Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111026254/mx3051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Iasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Ibsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Ic1sup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Ic2sup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Ic3sup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Idsup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026254/mx3051Iesup8.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270111026254/mx3051sup9.pdf |
CCDC references: 842156; 842157; 842158; 842159; 842160; 842161; 842162
The synthesis of 6-methyl-5-hydroxy-2-pyridone has been described in several publications (Behrman, 2008; Loth & Hempel, 1972). Crystals of (Ia) suitable for X-ray diffraction analysis were prepared by dissolving (I) (100 mg) in hot ethanol (6 ml) and then slowly adding acetone (10 ml). The other solvates were prepared as follows (mass of 5-hydroxy-6-methyl-2-pyridone, volume of solvent): (Ib) 50 mg, 5 ml propan-2-ol; (Ic) 50 mg, 3 ml methanol; (Id) 50 mg, 2 ml water; (Ie) 50 mg, 3.5 ml benzonitrile; (If) 20 mg, 0.5 ml benzyl alcohol. Crystals from benzonitrile and benzyl alcohol were washed with diethyl ether. Sublimation was carried out at about 0.5 mm Hg and at a temperature gradually rising from room temperature to about 423 K. 1H NMR spectra were measured in DMSO-d6 at 600 MHz. They gave host–solvent ratios consistent with disordered model refinement for the acetone and propan-2-ol solvates, or from a count of the number of electrons present within the channels using SQUEEZE in PLATON (Spek, 2009). Data for the IR, UV and NMR spectra are given by Behrman (2008) and Loth & Hempel (1972).
H atoms on the molecules of (I) in each of the structures were found in difference Fourier maps and subsequently placed at idealized positions. For the low-temperature structures, riding models with constrained distances of 0.95 (CArH), 0.98 (RCH3), 0.88 (NH) and 0.84 Å (OH) were used. For the room-temperature structure, (Ic2), the distances were 0.93 (CArH), 0.96 (RCH3), 0.86 (NH) and 0.82 Å (OH). In (Ia) and (Ib), owing to extensive disorder, the H atoms of the solvent molecules were not found in difference maps. They were placed using geometric criteria and refined using riding models, with constrained distances of 0.98 (RCH3), 0.99 (R2CH2) and 0.84 Å (OH). Values for Uiso(H) were set to 1.2Ueq(parent atom), or 1.5Ueq(parent atom) for OH and CH3. We considered inclusion here of the structures processed using SQUEEZE (Spek, 2009), but there seemed little point as they would have added no additional insight.
In (Ia) and (Ib), the solvent molecules are disordered on sites of 3 point symmetry and required restraints to maintain chemically sensible geometry and physically reasonable displacement parameters. The SHELXL97 (Sheldrick, 2008) commands DFIX, SAME, FLAT and SIMU were used to restrain interatomic distances, maintain geometric similarity and flatness, and keep the displacement parameters of closely proximate atoms similar. In both (Ia) and (Ib), several different disorder models were tried. The best model in each case was chosen by visual inspection and by careful analysis of refinement statistics, including an R tensor (Parkin, 2000), which quantifies the spatial quality of a crystallographic refinement. In (Ic1), (Ic2), (Ic3), (Id) and (Ie), the solvent molecules were also disordered on sites of 3 point symmetry, but suitable disorder models were not constructed.
Data collection: APEX2 (Bruker, 2006) for (Ia), (Ib), (Id), (Ie); COLLECT (Nonius, 1998) for Ic1, Ic2, Ic3. Cell refinement: APEX2 (Bruker, 2006) for (Ia), (Ib), (Id), (Ie); SCALEPACK (Otwinowski & Minor, 1997) for Ic1, Ic2, Ic3. Data reduction: APEX2 (Bruker, 2006) for (Ia), (Ib), (Id), (Ie); DENZO-SMN (Otwinowski & Minor, 1997) for Ic1, Ic2, Ic3. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures.
C6H7NO2·0.1667C3H6O | Dx = 1.430 Mg m−3 |
Mr = 134.81 | Cu Kα radiation, λ = 1.54178 Å |
Trigonal, R3 | Cell parameters from 3409 reflections |
Hall symbol: -R 3 | θ = 3.6–68.0° |
a = 24.7962 (3) Å | µ = 0.91 mm−1 |
c = 5.2924 (1) Å | T = 90 K |
V = 2818.08 (7) Å3 | Needle, colourless |
Z = 18 | 0.12 × 0.01 × 0.01 mm |
F(000) = 1284 |
Bruker X8 Proteum diffractometer | 854 reflections with I > 2σ(I) |
Radiation source: fine-focus rotating anode | Rint = 0.077 |
Graded multilayer optics monochromator | θmax = 68.2°, θmin = 3.6° |
Detector resolution: 5.6 pixels mm-1 | h = −29→29 |
ϕ and ω scans | k = −29→29 |
14372 measured reflections | l = −4→6 |
1153 independent reflections |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0629P)2 + 5.4027P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
1153 reflections | Δρmax = 0.17 e Å−3 |
101 parameters | Δρmin = −0.39 e Å−3 |
6 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: 0.00073 (18) |
C6H7NO2·0.1667C3H6O | Z = 18 |
Mr = 134.81 | Cu Kα radiation |
Trigonal, R3 | µ = 0.91 mm−1 |
a = 24.7962 (3) Å | T = 90 K |
c = 5.2924 (1) Å | 0.12 × 0.01 × 0.01 mm |
V = 2818.08 (7) Å3 |
Bruker X8 Proteum diffractometer | 854 reflections with I > 2σ(I) |
14372 measured reflections | Rint = 0.077 |
1153 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 6 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
1153 reflections | Δρmin = −0.39 e Å−3 |
101 parameters |
