Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020958/fl2129sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020958/fl2129Isup2.hkl |
CCDC reference: 651368
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C) = 0.003 Å
- R factor = 0.052
- wR factor = 0.156
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 6 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C6 H5 N O3 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C6 H5 N O3 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 C6 H5 N O3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
See Tinschert et al. (1997) for background; Dogra (2005) for spectral studies; Etter (1990) for hydrogen bonding motifs; Long et al. (2006) for a similar structure.
6-Hydroxynicotinic acid was purchased from Alfa Aesar. Crystals of the title compound were grown from dimethylsulfoxide solution by slow evaporation.
The title compound (I), along with 2-hydroxynicotinic acid (II), are useful intermediates for the synthesis of pharmaceuticals and agrochemicals. Microbial production of both compounds from just nicotinic acid has been investigated by different groups. Bacteria which can regio-selectively hydrolyze nicotinic acid at positions 2 and 6 have been isolated successfully (Tinschert et al., 1997). The spectral characteristics of II, and the factors affecting it, have been studied by Dogra (2005). The presence of II was found to be insignificant in various types of solvents because tautomerization led to 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid, the tautomer of II. We reported the first crystal structure of II previously (Long et al., 2006). The solid state structure of II turned out to be 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid. That was in agreement with Dogra's findings. In addition, the compound formed one-dimensional hydrogen-bonded chains along the [-1 0 1] direction via intermolecular N—H···O hydrogen bonds. Intramolecular R11(6) O—H···O hydrogen bonds were also found (Etter, 1990).
To systematically study the solid state structures of hydroxynicotinic acids, we further examined the crystal structure of 6-hydroxynicotinic acid, a structural isomer of II in this report.
The asymmetric unit of (I), (Fig. 1), contains four molecules and all the molecules have an almost perfectly planar conformation. Like II, the molecule was measured as 1,6-dihydro-6-oxo-3-pyridinecarboxylic acid, the tautomer of 6-hydroxynicotinic acid. Unlike 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid, whose carboxyl group has an anti conformation, the carboxyl group of I has a syn conformation.
The hydrogen bonding network in the crystal (I) is more complicated compared with that of 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid. In the title compound, the hydrogen bonding network can be described as hydrogen-bonded sheets along the [0 0 1] direction via intermolecular N—H···O and O—H···O hydrogen bonds (Table 1, Fig. 2). Careful examination of the sheets finds that each sheet consists of inter-connected dimers created by R22(8) N—H···O hydrogen-bonded motifs and infinite chains formed by C(7) hydrogen-bonded motifs according to Etter's notation. Alternately, these sheets can be viewed as infinitely fused 32-membered hydrogen bonded rings.
See Tinschert et al. (1997) for background; Dogra (2005) for spectral studies; Etter (1990) for hydrogen bonding motifs; Long et al. (2006) for a similar structure.
Data collection: COLLECT (Nonius, 2002); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1995) and local procedures.
Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms). | |
Fig. 2. A packing diagram of (I) along a axis. |
C6H5NO3 | Z = 8 |
Mr = 139.11 | F(000) = 576 |
Triclinic, P1 | Dx = 1.580 Mg m−3 |
a = 6.8130 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.1340 (3) Å | Cell parameters from 5285 reflections |
c = 16.2780 (4) Å | θ = 1.0–27.5° |
α = 82.5570 (9)° | µ = 0.13 mm−1 |
β = 78.106 (1)° | T = 90 K |
γ = 76.251 (1)° | Irregular block, colourless |
V = 1169.43 (5) Å3 | 0.30 × 0.20 × 0.10 mm |
Nonius KappaCCD diffractometer | 5330 independent reflections |
Radiation source: fine-focus sealed tube | 3206 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 18 pixels mm-1 | θmax = 27.5°, θmin = 1.3° |
ω scans at fixed χ = 55° | h = −8→8 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −14→14 |
Tmin = 0.962, Tmax = 0.987 | l = −21→21 |
10567 measured reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0889P)2] where P = (Fo2 + 2Fc2)/3 |
5330 reflections | (Δ/σ)max < 0.001 |
365 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C6H5NO3 | γ = 76.251 (1)° |
Mr = 139.11 | V = 1169.43 (5) Å3 |
Triclinic, P1 | Z = 8 |
a = 6.8130 (1) Å | Mo Kα radiation |
b = 11.1340 (3) Å | µ = 0.13 mm−1 |
c = 16.2780 (4) Å | T = 90 K |
α = 82.5570 (9)° | 0.30 × 0.20 × 0.10 mm |
β = 78.106 (1)° |
Nonius KappaCCD diffractometer | 5330 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 3206 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.987 | Rint = 0.042 |
10567 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.44 e Å−3 |
5330 reflections | Δρmin = −0.33 e Å−3 |
365 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 | ||
O1A | −0.2663 (2) | 0.02267 (12) | 0.12836 (9) | 0.0246 (4) | |
N1A | 0.0776 (2) | −0.31841 (14) | 0.28713 (10) | 0.0172 (4) | |
H1A | 0.1450 | −0.3964 | 0.2874 | 0.021* | |
O2A | −0.0747 (2) | −0.14740 (12) | 0.06663 (9) | 0.0228 (4) | |
H2A | −0.1243 | −0.1118 | 0.0244 | 0.034* | |
C2A | 0.0217 (3) | −0.26190 (18) | 0.21448 (12) | 0.0170 (4) | |
H2A1 | 0.0576 | −0.3062 | 0.1655 | 0.020* | |
O3A | 0.0935 (2) | −0.32412 (12) | 0.42539 (8) | 0.0208 (3) | |
C3A | −0.0858 (3) | −0.14206 (18) | 0.21055 (12) | 0.0167 (4) | |
C4A | −0.1339 (3) | −0.07843 (18) | 0.28476 (13) | 0.0190 (5) | |
H4A | −0.2095 | 0.0051 | 0.2837 | 0.023* | |
C5A | −0.0734 (3) | −0.13532 (18) | 0.35741 (13) | 0.0202 (5) | |
H5A | −0.1038 | −0.0908 | 0.4061 | 0.024* | |
C6A | 0.0358 (3) | −0.26180 (18) | 0.36048 (12) | 0.0178 (5) | |
C7A | −0.1531 (3) | −0.07933 (18) | 0.13204 (12) | 0.0184 (5) | |
