Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031601/ym2052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031601/ym2052Isup2.hkl |
CCDC reference: 657705
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (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
For related literature, see: Chen & Mak (1991); Gao et al. (2004); Tomono et al. (2005).
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.
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)].
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).
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.
Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. displacement ellipsoids are shown at the 30% probability level. | |
Fig. 2. A packing of (I) viewed down the c axis. |
C8H7NO5 | F(000) = 408 |
Mr = 197.15 | Dx = 1.547 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6859 reflections |
a = 8.0116 (3) Å | θ = 2.6–25.0° |
b = 10.1247 (4) Å | µ = 0.13 mm−1 |
c = 10.6618 (4) Å | T = 296 K |
β = 101.788 (2)° | Block, colourless |
V = 846.59 (6) Å3 | 0.31 × 0.24 × 0.22 mm |
Z = 4 |
Bruker APEX II area-detector diffractometer | 1480 independent reflections |
Radiation source: fine-focus sealed tube | 1311 reflections with I > 2/s(I) |
Graphite monochromator | Rint = 0.054 |
ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.960, Tmax = 0.972 | k = −12→10 |
5747 measured reflections | l = −12→12 |
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)] = 0.036 | H 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 reflections | Δρmax = 0.16 e Å−3 |
134 parameters | Δρmin = −0.19 e Å−3 |
2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (6) |
C8H7NO5 | V = 846.59 (6) Å3 |
Mr = 197.15 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0116 (3) Å | µ = 0.13 mm−1 |
b = 10.1247 (4) Å | T = 296 K |
c = 10.6618 (4) Å | 0.31 × 0.24 × 0.22 mm |
β = 101.788 (2)° |
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 = 0.972 | Rint = 0.054 |
5747 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 2 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.16 e Å−3 |
1480 reflections | Δρmin = −0.19 e Å−3 |
134 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.00147 (19) | 0.14327 (14) | −0.09773 (12) | 0.0710 (4) | |
H1A | −0.038 (3) | 0.0630 (19) | −0.099 (3) | 0.106* | |
O2 | 0.13230 (14) | 0.09344 (11) | 0.10199 (10) | 0.0518 (3) | |
O3 | 0.39426 (15) | 0.66491 (11) | 0.08187 (10) | 0.0549 (3) | |
O4 | 0.47211 (14) | 0.65489 (12) | 0.43812 (11) | 0.0539 (4) | |
H4A | 0.427 (3) | 0.713 (2) | 0.479 (2) | 0.081* | |
O5 | 0.21283 (15) | 0.62620 (16) | 0.32046 (13) | 0.0746 (5) | |
N1 | 0.33915 (15) | 0.46367 (12) | 0.15334 (11) | 0.0396 (3) | |
C1 | 0.26468 (18) | 0.34362 (14) | 0.13670 (13) | 0.0396 (4) | |
H1 | 0.2821 | 0.2842 | 0.2047 | 0.048* | |
C2 | 0.16493 (17) | 0.30746 (15) | 0.02314 (13) | 0.0398 (4) | |
C3 | 0.13783 (18) | 0.40021 (16) | −0.07807 (13) | 0.0432 (4) | |
H3 | 0.0688 | 0.3781 | −0.1564 | 0.052* | |
C4 | 0.21137 (19) | 0.52053 (16) | −0.06178 (13) | 0.0443 (4) | |
H4 | 0.1920 | 0.5803 | −0.1294 | 0.053* | |
C5 | 0.31834 (18) | 0.55812 (15) | 0.05714 (13) | 0.0409 (4) | |
C6 | 0.09656 (18) | 0.17228 (16) | 0.01153 (13) | 0.0434 (4) | |
C7 | 0.44647 (19) | 0.49939 (15) | 0.27633 (13) | 0.0441 (4) | |
H7B | 0.5537 | 0.5348 | 0.2623 | 0.053* | |
H7A | 0.4712 | 0.4209 | 0.3291 | 0.053* | |
C8 | 0.36079 (18) | 0.60041 (16) | 0.34566 (13) | 0.0417 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0968 (10) | 0.0518 (8) | 0.0493 (7) | −0.0166 (7) | −0.0205 (6) | −0.0018 (6) |
O2 | 0.0569 (7) | 0.0487 (7) | 0.0449 (6) | −0.0075 (5) | −0.0012 (5) | 0.0029 (5) |
O3 | 0.0720 (7) | 0.0442 (7) | 0.0446 (6) | −0.0102 (5) | 0.0028 (5) | 0.0066 (5) |
O4 | 0.0523 (6) | 0.0536 (8) | 0.0500 (7) | 0.0001 (5) | −0.0034 (5) | −0.0182 (5) |
O5 | 0.0466 (7) | 0.1110 (12) | 0.0615 (8) | 0.0029 (7) | 0.0000 (5) | −0.0302 (8) |