Experimental. The Comment section mentions synthesis of three related compounds, namely the 6-H (Behrman, 2008), 6-nitroso (Krowicki, 1977) and 6-Br. Synthesis of the latter is unpublished (Eikhoff & Behrman, 2009), so for the sake of completeness we give it here: The precursor 6-bromo-2-pyridone was made as described by Newkome et al.(1974). Elbs oxidation of this material yielded 6-bromo-2-pyridone-5-sulfate which was isolated according to the method of Smith (1951). The ester was hydrolyzed at room temperature with 48% HBr as hydrolysis under the usual conditions yields mostly 2,3,6-trihydroxypyridine. Neutralization and sublimation in vacuo gave the title compound which was then crystallized from dichloromethane (m.p. 427–428 K (decomposition)]. Calculated for C5H4BrNO2: Br 42.05%; found: Br 42.06%. UV (water): λmax 304 nm, 4700 M-1 cm-1, sh 334, 225 nm. Ferric chloride color: pink, λmax 509 nm, sh 544. IR (Nujol): 1660, 1605, 1530, 1456, 1401, 1288, 1267, 1246, 1051, 925, 815 cm-1. 1H NMR(DMSO-d6) 600 MHz: δ 10.58 (s, NH), 9.94 (s, OH), 7.22 (d, H-4, J = 8.5 Hz), 6.50 (d, H-3, J = 8.5 Hz). With drier solvent, NH coupling was observed: δ 7.09 (t, J = 51 Hz). References Newkome, G. R., Broussard, J., Staires, S. K. & Sauer, J. D. (1974). Synthesis, p. 707. Smith, J. N. (1951). J. Chem. Soc. pp. 2861–2863. |
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 > 2σ(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 | Occ. (<1) | |
N1 | 0.55395 (8) | 0.50854 (8) | 0.2534 (3) | 0.0290 (5) | |
H1 | 0.5336 | 0.4842 | 0.1252 | 0.035* | |
C2 | 0.55002 (9) | 0.56112 (10) | 0.2845 (4) | 0.0283 (5) | |
C3 | 0.58299 (10) | 0.59894 (10) | 0.4935 (4) | 0.0301 (5) | |
H3 | 0.5820 | 0.6361 | 0.5267 | 0.036* | |
C4 | 0.61623 (10) | 0.58200 (10) | 0.6475 (4) | 0.0306 (5) | |
H4 | 0.6379 | 0.6077 | 0.7875 | 0.037* | |
C5 | 0.61921 (10) | 0.52778 (10) | 0.6048 (4) | 0.0301 (5) | |
C6 | 0.58679 (10) | 0.49035 (10) | 0.4044 (4) | 0.0303 (5) | |
O1 | 0.51734 (7) | 0.57242 (7) | 0.1304 (3) | 0.0311 (4) | |
O2 | 0.65110 (7) | 0.50989 (7) | 0.7627 (3) | 0.0368 (5) | |
H2 | 0.6853 | 0.5411 | 0.8017 | 0.055* | |
C7 | 0.58305 (12) | 0.43014 (11) | 0.3433 (5) | 0.0375 (6) | |
H7A | 0.6167 | 0.4277 | 0.4296 | 0.056* | |
H7B | 0.5871 | 0.4272 | 0.1603 | 0.056* | |
H7C | 0.5428 | 0.3957 | 0.3994 | 0.056* | |
O1S | 0.6492 (7) | 0.3252 (11) | 0.487 (2) | 0.075 (5)* | 0.17 |
C1S | 0.6727 (5) | 0.3358 (10) | 0.716 (2) | 0.050 (3)* | 0.17 |
C2S | 0.682 (4) | 0.3889 (14) | 0.831 (5) | 0.064 (6)* | 0.17 |
H2S1 | 0.6589 | 0.4055 | 0.7383 | 0.096* | 0.17 |
H2S2 | 0.7263 | 0.4198 | 0.8307 | 0.096* | 0.17 |
H2S3 | 0.6666 | 0.3796 | 1.0050 | 0.096* | 0.17 |
C3S | 0.685 (4) | 0.292 (3) | 0.811 (4) | 0.063 (5)* | 0.17 |
H3S1 | 0.6643 | 0.2544 | 0.7070 | 0.094* | 0.17 |
H3S2 | 0.6694 | 0.2820 | 0.9849 | 0.094* | 0.17 |
H3S3 | 0.7300 | 0.3083 | 0.8100 | 0.094* | 0.17 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0314 (9) | 0.0283 (9) | 0.0205 (9) | 0.0100 (8) | −0.0001 (7) | −0.0003 (7) |
C2 | 0.0285 (11) | 0.0291 (11) | 0.0201 (10) | 0.0090 (9) | 0.0047 (8) | 0.0015 (8) |
C3 | 0.0334 (11) | 0.0300 (11) | 0.0214 (10) | 0.0117 (9) | 0.0022 (8) | −0.0019 (8) |
C4 | 0.0312 (11) | 0.0322 (11) | 0.0197 (10) | 0.0094 (9) | 0.0017 (8) | −0.0007 (8) |
C5 | 0.0296 (11) | 0.0333 (11) | 0.0218 (10) | 0.0116 (9) | 0.0025 (8) | 0.0042 (8) |
C6 | 0.0305 (11) | 0.0315 (11) | 0.0226 (10) | 0.0108 (9) | 0.0037 (8) | 0.0029 (8) |
O1 | 0.0344 (8) | 0.0325 (8) | 0.0224 (8) | 0.0137 (7) | −0.0018 (6) | 0.0003 (6) |
O2 | 0.0381 (9) | 0.0371 (9) | 0.0292 (8) | 0.0143 (7) | −0.0044 (7) | 0.0027 (6) |
C7 | 0.0420 (13) | 0.0341 (12) | 0.0334 (12) | 0.0168 (10) | −0.0018 (10) | 0.0001 (10) |
N1—C2 | 1.365 (3) | C7—H7A | 0.9800 |
N1—C6 | 1.368 (3) | C7—H7B | 0.9800 |
N1—H1 | 0.8800 | C7—H7C | 0.9800 |
C2—O1 | 1.276 (3) | O1S—C1S | 1.312 (16) |
C2—C3 | 1.416 (3) | C1S—C2S | 1.361 (14) |
C3—C4 | 1.366 (3) | C1S—C3S | 1.361 (14) |
C3—H3 | 0.9500 | C2S—H2S1 | 0.9800 |
C4—C5 | 1.401 (3) | C2S—H2S2 | 0.9800 |
C4—H4 | 0.9500 | C2S—H2S3 | 0.9800 |
C5—O2 | 1.368 (3) | C3S—H3S1 | 0.9800 |
C5—C6 | 1.373 (3) | C3S—H3S2 | 0.9800 |
C6—C7 | 1.485 (3) | C3S—H3S3 | 0.9800 |
O2—H2 | 0.8400 | ||
C2—N1—C6 | 125.66 (18) | C6—C7—H7B | 109.5 |
C2—N1—H1 | 117.2 | H7A—C7—H7B | 109.5 |
C6—N1—H1 | 117.2 | C6—C7—H7C | 109.5 |
O1—C2—N1 | 119.29 (18) | H7A—C7—H7C | 109.5 |
O1—C2—C3 | 125.0 (2) | H7B—C7—H7C | 109.5 |
N1—C2—C3 | 115.68 (19) | O1S—C1S—C2S | 116.5 (12) |
C4—C3—C2 | 120.0 (2) | O1S—C1S—C3S | 115.8 (12) |
C4—C3—H3 | 120.0 | C2S—C1S—C3S | 127.7 (16) |
C2—C3—H3 | 120.0 | C1S—C2S—H2S1 | 109.5 |
C3—C4—C5 | 121.9 (2) | C1S—C2S—H2S2 | 109.5 |
C3—C4—H4 | 119.1 | H2S1—C2S—H2S2 | 109.5 |
C5—C4—H4 | 119.1 | C1S—C2S—H2S3 | 109.5 |
O2—C5—C6 | 119.4 (2) | H2S1—C2S—H2S3 | 109.5 |
O2—C5—C4 | 121.95 (19) | H2S2—C2S—H2S3 | 109.5 |
C6—C5—C4 | 118.6 (2) | C1S—C3S—H3S1 | 109.5 |
N1—C6—C5 | 118.2 (2) | C1S—C3S—H3S2 | 109.5 |
N1—C6—C7 | 117.13 (19) | H3S1—C3S—H3S2 | 109.5 |
C5—C6—C7 | 124.7 (2) | C1S—C3S—H3S3 | 109.5 |
C5—O2—H2 | 109.5 | H3S1—C3S—H3S3 | 109.5 |
C6—C7—H7A | 109.5 | H3S2—C3S—H3S3 | 109.5 |
C6—N1—C2—O1 | −179.56 (18) | C2—N1—C6—C5 | −0.4 (3) |
C6—N1—C2—C3 | −0.4 (3) | C2—N1—C6—C7 | 177.8 (2) |
O1—C2—C3—C4 | 179.5 (2) | O2—C5—C6—N1 | 178.30 (17) |
N1—C2—C3—C4 | 0.4 (3) | C4—C5—C6—N1 | 1.1 (3) |
C2—C3—C4—C5 | 0.3 (3) | O2—C5—C6—C7 | 0.3 (3) |
C3—C4—C5—O2 | −178.22 (19) | C4—C5—C6—C7 | −176.9 (2) |
C3—C4—C5—C6 | −1.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.90 | 2.781 (2) | 174 |
O2—H2···O1ii | 0.84 | 1.81 | 2.634 (2) | 165 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
C6H7NO2·0.1667C3H8O | Dx = 1.424 Mg m−3 |
Mr = 135.14 | Cu Kα radiation, λ = 1.54178 Å |
Trigonal, R3 | Cell parameters from 2347 reflections |
Hall symbol: -R 3 | θ = 3.6–68.0° |
a = 24.9208 (5) Å | µ = 0.90 mm−1 |
c = 5.2738 (1) Å | T = 90 K |
V = 2836.47 (10) Å3 | Needle, colourless |
Z = 18 | 0.13 × 0.01 × 0.01 mm |
F(000) = 1290 |
Bruker X8 Proteum diffractometer | 908 reflections with I > 2σ(I) |
Radiation source: fine-focus rotating anode | Rint = 0.071 |
Graded multilayer optics monochromator | θmax = 68.3°, θmin = 3.6° |
Detector resolution: 5.6 pixels mm-1 | h = −30→30 |
ϕ and ω scans | k = −23→29 |
14474 measured reflections | l = −6→6 |
1163 independent reflections |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0645P)2 + 5.3911P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1163 reflections | Δρmax = 0.27 e Å−3 |
101 parameters | Δρmin = −0.30 e Å−3 |
11 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: 0.00069 (19) |