O1B | 0.3848 (2) | −0.08869 (13) | 0.40114 (9) | 0.0266 (4) | |
N1B | 0.6711 (2) | −0.43693 (14) | 0.57089 (10) | 0.0178 (4) | |
H1B | 0.7396 | −0.5146 | 0.5717 | 0.021* | |
O2B | 0.5393 (2) | −0.27162 (12) | 0.34799 (9) | 0.0223 (3) | |
H2B | 0.5115 | −0.2324 | 0.3027 | 0.033* | |
C2B | 0.6289 (3) | −0.37921 (18) | 0.49640 (12) | 0.0177 (5) | |
H2B1 | 0.6717 | −0.4232 | 0.4473 | 0.021* | |
O3B | 0.6605 (2) | −0.44604 (12) | 0.71141 (9) | 0.0225 (4) | |
C3B | 0.5257 (3) | −0.25881 (18) | 0.49095 (12) | 0.0173 (4) | |
C4B | 0.4673 (3) | −0.19573 (19) | 0.56541 (13) | 0.0190 (5) | |
H4B | 0.3986 | −0.1108 | 0.5629 | 0.023* | |
C5B | 0.5084 (3) | −0.25521 (17) | 0.64043 (13) | 0.0179 (4) | |
H5B | 0.4665 | −0.2120 | 0.6899 | 0.021* | |
C6B | 0.6141 (3) | −0.38239 (19) | 0.64511 (13) | 0.0184 (5) | |
C7B | 0.4748 (3) | −0.19628 (18) | 0.40984 (13) | 0.0194 (5) | |
N1C | 0.4331 (2) | −0.18372 (15) | 0.06937 (10) | 0.0177 (4) | |
H1C | 0.3515 | −0.1095 | 0.0698 | 0.021* | |
O1C | 0.7973 (2) | −0.51108 (12) | −0.09714 (9) | 0.0256 (4) | |
O2C | 0.5683 (2) | −0.35163 (12) | −0.14625 (9) | 0.0249 (4) | |
H2C | 0.6060 | −0.3885 | −0.1906 | 0.037* | |
C2C | 0.4836 (3) | −0.23954 (18) | −0.00307 (12) | 0.0169 (4) | |
H2C1 | 0.4297 | −0.1989 | −0.0512 | 0.020* | |
O3C | 0.4444 (2) | −0.17246 (12) | 0.20599 (8) | 0.0204 (3) | |
C3C | 0.6111 (3) | −0.35363 (17) | −0.00764 (12) | 0.0167 (4) | |
C4C | 0.6874 (3) | −0.41203 (18) | 0.06576 (13) | 0.0198 (5) | |
H4C | 0.7786 | −0.4912 | 0.0638 | 0.024* | |
C5C | 0.6310 (3) | −0.35561 (17) | 0.13909 (13) | 0.0189 (5) | |
H5C | 0.6791 | −0.3970 | 0.1883 | 0.023* | |
C6C | 0.5007 (3) | −0.23520 (18) | 0.14232 (12) | 0.0165 (4) | |
C7C | 0.6702 (3) | −0.41509 (18) | −0.08724 (13) | 0.0186 (5) | |
O1D | −0.1487 (2) | 0.40702 (12) | 0.36990 (9) | 0.0247 (4) | |
N1D | 0.2167 (2) | 0.07385 (15) | 0.20876 (10) | 0.0185 (4) | |
H1D | 0.3099 | 0.0039 | 0.2075 | 0.022* | |
O2D | 0.0118 (2) | 0.22789 (12) | 0.43099 (9) | 0.0243 (4) | |
H2D | −0.0248 | 0.2668 | 0.4744 | 0.036* | |
C2D | 0.1569 (3) | 0.12889 (17) | 0.28185 (12) | 0.0174 (5) | |
H2D1 | 0.2118 | 0.0904 | 0.3302 | 0.021* | |
O3D | 0.2057 (2) | 0.05834 (12) | 0.07258 (8) | 0.0202 (3) | |
C3D | 0.0185 (3) | 0.23908 (18) | 0.28634 (12) | 0.0170 (4) | |
C4D | −0.0627 (3) | 0.29300 (18) | 0.21338 (13) | 0.0202 (5) | |
H4D | −0.1589 | 0.3704 | 0.2152 | 0.024* | |
C5D | −0.0047 (3) | 0.23539 (18) | 0.14063 (13) | 0.0197 (5) | |
H5D | −0.0617 | 0.2721 | 0.0924 | 0.024* | |
