11—N3—C10—C9	−172.7 (2)
N1—C2—C6—N2	0.5 (3)	O6—C9—C10—N3	134.4 (2)
C1—C2—C6—N2	−177.0 (2)	O5—C9—C10—N3	−44.4 (3)
N1—C2—C6—C5	−177.3 (2)	O6—C9—C10—C10ⁱ	−41.3 (4)
C1—C2—C6—C5	5.3 (3)	O5—C9—C10—C10ⁱ	140.0 (3)
O4—C5—C6—N2	−84.5 (3)	C10—N3—C11—C11ⁱ	2.3 (4)
O3—C5—C6—N2	90.6 (2)	C10—N3—C11—C12	−176.5 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱⁱ	0.82 (1)	2.04	2.845 (2)	167
O3—H3···N3ⁱⁱⁱ	0.82 (1)	2.00	2.803 (2)	165
O5—H5···N1^iv	0.82 (1)	2.06	2.874 (2)	169

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₂O₄
M_r	196.16
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.873 (3), 14.057 (3), 11.991 (2)
β (°)	109.21 (3)
V (Å³)	2526.6 (9)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCX-mini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10832, 2230, 1937
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.133, 1.07
No. of reflections	2230
No. of parameters	196
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.39

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.820 (0)	2.040	2.845 (2)	167.00
O3—H3···N3ⁱⁱ	0.820 (0)	2.000	2.803 (2)	165.00
O5—H5···N1ⁱⁱⁱ	0.820 (0)	2.060	2.874 (2)	169.00

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

Acknowledgements

The author thanks the Jilin Business and Technology College for financial support.

References

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