C6H7NO2·0.1667C3H8O | Z = 18 |
Mr = 135.14 | Cu Kα radiation |
Trigonal, R3 | µ = 0.90 mm−1 |
a = 24.9208 (5) Å | T = 90 K |
c = 5.2738 (1) Å | 0.13 × 0.01 × 0.01 mm |
V = 2836.47 (10) Å3 |
Bruker X8 Proteum diffractometer | 908 reflections with I > 2σ(I) |
14474 measured reflections | Rint = 0.071 |
1163 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 11 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.27 e Å−3 |
1163 reflections | Δρmin = −0.30 e Å−3 |
101 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 > 2σ(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 | Occ. (<1) | |
N1 | 0.55385 (8) | 0.50878 (8) | 0.2534 (3) | 0.0253 (4) | |
H1 | 0.5336 | 0.4846 | 0.1248 | 0.030* | |
C2 | 0.54990 (9) | 0.56108 (9) | 0.2850 (4) | 0.0248 (5) | |
C3 | 0.58313 (9) | 0.59890 (10) | 0.4940 (4) | 0.0260 (5) | |
H3 | 0.5822 | 0.6359 | 0.5270 | 0.031* | |
C4 | 0.61643 (9) | 0.58225 (10) | 0.6482 (4) | 0.0272 (5) | |
H4 | 0.6382 | 0.6079 | 0.7883 | 0.033* | |
C5 | 0.61934 (9) | 0.52822 (10) | 0.6052 (4) | 0.0270 (5) | |
C6 | 0.58666 (10) | 0.49079 (10) | 0.4048 (4) | 0.0265 (5) | |
O1 | 0.51736 (7) | 0.57235 (6) | 0.1302 (3) | 0.0275 (4) | |
O2 | 0.65125 (8) | 0.51075 (8) | 0.7629 (3) | 0.0363 (5) | |
H2 | 0.6863 | 0.5414 | 0.7937 | 0.054* | |
C7 | 0.58304 (11) | 0.43091 (10) | 0.3429 (5) | 0.0338 (6) | |
H7A | 0.6147 | 0.4272 | 0.4388 | 0.051* | |
H7B | 0.5901 | 0.4293 | 0.1609 | 0.051* | |
H7C | 0.5419 | 0.3967 | 0.3882 | 0.051* | |
O1S | 0.680 (3) | 0.355 (2) | 0.520 (5) | 0.232 (17)* | 0.17 |
H1SO | 0.6718 | 0.3820 | 0.5669 | 0.348* | 0.17 |
C1S | 0.6813 (16) | 0.3208 (14) | 0.730 (6) | 0.182 (15)* | 0.17 |
H1S | 0.6875 | 0.2873 | 0.6574 | 0.218* | 0.17 |
C2S | 0.620 (2) | 0.288 (3) | 0.861 (9) | 0.131 (13)* | 0.17 |
H2S1 | 0.5877 | 0.2648 | 0.7361 | 0.197* | 0.17 |
H2S2 | 0.6125 | 0.3179 | 0.9479 | 0.197* | 0.17 |
H2S3 | 0.6209 | 0.2588 | 0.9853 | 0.197* | 0.17 |
C3S | 0.736 (2) | 0.358 (3) | 0.893 (9) | 0.150 (16)* | 0.17 |
H3S1 | 0.7730 | 0.3806 | 0.7865 | 0.224* | 0.17 |
H3S2 | 0.7423 | 0.3296 | 1.0053 | 0.224* | 0.17 |
H3S3 | 0.7298 | 0.3866 | 0.9958 | 0.224* | 0.17 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0245 (9) | 0.0224 (9) | 0.0241 (8) | 0.0080 (7) | 0.0000 (7) | −0.0004 (7) |
C2 | 0.0223 (10) | 0.0236 (10) | 0.0251 (10) | 0.0089 (8) | 0.0046 (8) | 0.0026 (8) |
C3 | 0.0254 (10) | 0.0230 (10) | 0.0246 (10) | 0.0083 (8) | 0.0038 (8) | −0.0009 (8) |
C4 | 0.0243 (10) | 0.0269 (11) | 0.0230 (10) | 0.0073 (8) | 0.0019 (8) | −0.0012 (8) |
C5 | 0.0224 (10) | 0.0279 (11) | 0.0260 (10) | 0.0091 (9) | 0.0030 (8) | 0.0046 (8) |
C6 | 0.0228 (10) | 0.0239 (10) | 0.0278 (10) | 0.0078 (8) | 0.0032 (8) | 0.0027 (8) |
O1 | 0.0282 (8) | 0.0261 (8) | 0.0262 (8) | 0.0120 (6) | −0.0009 (6) | 0.0004 (6) |
O2 | 0.0327 (9) | 0.0332 (9) | 0.0380 (9) | 0.0128 (7) | −0.0043 (7) | 0.0032 (7) |
C7 | 0.0339 (12) | 0.0287 (12) | 0.0375 (12) | 0.0149 (10) | −0.0035 (10) | −0.0010 (9) |
N1—C2 | 1.365 (3) | C7—H7B | 0.9800 |
N1—C6 | 1.369 (3) | C7—H7C | 0.9800 |
N1—H1 | 0.8800 | O1S—C1S | 1.403 (10) |
C2—O1 | 1.277 (3) | O1S—H1SO | 0.8400 |
C2—C3 | 1.417 (3) | C1S—C3S | 1.483 (9) |
C3—C4 | 1.366 (3) | C1S—C2S | 1.484 (9) |
C3—H3 | 0.9500 | C1S—H1S | 1.0000 |
C4—C5 | 1.403 (3) | C2S—H2S1 | 0.9800 |
C4—H4 | 0.9500 | C2S—H2S2 | 0.9800 |
C5—O2 | 1.364 (3) | C2S—H2S3 | 0.9800 |
C5—C6 | 1.375 (3) | C3S—H3S1 | 0.9800 |
C6—C7 | 1.486 (3) | C3S—H3S2 | 0.9800 |
O2—H2 | 0.8400 | C3S—H3S3 | 0.9800 |
C7—H7A | 0.9800 | ||
C2—N1—C6 | 125.54 (18) | C6—C7—H7C | 109.5 |
C2—N1—H1 | 117.2 | H7A—C7—H7C | 109.5 |
C6—N1—H1 | 117.2 | H7B—C7—H7C | 109.5 |
O1—C2—N1 | 119.25 (18) | C1S—O1S—H1SO | 110.1 |
O1—C2—C3 | 125.11 (19) | O1S—C1S—C3S | 112.3 (11) |
N1—C2—C3 | 115.65 (18) | O1S—C1S—C2S | 112.1 (11) |
C4—C3—C2 | 120.2 (2) | C3S—C1S—C2S | 116.5 (11) |
C4—C3—H3 | 119.9 | O1S—C1S—H1S | 104.9 |
C2—C3—H3 | 119.9 | C3S—C1S—H1S | 104.9 |
C3—C4—C5 | 121.7 (2) | C2S—C1S—H1S | 104.9 |
C3—C4—H4 | 119.1 | C1S—C2S—H2S1 | 109.5 |
C5—C4—H4 | 119.1 | C1S—C2S—H2S2 | 109.5 |
O2—C5—C6 | 119.6 (2) | H2S1—C2S—H2S2 | 109.5 |
O2—C5—C4 | 121.73 (19) | C1S—C2S—H2S3 | 109.5 |
C6—C5—C4 | 118.6 (2) | H2S1—C2S—H2S3 | 109.5 |
N1—C6—C5 | 118.31 (19) | H2S2—C2S—H2S3 | 109.5 |
N1—C6—C7 | 117.04 (19) | C1S—C3S—H3S1 | 109.5 |
C5—C6—C7 | 124.6 (2) | C1S—C3S—H3S2 | 109.5 |
C5—O2—H2 | 109.5 | H3S1—C3S—H3S2 | 109.5 |
C6—C7—H7A | 109.5 | C1S—C3S—H3S3 | 109.5 |
C6—C7—H7B | 109.5 | H3S1—C3S—H3S3 | 109.5 |
H7A—C7—H7B | 109.5 | H3S2—C3S—H3S3 | 109.5 |
C6—N1—C2—O1 | −179.70 (18) | C2—N1—C6—C5 | −0.8 (3) |
C6—N1—C2—C3 | 0.0 (3) | C2—N1—C6—C7 | 177.83 (19) |
O1—C2—C3—C4 | 179.84 (19) | O2—C5—C6—N1 | 178.43 (18) |
N1—C2—C3—C4 | 0.2 (3) | C4—C5—C6—N1 | 1.4 (3) |
C2—C3—C4—C5 | 0.5 (3) | O2—C5—C6—C7 | −0.1 (3) |
C3—C4—C5—O2 | −178.25 (19) | C4—C5—C6—C7 | −177.1 (2) |
C3—C4—C5—C6 | −1.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.91 | 2.782 (2) | 174 |
O2—H2···O1ii | 0.84 | 1.81 | 2.638 (2) | 169 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
C6H7NO2 | Dx = 1.326 Mg m−3 |
Mr = 125.13 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 1434 reflections |
Hall symbol: -R 3 | θ = 1.0–27.5° |
a = 24.9131 (11) Å | µ = 0.10 mm−1 |
c = 5.2462 (3) Å | T = 90 K |
V = 2819.9 (2) Å3 | Block, pale yellow |
Z = 18 | 0.28 × 0.20 × 0.10 mm |
F(000) = 1188 |
Nonius KappaCCD area-detector diffractometer | 958 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 27.5°, θmin = 2.8° |
Detector resolution: 9.1 pixels mm-1 | h = −32→32 |
ω scans at fixed χ = 55° | k = −27→27 |
7559 measured reflections | l = −6→6 |
1434 independent 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 = 1.04 | w = 1/[σ2(Fo2) + (0.0907P)2 + 1.2147P] where P = (Fo2 + 2Fc2)/3 |
1434 reflections | (Δ/σ)max < 0.001 |
84 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C6H7NO2 | Z = 18 |
Mr = 125.13 | Mo Kα radiation |
Trigonal, R3 | µ = 0.10 mm−1 |
a = 24.9131 (11) Å | T = 90 K |
c = 5.2462 (3) Å | 0.28 × 0.20 × 0.10 mm |
V = 2819.9 (2) Å3 |
Nonius KappaCCD area-detector diffractometer | 958 reflections with I > 2σ(I) |