C6D | 0.1415 (3) | 0.12008 (18) | 0.13673 (12) | 0.0170 (4) | |
C7D | −0.0489 (3) | 0.30178 (18) | 0.36576 (13) | 0.0182 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0280 (8) | 0.0195 (8) | 0.0241 (9) | 0.0008 (6) | −0.0087 (7) | 0.0007 (7) |
N1A | 0.0215 (9) | 0.0129 (9) | 0.0154 (10) | 0.0005 (7) | −0.0047 (7) | −0.0013 (7) |
O2A | 0.0314 (9) | 0.0193 (8) | 0.0170 (8) | 0.0006 (6) | −0.0106 (7) | −0.0011 (6) |
C2A | 0.0202 (11) | 0.0195 (11) | 0.0112 (11) | −0.0026 (9) | −0.0043 (8) | −0.0021 (8) |
O3A | 0.0283 (8) | 0.0190 (8) | 0.0135 (8) | 0.0012 (6) | −0.0068 (6) | −0.0025 (6) |
C3A | 0.0181 (10) | 0.0159 (10) | 0.0161 (11) | −0.0040 (8) | −0.0040 (8) | 0.0004 (8) |
C4A | 0.0197 (11) | 0.0140 (10) | 0.0223 (12) | −0.0004 (8) | −0.0042 (9) | −0.0036 (9) |
C5A | 0.0237 (11) | 0.0180 (11) | 0.0185 (12) | −0.0021 (9) | −0.0028 (9) | −0.0058 (9) |
C6A | 0.0184 (10) | 0.0215 (11) | 0.0140 (11) | −0.0038 (8) | −0.0045 (9) | −0.0015 (9) |
C7A | 0.0180 (11) | 0.0201 (12) | 0.0189 (12) | −0.0058 (9) | −0.0047 (9) | −0.0030 (9) |
O1B | 0.0340 (9) | 0.0199 (8) | 0.0220 (9) | 0.0033 (7) | −0.0083 (7) | 0.0003 (6) |
N1B | 0.0218 (9) | 0.0135 (9) | 0.0168 (10) | 0.0006 (7) | −0.0053 (7) | −0.0024 (7) |
O2B | 0.0308 (8) | 0.0209 (8) | 0.0142 (8) | −0.0014 (7) | −0.0076 (7) | −0.0003 (6) |
C2B | 0.0214 (11) | 0.0187 (11) | 0.0134 (11) | −0.0033 (9) | −0.0052 (9) | −0.0016 (8) |
O3B | 0.0296 (8) | 0.0199 (8) | 0.0159 (8) | 0.0021 (6) | −0.0081 (6) | −0.0017 (6) |
C3B | 0.0181 (10) | 0.0174 (11) | 0.0164 (11) | −0.0036 (8) | −0.0049 (9) | 0.0005 (8) |
C4B | 0.0190 (11) | 0.0154 (10) | 0.0218 (12) | −0.0008 (8) | −0.0053 (9) | −0.0017 (9) |
C5B | 0.0193 (11) | 0.0178 (11) | 0.0153 (11) | −0.0004 (8) | −0.0019 (8) | −0.0056 (8) |
C6B | 0.0184 (11) | 0.0238 (11) | 0.0133 (11) | −0.0042 (9) | −0.0032 (9) | −0.0039 (9) |
C7B | 0.0203 (11) | 0.0188 (12) | 0.0187 (12) | −0.0030 (9) | −0.0045 (9) | −0.0005 (9) |
N1C | 0.0211 (9) | 0.0155 (9) | 0.0145 (9) | 0.0016 (7) | −0.0055 (7) | −0.0011 (7) |
O1C | 0.0300 (9) | 0.0208 (8) | 0.0240 (9) | 0.0026 (7) | −0.0065 (7) | −0.0073 (7) |
O2C | 0.0326 (9) | 0.0223 (8) | 0.0174 (8) | 0.0035 (7) | −0.0086 (7) | −0.0045 (6) |
C2C | 0.0206 (11) | 0.0182 (11) | 0.0119 (11) | −0.0038 (8) | −0.0043 (8) | −0.0003 (8) |
O3C | 0.0259 (8) | 0.0187 (8) | 0.0154 (8) | −0.0010 (6) | −0.0044 (6) | −0.0037 (6) |
C3C | 0.0193 (11) | 0.0166 (11) | 0.0140 (11) | −0.0034 (8) | −0.0026 (8) | −0.0026 (8) |
C4C | 0.0215 (11) | 0.0130 (10) | 0.0236 (12) | 0.0003 (8) | −0.0057 (9) | −0.0015 (9) |