N1 | 0.0501 (7) | 0.0360 (7) | 0.0293 (6) | 0.0008 (5) | −0.0001 (5) | 0.0004 (5) |
C1 | 0.0486 (8) | 0.0361 (8) | 0.0326 (7) | 0.0035 (6) | 0.0045 (6) | 0.0012 (6) |
C2 | 0.0419 (7) | 0.0410 (8) | 0.0349 (7) | 0.0045 (6) | 0.0038 (5) | −0.0037 (6) |
C3 | 0.0457 (8) | 0.0508 (10) | 0.0303 (7) | 0.0065 (7) | 0.0012 (6) | −0.0025 (6) |
C4 | 0.0523 (8) | 0.0476 (9) | 0.0310 (7) | 0.0064 (7) | 0.0040 (6) | 0.0061 (6) |
C5 | 0.0485 (8) | 0.0394 (8) | 0.0342 (7) | 0.0033 (6) | 0.0070 (6) | 0.0031 (6) |
C6 | 0.0457 (8) | 0.0451 (9) | 0.0362 (7) | 0.0010 (6) | 0.0013 (6) | −0.0049 (7) |
C7 | 0.0537 (8) | 0.0391 (9) | 0.0334 (7) | 0.0005 (6) | −0.0053 (6) | 0.0006 (6) |
C8 | 0.0455 (8) | 0.0457 (9) | 0.0312 (7) | −0.0078 (6) | 0.0015 (6) | 0.0011 (6) |
O1—C6 | 1.2888 (18) | C1—H1 | 0.9300 |
O1—H1A | 0.872 (17) | C2—C3 | 1.413 (2) |
O2—C6 | 1.2396 (18) | C2—C6 | 1.470 (2) |
O3—C5 | 1.2422 (19) | C3—C4 | 1.349 (2) |
O4—C8 | 1.3086 (18) | C3—H3 | 0.9300 |
O4—H4A | 0.855 (16) | C4—C5 | 1.429 (2) |
O5—C8 | 1.1897 (19) | C4—H4 | 0.9300 |
N1—C1 | 1.3497 (19) | C7—C8 | 1.507 (2) |
N1—C5 | 1.3872 (19) | C7—H7B | 0.9700 |
N1—C7 | 1.4591 (17) | C7—H7A | 0.9700 |
C1—C2 | 1.3577 (19) | ||
C6—O1—H1A | 111.6 (18) | C5—C4—H4 | 119.3 |
C8—O4—H4A | 112.2 (15) | O3—C5—N1 | 117.60 (13) |
C1—N1—C5 | 122.72 (12) | O3—C5—C4 | 126.79 (14) |
C1—N1—C7 | 120.32 (12) | N1—C5—C4 | 115.60 (13) |
C5—N1—C7 | 116.96 (12) | O2—C6—O1 | 123.81 (15) |
N1—C1—C2 | 121.59 (13) | O2—C6—C2 | 120.74 (13) |
N1—C1—H1 | 119.2 | O1—C6—C2 | 115.44 (14) |
C2—C1—H1 | 119.2 | N1—C7—C8 | 111.42 (12) |
C1—C2—C3 | 118.19 (14) | N1—C7—H7B | 109.3 |
C1—C2—C6 | 117.87 (13) | C8—C7—H7B | 109.3 |
C3—C2—C6 | 123.90 (13) | N1—C7—H7A | 109.3 |
C4—C3—C2 | 120.45 (13) | C8—C7—H7A | 109.3 |
C4—C3—H3 | 119.8 | H7B—C7—H7A | 108.0 |
C2—C3—H3 | 119.8 | O5—C8—O4 | 124.89 (15) |
C3—C4—C5 | 121.44 (13) | O5—C8—C7 | 124.81 (14) |
C3—C4—H4 | 119.3 | O4—C8—C7 | 110.30 (12) |
C5—N1—C1—C2 | 0.5 (2) | C3—C4—C5—O3 | 178.75 (15) |
C7—N1—C1—C2 | −179.65 (13) | C3—C4—C5—N1 | −0.6 (2) |
N1—C1—C2—C3 | −1.1 (2) | C1—C2—C6—O2 | −1.5 (2) |
N1—C1—C2—C6 | 176.75 (12) | C3—C2—C6—O2 | 176.21 (13) |
C1—C2—C3—C4 | 0.8 (2) | C1—C2—C6—O1 | 179.41 (13) |
C6—C2—C3—C4 | −176.91 (13) | C3—C2—C6—O1 | −2.9 (2) |
C2—C3—C4—C5 | 0.1 (2) | C1—N1—C7—C8 | −108.72 (15) |
C1—N1—C5—O3 | −179.10 (13) | C5—N1—C7—C8 | 71.10 (16) |
C7—N1—C5—O3 | 1.1 (2) | N1—C7—C8—O5 | 16.2 (2) |
C1—N1—C5—C4 | 0.3 (2) | N1—C7—C8—O4 | −164.33 (12) |
C7—N1—C5—C4 | −179.49 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.87 (2) | 1.75 (2) | 2.6219 (17) | 176 (3) |
O4—H4A···O3ii | 0.86 (2) | 1.71 (2) | 2.5411 (16) | 164 (2) |
C3—H3···O5iii | 0.93 | 2.56 | 3.4170 (17) | 154 |
C7—H7A···O4iv | 0.97 | 2.55 | 3.3649 (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 formula | C8H7NO5 |
Mr | 197.15 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 8.0116 (3), 10.1247 (4), 10.6618 (4) |
β (°) | 101.788 (2) |
V (Å3) | 846.59 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.31 × 0.24 × 0.22 |
Data collection | |
Diffractometer | Bruker APEX II area-detector |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.960, 0.972 |
No. of measured, independent and observed [I > 2/s(I)] reflections | 5747, 1480, 1311 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.106, 1.09 |
No. of reflections | 1480 |
No. of parameters | 134 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.19 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.872 (17) | 1.752 (18) | 2.6219 (17) | 176 (3) |
O4—H4A···O3ii | 0.855 (16) | 1.709 (18) | 2.5411 (16) | 164 (2) |
C3—H3···O5iii | 0.93 | 2.56 | 3.4170 (17) | 154 |
C7—H7A···O4iv | 0.97 | 2.55 | 3.3649 (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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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).