Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105027812/dn1097sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105027812/dn1097Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105027812/dn1097IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105027812/dn1097IIIsup4.hkl |
CCDC references: 288628; 288629; 288630
Compound (I) was prepared according to the procedure of Kobayashi et al. (1984). In the first step, 2-hydroxybenzoic acid methyl ester was reacted with an excess of ethanolamine at 413 K to give the corresponding hydroxyamide. This, in the next step upon treatment with thionyl chloride, afforded the required compound, (I). Compounds (II) and (III) were prepared analogously starting from the 3-hydroxy- or 4-hydroxybenzoic acid methyl ester, respectively. The analytical data of all three title compounds were in accordance with those published previously. Colourless single crystals of adequate quality for diffraction analysis [with the exception of (II)] were obtained by slow crystallization from nearly saturated solutions in ethanol under moderate cooling in a refrigerator.
The sample of (II) used for data collection was not a single-crystal. Nevertheless, it was possible to resolve one set of diffractions from one domain. As a result, there were overlapping reflections: 118 reflections were omitted from the data set due to severe Fo/Fc discrepancies (Fo >> Fc). H atoms for all compounds were refined isotropically and constrained to the ideal geometry using an appropriate riding model. For aromatic H atoms, the C—H distance was kept fixed at 0.95 Å, and for secondary H atoms, C—H = 0.99 Å. For the hydroxyl groups, the O—H distances (0.84 Å) and C—O—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine, with the starting position based on the circular Fourier synthesis.
For all compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.
C9H9NO2 | F(000) = 344 |
Mr = 163.17 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8192 reflections |
a = 5.7562 (1) Å | θ = 2.5–33.0° |
b = 11.2464 (1) Å | µ = 0.10 mm−1 |
c = 12.1365 (1) Å | T = 173 K |
β = 98.162 (1)° | Block, colourless |
V = 777.72 (2) Å3 | 0.80 × 0.42 × 0.40 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2785 independent reflections |
Radiation source: fine-focus sealed tube | 2451 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 33.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −8→8 |
Tmin = 0.724, Tmax = 0.961 | k = −16→17 |
13125 measured reflections | l = −18→17 |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0707P)2 + 0.1146P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2785 reflections | Δρmax = 0.36 e Å−3 |
120 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Bruker, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (7) |
C9H9NO2 | V = 777.72 (2) Å3 |
Mr = 163.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.7562 (1) Å | µ = 0.10 mm−1 |
b = 11.2464 (1) Å | T = 173 K |
c = 12.1365 (1) Å | 0.80 × 0.42 × 0.40 mm |
β = 98.162 (1)° |
Siemens SMART CCD area-detector diffractometer | 2785 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2451 reflections with I > 2σ(I) |
Tmin = 0.724, Tmax = 0.961 | Rint = 0.026 |
13125 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
2785 reflections | Δρmin = −0.20 e Å−3 |
120 parameters |
Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with an LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 10 s per frame. The preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix, which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8192 reflections with I > 10σ(I) after integration of all the frames data using SAINT (Siemens, 1995). |
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 | −0.31502 (11) | 0.53523 (5) | 0.92298 (5) | 0.03030 (15) | |
O2 | 0.22761 (12) | 0.67838 (6) | 0.76625 (5) | 0.03624 (17) | |
H2 | 0.1385 | 0.6207 | 0.7469 | 0.067 (5)* | |
N1 | −0.10084 (12) | 0.51985 (6) | 0.78128 (5) | 0.02756 (15) | |
C1 | −0.14136 (12) | 0.57529 (6) | 0.86899 (6) | 0.02236 (15) | |
C2 | −0.26962 (16) | 0.42099 (7) | 0.76396 (7) | 0.03023 (18) | |
H2A | −0.1873 | 0.3435 | 0.7685 | 0.030 (3)* | |