7559 measured reflections | Rint = 0.048 |
1434 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.43 e Å−3 |
1434 reflections | Δρmin = −0.24 e Å−3 |
84 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 > 2σ(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 | ||
N1 | 0.55416 (7) | 0.50846 (7) | 0.2548 (3) | 0.0204 (4) | |
H1 | 0.5337 | 0.4840 | 0.1265 | 0.024* | |
C2 | 0.55001 (8) | 0.56070 (8) | 0.2857 (3) | 0.0202 (4) | |
C3 | 0.58352 (8) | 0.59872 (8) | 0.4970 (3) | 0.0220 (4) | |
H3 | 0.5826 | 0.6357 | 0.5303 | 0.026* | |
C4 | 0.61677 (8) | 0.58222 (8) | 0.6513 (3) | 0.0220 (4) | |
H4 | 0.6385 | 0.6079 | 0.7921 | 0.026* | |
C5 | 0.61978 (8) | 0.52811 (9) | 0.6076 (3) | 0.0217 (5) | |
C6 | 0.58743 (8) | 0.49090 (8) | 0.4061 (3) | 0.0210 (4) | |
O1 | 0.51731 (6) | 0.57186 (6) | 0.1321 (2) | 0.0229 (4) | |
O2 | 0.65202 (6) | 0.51054 (6) | 0.7664 (3) | 0.0276 (4) | |
H2 | 0.6881 | 0.5405 | 0.7873 | 0.041* | |
C7 | 0.58352 (10) | 0.43069 (9) | 0.3441 (4) | 0.0281 (5) | |
H7A | 0.6115 | 0.4245 | 0.4561 | 0.042* | |
H7B | 0.5956 | 0.4311 | 0.1661 | 0.042* | |
H7C | 0.5409 | 0.3969 | 0.3694 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0208 (8) | 0.0188 (8) | 0.0175 (8) | 0.0069 (6) | −0.0008 (6) | −0.0015 (6) |
C2 | 0.0171 (9) | 0.0207 (9) | 0.0190 (9) | 0.0067 (8) | 0.0041 (7) | 0.0023 (7) |
C3 | 0.0237 (10) | 0.0189 (9) | 0.0199 (9) | 0.0080 (8) | 0.0028 (7) | −0.0008 (7) |
C4 | 0.0216 (10) | 0.0220 (10) | 0.0166 (9) | 0.0066 (8) | 0.0010 (7) | −0.0009 (7) |
C5 | 0.0192 (9) | 0.0232 (9) | 0.0201 (9) | 0.0088 (8) | 0.0016 (7) | 0.0040 (7) |
C6 | 0.0192 (9) | 0.0198 (9) | 0.0205 (9) | 0.0071 (8) | 0.0035 (7) | 0.0032 (7) |
O1 | 0.0228 (7) | 0.0229 (7) | 0.0209 (7) | 0.0100 (6) | −0.0021 (5) | −0.0005 (5) |
O2 | 0.0254 (8) | 0.0266 (8) | 0.0280 (8) | 0.0109 (6) | −0.0044 (6) | 0.0022 (6) |
C7 | 0.0295 (11) | 0.0237 (10) | 0.0299 (10) | 0.0123 (9) | −0.0031 (9) | −0.0019 (8) |
N1—C2 | 1.366 (2) | C4—H4 | 0.9500 |
N1—C6 | 1.368 (2) | C5—C6 | 1.371 (3) |
N1—H1 | 0.8800 | C5—O2 | 1.372 (2) |
C2—O1 | 1.271 (2) | C6—C7 | 1.490 (3) |
C2—C3 | 1.426 (2) | O2—H2 | 0.8400 |
C3—C4 | 1.360 (3) | C7—H7A | 0.9800 |
C3—H3 | 0.9500 | C7—H7B | 0.9800 |
C4—C5 | 1.406 (3) | C7—H7C | 0.9800 |
C2—N1—C6 | 125.63 (15) | C6—C5—C4 | 118.61 (17) |
C2—N1—H1 | 117.2 | O2—C5—C4 | 121.84 (16) |
C6—N1—H1 | 117.2 | N1—C6—C5 | 118.46 (17) |
O1—C2—N1 | 119.68 (15) | N1—C6—C7 | 116.76 (16) |
O1—C2—C3 | 125.03 (17) | C5—C6—C7 | 124.73 (17) |
N1—C2—C3 | 115.28 (16) | C5—O2—H2 | 109.5 |
C4—C3—C2 | 120.31 (18) | C6—C7—H7A | 109.5 |
C4—C3—H3 | 119.8 | C6—C7—H7B | 109.5 |
C2—C3—H3 | 119.8 | H7A—C7—H7B | 109.5 |
C3—C4—C5 | 121.69 (17) | C6—C7—H7C | 109.5 |
C3—C4—H4 | 119.2 | H7A—C7—H7C | 109.5 |
C5—C4—H4 | 119.2 | H7B—C7—H7C | 109.5 |
C6—C5—O2 | 119.49 (17) | ||
C6—N1—C2—O1 | −179.81 (16) | C2—N1—C6—C5 | 0.1 (3) |
C6—N1—C2—C3 | −0.5 (2) | C2—N1—C6—C7 | 177.63 (16) |
O1—C2—C3—C4 | 179.45 (16) | O2—C5—C6—N1 | 178.12 (15) |
N1—C2—C3—C4 | 0.2 (2) | C4—C5—C6—N1 | 0.7 (3) |
C2—C3—C4—C5 | 0.6 (3) | O2—C5—C6—C7 | 0.8 (3) |
C3—C4—C5—C6 | −1.0 (3) | C4—C5—C6—C7 | −176.70 (17) |
C3—C4—C5—O2 | −178.37 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.90 | 2.7805 (19) | 175 |
O2—H2···O1ii | 0.84 | 1.81 | 2.6398 (18) | 170 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
C6H7NO2 | Dx = 1.285 Mg m−3 |
Mr = 125.13 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 10421 reflections |
Hall symbol: -R 3 | θ = 1.0–25.4° |
a = 25.2734 (7) Å | µ = 0.10 mm−1 |
c = 5.2602 (7) Å | T = 293 K |
V = 2909.8 (4) Å3 | Block, pale yellow |
Z = 18 | 0.20 × 0.10 × 0.10 mm |
F(000) = 1188 |
Nonius KappaCCD area-detector diffractometer | 699 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.089 |
Graphite monochromator | θmax = 25.3°, θmin = 2.8° |
Detector resolution: 9.1 pixels mm-1 | h = −30→30 |
ω scans at fixed χ = 55° | k = −30→30 |
10602 measured reflections | l = −6→6 |
1184 independent 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1252P)2] where P = (Fo2 + 2Fc2)/3 |
1184 reflections | (Δ/σ)max = 0.002 |
84 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C6H7NO2 | Z = 18 |
Mr = 125.13 | Mo Kα radiation |
Trigonal, R3 | µ = 0.10 mm−1 |
a = 25.2734 (7) Å | T = 293 K |
c = 5.2602 (7) Å | 0.20 × 0.10 × 0.10 mm |
V = 2909.8 (4) Å3 |
Nonius KappaCCD area-detector diffractometer | 699 reflections with I > 2σ(I) |
10602 measured reflections | Rint = 0.089 |
1184 independent reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.38 e Å−3 |
1184 reflections | Δρmin = −0.18 e Å−3 |
84 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 > 2σ(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 | ||
N1 | 0.55471 (9) | 0.50936 (10) | 0.2540 (4) | 0.0469 (7) | |
H1 | 0.5347 | 0.4855 | 0.1299 | 0.056* | |
C2 | 0.55043 (12) | 0.56042 (12) | 0.2842 (5) | 0.0451 (8) | |
C3 | 0.58337 (13) | 0.59843 (13) | 0.4906 (5) | 0.0498 (8) | |
H3 | 0.5821 | 0.6340 | 0.5219 | 0.060* | |
C4 | 0.61702 (12) | 0.58290 (12) | 0.6440 (5) | 0.0503 (8) | |
H4 | 0.6381 | 0.6079 | 0.7808 | 0.060* | |
C5 | 0.62045 (12) | 0.53019 (13) | 0.6001 (5) | 0.0486 (8) | |
C6 | 0.58800 (12) | 0.49263 (12) | 0.4034 (5) | 0.0485 (8) | |
O1 | 0.51767 (8) | 0.57110 (8) | 0.1310 (3) | 0.0534 (7) | |
O2 | 0.65333 (10) | 0.51347 (9) | 0.7566 (4) | 0.0633 (7) | |
H2 | 0.6878 | 0.5427 | 0.7770 | 0.095* | |
C7 | 0.58497 (15) | 0.43381 (14) | 0.3428 (6) | 0.0664 (9) | |
H7A | 0.6085 | 0.4260 | 0.4651 | 0.100* | |
H7B | 0.6013 | 0.4360 | 0.1758 | 0.100* | |
H7C | 0.5432 | 0.4014 | 0.3483 | 0.100* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0489 (14) | 0.0411 (14) | 0.0438 (13) | 0.0174 (11) | −0.0034 (11) | −0.0057 (10) |
C2 | 0.0422 (16) | 0.0419 (16) | 0.0418 (16) | 0.0140 (14) | 0.0057 (13) | 0.0020 (13) |
C3 | 0.0541 (18) | 0.0432 (16) | 0.0455 (16) | 0.0195 (14) | 0.0028 (14) | −0.0029 (13) |
C4 | 0.0477 (17) | 0.0488 (17) | 0.0396 (15) | 0.0130 (14) | −0.0014 (13) | −0.0039 (13) |
