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The title compound, C8H7NO5, is a new betaine derivative obtained by the reaction of chloro­acetic acid with 6-hydroxy­nicotinic acid under basic conditions. The molecule is planar except for the carboxymethyl group, which makes a dihedral angle of 77.40 (2)° with the pyridinium ring. The crystal structure is stabilized by inter­molecular C—H...O and O—H...O hydrogen bonds to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031601/ym2052sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031601/ym2052Isup2.hkl
Contains datablock I

CCDC reference: 657705

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.036
  • wR factor = 0.106
  • Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTY02_ALERT_1_C An _exptl_absorpt_correction_type has been given without a literature citation. This should be contained in the _exptl_absorpt_process_details field. Absorption correction given as empirical PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8
Alert level G PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Pyridinium carboxylate salts, the analogue of betaine compounds are normally zwitterions containing a carboxylate group and a quaternary ammonium group. Owing to its versatile coordination behavior to metal ions, a large amount of betaine complexes have been reported,such as bis(pyridiniopropionato)disilver diperchlorate and dinitratobis(pyridiniopropionato)disilver(Chen & Mak, 1991), Mg(C7H6NO3)2(H2O)4(Gao et al., 2004) and 3-Methoxycarbonyl-1- methylpyridiniumbis(2-thioxo-1,3-dithiole-4,5-dithiolato) nickelate(II) (Tomono et al., 2005). The title compound (1), is a dicarboxylic acid analogue of betaine (Fig.1). The 6-oxo-1,6-dihydropyridine-3-carboxylate fragment, O1/O2/O3/(C1—C6), is essentially planar with maximum deviation of 0.061 (1)Å for O2 atom from the least square plane and perpendicular to the acetate fragment, O4/O5/C8/C7, by 76.39 (7) Å.

The 1H NMR spectrum reveals the hydroxyl is deprotonated and the two carboxyl are all protonated, which means the title compound is a traditional inner salt.

In the crystal structure, the molecules are linked by C—H···O and O—H···O intermolecular hydrogen bonds (symmetry codes as in table 2) to form a three dimensional network (Fig.2).

Related literature top

For related literature, see: Chen & Mak (1991); Gao et al. (2004); Tomono et al. (2005).

Experimental top

The mixture of chloroacetic acid (2.84 g, 30 mmol) and 6-hydroxy-nicotinic acid (1.39 g, 10 mmol) was stirred under basic condition and refluxed at 90°C for 3 h, in which sodium hydroxide solution was added to keep the pH value around 11. Then the pH value was adjusted to about 3 by adding concentrated hydrochloric acid. Large quantity of light yellow precipitate was obtained with the yield of 90%.

Then colorless rhombus-shaped crystal of (I) were gained in the filtrate. And the melting point of the crystal is about 299°C.

Refinement top

The H atoms bonded to C atoms were positioned geometrically [aromatic C—H 0.93 Å and aliphatic C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C)]. The H atoms bonded to O atoms were located in a difference Fourier maps and refined with the O—H distance restrained to 0.82 (2)Å [Uiso(H) = -1.5Ueq(O)].

Structure description top

Pyridinium carboxylate salts, the analogue of betaine compounds are normally zwitterions containing a carboxylate group and a quaternary ammonium group. Owing to its versatile coordination behavior to metal ions, a large amount of betaine complexes have been reported,such as bis(pyridiniopropionato)disilver diperchlorate and dinitratobis(pyridiniopropionato)disilver(Chen & Mak, 1991), Mg(C7H6NO3)2(H2O)4(Gao et al., 2004) and 3-Methoxycarbonyl-1- methylpyridiniumbis(2-thioxo-1,3-dithiole-4,5-dithiolato) nickelate(II) (Tomono et al., 2005). The title compound (1), is a dicarboxylic acid analogue of betaine (Fig.1). The 6-oxo-1,6-dihydropyridine-3-carboxylate fragment, O1/O2/O3/(C1—C6), is essentially planar with maximum deviation of 0.061 (1)Å for O2 atom from the least square plane and perpendicular to the acetate fragment, O4/O5/C8/C7, by 76.39 (7) Å.

The 1H NMR spectrum reveals the hydroxyl is deprotonated and the two carboxyl are all protonated, which means the title compound is a traditional inner salt.

In the crystal structure, the molecules are linked by C—H···O and O—H···O intermolecular hydrogen bonds (symmetry codes as in table 2) to form a three dimensional network (Fig.2).