H2B | −0.3684 | 0.4275 | 0.6905 | 0.041 (3)* | |
C3 | −0.41902 (15) | 0.43393 (7) | 0.85872 (7) | 0.02926 (17) | |
H3A | −0.5853 | 0.4497 | 0.8289 | 0.034 (3)* | |
H3B | −0.4102 | 0.3612 | 0.9050 | 0.033 (3)* | |
C4 | −0.01057 (12) | 0.67954 (6) | 0.91529 (6) | 0.02151 (15) | |
C5 | 0.17266 (13) | 0.72529 (7) | 0.86198 (6) | 0.02536 (16) | |
C6 | 0.30083 (15) | 0.82308 (8) | 0.90818 (7) | 0.03128 (18) | |
H6 | 0.4265 | 0.8535 | 0.8736 | 0.054 (4)* | |
C7 | 0.24526 (15) | 0.87594 (8) | 1.00426 (7) | 0.03189 (18) | |
H7 | 0.3333 | 0.9425 | 1.0350 | 0.046 (3)* | |
C8 | 0.06187 (15) | 0.83266 (7) | 1.05639 (7) | 0.02959 (17) | |
H8 | 0.0239 | 0.8698 | 1.1218 | 0.045 (3)* | |
C9 | −0.06450 (13) | 0.73495 (7) | 1.01192 (6) | 0.02515 (16) | |
H9 | −0.1894 | 0.7051 | 1.0474 | 0.043 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0328 (3) | 0.0291 (3) | 0.0312 (3) | −0.0091 (2) | 0.0123 (2) | −0.0052 (2) |
O2 | 0.0395 (3) | 0.0433 (4) | 0.0294 (3) | −0.0078 (3) | 0.0170 (3) | −0.0050 (2) |
N1 | 0.0320 (3) | 0.0279 (3) | 0.0231 (3) | −0.0025 (2) | 0.0051 (2) | −0.0019 (2) |
C1 | 0.0234 (3) | 0.0224 (3) | 0.0213 (3) | 0.0008 (2) | 0.0031 (2) | 0.0028 (2) |
C2 | 0.0388 (4) | 0.0259 (4) | 0.0255 (3) | −0.0045 (3) | 0.0030 (3) | −0.0012 (3) |
C3 | 0.0292 (4) | 0.0256 (3) | 0.0328 (4) | −0.0046 (3) | 0.0037 (3) | −0.0020 (3) |
C4 | 0.0217 (3) | 0.0219 (3) | 0.0212 (3) | 0.0003 (2) | 0.0039 (2) | 0.0021 (2) |
C5 | 0.0256 (3) | 0.0285 (4) | 0.0231 (3) | −0.0005 (3) | 0.0071 (2) | 0.0027 (2) |
C6 | 0.0287 (4) | 0.0334 (4) | 0.0331 (4) | −0.0073 (3) | 0.0091 (3) | 0.0021 (3) |
C7 | 0.0331 (4) | 0.0289 (4) | 0.0338 (4) | −0.0083 (3) | 0.0054 (3) | −0.0018 (3) |
C8 | 0.0336 (4) | 0.0270 (4) | 0.0292 (4) | −0.0034 (3) | 0.0079 (3) | −0.0040 (3) |
C9 | 0.0262 (3) | 0.0251 (3) | 0.0254 (3) | −0.0019 (2) | 0.0078 (2) | −0.0010 (2) |
O1—C1 | 1.3481 (9) | C3—H3B | 0.9900 |
O1—C3 | 1.4601 (10) | C4—C9 | 1.4012 (10) |
O2—C5 | 1.3537 (9) | C4—C5 | 1.4104 (10) |
O2—H2 | 0.8400 | C5—C6 | 1.3968 (11) |
N1—C1 | 1.2832 (10) | C6—C7 | 1.3861 (12) |
N1—C2 | 1.4718 (11) | C6—H6 | 0.9500 |
C1—C4 | 1.4619 (10) | C7—C8 | 1.3932 (11) |
C2—C3 | 1.5376 (12) | C7—H7 | 0.9500 |
C2—H2A | 0.9900 | C8—C9 | 1.3843 (11) |
C2—H2B | 0.9900 | C8—H8 | 0.9500 |
C3—H3A | 0.9900 | C9—H9 | 0.9500 |
C1—O1—C3 | 106.10 (6) | C9—C4—C5 | 119.38 (7) |
C5—O2—H2 | 109.5 | C9—C4—C1 | 121.01 (6) |
C1—N1—C2 | 106.95 (7) | C5—C4—C1 | 119.61 (6) |
N1—C1—O1 | 118.38 (7) | O2—C5—C6 | 118.48 (7) |
N1—C1—C4 | 124.35 (7) | O2—C5—C4 | 122.18 (7) |
O1—C1—C4 | 117.27 (6) | C6—C5—C4 | 119.33 (7) |
N1—C2—C3 | 104.45 (6) | C7—C6—C5 | 120.23 (7) |
N1—C2—H2A | 110.9 | C7—C6—H6 | 119.9 |
C3—C2—H2A | 110.9 | C5—C6—H6 | 119.9 |
N1—C2—H2B | 110.9 | C6—C7—C8 | 120.82 (7) |
C3—C2—H2B | 110.9 | C6—C7—H7 | 119.6 |
H2A—C2—H2B | 108.9 | C8—C7—H7 | 119.6 |
O1—C3—C2 | 104.06 (6) | C9—C8—C7 | 119.37 (7) |
O1—C3—H3A | 110.9 | C9—C8—H8 | 120.3 |
C2—C3—H3A | 110.9 | C7—C8—H8 | 120.3 |
O1—C3—H3B | 110.9 | C8—C9—C4 | 120.84 (7) |
C2—C3—H3B | 110.9 | C8—C9—H9 | 119.6 |
H3A—C3—H3B | 109.0 | C4—C9—H9 | 119.6 |
C2—N1—C1—O1 | 0.07 (10) | C9—C4—C5—O2 | −177.58 (7) |
C2—N1—C1—C4 | 179.78 (7) | C1—C4—C5—O2 | 2.37 (11) |
C3—O1—C1—N1 | −1.64 (10) | C9—C4—C5—C6 | 1.65 (11) |
C3—O1—C1—C4 | 178.64 (6) | C1—C4—C5—C6 | −178.40 (7) |
C1—N1—C2—C3 | 1.43 (8) | O2—C5—C6—C7 | 178.02 (8) |
C1—O1—C3—C2 | 2.32 (8) | C4—C5—C6—C7 | −1.24 (12) |
N1—C2—C3—O1 | −2.27 (8) | C5—C6—C7—C8 | 0.11 (13) |
N1—C1—C4—C9 | −179.65 (7) | C6—C7—C8—C9 | 0.60 (13) |
O1—C1—C4—C9 | 0.06 (10) | C7—C8—C9—C4 | −0.17 (12) |
N1—C1—C4—C5 | 0.40 (11) | C5—C4—C9—C8 | −0.96 (11) |
O1—C1—C4—C5 | −179.89 (6) | C1—C4—C9—C8 | 179.10 (7) |
C9H9NO2 | F(000) = 688 |
Mr = 163.17 | Dx = 1.360 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8192 reflections |
a = 11.3650 (2) Å | θ = 2.4–25.0° |
b = 12.5867 (1) Å | µ = 0.10 mm−1 |
c = 11.2966 (2) Å | T = 173 K |
β = 99.534 (1)° | Needle, colourless |
V = 1593.63 (4) Å3 | 0.58 × 0.18 × 0.16 mm |
Z = 8 |
Siemens SMART CCD area-detector diffractometer | 2663 independent reflections |
Radiation source: fine-focus sealed tube | 2167 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −13→13 |