C5 | 0.0432 (16) | 0.0472 (17) | 0.0455 (16) | 0.0152 (14) | 0.0001 (13) | 0.0070 (14) |
C6 | 0.0452 (16) | 0.0447 (16) | 0.0492 (16) | 0.0178 (14) | 0.0045 (14) | 0.0039 (13) |
O1 | 0.0549 (12) | 0.0521 (13) | 0.0503 (12) | 0.0246 (10) | −0.0083 (9) | −0.0017 (9) |
O2 | 0.0576 (14) | 0.0575 (13) | 0.0651 (14) | 0.0215 (11) | −0.0102 (11) | 0.0054 (10) |
C7 | 0.071 (2) | 0.056 (2) | 0.075 (2) | 0.0338 (17) | −0.0127 (18) | −0.0051 (17) |
N1—C2 | 1.357 (3) | C4—H4 | 0.9300 |
N1—C6 | 1.364 (3) | C5—C6 | 1.366 (4) |
N1—H1 | 0.8600 | C5—O2 | 1.378 (3) |
C2—O1 | 1.278 (3) | C6—C7 | 1.484 (4) |
C2—C3 | 1.412 (4) | O2—H2 | 0.8200 |
C3—C4 | 1.365 (4) | C7—H7A | 0.9600 |
C3—H3 | 0.9300 | C7—H7B | 0.9600 |
C4—C5 | 1.397 (4) | C7—H7C | 0.9600 |
C2—N1—C6 | 125.6 (2) | C6—C5—C4 | 119.1 (3) |
C2—N1—H1 | 117.2 | O2—C5—C4 | 121.9 (2) |
C6—N1—H1 | 117.2 | N1—C6—C5 | 118.0 (3) |
O1—C2—N1 | 119.7 (2) | N1—C6—C7 | 117.1 (2) |
O1—C2—C3 | 124.4 (3) | C5—C6—C7 | 124.8 (3) |
N1—C2—C3 | 115.9 (3) | C5—O2—H2 | 109.5 |
C4—C3—C2 | 119.9 (3) | C6—C7—H7A | 109.5 |
C4—C3—H3 | 120.0 | C6—C7—H7B | 109.5 |
C2—C3—H3 | 120.0 | H7A—C7—H7B | 109.5 |
C3—C4—C5 | 121.4 (3) | C6—C7—H7C | 109.5 |
C3—C4—H4 | 119.3 | H7A—C7—H7C | 109.5 |
C5—C4—H4 | 119.3 | H7B—C7—H7C | 109.5 |
C6—C5—O2 | 119.0 (3) | ||
C6—N1—C2—O1 | 180.0 (2) | C2—N1—C6—C5 | −0.5 (4) |
C6—N1—C2—C3 | −0.5 (4) | C2—N1—C6—C7 | 178.1 (2) |
O1—C2—C3—C4 | 179.9 (2) | O2—C5—C6—N1 | 178.6 (2) |
N1—C2—C3—C4 | 0.3 (4) | C4—C5—C6—N1 | 1.7 (4) |
C2—C3—C4—C5 | 0.8 (4) | O2—C5—C6—C7 | 0.1 (4) |
C3—C4—C5—C6 | −1.9 (4) | C4—C5—C6—C7 | −176.8 (3) |
C3—C4—C5—O2 | −178.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 1.95 | 2.804 (3) | 174 |
O2—H2···O1ii | 0.82 | 1.84 | 2.653 (3) | 173 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
C6H7NO2 | Dx = 1.324 Mg m−3 |
Mr = 125.13 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 1437 reflections |
Hall symbol: -R 3 | θ = 1.0–27.5° |
a = 24.9194 (5) Å | µ = 0.10 mm−1 |
c = 5.2541 (10) Å | T = 90 K |
V = 2825.6 (5) Å3 | Needle, colourless |
Z = 18 | 0.20 × 0.10 × 0.10 mm |
F(000) = 1188 |
Nonius KappaCCD area-detector diffractometer | 1085 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.056 |
Graphite monochromator | θmax = 27.5°, θmin = 1.6° |
Detector resolution: 9.1 pixels mm-1 | h = −32→32 |
ω scans at fixed χ = 55° | k = −27→27 |
23187 measured reflections | l = −6→6 |
1437 independent 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0753P)2 + 2.2624P] where P = (Fo2 + 2Fc2)/3 |
1437 reflections | (Δ/σ)max = 0.001 |
84 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C6H7NO2 | Z = 18 |
Mr = 125.13 | Mo Kα radiation |
Trigonal, R3 | µ = 0.10 mm−1 |
a = 24.9194 (5) Å | T = 90 K |
c = 5.2541 (10) Å | 0.20 × 0.10 × 0.10 mm |
V = 2825.6 (5) Å3 |
Nonius KappaCCD area-detector diffractometer | 1085 reflections with I > 2σ(I) |
23187 measured reflections | Rint = 0.056 |
1437 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.43 e Å−3 |
1437 reflections | Δρmin = −0.29 e Å−3 |
84 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 > 2σ(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 | ||
N1 | 0.55416 (5) | 0.50848 (6) | 0.2543 (2) | 0.0190 (3) | |
H1 | 0.5338 | 0.4842 | 0.1257 | 0.023* | |
C2 | 0.55011 (6) | 0.56080 (7) | 0.2860 (3) | 0.0187 (3) | |
C3 | 0.58347 (7) | 0.59881 (7) | 0.4962 (3) | 0.0204 (4) | |
H3 | 0.5826 | 0.6359 | 0.5290 | 0.024* | |
C4 | 0.61670 (7) | 0.58224 (7) | 0.6507 (3) | 0.0208 (4) | |
H4 | 0.6384 | 0.6079 | 0.7914 | 0.025* | |
C5 | 0.61975 (7) | 0.52810 (7) | 0.6075 (3) | 0.0202 (4) | |
C6 | 0.58723 (7) | 0.49080 (7) | 0.4061 (3) | 0.0202 (4) | |
O1 | 0.51737 (5) | 0.57193 (5) | 0.13160 (19) | 0.0215 (3) | |
O2 | 0.65200 (5) | 0.51063 (5) | 0.7664 (2) | 0.0255 (3) | |
H2 | 0.6876 | 0.5410 | 0.7918 | 0.038* | |
C7 | 0.58353 (8) | 0.43058 (7) | 0.3440 (3) | 0.0267 (4) | |
H7A | 0.6130 | 0.4254 | 0.4500 | 0.040* | |
H7B | 0.5937 | 0.4303 | 0.1640 | 0.040* | |
H7C | 0.5414 | 0.3965 | 0.3770 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0183 (6) | 0.0165 (6) | 0.0184 (6) | 0.0059 (5) | −0.0008 (5) | −0.0013 (5) |
C2 | 0.0156 (7) | 0.0178 (7) | 0.0192 (8) | 0.0058 (6) | 0.0033 (6) | 0.0025 (6) |
C3 | 0.0200 (7) | 0.0175 (7) | 0.0203 (8) | 0.0069 (6) | 0.0022 (6) | −0.0009 (6) |
C4 | 0.0193 (7) | 0.0191 (7) | 0.0182 (7) | 0.0051 (6) | 0.0012 (6) | −0.0007 (6) |
C5 | 0.0166 (7) | 0.0204 (7) | 0.0201 (8) | 0.0066 (6) | 0.0014 (6) | 0.0037 (6) |
C6 | 0.0165 (7) | 0.0187 (7) | 0.0223 (8) | 0.0065 (6) | 0.0034 (6) | 0.0028 (6) |
O1 | 0.0205 (6) | 0.0205 (6) | 0.0217 (6) | 0.0089 (4) | −0.0021 (4) | 0.0000 (4) |
O2 | 0.0218 (6) | 0.0228 (6) | 0.0282 (6) | 0.0084 (4) | −0.0047 (4) | 0.0020 (5) |
C7 | 0.0279 (8) | 0.0216 (8) | 0.0305 (9) | 0.0124 (7) | −0.0038 (7) | −0.0017 (6) |
N1—C2 | 1.3671 (18) | C4—H4 | 0.9500 |
N1—C6 | 1.3685 (19) | C5—O2 | 1.3717 (18) |
N1—H1 | 0.8800 | C5—C6 | 1.374 (2) |
C2—O1 | 1.2755 (17) | C6—C7 | 1.493 (2) |
C2—C3 | 1.421 (2) | O2—H2 | 0.8400 |
C3—C4 | 1.363 (2) | C7—H7A | 0.9800 |
C3—H3 | 0.9500 | C7—H7B | 0.9800 |
C4—C5 | 1.407 (2) | C7—H7C | 0.9800 |
C2—N1—C6 | 125.43 (13) | O2—C5—C4 | 121.82 (13) |
C2—N1—H1 | 117.3 | C6—C5—C4 | 118.46 (14) |
C6—N1—H1 | 117.3 | N1—C6—C5 | 118.52 (14) |
O1—C2—N1 | 119.36 (13) | N1—C6—C7 | 116.86 (13) |
O1—C2—C3 | 125.01 (14) | C5—C6—C7 | 124.59 (14) |
N1—C2—C3 | 115.63 (13) | C5—O2—H2 | 109.5 |
C4—C3—C2 | 120.16 (14) | C6—C7—H7A | 109.5 |
C4—C3—H3 | 119.9 | C6—C7—H7B | 109.5 |
C2—C3—H3 | 119.9 | H7A—C7—H7B | 109.5 |
C3—C4—C5 | 121.79 (14) | C6—C7—H7C | 109.5 |
C3—C4—H4 | 119.1 | H7A—C7—H7C | 109.5 |
C5—C4—H4 | 119.1 | H7B—C7—H7C | 109.5 |
O2—C5—C6 | 119.66 (14) | ||
C6—N1—C2—O1 | −179.65 (13) | C2—N1—C6—C5 | −0.4 (2) |
C6—N1—C2—C3 | −0.2 (2) | C2—N1—C6—C7 | 177.74 (13) |
O1—C2—C3—C4 | 179.48 (13) | O2—C5—C6—N1 | 178.35 (12) |
N1—C2—C3—C4 | 0.0 (2) | C4—C5—C6—N1 | 1.0 (2) |
C2—C3—C4—C5 | 0.6 (2) | O2—C5—C6—C7 | 0.4 (2) |
C3—C4—C5—O2 | −178.45 (13) | C4—C5—C6—C7 | −176.95 (14) |
C3—C4—C5—C6 | −1.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.90 | 2.7808 (16) | 174 |