C5C | 0.0238 (11) | 0.0143 (11) | 0.0178 (11) | 0.0006 (8) | −0.0092 (9) | 0.0014 (8) |
C6C | 0.0200 (11) | 0.0188 (11) | 0.0115 (11) | −0.0063 (8) | −0.0031 (8) | −0.0001 (9) |
C7C | 0.0217 (11) | 0.0169 (11) | 0.0181 (11) | −0.0049 (9) | −0.0042 (9) | −0.0022 (9) |
O1D | 0.0304 (8) | 0.0187 (8) | 0.0230 (9) | 0.0010 (7) | −0.0040 (7) | −0.0072 (6) |
N1D | 0.0226 (9) | 0.0160 (9) | 0.0152 (9) | 0.0015 (7) | −0.0049 (7) | −0.0033 (7) |
O2D | 0.0311 (9) | 0.0237 (8) | 0.0161 (8) | 0.0019 (7) | −0.0060 (7) | −0.0065 (6) |
C2D | 0.0236 (11) | 0.0163 (11) | 0.0133 (11) | −0.0050 (9) | −0.0047 (9) | −0.0011 (8) |
O3D | 0.0270 (8) | 0.0171 (8) | 0.0156 (8) | −0.0006 (6) | −0.0052 (6) | −0.0044 (6) |
C3D | 0.0190 (11) | 0.0166 (11) | 0.0157 (11) | −0.0042 (8) | −0.0020 (9) | −0.0039 (8) |
C4D | 0.0208 (11) | 0.0158 (11) | 0.0226 (12) | 0.0003 (8) | −0.0061 (9) | −0.0017 (9) |
C5D | 0.0236 (11) | 0.0184 (11) | 0.0170 (11) | −0.0035 (9) | −0.0073 (9) | 0.0027 (9) |
C6D | 0.0224 (11) | 0.0154 (10) | 0.0146 (11) | −0.0059 (8) | −0.0046 (9) | −0.0008 (8) |
C7D | 0.0177 (10) | 0.0183 (11) | 0.0190 (12) | −0.0025 (9) | −0.0042 (9) | −0.0036 (9) |
O1A—C7A | 1.214 (2) | N1C—C2C | 1.348 (2) |
N1A—C2A | 1.348 (2) | N1C—C6C | 1.369 (2) |
N1A—C6A | 1.369 (2) | N1C—H1C | 0.8800 |
N1A—H1A | 0.8800 | O1C—C7C | 1.211 (2) |
O2A—C7A | 1.333 (2) | O2C—C7C | 1.330 (2) |
O2A—H2A | 0.8400 | O2C—H2C | 0.8400 |
C2A—C3A | 1.361 (3) | C2C—C3C | 1.359 (3) |
C2A—H2A1 | 0.9500 | C2C—H2C1 | 0.9500 |
O3A—C6A | 1.267 (2) | O3C—C6C | 1.267 (2) |
C3A—C4A | 1.420 (3) | C3C—C4C | 1.419 (3) |
C3A—C7A | 1.480 (3) | C3C—C7C | 1.481 (3) |
C4A—C5A | 1.361 (3) | C4C—C5C | 1.363 (3) |
C4A—H4A | 0.9500 | C4C—H4C | 0.9500 |
C5A—C6A | 1.428 (3) | C5C—C6C | 1.422 (3) |
C5A—H5A | 0.9500 | C5C—H5C | 0.9500 |
O1B—C7B | 1.214 (2) | O1D—C7D | 1.209 (2) |
N1B—C2B | 1.349 (2) | N1D—C2D | 1.352 (2) |
N1B—C6B | 1.365 (2) | N1D—C6D | 1.367 (2) |
N1B—H1B | 0.8800 | N1D—H1D | 0.8800 |
O2B—C7B | 1.331 (2) | O2D—C7D | 1.330 (2) |
O2B—H2B | 0.8400 | O2D—H2D | 0.8400 |
C2B—C3B | 1.359 (3) | C2D—C3D | 1.358 (3) |
C2B—H2B1 | 0.9500 | C2D—H2D1 | 0.9500 |
O3B—C6B | 1.266 (2) | O3D—C6D | 1.269 (2) |
C3B—C4B | 1.418 (3) | C3D—C4D | 1.416 (3) |
C3B—C7B | 1.478 (3) | C3D—C7D | 1.485 (3) |
C4B—C5B | 1.361 (3) | C4D—C5D | 1.361 (3) |
C4B—H4B | 0.9500 | C4D—H4D | 0.9500 |
C5B—C6B | 1.428 (3) | C5D—C6D | 1.425 (3) |
C5B—H5B | 0.9500 | C5D—H5D | 0.9500 |
C2A—N1A—C6A | 123.93 (17) | C2C—N1C—C6C | 124.17 (17) |
C2A—N1A—H1A | 118.0 | C2C—N1C—H1C | 117.9 |