Tmin = 0.816, Tmax = 0.985 | k = −14→14 |
14444 measured reflections | l = −13→13 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.079P)2 + 2.9545P] where P = (Fo2 + 2Fc2)/3 |
2663 reflections | (Δ/σ)max < 0.001 |
237 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C9H9NO2 | V = 1593.63 (4) Å3 |
Mr = 163.17 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3650 (2) Å | µ = 0.10 mm−1 |
b = 12.5867 (1) Å | T = 173 K |
c = 11.2966 (2) Å | 0.58 × 0.18 × 0.16 mm |
β = 99.534 (1)° |
Siemens SMART CCD area-detector diffractometer | 2663 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2167 reflections with I > 2σ(I) |
Tmin = 0.816, Tmax = 0.985 | Rint = 0.056 |
14444 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.39 e Å−3 |
2663 reflections | Δρmin = −0.22 e Å−3 |
237 parameters |
Experimental. The sample used was not a single-crystal. Nevertheless, it was possible to resolve one set of diffractions from one domain. As a result, there were overlapping reflections; 118 reflections were omitted from the data set due to severe Fo/Fc discrepancies (Fo >> Fc). Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with an LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 30 s per frame. The preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix, which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8192 reflections with I > 10σ(I) after integration of all the frames data using SAINT (Siemens, 1995). |
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 | 0.40833 (18) | 0.30148 (17) | 0.02099 (19) | 0.0298 (5) | |
O2A | 0.6332 (2) | 0.5838 (2) | −0.3143 (2) | 0.0374 (6) | |
H2A | 0.7006 | 0.5612 | −0.2821 | 0.10 (2)* | |
N1A | 0.6025 (2) | 0.2864 (2) | 0.0037 (2) | 0.0258 (6) | |
C1A | 0.5023 (2) | 0.3329 (2) | −0.0302 (2) | 0.0217 (6) | |
C2A | 0.5856 (3) | 0.2091 (3) | 0.0989 (3) | 0.0286 (7) | |
H2A1 | 0.6327 | 0.2300 | 0.1772 | 0.041 (10)* | |
H2A2 | 0.6096 | 0.1368 | 0.0782 | 0.028 (8)* | |
C3A | 0.4508 (3) | 0.2139 (3) | 0.1028 (3) | 0.0351 (8) | |
H3A1 | 0.4112 | 0.1463 | 0.0747 | 0.043 (10)* | |
H3A2 | 0.4360 | 0.2289 | 0.1851 | 0.046 (11)* | |
C4A | 0.4774 (2) | 0.4158 (2) | −0.1222 (3) | 0.0221 (6) | |
C5A | 0.5708 (2) | 0.4592 (2) | −0.1727 (3) | 0.0227 (6) | |
H5A | 0.6503 | 0.4357 | −0.1470 | 0.031 (9)* | |
C6A | 0.5470 (3) | 0.5371 (2) | −0.2610 (3) | 0.0249 (7) | |
C7A | 0.4300 (3) | 0.5723 (3) | −0.2977 (3) | 0.0297 (7) | |
H7A | 0.4136 | 0.6255 | −0.3578 | 0.041 (10)* | |
C8A | 0.3378 (3) | 0.5294 (3) | −0.2463 (3) | 0.0295 (7) | |
H8A | 0.2586 | 0.5541 | −0.2714 | 0.037 (9)* | |
C9A | 0.3594 (3) | 0.4516 (2) | −0.1593 (3) | 0.0265 (7) | |
H9A | 0.2957 | 0.4225 | −0.1249 | 0.053 (11)* | |
O1B | 0.94268 (18) | 0.51245 (18) | 0.2167 (2) | 0.0308 (5) | |
O2B | 0.79400 (19) | 0.24456 (19) | −0.1031 (2) | 0.0350 (6) | |
H2B | 0.7408 | 0.2658 | −0.0652 | 0.040 (11)* | |
N1B | 1.1424 (2) | 0.4989 (2) | 0.2554 (2) | 0.0286 (6) | |
C1B | 1.0449 (2) | 0.4678 (2) | 0.1923 (3) | 0.0222 (6) | |
C2B | 1.1129 (3) | 0.5829 (3) | 0.3369 (3) | 0.0351 (8) | |
H2B1 | 1.1418 | 0.6529 | 0.3142 | 0.024 (8)* | |
H2B2 | 1.1488 | 0.5672 | 0.4211 | 0.037 (9)* | |
C3B | 0.9764 (3) | 0.5809 (3) | 0.3210 (3) | 0.0330 (8) | |
H3B1 | 0.9489 | 0.5509 | 0.3928 | 0.031 (9)* | |
H3B2 | 0.9427 | 0.6531 | 0.3058 | 0.050 (11)* | |
C4B | 1.0302 (2) | 0.3875 (2) | 0.0969 (3) | 0.0224 (6) | |
C5B | 0.9157 (3) | 0.3550 (2) | 0.0437 (3) | 0.0239 (6) | |
H5B | 0.8473 | 0.3848 | 0.0694 | 0.028 (8)* | |
C6B | 0.9024 (3) | 0.2791 (2) | −0.0469 (3) | 0.0252 (7) | |
C7B | 1.0028 (3) | 0.2351 (3) | −0.0846 (3) | 0.0304 (7) | |
H7B | 0.9935 | 0.1830 | −0.1463 | 0.031 (9)* | |
C8B | 1.1161 (3) | 0.2675 (3) | −0.0319 (3) | 0.0293 (7) | |
H8B | 1.1842 | 0.2377 | −0.0581 | 0.020 (8)* | |
C9B | 1.1310 (3) | 0.3435 (2) | 0.0590 (3) | 0.0278 (7) | |
H9B | 1.2088 | 0.3652 | 0.0951 | 0.040 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0215 (11) | 0.0321 (12) | 0.0376 (12) | 0.0037 (9) | 0.0100 (9) | 0.0086 (10) |
O2A | 0.0249 (12) | 0.0423 (14) | 0.0463 (14) | −0.0004 (10) | 0.0096 (11) | 0.0148 (12) |
N1A | 0.0220 (13) | 0.0253 (13) | 0.0305 (14) | 0.0023 (10) | 0.0061 (10) | 0.0045 (11) |