O2—H2···O1ii | 0.84 | 1.81 | 2.6383 (15) | 170 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
C6H7NO2 | Dx = 1.325 Mg m−3 |
Mr = 125.13 | Cu Kα radiation, λ = 1.54178 Å |
Trigonal, R3 | Cell parameters from 8747 reflections |
Hall symbol: -R 3 | θ = 3.6–68.4° |
a = 24.9344 (4) Å | µ = 0.85 mm−1 |
c = 5.2415 (1) Å | T = 90 K |
V = 2822.17 (8) Å3 | Needle, colourless |
Z = 18 | 0.15 × 0.02 × 0.02 mm |
F(000) = 1188 |
Bruker X8 Proteum diffractometer | 1077 reflections with I > 2σ(I) |
Radiation source: fine-focus rotating anode | Rint = 0.043 |
Graded multilayer optics monochromator | θmax = 68.4°, θmin = 3.6° |
Detector resolution: 5.6 pixels mm-1 | h = −30→26 |
ϕ and ω scans | k = −30→30 |
14184 measured reflections | l = −6→6 |
1161 independent reflections |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0657P)2 + 2.778P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
1161 reflections | Δρmax = 0.36 e Å−3 |
85 parameters | Δρmin = −0.16 e Å−3 |
0 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: 0.00050 (14) |
C6H7NO2 | Z = 18 |
Mr = 125.13 | Cu Kα radiation |
Trigonal, R3 | µ = 0.85 mm−1 |
a = 24.9344 (4) Å | T = 90 K |
c = 5.2415 (1) Å | 0.15 × 0.02 × 0.02 mm |
V = 2822.17 (8) Å3 |
Bruker X8 Proteum diffractometer | 1077 reflections with I > 2σ(I) |
14184 measured reflections | Rint = 0.043 |
1161 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.36 e Å−3 |
1161 reflections | Δρmin = −0.16 e Å−3 |
85 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 > 2σ(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 | ||
N1 | 0.55416 (5) | 0.50869 (5) | 0.2548 (2) | 0.0215 (3) | |
H1 | 0.5338 | 0.4844 | 0.1259 | 0.026* | |
C2 | 0.55001 (6) | 0.56082 (6) | 0.2862 (2) | 0.0210 (3) | |
C3 | 0.58341 (6) | 0.59881 (6) | 0.4965 (2) | 0.0225 (3) | |
H3 | 0.5825 | 0.6358 | 0.5295 | 0.027* | |
C4 | 0.61678 (6) | 0.58233 (6) | 0.6512 (2) | 0.0230 (3) | |
H4 | 0.6385 | 0.6081 | 0.7921 | 0.028* | |
C5 | 0.61991 (6) | 0.52825 (6) | 0.6079 (2) | 0.0227 (3) | |
C6 | 0.58723 (6) | 0.49097 (6) | 0.4062 (2) | 0.0224 (3) | |
O1 | 0.51731 (4) | 0.57183 (4) | 0.13173 (16) | 0.0235 (3) | |
O2 | 0.65212 (4) | 0.51098 (4) | 0.76609 (18) | 0.0272 (3) | |
H2 | 0.6874 | 0.5415 | 0.7935 | 0.041* | |
C7 | 0.58358 (7) | 0.43091 (6) | 0.3439 (3) | 0.0283 (4) | |
H7A | 0.6133 | 0.4259 | 0.4491 | 0.042* | |
H7B | 0.5934 | 0.4305 | 0.1632 | 0.042* | |
H7C | 0.5416 | 0.3968 | 0.3783 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0213 (6) | 0.0197 (6) | 0.0195 (5) | 0.0073 (4) | −0.0006 (4) | −0.0010 (4) |
C2 | 0.0192 (6) | 0.0202 (6) | 0.0205 (6) | 0.0074 (5) | 0.0040 (5) | 0.0025 (5) |
C3 | 0.0221 (6) | 0.0202 (6) | 0.0221 (6) | 0.0083 (5) | 0.0035 (5) | 0.0001 (5) |
C4 | 0.0211 (6) | 0.0226 (7) | 0.0192 (6) | 0.0065 (5) | 0.0015 (5) | −0.0008 (5) |
C5 | 0.0205 (6) | 0.0229 (7) | 0.0212 (6) | 0.0083 (5) | 0.0024 (5) | 0.0043 (5) |
C6 | 0.0198 (6) | 0.0212 (7) | 0.0226 (6) | 0.0077 (5) | 0.0033 (5) | 0.0031 (5) |
O1 | 0.0242 (5) | 0.0222 (5) | 0.0225 (5) | 0.0105 (4) | −0.0015 (3) | 0.0001 (3) |
O2 | 0.0247 (5) | 0.0254 (5) | 0.0278 (5) | 0.0098 (4) | −0.0043 (4) | 0.0023 (4) |
C7 | 0.0290 (7) | 0.0231 (7) | 0.0317 (7) | 0.0121 (6) | −0.0030 (5) | −0.0015 (5) |
N1—C2 | 1.3644 (17) | C4—H4 | 0.9500 |
N1—C6 | 1.3673 (17) | C5—O2 | 1.3650 (16) |
N1—H1 | 0.8800 | C5—C6 | 1.3741 (19) |
C2—O1 | 1.2725 (15) | C6—C7 | 1.4903 (19) |
C2—C3 | 1.4203 (17) | O2—H2 | 0.8400 |
C3—C4 | 1.3643 (19) | C7—H7A | 0.9800 |
C3—H3 | 0.9500 | C7—H7B | 0.9800 |
C4—C5 | 1.4075 (19) | C7—H7C | 0.9800 |
C2—N1—C6 | 125.68 (11) | O2—C5—C4 | 121.83 (12) |
C2—N1—H1 | 117.2 | C6—C5—C4 | 118.29 (12) |
C6—N1—H1 | 117.2 | N1—C6—C5 | 118.52 (12) |
O1—C2—N1 | 119.40 (11) | N1—C6—C7 | 116.97 (11) |
O1—C2—C3 | 125.11 (12) | C5—C6—C7 | 124.48 (12) |
N1—C2—C3 | 115.49 (11) | C5—O2—H2 | 109.5 |
C4—C3—C2 | 120.20 (12) | C6—C7—H7A | 109.5 |
C4—C3—H3 | 119.9 | C6—C7—H7B | 109.5 |
C2—C3—H3 | 119.9 | H7A—C7—H7B | 109.5 |
C3—C4—C5 | 121.81 (12) | C6—C7—H7C | 109.5 |
C3—C4—H4 | 119.1 | H7A—C7—H7C | 109.5 |
C5—C4—H4 | 119.1 | H7B—C7—H7C | 109.5 |
O2—C5—C6 | 119.82 (12) | ||
C6—N1—C2—O1 | −179.71 (11) | C2—N1—C6—C5 | −0.46 (19) |
C6—N1—C2—C3 | −0.15 (18) | C2—N1—C6—C7 | 177.76 (11) |
O1—C2—C3—C4 | 179.59 (12) | O2—C5—C6—N1 | 178.39 (10) |
N1—C2—C3—C4 | 0.07 (17) | C4—C5—C6—N1 | 1.12 (18) |
C2—C3—C4—C5 | 0.63 (19) | O2—C5—C6—C7 | 0.31 (19) |
C3—C4—C5—O2 | −178.45 (11) | C4—C5—C6—C7 | −176.95 (12) |
C3—C4—C5—C6 | −1.24 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.90 | 2.7809 (14) | 174 |
O2—H2···O1ii | 0.84 | 1.81 | 2.6366 (13) | 170 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
C6H7NO2 | Dx = 1.303 Mg m−3 |
Mr = 125.13 | Cu Kα radiation, λ = 1.54178 Å |
Trigonal, R3 | Cell parameters from 2933 reflections |
Hall symbol: -R 3 | θ = 3.5–67.4° |
a = 25.282 (6) Å | µ = 0.83 mm−1 |
c = 5.1838 (14) Å | T = 90 K |
V = 2869.6 (12) Å3 | Needle, colourless |
Z = 18 | 0.15 × 0.01 × 0.01 mm |
F(000) = 1188 |
Bruker X8 Proteum diffractometer | 868 reflections with I > 2σ(I) |
Radiation source: fine-focus rotating anode | Rint = 0.081 |
Graded multilayer optics monochromator | θmax = 68.3°, θmin = 3.5° |
Detector resolution: 5.6 pixels mm-1 | h = −30→30 |
ϕ and ω scans | k = −30→29 |
13477 measured reflections | l = −6→6 |
1169 independent 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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.246 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.1548P)2 + 2.6539P] where P = (Fo2 + 2Fc2)/3 |
1169 reflections | (Δ/σ)max = 0.001 |
84 parameters | Δρmax = 1.13 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C6H7NO2 | Z = 18 |
Mr = 125.13 | Cu Kα radiation |
Trigonal, R3 | µ = 0.83 mm−1 |
a = 25.282 (6) Å | T = 90 K |
c = 5.1838 (14) Å | 0.15 × 0.01 × 0.01 mm |
V = 2869.6 (12) Å3 |
Bruker X8 Proteum diffractometer | 868 reflections with I > 2σ(I) |
13477 measured reflections | Rint = 0.081 |
1169 independent reflections |