C6A—N1A—H1A | 118.0 | C6C—N1C—H1C | 117.9 |
C7A—O2A—H2A | 109.5 | C7C—O2C—H2C | 109.5 |
N1A—C2A—C3A | 120.71 (18) | N1C—C2C—C3C | 120.42 (18) |
N1A—C2A—H2A1 | 119.6 | N1C—C2C—H2C1 | 119.8 |
C3A—C2A—H2A1 | 119.6 | C3C—C2C—H2C1 | 119.8 |
C2A—C3A—C4A | 117.94 (18) | C2C—C3C—C4C | 118.25 (18) |
C2A—C3A—C7A | 121.57 (18) | C2C—C3C—C7C | 120.91 (18) |
C4A—C3A—C7A | 120.48 (17) | C4C—C3C—C7C | 120.84 (17) |
C5A—C4A—C3A | 121.00 (18) | C5C—C4C—C3C | 120.62 (18) |
C5A—C4A—H4A | 119.5 | C5C—C4C—H4C | 119.7 |
C3A—C4A—H4A | 119.5 | C3C—C4C—H4C | 119.7 |
C4A—C5A—C6A | 120.07 (18) | C4C—C5C—C6C | 120.38 (18) |
C4A—C5A—H5A | 120.0 | C4C—C5C—H5C | 119.8 |
C6A—C5A—H5A | 120.0 | C6C—C5C—H5C | 119.8 |
O3A—C6A—N1A | 118.68 (17) | O3C—C6C—N1C | 118.10 (17) |
O3A—C6A—C5A | 124.99 (18) | O3C—C6C—C5C | 125.77 (18) |
N1A—C6A—C5A | 116.33 (18) | N1C—C6C—C5C | 116.12 (17) |
O1A—C7A—O2A | 124.41 (18) | O1C—C7C—O2C | 124.41 (18) |
O1A—C7A—C3A | 123.34 (19) | O1C—C7C—C3C | 123.70 (18) |
O2A—C7A—C3A | 112.25 (16) | O2C—C7C—C3C | 111.89 (16) |
C2B—N1B—C6B | 124.13 (17) | C2D—N1D—C6D | 124.12 (16) |
C2B—N1B—H1B | 117.9 | C2D—N1D—H1D | 117.9 |
C6B—N1B—H1B | 117.9 | C6D—N1D—H1D | 117.9 |
C7B—O2B—H2B | 109.5 | C7D—O2D—H2D | 109.5 |
N1B—C2B—C3B | 120.68 (18) | N1D—C2D—C3D | 120.23 (18) |
N1B—C2B—H2B1 | 119.7 | N1D—C2D—H2D1 | 119.9 |
C3B—C2B—H2B1 | 119.7 | C3D—C2D—H2D1 | 119.9 |
C2B—C3B—C4B | 117.98 (18) | C2D—C3D—C4D | 118.41 (18) |
C2B—C3B—C7B | 120.79 (18) | C2D—C3D—C7D | 121.28 (18) |
C4B—C3B—C7B | 121.23 (17) | C4D—C3D—C7D | 120.30 (17) |
C5B—C4B—C3B | 120.88 (18) | C5D—C4D—C3D | 120.83 (18) |
C5B—C4B—H4B | 119.6 | C5D—C4D—H4D | 119.6 |
C3B—C4B—H4B | 119.6 | C3D—C4D—H4D | 119.6 |
C4B—C5B—C6B | 120.28 (18) | C4D—C5D—C6D | 120.13 (19) |
C4B—C5B—H5B | 119.9 | C4D—C5D—H5D | 119.9 |
C6B—C5B—H5B | 119.9 | C6D—C5D—H5D | 119.9 |
O3B—C6B—N1B | 118.63 (18) | O3D—C6D—N1D | 118.35 (17) |
O3B—C6B—C5B | 125.34 (18) | O3D—C6D—C5D | 125.40 (18) |
N1B—C6B—C5B | 116.02 (18) | N1D—C6D—C5D | 116.25 (17) |
O1B—C7B—O2B | 124.30 (19) | O1D—C7D—O2D | 124.66 (18) |
O1B—C7B—C3B | 123.60 (19) | O1D—C7D—C3D | 123.49 (18) |
O2B—C7B—C3B | 112.10 (16) | O2D—C7D—C3D | 111.84 (16) |
C6A—N1A—C2A—C3A | −1.1 (3) | C6C—N1C—C2C—C3C | −0.8 (3) |
N1A—C2A—C3A—C4A | 0.9 (3) | N1C—C2C—C3C—C4C | 0.5 (3) |
N1A—C2A—C3A—C7A | −178.44 (17) | N1C—C2C—C3C—C7C | −179.07 (17) |
C2A—C3A—C4A—C5A | 0.4 (3) | C2C—C3C—C4C—C5C | 1.0 (3) |
C7A—C3A—C4A—C5A | 179.77 (17) | C7C—C3C—C4C—C5C | −179.38 (17) |
C3A—C4A—C5A—C6A | −1.6 (3) | C3C—C4C—C5C—C6C | −2.3 (3) |