C1A | 0.0208 (14) | 0.0209 (15) | 0.0240 (15) | −0.0021 (11) | 0.0058 (12) | −0.0040 (12) |
C2A | 0.0286 (17) | 0.0264 (16) | 0.0320 (17) | 0.0072 (13) | 0.0088 (13) | 0.0053 (13) |
C3A | 0.0320 (18) | 0.0320 (18) | 0.043 (2) | 0.0042 (14) | 0.0106 (15) | 0.0159 (15) |
C4A | 0.0220 (15) | 0.0210 (15) | 0.0232 (14) | 0.0010 (11) | 0.0036 (11) | −0.0046 (12) |
C5A | 0.0192 (14) | 0.0242 (15) | 0.0241 (15) | 0.0023 (11) | 0.0018 (12) | −0.0033 (12) |
C6A | 0.0224 (15) | 0.0277 (16) | 0.0253 (15) | −0.0016 (12) | 0.0059 (12) | 0.0030 (13) |
C7A | 0.0304 (17) | 0.0302 (17) | 0.0277 (16) | 0.0037 (13) | 0.0027 (13) | 0.0055 (14) |
C8A | 0.0228 (15) | 0.0318 (17) | 0.0332 (17) | 0.0068 (13) | 0.0028 (13) | 0.0015 (14) |
C9A | 0.0215 (15) | 0.0279 (16) | 0.0302 (16) | 0.0031 (12) | 0.0050 (12) | −0.0023 (13) |
O1B | 0.0184 (10) | 0.0365 (13) | 0.0379 (12) | 0.0007 (9) | 0.0055 (9) | −0.0137 (10) |
O2B | 0.0222 (11) | 0.0422 (14) | 0.0415 (13) | −0.0051 (10) | 0.0077 (10) | −0.0133 (11) |
N1B | 0.0223 (13) | 0.0308 (14) | 0.0334 (14) | −0.0027 (11) | 0.0070 (11) | −0.0039 (12) |
C1B | 0.0172 (14) | 0.0235 (15) | 0.0277 (15) | 0.0000 (11) | 0.0089 (12) | 0.0043 (12) |
C2B | 0.0303 (17) | 0.0389 (19) | 0.0360 (18) | −0.0038 (14) | 0.0047 (14) | −0.0109 (15) |
C3B | 0.0307 (17) | 0.0359 (18) | 0.0340 (17) | −0.0006 (14) | 0.0101 (14) | −0.0132 (15) |
C4B | 0.0209 (14) | 0.0208 (15) | 0.0258 (15) | −0.0007 (12) | 0.0052 (11) | 0.0036 (12) |
C5B | 0.0189 (14) | 0.0257 (15) | 0.0280 (15) | 0.0019 (12) | 0.0063 (12) | 0.0007 (13) |
C6B | 0.0236 (15) | 0.0239 (15) | 0.0288 (16) | −0.0033 (12) | 0.0063 (12) | 0.0010 (13) |
C7B | 0.0360 (18) | 0.0265 (16) | 0.0306 (16) | 0.0007 (13) | 0.0108 (14) | −0.0055 (14) |
C8B | 0.0217 (15) | 0.0324 (17) | 0.0360 (17) | 0.0047 (13) | 0.0113 (13) | −0.0022 (14) |
C9B | 0.0211 (15) | 0.0293 (17) | 0.0340 (17) | −0.0016 (12) | 0.0077 (13) | −0.0028 (13) |
O1A—C1A | 1.356 (3) | O1B—C1B | 1.359 (3) |
O1A—C3A | 1.468 (4) | O1B—C3B | 1.459 (4) |
O2A—C6A | 1.364 (4) | O2B—C6B | 1.360 (4) |
O2A—H2A | 0.8400 | O2B—H2B | 0.8400 |
N1A—C1A | 1.281 (4) | N1B—C1B | 1.276 (4) |
N1A—C2A | 1.486 (4) | N1B—C2B | 1.476 (4) |
C1A—C4A | 1.466 (4) | C1B—C4B | 1.467 (4) |
C2A—C3A | 1.540 (4) | C2B—C3B | 1.533 (4) |
C2A—H2A1 | 0.9900 | C2B—H2B1 | 0.9900 |
C2A—H2A2 | 0.9900 | C2B—H2B2 | 0.9900 |
C3A—H3A1 | 0.9900 | C3B—H3B1 | 0.9900 |
C3A—H3A2 | 0.9900 | C3B—H3B2 | 0.9900 |
C4A—C9A | 1.411 (4) | C4B—C9B | 1.402 (4) |
C4A—C5A | 1.398 (4) | C4B—C5B | 1.402 (4) |
C5A—C6A | 1.393 (4) | C5B—C6B | 1.390 (4) |
C5A—H5A | 0.9500 | C5B—H5B | 0.9500 |
C6A—C7A | 1.398 (4) | C6B—C7B | 1.397 (4) |
C7A—C8A | 1.389 (4) | C7B—C8B | 1.388 (4) |
C7A—H7A | 0.9500 | C7B—H7B | 0.9500 |
C8A—C9A | 1.380 (4) | C8B—C9B | 1.393 (4) |
C8A—H8A | 0.9500 | C8B—H8B | 0.9500 |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C1A—O1A—C3A | 106.7 (2) | C1B—O1B—C3B | 106.8 (2) |
C6A—O2A—H2A | 109.5 | C6B—O2B—H2B | 109.5 |
C1A—N1A—C2A | 107.5 (2) | C1B—N1B—C2B | 107.6 (2) |
N1A—C1A—O1A | 117.6 (3) | N1B—C1B—O1B | 116.9 (3) |
N1A—C1A—C4A | 126.5 (3) | N1B—C1B—C4B | 127.2 (3) |
O1A—C1A—C4A | 115.9 (2) | O1B—C1B—C4B | 115.9 (2) |
N1A—C2A—C3A | 104.1 (2) | N1B—C2B—C3B | 104.2 (2) |
N1A—C2A—H2A1 | 110.9 | N1B—C2B—H2B1 | 110.9 |
C3A—C2A—H2A1 | 110.9 | C3B—C2B—H2B1 | 110.9 |
N1A—C2A—H2A2 | 110.9 | N1B—C2B—H2B2 | 110.9 |
C3A—C2A—H2A2 | 110.9 | C3B—C2B—H2B2 | 110.9 |
H2A1—C2A—H2A2 | 109.0 | H2B1—C2B—H2B2 | 108.9 |
O1A—C3A—C2A | 103.7 (2) | O1B—C3B—C2B | 103.3 (2) |
O1A—C3A—H3A1 | 111.0 | O1B—C3B—H3B1 | 111.1 |
C2A—C3A—H3A1 | 111.0 | C2B—C3B—H3B1 | 111.1 |
O1A—C3A—H3A2 | 111.0 | O1B—C3B—H3B2 | 111.1 |
C2A—C3A—H3A2 | 111.0 | C2B—C3B—H3B2 | 111.1 |
H3A1—C3A—H3A2 | 109.0 | H3B1—C3B—H3B2 | 109.1 |
C9A—C4A—C5A | 120.2 (3) | C9B—C4B—C5B | 120.1 (3) |
C9A—C4A—C1A | 120.1 (3) | C9B—C4B—C1B | 119.8 (3) |
C5A—C4A—C1A | 119.8 (3) | C5B—C4B—C1B | 120.0 (3) |
C6A—C5A—C4A | 119.9 (3) | C6B—C5B—C4B | 119.7 (3) |
C6A—C5A—H5A | 120.1 | C6B—C5B—H5B | 120.1 |
C4A—C5A—H5A | 120.1 | C4B—C5B—H5B | 120.1 |
O2A—C6A—C5A | 123.4 (3) | O2B—C6B—C5B | 122.8 (3) |
O2A—C6A—C7A | 116.8 (3) | O2B—C6B—C7B | 117.0 (3) |
C5A—C6A—C7A | 119.8 (3) | C5B—C6B—C7B | 120.2 (3) |