For related literature, see: Chen & Mak (1991); Gao et al. (2004); Tomono et al. (2005).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. displacement ellipsoids are shown at the 30% probability level.
[Figure 2] Fig. 2. A packing of (I) viewed down the c axis.
5-Carboxy-1-carboxymethyl-2-oxidopyridinium top
Crystal data top
C8H7NO5F(000) = 408
Mr = 197.15Dx = 1.547 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6859 reflections
a = 8.0116 (3) Åθ = 2.6–25.0°
b = 10.1247 (4) ŵ = 0.13 mm1
c = 10.6618 (4) ÅT = 296 K
β = 101.788 (2)°Block, colourless
V = 846.59 (6) Å30.31 × 0.24 × 0.22 mm
Z = 4
Data collection top
Bruker APEX II area-detector
diffractometer
1480 independent reflections
Radiation source: fine-focus sealed tube1311 reflections with I > 2/s(I)
Graphite monochromatorRint = 0.054
ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.960, Tmax = 0.972k = 1210
5747 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0568P)2 + 0.1486P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.003
1480 reflectionsΔρmax = 0.16 e Å3
134 parametersΔρmin = 0.19 e Å3
2 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.051 (6)
Crystal data top
C8H7NO5V = 846.59 (6) Å3
Mr = 197.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.0116 (3) ŵ = 0.13 mm1
b = 10.1247 (4) ÅT = 296 K
c = 10.6618 (4) Å0.31 × 0.24 × 0.22 mm
β = 101.788 (2)°
Data collection top
Bruker APEX II area-detector
diffractometer
1480 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1311 reflections with I > 2/s(I)
Tmin = 0.960, Tmax = 0.972Rint = 0.054
5747 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0362 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.16 e Å3
1480 reflectionsΔρmin = 0.19 e Å3
134 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 &gt; 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
xyzUiso*/Ueq
O10.00147 (19)0.14327 (14)0.09773 (12)0.0710 (4)
H1A0.038 (3)0.0630 (19)0.099 (3)0.106*
O20.13230 (14)0.09344 (11)0.10199 (10)0.0518 (3)
O30.39426 (15)0.66491 (11)0.08187 (10)0.0549 (3)
O40.47211 (14)0.65489 (12)0.43812 (11)0.0539 (4)
H4A0.427 (3)0.713 (2)0.479 (2)0.081*
O50.21283 (15)0.62620 (16)0.32046 (13)0.0746 (5)
N10.33915 (15)0.46367 (12)0.15334 (11)0.0396 (3)
C10.26468 (18)0.34362 (14)0.13670 (13)0.0396 (4)
H10.28210.28420.20470.048*
C20.16493 (17)0.30746 (15)0.02314 (13)0.0398 (4)
C30.13783 (18)0.40021 (16)0.07807 (13)0.0432 (4)
H30.06880.37810.15640.052*
C40.21137 (19)0.52053 (16)0.06178 (13)0.0443 (4)
H40.19200.58030.12940.053*
C50.31834 (18)0.55812 (15)0.05714 (13)0.0409 (4)
C60.09656 (18)0.17228 (16)0.01153 (13)0.0434 (4)
C70.44647 (19)0.49939 (15)0.27633 (13)0.0441 (4)
H7B0.55370.53480.26230.053*
H7A0.47120.42090.32910.053*
C80.36079 (18)0.60041 (16)0.34566 (13)0.0417 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0968 (10)0.0518 (8)0.0493 (7)0.0166 (7)0.0205 (6)0.0018 (6)
O20.0569 (7)0.0487 (7)0.0449 (6)0.0075 (5)0.0012 (5)0.0029 (5)
O30.0720 (7)0.0442 (7)0.0446 (6)0.0102 (5)0.0028 (5)0.0066 (5)
O40.0523 (6)0.0536 (8)0.0500 (7)0.0001 (5)0.0034 (5)0.0182 (5)
O50.0466 (7)0.1110 (12)0.0615 (8)0.0029 (7)0.0000 (5)0.0302 (8)
N10.0501 (7)0.0360 (7)0.0293 (6)0.0008 (5)0.0001 (5)0.0004 (5)