C2A—N1A—C6A—O3A | 179.19 (17) | C2C—N1C—C6C—O3C | 179.05 (16) |
C2A—N1A—C6A—C5A | −0.1 (3) | C2C—N1C—C6C—C5C | −0.4 (3) |
C4A—C5A—C6A—O3A | −177.83 (19) | C4C—C5C—C6C—O3C | −177.47 (19) |
C4A—C5A—C6A—N1A | 1.4 (3) | C4C—C5C—C6C—N1C | 2.0 (3) |
C2A—C3A—C7A—O1A | 172.31 (19) | C2C—C3C—C7C—O1C | 173.01 (19) |
C4A—C3A—C7A—O1A | −7.0 (3) | C4C—C3C—C7C—O1C | −6.6 (3) |
C2A—C3A—C7A—O2A | −7.9 (3) | C2C—C3C—C7C—O2C | −6.5 (3) |
C4A—C3A—C7A—O2A | 172.71 (16) | C4C—C3C—C7C—O2C | 173.96 (17) |
C6B—N1B—C2B—C3B | 0.8 (3) | C6D—N1D—C2D—C3D | −2.2 (3) |
N1B—C2B—C3B—C4B | 1.0 (3) | N1D—C2D—C3D—C4D | 1.0 (3) |
N1B—C2B—C3B—C7B | −178.48 (17) | N1D—C2D—C3D—C7D | −179.68 (17) |
C2B—C3B—C4B—C5B | −1.8 (3) | C2D—C3D—C4D—C5D | 0.5 (3) |
C7B—C3B—C4B—C5B | 177.66 (17) | C7D—C3D—C4D—C5D | −178.90 (17) |
C3B—C4B—C5B—C6B | 0.9 (3) | C3D—C4D—C5D—C6D | −0.8 (3) |
C2B—N1B—C6B—O3B | 179.36 (17) | C2D—N1D—C6D—O3D | −178.20 (16) |
C2B—N1B—C6B—C5B | −1.8 (3) | C2D—N1D—C6D—C5D | 1.8 (3) |
C4B—C5B—C6B—O3B | 179.67 (19) | C4D—C5D—C6D—O3D | 179.71 (18) |
C4B—C5B—C6B—N1B | 0.9 (3) | C4D—C5D—C6D—N1D | −0.3 (3) |
C2B—C3B—C7B—O1B | −179.27 (19) | C2D—C3D—C7D—O1D | 169.38 (19) |
C4B—C3B—C7B—O1B | 1.3 (3) | C4D—C3D—C7D—O1D | −11.3 (3) |
C2B—C3B—C7B—O2B | 0.7 (3) | C2D—C3D—C7D—O2D | −11.3 (3) |
C4B—C3B—C7B—O2B | −178.76 (17) | C4D—C3D—C7D—O2D | 168.02 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···O3Di | 0.84 | 1.76 | 2.5971 (18) | 171 |
N1D—H1D···O3C | 0.88 | 1.96 | 2.813 (2) | 163 |
O2D—H2D···O3Aii | 0.84 | 1.76 | 2.5925 (19) | 171 |
O2B—H2B···O3C | 0.84 | 1.74 | 2.5681 (19) | 171 |
N1B—H1B···O3Aiii | 0.88 | 1.88 | 2.761 (2) | 175 |
N1A—H1A···O3Biii | 0.88 | 1.93 | 2.800 (2) | 169 |
O2C—H2C···O3Biv | 0.84 | 1.73 | 2.5661 (19) | 172 |
N1C—H1C···O3D | 0.88 | 1.90 | 2.772 (2) | 173 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z+1; (iii) −x+1, −y−1, −z+1; (iv) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C6H5NO3 |
Mr | 139.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 90 |
a, b, c (Å) | 6.8130 (1), 11.1340 (3), 16.2780 (4) |
α, β, γ (°) | 82.5570 (9), 78.106 (1), 76.251 (1) |
V (Å3) | 1169.43 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.962, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10567, 5330, 3206 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.156, 1.00 |
No. of reflections | 5330 |
No. of parameters | 365 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.33 |
Computer programs: COLLECT (Nonius, 2002), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1995) and local procedures.