C8A—C7A—C6A | 120.0 (3) | C8B—C7B—C6B | 120.0 (3) |
C8A—C7A—H7A | 120.0 | C8B—C7B—H7B | 120.0 |
C6A—C7A—H7A | 120.0 | C6B—C7B—H7B | 120.0 |
C7A—C8A—C9A | 121.0 (3) | C7B—C8B—C9B | 120.6 (3) |
C7A—C8A—H8A | 119.5 | C7B—C8B—H8B | 119.7 |
C9A—C8A—H8A | 119.5 | C9B—C8B—H8B | 119.7 |
C4A—C9A—C8A | 119.1 (3) | C8B—C9B—C4B | 119.4 (3) |
C4A—C9A—H9A | 120.4 | C8B—C9B—H9B | 120.3 |
C8A—C9A—H9A | 120.4 | C4B—C9B—H9B | 120.3 |
C2A—N1A—C1A—O1A | −2.1 (4) | C2B—N1B—C1B—O1B | −2.8 (4) |
C2A—N1A—C1A—C4A | 179.6 (3) | C2B—N1B—C1B—C4B | 178.3 (3) |
C3A—O1A—C1A—N1A | −2.4 (4) | C3B—O1B—C1B—N1B | −4.7 (4) |
C3A—O1A—C1A—C4A | 176.0 (2) | C3B—O1B—C1B—C4B | 174.3 (2) |
C1A—N1A—C2A—C3A | 5.5 (3) | C1B—N1B—C2B—C3B | 8.7 (3) |
C1A—O1A—C3A—C2A | 5.6 (3) | C1B—O1B—C3B—C2B | 9.5 (3) |
N1A—C2A—C3A—O1A | −6.6 (3) | N1B—C2B—C3B—O1B | −10.9 (3) |
N1A—C1A—C4A—C9A | 173.1 (3) | N1B—C1B—C4B—C9B | −6.2 (5) |
O1A—C1A—C4A—C9A | −5.2 (4) | O1B—C1B—C4B—C9B | 174.9 (3) |
N1A—C1A—C4A—C5A | −6.9 (4) | N1B—C1B—C4B—C5B | 173.9 (3) |
O1A—C1A—C4A—C5A | 174.8 (2) | O1B—C1B—C4B—C5B | −5.0 (4) |
C9A—C4A—C5A—C6A | −0.7 (4) | C9B—C4B—C5B—C6B | −0.1 (4) |
C1A—C4A—C5A—C6A | 179.3 (3) | C1B—C4B—C5B—C6B | 179.8 (3) |
C4A—C5A—C6A—O2A | 179.6 (3) | C4B—C5B—C6B—O2B | −179.5 (3) |
C4A—C5A—C6A—C7A | 0.7 (4) | C4B—C5B—C6B—C7B | 0.2 (4) |
O2A—C6A—C7A—C8A | −179.2 (3) | O2B—C6B—C7B—C8B | 179.4 (3) |
C5A—C6A—C7A—C8A | −0.1 (5) | C5B—C6B—C7B—C8B | −0.3 (5) |
C6A—C7A—C8A—C9A | −0.4 (5) | C6B—C7B—C8B—C9B | 0.3 (5) |
C5A—C4A—C9A—C8A | 0.3 (4) | C7B—C8B—C9B—C4B | −0.3 (5) |
C1A—C4A—C9A—C8A | −179.7 (3) | C5B—C4B—C9B—C8B | 0.2 (4) |
C7A—C8A—C9A—C4A | 0.3 (5) | C1B—C4B—C9B—C8B | −179.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···N1Bi | 0.84 | 1.92 | 2.732 (3) | 164 |
O2B—H2B···N1A | 0.84 | 1.88 | 2.709 (3) | 167 |
C5B—H5B···O1B | 0.95 | 2.43 | 2.764 (4) | 100 |
C7A—H7A···N1Aii | 0.95 | 2.60 | 3.540 (4) | 171 |
C9A—H9A···O1A | 0.95 | 2.45 | 2.767 (4) | 100 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, y+1/2, −z−1/2. |
C9H9NO2 | F(000) = 344 |
Mr = 163.17 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6730 reflections |
a = 4.7778 (1) Å | θ = 2.3–33.1° |
b = 14.9883 (2) Å | µ = 0.10 mm−1 |
c = 10.9194 (1) Å | T = 173 K |
β = 95.945 (1)° | Plate, colourless |
V = 777.74 (2) Å3 | 0.60 × 0.32 × 0.06 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2784 independent reflections |
Radiation source: fine-focus sealed tube | 2064 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 33.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −7→7 |
Tmin = 0.710, Tmax = 0.994 | k = −22→22 |
13219 measured reflections | l = −16→16 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0613P)2 + 0.2076P] where P = (Fo2 + 2Fc2)/3 |
2784 reflections | (Δ/σ)max < 0.001 |
119 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C9H9NO2 | V = 777.74 (2) Å3 |
Mr = 163.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.7778 (1) Å | µ = 0.10 mm−1 |
b = 14.9883 (2) Å | T = 173 K |
c = 10.9194 (1) Å | 0.60 × 0.32 × 0.06 mm |
β = 95.945 (1)° |
Siemens SMART CCD area-detector diffractometer | 2784 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2064 reflections with I > 2σ(I) |
Tmin = 0.710, Tmax = 0.994 | Rint = 0.038 |
13219 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.32 e Å−3 |
2784 reflections | Δρmin = −0.21 e Å−3 |
119 parameters |
Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with an LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 10 s per frame. The preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix, which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 6730 reflections with I > 10σ(I) after integration of all the frames data using SAINT (Siemens, 1995). |
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 | 0.8194 (2) | 0.53816 (6) | 0.60741 (8) | 0.0375 (2) | |
O2 | 0.04190 (19) | 0.88041 (6) | 0.51369 (8) | 0.0319 (2) | |
H2 | 0.0943 | 0.8987 | 0.4470 | 0.068 (6)* | |
N1 | 0.7108 (2) | 0.55667 (7) | 0.80165 (9) | 0.0294 (2) | |
C1 | 0.6770 (2) | 0.58270 (7) | 0.68969 (10) | 0.0259 (2) | |
C2 | 0.9168 (3) | 0.48288 (8) | 0.80957 (12) | 0.0343 (3) | |
H2A | 0.8371 | 0.4286 | 0.8443 | 0.046 (4)* | |