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.246 | H-atom parameters constrained |
S = 1.16 | Δρmax = 1.13 e Å−3 |
1169 reflections | Δρmin = −0.20 e Å−3 |
84 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 > 2σ(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 | ||
N1 | 0.55380 (12) | 0.50951 (12) | 0.2552 (5) | 0.0336 (7) | |
H1 | 0.5330 | 0.4851 | 0.1271 | 0.040* | |
C2 | 0.54988 (14) | 0.56095 (14) | 0.2861 (6) | 0.0326 (8) | |
C3 | 0.58345 (14) | 0.59885 (15) | 0.4969 (6) | 0.0340 (8) | |
H3 | 0.5823 | 0.6352 | 0.5308 | 0.041* | |
C4 | 0.61736 (14) | 0.58324 (14) | 0.6512 (6) | 0.0344 (8) | |
H4 | 0.6392 | 0.6089 | 0.7921 | 0.041* | |
C5 | 0.62074 (15) | 0.53023 (15) | 0.6068 (6) | 0.0350 (8) | |
C6 | 0.58736 (15) | 0.49258 (14) | 0.4067 (6) | 0.0347 (8) | |
O1 | 0.51708 (10) | 0.57130 (10) | 0.1316 (4) | 0.0358 (7) | |
O2 | 0.65331 (11) | 0.51356 (11) | 0.7642 (5) | 0.0415 (7) | |
H2 | 0.6891 | 0.5430 | 0.7805 | 0.062* | |
C7 | 0.58396 (18) | 0.43349 (16) | 0.3438 (7) | 0.0442 (9) | |
H7A | 0.6083 | 0.4256 | 0.4686 | 0.066* | |
H7B | 0.6000 | 0.4356 | 0.1697 | 0.066* | |
H7C | 0.5413 | 0.4005 | 0.3516 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0320 (14) | 0.0284 (13) | 0.0315 (13) | 0.0084 (11) | 0.0016 (11) | −0.0003 (10) |
C2 | 0.0294 (15) | 0.0293 (16) | 0.0305 (15) | 0.0082 (12) | 0.0043 (12) | 0.0016 (12) |
C3 | 0.0354 (16) | 0.0298 (15) | 0.0303 (15) | 0.0114 (13) | 0.0043 (12) | −0.0003 (12) |
C4 | 0.0327 (16) | 0.0336 (16) | 0.0289 (15) | 0.0105 (13) | 0.0023 (12) | −0.0007 (12) |
C5 | 0.0313 (16) | 0.0345 (16) | 0.0323 (16) | 0.0114 (13) | 0.0045 (12) | 0.0056 (13) |
C6 | 0.0325 (16) | 0.0317 (16) | 0.0334 (15) | 0.0112 (13) | 0.0060 (12) | 0.0047 (12) |
O1 | 0.0351 (12) | 0.0343 (12) | 0.0336 (12) | 0.0141 (10) | −0.0006 (9) | 0.0002 (9) |
O2 | 0.0403 (13) | 0.0379 (13) | 0.0421 (13) | 0.0165 (10) | −0.0033 (10) | 0.0051 (10) |
C7 | 0.046 (2) | 0.0339 (17) | 0.0482 (18) | 0.0170 (15) | −0.0058 (16) | −0.0045 (15) |
N1—C2 | 1.362 (4) | C4—H4 | 0.9500 |
N1—C6 | 1.372 (4) | C5—O2 | 1.367 (4) |
N1—H1 | 0.8800 | C5—C6 | 1.375 (5) |
C2—O1 | 1.270 (4) | C6—C7 | 1.489 (5) |
C2—C3 | 1.421 (4) | O2—H2 | 0.8400 |
C3—C4 | 1.367 (5) | C7—H7A | 0.9800 |
C3—H3 | 0.9500 | C7—H7B | 0.9800 |
C4—C5 | 1.404 (5) | C7—H7C | 0.9800 |
C2—N1—C6 | 125.6 (3) | O2—C5—C4 | 122.0 (3) |
C2—N1—H1 | 117.2 | C6—C5—C4 | 118.4 (3) |
C6—N1—H1 | 117.2 | N1—C6—C5 | 118.5 (3) |
O1—C2—N1 | 119.3 (3) | N1—C6—C7 | 116.9 (3) |
O1—C2—C3 | 125.3 (3) | C5—C6—C7 | 124.6 (3) |
N1—C2—C3 | 115.5 (3) | C5—O2—H2 | 109.5 |
C4—C3—C2 | 120.3 (3) | C6—C7—H7A | 109.5 |
C4—C3—H3 | 119.9 | C6—C7—H7B | 109.5 |
C2—C3—H3 | 119.9 | H7A—C7—H7B | 109.5 |
C3—C4—C5 | 121.8 (3) | C6—C7—H7C | 109.5 |
C3—C4—H4 | 119.1 | H7A—C7—H7C | 109.5 |
C5—C4—H4 | 119.1 | H7B—C7—H7C | 109.5 |
O2—C5—C6 | 119.5 (3) | ||
C6—N1—C2—O1 | 180.0 (3) | C2—N1—C6—C5 | −0.6 (5) |
C6—N1—C2—C3 | −0.7 (4) | C2—N1—C6—C7 | 178.3 (3) |
O1—C2—C3—C4 | −180.0 (3) | O2—C5—C6—N1 | 178.4 (3) |
N1—C2—C3—C4 | 0.8 (4) | C4—C5—C6—N1 | 1.9 (4) |
C2—C3—C4—C5 | 0.5 (5) | O2—C5—C6—C7 | −0.5 (5) |
C3—C4—C5—O2 | −178.3 (3) | C4—C5—C6—C7 | −177.0 (3) |
C3—C4—C5—C6 | −1.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.90 | 2.783 (3) | 176 |
O2—H2···O1ii | 0.84 | 1.80 | 2.639 (3) | 173 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
Experimental details
(Ia) | (Ib) | (Ic1) | (Ic2) | |
Crystal data | ||||
Chemical formula | C6H7NO2·0.1667C3H6O | C6H7NO2·0.1667C3H8O | C6H7NO2 | C6H7NO2 |
Mr | 134.81 | 135.14 | 125.13 | 125.13 |
Crystal system, space group | Trigonal, R3 | Trigonal, R3 | Trigonal, R3 | Trigonal, R3 |
Temperature (K) | 90 | 90 | 90 | 293 |
a, c (Å) | 24.7962 (3), 5.2924 (1) | 24.9208 (5), 5.2738 (1) | 24.9131 (11), 5.2462 (3) | 25.2734 (7), 5.2602 (7) |
V (Å3) | 2818.08 (7) | 2836.47 (10) | 2819.9 (2) | 2909.8 (4) |
Z | 18 | 18 | 18 | 18 |
Radiation type | Cu Kα | Cu Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.91 | 0.90 | 0.10 | 0.10 |
Crystal size (mm) | 0.12 × 0.01 × 0.01 | 0.13 × 0.01 × 0.01 | 0.28 × 0.20 × 0.10 | 0.20 × 0.10 × 0.10 |
Data collection | ||||
Diffractometer | Bruker X8 Proteum diffractometer | Bruker X8 Proteum diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14372, 1153, 854 | 14474, 1163, 908 | 7559, 1434, 958 | 10602, 1184, 699 |
Rint | 0.077 | 0.071 | 0.048 | 0.089 |
(sin θ/λ)max (Å−1) | 0.602 | 0.603 | 0.649 | 0.602 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.130, 1.03 | 0.047, 0.132, 1.07 | 0.052, 0.156, 1.04 | 0.063, 0.198, 1.02 |
No. of reflections | 1153 | 1163 | 1434 | 1184 |
No. of parameters | 101 | 101 | 84 | 84 |
No. of restraints | 6 | 11 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.39 | 0.27, −0.30 | 0.43, −0.24 | 0.38, −0.18 |
(Ic3) | (Id) | (Ie) | |
Crystal data | |||
Chemical formula | C6H7NO2 | C6H7NO2 | C6H7NO2 |
Mr | 125.13 | 125.13 | 125.13 |
Crystal system, space group | Trigonal, R3 | Trigonal, R3 | Trigonal, R3 |
Temperature (K) | 90 | 90 | 90 |
a, c (Å) | 24.9194 (5), 5.2541 (10) | 24.9344 (4), 5.2415 (1) | 25.282 (6), 5.1838 (14) |
V (Å3) | 2825.6 (5) | 2822.17 (8) | 2869.6 (12) |
Z | 18 | 18 | 18 |
Radiation type | Mo Kα | Cu Kα | Cu Kα |
µ (mm−1) | 0.10 | 0.85 | 0.83 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 | 0.15 × 0.02 × 0.02 | 0.15 × 0.01 × 0.01 |
Data collection | |||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Bruker X8 Proteum diffractometer | Bruker X8 Proteum diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23187, 1437, 1085 | 14184, 1161, 1077 | 13477, 1169, 868 |
Rint | 0.056 | 0.043 | 0.081 |
(sin θ/λ)max (Å−1) | 0.649 | 0.603 | 0.603 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.135, 1.07 | 0.037, 0.113, 1.10 | 0.073, 0.246, 1.16 |
No. of reflections | 1437 | 1161 | 1169 |
No. of parameters | 84 | 85 | 84 |
No. of restraints | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.29 | 0.36, −0.16 | 1.13, −0.20 |
Computer programs: APEX2 (Bruker, 2006), COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures.