C10.0486 (8)0.0361 (8)0.0326 (7)0.0035 (6)0.0045 (6)0.0012 (6)
C20.0419 (7)0.0410 (8)0.0349 (7)0.0045 (6)0.0038 (5)0.0037 (6)
C30.0457 (8)0.0508 (10)0.0303 (7)0.0065 (7)0.0012 (6)0.0025 (6)
C40.0523 (8)0.0476 (9)0.0310 (7)0.0064 (7)0.0040 (6)0.0061 (6)
C50.0485 (8)0.0394 (8)0.0342 (7)0.0033 (6)0.0070 (6)0.0031 (6)
C60.0457 (8)0.0451 (9)0.0362 (7)0.0010 (6)0.0013 (6)0.0049 (7)
C70.0537 (8)0.0391 (9)0.0334 (7)0.0005 (6)0.0053 (6)0.0006 (6)
C80.0455 (8)0.0457 (9)0.0312 (7)0.0078 (6)0.0015 (6)0.0011 (6)
Geometric parameters (Å, º) top
O1—C61.2888 (18)C1—H10.9300
O1—H1A0.872 (17)C2—C31.413 (2)
O2—C61.2396 (18)C2—C61.470 (2)
O3—C51.2422 (19)C3—C41.349 (2)
O4—C81.3086 (18)C3—H30.9300
O4—H4A0.855 (16)C4—C51.429 (2)
O5—C81.1897 (19)C4—H40.9300
N1—C11.3497 (19)C7—C81.507 (2)
N1—C51.3872 (19)C7—H7B0.9700
N1—C71.4591 (17)C7—H7A0.9700
C1—C21.3577 (19)
C6—O1—H1A111.6 (18)C5—C4—H4119.3
C8—O4—H4A112.2 (15)O3—C5—N1117.60 (13)
C1—N1—C5122.72 (12)O3—C5—C4126.79 (14)
C1—N1—C7120.32 (12)N1—C5—C4115.60 (13)
C5—N1—C7116.96 (12)O2—C6—O1123.81 (15)
N1—C1—C2121.59 (13)O2—C6—C2120.74 (13)
N1—C1—H1119.2O1—C6—C2115.44 (14)
C2—C1—H1119.2N1—C7—C8111.42 (12)
C1—C2—C3118.19 (14)N1—C7—H7B109.3
C1—C2—C6117.87 (13)C8—C7—H7B109.3
C3—C2—C6123.90 (13)N1—C7—H7A109.3
C4—C3—C2120.45 (13)C8—C7—H7A109.3
C4—C3—H3119.8H7B—C7—H7A108.0
C2—C3—H3119.8O5—C8—O4124.89 (15)
C3—C4—C5121.44 (13)O5—C8—C7124.81 (14)
C3—C4—H4119.3O4—C8—C7110.30 (12)
C5—N1—C1—C20.5 (2)C3—C4—C5—O3178.75 (15)
C7—N1—C1—C2179.65 (13)C3—C4—C5—N10.6 (2)
N1—C1—C2—C31.1 (2)C1—C2—C6—O21.5 (2)
N1—C1—C2—C6176.75 (12)C3—C2—C6—O2176.21 (13)
C1—C2—C3—C40.8 (2)C1—C2—C6—O1179.41 (13)
C6—C2—C3—C4176.91 (13)C3—C2—C6—O12.9 (2)
C2—C3—C4—C50.1 (2)C1—N1—C7—C8108.72 (15)
C1—N1—C5—O3179.10 (13)C5—N1—C7—C871.10 (16)
C7—N1—C5—O31.1 (2)N1—C7—C8—O516.2 (2)
C1—N1—C5—C40.3 (2)N1—C7—C8—O4164.33 (12)
C7—N1—C5—C4179.49 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.87 (2)1.75 (2)2.6219 (17)176 (3)
O4—H4A···O3ii0.86 (2)1.71 (2)2.5411 (16)164 (2)
C3—H3···O5iii0.932.563.4170 (17)154
C7—H7A···O4iv0.972.553.3649 (19)142
Symmetry codes: (i) x, y, z; (ii) x, y+3/2, z+1/2; (iii) x, y+1, z; (iv) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC8H7NO5
Mr197.15
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)8.0116 (3), 10.1247 (4), 10.6618 (4)
β (°) 101.788 (2)
V3)846.59 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.31 × 0.24 × 0.22
Data collection
DiffractometerBruker APEX II area-detector
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.960, 0.972
No. of measured, independent and
observed [I > 2/s(I)] reflections
5747, 1480, 1311
Rint0.054
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.106, 1.09
No. of reflections1480
No. of parameters134
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.19

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.872 (17)1.752 (18)2.6219 (17)176 (3)
O4—H4A···O3ii0.855 (16)1.709 (18)2.5411 (16)164 (2)
C3—H3···O5iii0.932.563.4170 (17)154
C7—H7A···O4iv0.972.553.3649 (19)142
Symmetry codes: (i) x, y, z; (ii) x, y+3/2, z+1/2; (iii) x, y+1, z; (iv) x+1, y+1, z+1.
 

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