H2B | 1.0910 | 0.4998 | 0.8614 | 0.045 (4)* | |
C3 | 0.9756 (3) | 0.46749 (9) | 0.67567 (12) | 0.0348 (3) | |
H3A | 1.1794 | 0.4722 | 0.6672 | 0.040 (4)* | |
H3B | 0.9081 | 0.4080 | 0.6464 | 0.047 (4)* | |
C4 | 0.5040 (2) | 0.65798 (7) | 0.64100 (10) | 0.0254 (2) | |
C5 | 0.5233 (3) | 0.68982 (8) | 0.52173 (10) | 0.0307 (3) | |
H5 | 0.6436 | 0.6606 | 0.4705 | 0.050 (5)* | |
C6 | 0.3699 (3) | 0.76319 (8) | 0.47749 (10) | 0.0300 (2) | |
H6 | 0.3851 | 0.7838 | 0.3962 | 0.041 (4)* | |
C7 | 0.1922 (2) | 0.80737 (7) | 0.55155 (10) | 0.0253 (2) | |
C8 | 0.1695 (2) | 0.77513 (8) | 0.67048 (10) | 0.0306 (2) | |
H8 | 0.0473 | 0.8039 | 0.7213 | 0.042 (4)* | |
C9 | 0.3237 (2) | 0.70175 (8) | 0.71444 (10) | 0.0292 (2) | |
H9 | 0.3070 | 0.6807 | 0.7955 | 0.038 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0452 (5) | 0.0399 (5) | 0.0288 (4) | 0.0132 (4) | 0.0105 (4) | −0.0020 (4) |
O2 | 0.0359 (5) | 0.0342 (5) | 0.0266 (4) | 0.0060 (3) | 0.0090 (3) | 0.0026 (3) |
N1 | 0.0328 (5) | 0.0287 (5) | 0.0272 (5) | 0.0015 (4) | 0.0060 (4) | 0.0001 (4) |
C1 | 0.0250 (5) | 0.0272 (5) | 0.0259 (5) | −0.0025 (4) | 0.0051 (4) | −0.0042 (4) |
C2 | 0.0356 (6) | 0.0322 (6) | 0.0359 (6) | 0.0042 (5) | 0.0070 (5) | 0.0033 (5) |
C3 | 0.0356 (6) | 0.0303 (6) | 0.0390 (7) | 0.0050 (5) | 0.0057 (5) | −0.0028 (5) |
C4 | 0.0248 (5) | 0.0287 (5) | 0.0233 (5) | −0.0016 (4) | 0.0048 (4) | −0.0024 (4) |
C5 | 0.0343 (6) | 0.0363 (6) | 0.0229 (5) | 0.0044 (5) | 0.0091 (4) | −0.0024 (4) |
C6 | 0.0346 (6) | 0.0357 (6) | 0.0209 (5) | 0.0023 (5) | 0.0091 (4) | 0.0006 (4) |
C7 | 0.0253 (5) | 0.0280 (5) | 0.0229 (5) | −0.0014 (4) | 0.0045 (4) | −0.0015 (4) |
C8 | 0.0315 (6) | 0.0381 (6) | 0.0237 (5) | 0.0046 (5) | 0.0102 (4) | 0.0005 (4) |
C9 | 0.0309 (6) | 0.0346 (6) | 0.0232 (5) | 0.0021 (4) | 0.0085 (4) | 0.0021 (4) |
O1—C1 | 1.3575 (13) | C3—H3B | 0.9900 |
O1—C3 | 1.4559 (16) | C4—C5 | 1.3989 (15) |
O2—C7 | 1.3505 (14) | C4—C9 | 1.3998 (15) |
O2—H2 | 0.8400 | C5—C6 | 1.3809 (17) |
N1—C1 | 1.2775 (14) | C5—H5 | 0.9500 |
N1—C2 | 1.4769 (15) | C6—C7 | 1.3982 (15) |
C1—C4 | 1.4654 (16) | C6—H6 | 0.9500 |
C2—C3 | 1.5347 (18) | C7—C8 | 1.4003 (15) |
C2—H2A | 0.9900 | C8—C9 | 1.3818 (16) |
C2—H2B | 0.9900 | C8—H8 | 0.9500 |
C3—H3A | 0.9900 | C9—H9 | 0.9500 |
C1—O1—C3 | 106.53 (9) | C5—C4—C9 | 118.51 (11) |
C7—O2—H2 | 109.5 | C5—C4—C1 | 120.76 (10) |
C1—N1—C2 | 107.60 (9) | C9—C4—C1 | 120.68 (10) |
N1—C1—O1 | 117.43 (10) | C6—C5—C4 | 120.91 (10) |
N1—C1—C4 | 126.39 (10) | C6—C5—H5 | 119.5 |
O1—C1—C4 | 116.16 (10) | C4—C5—H5 | 119.5 |
N1—C2—C3 | 104.09 (10) | C5—C6—C7 | 120.45 (10) |
N1—C2—H2A | 110.9 | C5—C6—H6 | 119.8 |
C3—C2—H2A | 110.9 | C7—C6—H6 | 119.8 |
N1—C2—H2B | 110.9 | O2—C7—C8 | 118.29 (10) |
C3—C2—H2B | 110.9 | O2—C7—C6 | 122.83 (10) |
H2A—C2—H2B | 109.0 | C8—C7—C6 | 118.88 (10) |
O1—C3—C2 | 104.10 (9) | C9—C8—C7 | 120.47 (10) |
O1—C3—H3A | 110.9 | C9—C8—H8 | 119.8 |
C2—C3—H3A | 110.9 | C7—C8—H8 | 119.8 |
O1—C3—H3B | 110.9 | C8—C9—C4 | 120.77 (10) |
C2—C3—H3B | 110.9 | C8—C9—H9 | 119.6 |
H3A—C3—H3B | 109.0 | C4—C9—H9 | 119.6 |
C2—N1—C1—O1 | 2.11 (14) | C9—C4—C5—C6 | 0.52 (18) |
C2—N1—C1—C4 | −176.15 (11) | C1—C4—C5—C6 | −177.13 (11) |
C3—O1—C1—N1 | 1.25 (14) | C4—C5—C6—C7 | 0.18 (19) |
C3—O1—C1—C4 | 179.69 (10) | C5—C6—C7—O2 | 178.66 (11) |
C1—N1—C2—C3 | −4.32 (13) | C5—C6—C7—C8 | −0.95 (18) |
C1—O1—C3—C2 | −3.83 (13) | O2—C7—C8—C9 | −178.61 (11) |
N1—C2—C3—O1 | 4.86 (13) | C6—C7—C8—C9 | 1.02 (18) |
N1—C1—C4—C5 | 168.38 (12) | C7—C8—C9—C4 | −0.32 (18) |
O1—C1—C4—C5 | −9.90 (16) | C5—C4—C9—C8 | −0.45 (18) |
N1—C1—C4—C9 | −9.22 (18) | C1—C4—C9—C8 | 177.20 (11) |
O1—C1—C4—C9 | 172.50 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1i | 0.84 | 1.86 | 2.6997 (13) | 178 |
C5—H5···O1 | 0.95 | 2.46 | 2.7874 (15) | 100 |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C9H9NO2 | C9H9NO2 | C9H9NO2 |
Mr | 163.17 | 163.17 | 163.17 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 5.7562 (1), 11.2464 (1), 12.1365 (1) | 11.3650 (2), 12.5867 (1), 11.2966 (2) | 4.7778 (1), 14.9883 (2), 10.9194 (1) |
α, β, γ (°) | 90, 98.162 (1), 90 | 90, 99.534 (1), 90 | 90, 95.945 (1), 90 |