N1—C2 | 1.365 (3) | C4—C5 | 1.401 (3) |
N1—C6 | 1.368 (3) | C5—O2 | 1.368 (3) |
C2—O1 | 1.276 (3) | C5—C6 | 1.373 (3) |
C2—C3 | 1.416 (3) | C6—C7 | 1.485 (3) |
C3—C4 | 1.366 (3) | ||
C2—N1—C6 | 125.66 (18) | O2—C5—C6 | 119.4 (2) |
O1—C2—N1 | 119.29 (18) | O2—C5—C4 | 121.95 (19) |
O1—C2—C3 | 125.0 (2) | C6—C5—C4 | 118.6 (2) |
N1—C2—C3 | 115.68 (19) | N1—C6—C5 | 118.2 (2) |
C4—C3—C2 | 120.0 (2) | N1—C6—C7 | 117.13 (19) |
C3—C4—C5 | 121.9 (2) | C5—C6—C7 | 124.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.90 | 2.781 (2) | 174.3 |
O2—H2···O1ii | 0.84 | 1.81 | 2.634 (2) | 165.0 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
N1—C2 | 1.365 (3) | C4—C5 | 1.403 (3) |
N1—C6 | 1.369 (3) | C5—O2 | 1.364 (3) |
C2—O1 | 1.277 (3) | C5—C6 | 1.375 (3) |
C2—C3 | 1.417 (3) | C6—C7 | 1.486 (3) |
C3—C4 | 1.366 (3) | ||
C2—N1—C6 | 125.54 (18) | O2—C5—C6 | 119.6 (2) |
O1—C2—N1 | 119.25 (18) | O2—C5—C4 | 121.73 (19) |
O1—C2—C3 | 125.11 (19) | C6—C5—C4 | 118.6 (2) |
N1—C2—C3 | 115.65 (18) | N1—C6—C5 | 118.31 (19) |
C4—C3—C2 | 120.2 (2) | N1—C6—C7 | 117.04 (19) |
C3—C4—C5 | 121.7 (2) | C5—C6—C7 | 124.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.91 | 2.782 (2) | 174.0 |
O2—H2···O1ii | 0.84 | 1.81 | 2.638 (2) | 168.9 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −y+4/3, x−y+2/3, z+2/3. |
1H NMR data obtained from crystals of 6-methyl-5-hydroxy-2-pyridone, (I) (Behrman, 2008, 2009), grown from acetone or propan-2-ol exhibit unusual, and sometimes variable, ratios of pyridone to solvent. A similar observation for the 6-chloro analogue was established as being due to the presence of continuous solvent-accessible channels formed by extensive hydrogen-bonding networks within the crystals (Parkin & Behrman, 2009). The tautomeric equilibrium in the 6-chloro analogue was sensitive to the molecular environment, such that solvate crystals were exclusively the hydroxy tautomer while solvent-free crystals were the pyridone. Studies of related 6-substituted 2-pyridones over many years (summarized by Nichol & Clegg, 2005) show that electron-donating substituents at the 6-position drive the tautomeric equilibrium towards the pyridone, while electron-withdrawing groups favour the hydroxy form. In the present work, we found no evidence of the corresponding 6-methyl-2,5-dihydroxypyridine, (II).
Current work on intrinsic and extrinsic porous organic molecules has been the subject of several recent reviews, most notably by Cooper and coworkers (Holst et al., 2010; Cooper, 2011; Mastalerz et al., 2011; Jones et al., 2011). Given the general interest in hydrogen-bonded assemblies (e.g. Sisson et al., 2005; Glidewell et al., 2005; Hao et al., 2005), and of keto/enol tautomerism in 6-pyridones (Almlöf et al., 1971; Kvick, 1976; Johnson, 1984), we undertook a study of (I) crystallized from a series of solvents. Here, we report the structures of crystals grown from acetone, (Ia), propan-2-ol, (Ib), methanol, (Ic), water, (Id), and benzonitrile, (Ie). A probable structure grown from benzyl alcohol, (If), and a solvent-free crystalline powder obtained by sublimation, (Ig), are also discussed. Data tables are only presented here for structures (Ia) and (Ib); tables for structures (Ic1), (Ic2), (Ic3), (Id) and (Ie) are available in the archived CIF.
In contrast with the 6-chloro analogue, which formed tetragonal crystals (space group I41/a) with four channels per unit cell, all crystals of (I) are trigonal, space group R3, and have three channels per unit cell. The host-molecule frameworks in (Ia)–(Ie), and likely also in (If) and (Ig), are isostructural. Given the similarities, the following section concentrates on the structure of (Ia). Unless otherwise noted, the general features (aside from the nature of the solvent) also apply to (Ib)–(Ie), and probably also to (If) and (Ig).
The molecular structure of (I) (Fig. 1) is largely unremarkable. Bond lengths and angles are all within normal ranges and the molecules are flat [the r.m.s. deviation from planarity is 0.0140 (16) Å for non-H atoms]. The 2-hydroxy H atom is oriented away from the 6-methyl group, but is twisted out of the plane of the ring by ca 43° so as to participate in an O2—H2···O1(-y + 4/3, x - y + 2/3, z + 2/3) hydrogen bond to a symmetry-related molecule (Table 2). Inversion-related molecules of (I) interact via pairs of N1—H1···O1 hydrogen bonds to form R22(8) dimers (Fig. 2a) (for graph-set notation, see Bernstein et al., 1995). Six of these dimers join to form puckered rings (Fig. 2b) in which atom O1 of each N1—H1···O1 hydrogen bond is also the acceptor in an O2—H2···O1 hydrogen bond. The resulting large R126(42) rings surround the 3 axes and stack into columns via π–π interactions between inversion-related molecules of (I) [the mean π–π spacing is 3.254 (2) Å and the ring centroid-to-centroid is distance 3.688 (2) Å]. The channels are lined with 6-methyl groups which point towards the centre of their respective R126(42) rings. Appropriately sized solvent molecules can occupy the channels, but on average they are severely disordered as a result of the 3 site symmetry within the channels (Fig. 3). In spite of the inherent disorder, it was possible to model the acetone and propan-2-ol molecules in (Ia) and (Ib), albeit with extensive use of restraints (see Refinement section). These models had (in total) one solvent molecule per channel per unit cell. The occupancies of the solvent models were allowed to refine, but in both (Ia) and (Ib) the summed site occupancy of all disorder components was so close to unity that the solvent in the final cycles of refinement was fixed at full occupancy.
Although reasonably sized crystals could be grown from a variety of solvents, satisfactory disorder models for smaller solvents such as methanol in (Ic) and water in (Id) were not readily constructed. Crystals from methanol or water do appear to hold solvent less tightly, so that the solvent content varies depending on the method of drying (i.e. in air, in vacuo or at 373 K), from ca 2.5 molecules per channel per unit cell to less than one. A room-temperature determination of the methanol-containing structure, (Ic2), revealed no substantive differences from the low-temperature model, (Ic1). An attempt to drive the methanol guest molecules from the channels in (Ic) by annealing at 381 K for ca 30 min was also performed. In the resulting structure, (Ic3), the channels remained intact, though they appear to be partially de-populated. The electron count within the channels, as calculated by the SQUEEZE routine in PLATON (Spek, 2009), was reduced from 46 e in (Ic1) to 24 e in (Ic3), but it is worth mentioning that the electron count for the room temperature structure, (Ic2), was only 10 e. This variability is consistent with peak integrations of 1H NMR spectra for different samples of (Ic). We surmise that some small solvent species are able to vacate the channels to a degree that depends on crystal handling, treatment and environment. Crystallization from benzonitrile produced a similar structure, (Ie), but with shorter and broader channels (as evidenced by the cell dimensions), presumably to accommodate this larger molecule. Crystals grown from benzyl alcohol, (If), were too small for full data collection, but indexing of a miniscule crystal of (If) (ca 0.1 × 0.005 × 0.005 mm) revealed a trigonal unit cell similar to the other crystals.
All attempts to grow solvent-free crystals large enough for single-crystal work by sublimation up to ca 423 K were futile and resulted in a fine white powder, (Ig). Diffraction of Cu Kα X-rays by this sublimed powder was too weak to measure on conventional sealed-tube powder X-ray diffractometers. However, it was possible to collect two-dimensional diffraction images on a rotating-anode based Bruker X8 Proteum single-crystal diffractometer equipped with graded multilayer optics. Diffraction patterns from freshly sublimed (Ig) and from (Ig) that had aged undisturbed for about six months were essentially identical (see Supplementary Material). These two-dimensional images were radially integrated using DATASQUEEZE (Heiney, 2005) and compared with simulated powder patterns based on the single-crystal structures (calculated using Mercury; Macrae et al., 2008), as shown in Fig. 4. Diffraction peak positions from the sublimed powders are in excellent agreement with those in the simulated powder patterns. It is consistent with this that the IR spectrum of the sublimed material is identical to spectra of the solvent-containing crystals. It thus appears that the channel structure is maintained even in the absence of intrinsic solvent, in marked contrast with the 6-chloro crystals, which were found to collapse on solvent loss (Parkin & Behrman, 2009). Holst et al. (2010) regard molecular crystals that retain permanent micropore structures upon desolvation as atypical. We also considered that the channels of the sublimed material might have contained air. Elemental analysis showed no increase in the percentage of nitrogen; even one molecule of N2 per unit cell would have been easily detectable. The channels in the sublimed powder are substantially empty. 1H NMR spectra showed solvent:host ratios consistent with the X-ray data. A few other 6-substituted-5-hydroxy-2-pyridones were examined but these did not form channels: 6-H (Behrman, 2008), 6-Br (Eikhoff & Behrman, 2009, Supplementary Material; Smith, 1951; Newkome et al., 1974) and 6-nitroso (Krowicki, 1977).