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···O3Di | 0.84 | 1.76 | 2.5971 (18) | 170.7 |
N1D—H1D···O3C | 0.88 | 1.96 | 2.813 (2) | 162.7 |
O2D—H2D···O3Aii | 0.84 | 1.76 | 2.5925 (19) | 170.5 |
O2B—H2B···O3C | 0.84 | 1.74 | 2.5681 (19) | 171.1 |
N1B—H1B···O3Aiii | 0.88 | 1.88 | 2.761 (2) | 175.0 |
N1A—H1A···O3Biii | 0.88 | 1.93 | 2.800 (2) | 168.6 |
O2C—H2C···O3Biv | 0.84 | 1.73 | 2.5661 (19) | 171.5 |
N1C—H1C···O3D | 0.88 | 1.90 | 2.772 (2) | 172.5 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z+1; (iii) −x+1, −y−1, −z+1; (iv) x, y, z−1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The title compound (I), along with 2-hydroxynicotinic acid (II), are useful intermediates for the synthesis of pharmaceuticals and agrochemicals. Microbial production of both compounds from just nicotinic acid has been investigated by different groups. Bacteria which can regio-selectively hydrolyze nicotinic acid at positions 2 and 6 have been isolated successfully (Tinschert et al., 1997). The spectral characteristics of II, and the factors affecting it, have been studied by Dogra (2005). The presence of II was found to be insignificant in various types of solvents because tautomerization led to 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid, the tautomer of II. We reported the first crystal structure of II previously (Long et al., 2006). The solid state structure of II turned out to be 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid. That was in agreement with Dogra's findings. In addition, the compound formed one-dimensional hydrogen-bonded chains along the [-1 0 1] direction via intermolecular N—H···O hydrogen bonds. Intramolecular R11(6) O—H···O hydrogen bonds were also found (Etter, 1990).
To systematically study the solid state structures of hydroxynicotinic acids, we further examined the crystal structure of 6-hydroxynicotinic acid, a structural isomer of II in this report.
The asymmetric unit of (I), (Fig. 1), contains four molecules and all the molecules have an almost perfectly planar conformation. Like II, the molecule was measured as 1,6-dihydro-6-oxo-3-pyridinecarboxylic acid, the tautomer of 6-hydroxynicotinic acid. Unlike 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid, whose carboxyl group has an anti conformation, the carboxyl group of I has a syn conformation.
The hydrogen bonding network in the crystal (I) is more complicated compared with that of 1,2-dihydro-2-oxo-3-pyridinecarboxylic acid. In the title compound, the hydrogen bonding network can be described as hydrogen-bonded sheets along the [0 0 1] direction via intermolecular N—H···O and O—H···O hydrogen bonds (Table 1, Fig. 2). Careful examination of the sheets finds that each sheet consists of inter-connected dimers created by R22(8) N—H···O hydrogen-bonded motifs and infinite chains formed by C(7) hydrogen-bonded motifs according to Etter's notation. Alternately, these sheets can be viewed as infinitely fused 32-membered hydrogen bonded rings.