V (Å3) | 777.72 (2) | 1593.63 (4) | 777.74 (2) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 | 0.10 |
Crystal size (mm) | 0.80 × 0.42 × 0.40 | 0.58 × 0.18 × 0.16 | 0.60 × 0.32 × 0.06 |
Data collection | |||
Diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) | Multi-scan (SADABS; Sheldrick, 2002) | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.724, 0.961 | 0.816, 0.985 | 0.710, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13125, 2785, 2451 | 14444, 2663, 2167 | 13219, 2784, 2064 |
Rint | 0.026 | 0.056 | 0.038 |
(sin θ/λ)max (Å−1) | 0.766 | 0.595 | 0.768 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.119, 1.03 | 0.068, 0.175, 1.00 | 0.047, 0.133, 1.02 |
No. of reflections | 2785 | 2663 | 2784 |
No. of parameters | 120 | 237 | 119 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.20 | 0.39, −0.22 | 0.32, −0.21 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2002), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2005).
(I) | (IIA) | (IIB) | (III) | |
C1-C4 | 1.4619 (10) | 1.466 (4) | 1.467 (4) | 1.4654 (16) |
C1-O1 | 1.3481 (9) | 1.356 (3) | 1.359 (3) | 1.3575 (13) |
C1-N1 | 1.2832 (10) | 1.281 (4) | 1.276 (4) | 1.2775 (14) |
C2-N1-C1-O1 | 0.07 (10) | -2.1 (4) | -2.8 (4) | 2.11 (14) |
C3-O1-C1-N1 | -1.64 (10) | -2.4 (4) | -4.7 (4) | 1.25 (14) |
C1-N1-C2-C3 | 1.43 (8) | 5.5 (3) | 8.7 (3) | -4.32 (13) |
C1-O1-C3-C2 | 2.32 (8) | 5.6 (3) | 9.5 (3) | -3.83 (13) |
N1-C2-C3-O1 | -2.27 (8) | -6.6 (3) | -10.9 (3) | 4.86 (13) |
N1-C1-C4-C9 | -179.65 (7) | 173.1 (3) | -6.2 (5) | -9.22 (18) |
O1-C1-C4-C9 | 0.06 (10) | -5.2 (4) | 174.9 (3) | 172.50 (11) |
N1-C1-C4-C5 | 0.40 (11) | -6.9 (4) | 173.9 (3) | 168.38 (12) |
O1-C1-C4-C5 | -179.89 (6) | 174.8 (2) | -5.0 (4) | -9.90 (16) |
Notation | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | O2—H2···N1 | 0.84 | 1.88 | 2.6238 (9) | 147.5 |
DFT calculation | 1.052 | 1.513 | 2.481 | 150.22 | |
(IIa) | O2A—H2A···N1Bi | 0.84 | 1.92 | 2.732 (3) | 163.6 |
DFT calculation | 1.028 | 1.619 | 2.637 | 169.2 | |
(IIb) | O2B—H2B···N1A | 0.84 | 1.88 | 2.709 (3) | 167.0 |
DFT calculation | 1.05 | 1.582 | 2.615 | 166.97 | |
(IIc) | C5B—H5B···O1B | 0.95 | 2.43 | 2.764 (4) | 100.1 |
DFT calculation | 1.083 | 2.384 | 2.767 | 98.9 | |
(IId) | C7A—H7A···N1Aii | 0.95 | 2.60 | 3.540 (4) | 171.0 |
DFT calculation | 1.097 | 2.375 | 3.467 | 175.94 | |
(IIe) | C9A—H9A···O1A | 0.95 | 2.45 | 2.767 (4) | 99.6 |
DFT calculation | 1.083 | 2.388 | 2.769 | 98.84 | |
(IIIa) | O2—H2···N1iii | 0.84 | 1.86 | 2.6997 (13) | 178.0 |
DFT calculation | 1.043 | 1.480 | 2.522 | 177.43 | |
(IIIb) | C5—H5···O1 | 0.95 | 2.46 | 2.7874 (15) | 100.1 |
DFT calculation | 1.032 | 2.474 | 2.830 | 99.31 |
Symmetry codes: (i) 2 − x, 1 − y, − z; (ii) 1 − x, 1/2 + y, − 1/2 − z; (iii) x − 1/2, 3/2 − y, z − 1/2. |
Cyclic imino ethers, among them 2-oxazolines, are important intermediates in organic synthesis. The title compounds, (I)–(III), were prepared in the course of our research focused on cyclic imino ethers and their utilization in polymer chemistry (Kronek et al., 1998), as hydroxyphenyl-2-oxazolines are known to produce poly(ether-amides) on heating of the monomer (Wörner et al., 1995). Although the syntheses of these compounds have already been reported [for (I), Cwik et al., 2002; Black & Wade, 1972; Peterson et al., 1980; for (II), Kalle, 1969; for (III), Nonnenmacher & Plieninger, 1982], their crystal structures have not been published until now. Among 87 matches from the Cambridge Structural Database (CSD, February 2005 update, version 5.26; Allen, 2002) for (I), only 15 structures were relevant (i.e. having a 4,5-unsubstituted 2-oxazoline ring and a 3',4',5',6'-unsubstituted 2'-hydroxyphenyl moiety), but in all these compounds the [Text missing?]. 2-(2'-Hydroxyphenyl)-2-oxazoline has been reported as a ligand in several complexes with metals such as Fe, Mn, Ni, V, Zn, Al, In and Re (e.g. Qian et al., 2004; Kooijman et al., 2002; Miller et al., 1999; Melchior et al., 1999). For compounds (II) and (III), a CSD search revealed only one and 13 similar structures, respectively, but none of them had a relevant hydroxyl group in the meta or para position of the benzene ring.
Selected geometric parameters for (I), (II) and (III) are listed in Table 1. The numbering schemes, together with the corresponding atomic displacement ellipsoid plots, are shown in Figs. 1–3, respectively. The crystal packings of (I) and (II) are depicted in Figs. 4 and 5, respectively. The hydrogen-bonding schemes for (II) and (III) are shown in Figs. 6 and 7, respectively. The hydrogen-bonding geometries for (I), (II) and (III) are listed in Table 2. The theoretical investigation of hydrogen bonds was performed using the Vienna ab initio simulation package VASP (Kresse & Furthmüller, 1996; Kresse & Hafner, 1993). The calculations were based on density functional theory (DFT) with periodic boundary conditions (Jones & Gunnarsson, 1989).
The 2-oxazoline ring in (I) and (III) is nearly planar. Surprisingly, in the case of compound (II), with two molecules, A and B, in the asymmetric unit, the values of the relevant dihedral angles (Table 1) and puckering parameters (Cremer & Pople, 1975), Q = 0.108 (3) Å and ϕ = 310.3 (17)°, indicate that this ring in molecule B deviates significantly from planarity (twisting about the C3B—C2B bond) and adopts a 3T4 (C2TC3) conformation, while the 2-oxazoline ring in molecule A is again nearly planar. This difference may be due to the arrangement of molecule B in the tetramer, as well as hydrogen bonding.
As seen from the values of the acute angles between the planes of the oxazolinyl and phenyl rings [0.74 (4)° for (I), 4.75 (16) and 3.49 (17)° for molecules A and B of (II), respectively, and 11.22 (6)° for (III)], the mutual position of these rings reflects the location (ortho, meta or para, respectively) of the hydroxyl group on the phenyl ring. In this respect, the coplanarity of both rings in the o-hydroxy derivative, (I) (Fig. 1), and the most evident deviation from coplanarity in the p-hydroxy derivative, (III), is observed. We assume that the coplanar arrangement of the rings and the syn-periplanar orientation of atom O2 (ortho-hydroxyl group) with respect to the C10—N1 bond in (I) is stabilized by the strong intramolecular O2—H2···N1 hydrogen bond (Table 2). In this regard, free rotation about the sp2–sp2 C1—C4 bond could be sufficiently restricted, leading to possible atropisomerism, and this is probably responsible for the chirality because, although there is no chiral atom in (I), optical activity of [α]20D = 3.0 (c = 1, CHCl3) was observed for this compound. The syn-periplanar arrangement of atom N1 relative to the C4—C5 bond, with atom N1 directed slightly below the phenyl ring plane, is observed for both molecules A and B of the m-hydroxy derivative, (II) (Fig. 2). In the case of molecule A, similar to the C5—O2 and C1—N1 bonds in (I), the C6—O2 and C1—N1 bonds are oriented cis with respect to the plane perpendicular to the plane of the phenyl and oxazoline rings across the C1—C4 bond. In contrast, the orientation of the C6—O2 and C1—N1 bonds is trans in the case of molecule B. For the p-hydroxy derivative, (III), shown in Fig. 3, the C1—N1 and C4—C5 bonds are oriented antiperiplanar, with atom N1 directed slightly above the plane of the phenyl ring.
The C1—C4 bond in compounds (I)–(III) is significantly shorter than the usual single C—C bond (Table 1; Reference for standard value?), indicating a weak conjugation between the 2-oxazoline ring substituted at the C-2 position (C1) and the phenyl group.
The hydrogen-bonding patterns can be described using graph theory (Bernstein et al., 1995; Grell et al., 1999). For (I), there is just one intramolecular hydrogen bond of the O—H···N type, which is, on the first-level graph-set, described as an S(6) string. For (II), there are two strong hydrogen bonds of the O—H···N type, two weak intramolecular bonds of the C—H···O type and one weak intermolecular interaction of the C—H···N type. On the first-level graph-set, the hydrogen-bonding pattern can be classified as D(2) for hydrogen bonds (IIa) and (IIb), S(5) for (IIc) and (IIe), and as a C(7) chain for hydrogen bond (IId) (Table 2). On the second-level graph-set, the above-mentioned tetramer is described as an R44(28) ring formed by hydrogen bonds (IIa) and (IIb), apart from D33(14) and D23(10) for bonds (IIa) and (IId), and (IIb) and (IId), respectively. The first-level graph-set descriptors for (III) are C(8) for the strong hydrogen bond (IIIa) and S(5) for the weak intramolecular hydrogen bond (IIIb). The molecules thus form an infinite chain perpendicular to the b direction, diagonal in the ab plane. The assignment of graph-set descriptors was performed using PLUTO, as described by Motherwell et al. (1999), and the notation of the hydrogen bonds here is that given in Table 2.