Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008158/bt6270sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008158/bt6270Isup2.hkl |
CCDC reference: 214848
Key indicators
- Powder X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.052
- wR factor = 0.149
- Data-to-parameter ratio = 14.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
To a mixture of hydroxylammoniumchloride (460 mg, 6.6 mmol) and potassium acetate (668 mg, 6.8 mmol) in 40 ml e thanol azulene-1-carbaldehyde (1.0 g, 6.5 mmol) was added and heated to 323 K. After 1.5 h, the solvent was evaporated. Chromatography with silica gel (hexane/ethyl acetate 4:1) yielded the isomer oximes. Dark green crystals of (I) were obtained from a toluene solution by evaporation. (E)-Azulene-1-carboxaldehyde oxime, (I), m.p. 393–394 K; 1H NMR (500 MHz, [D6]DMSO): δ = 10.94 (s, 1H, H11O), 8.92 (d, 1H, H8), 8.72 (s, 1H, H11), 8.42 (d, 1H, H4), 8.13 (d, 1H, H2), 7.74 (app.t, 1H, H6), 7.43 (d, 1H, H3), 7.32 (app. q, 2H, H5,H7); J2,3 = 4.0, J4,5 = 9.3, J7,8 = 9.8, J5,6 = J6,7=9.8 Hz. 13C NMR (125.75 MHz, [D6]DMSO): δ = 144.9 (C11), 143.2 (C10), 139.6 (C6), 138.2 (C4), 136.4 (C2), 136.3 (C9), 136.1 (C8), 125.4 (C5), 125.1 (C7), 121.8 (C1), 119.2 (C3).
H atoms of (I) are treated as riding atoms. The position of the hydroyxl H atom was found in a difference Fourier map and refined.
Data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001) and ORTEPIII (Johnson & Burnett, 1998); software used to prepare material for publication: SHELXL97 CIF and IUCr SHELXL97 template.
Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. A packing plot of (I), viewed along the b axis. |
C11H9NO | Dx = 1.281 Mg m−3 |
Mr = 171.19 | Melting point = 120–121 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.931 (3) Å | Cell parameters from 5481 reflections |
b = 6.174 (2) Å | θ = 3.5–26.4° |
c = 17.028 (5) Å | µ = 0.08 mm−1 |
β = 94.00 (2)° | T = 293 K |
V = 1775.6 (8) Å3 | Needle, dark green |
Z = 8 | 0.52 × 0.28 × 0.14 mm |
F(000) = 720 |
Oxford Diffraction Excalibur (TM) single-crystal X-ray diffractometer with Sapphire CCD detector | 815 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.066 |
Graphite monochromator | θmax = 26.4°, θmin = 3.5° |
Rotation method data acquisition using ω and θ scans | h = −21→21 |
5481 measured reflections | k = −7→5 |
1803 independent reflections | l = −21→21 |
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) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0524P)2] where P = (Fo2 + 2Fc2)/3 |
1803 reflections | (Δ/σ)max < 0.001 |
121 parameters | Δρmax = 0.13 e Å−3 |
1 restraint | Δρmin = −0.14 e Å−3 |
C11H9NO | V = 1775.6 (8) Å3 |
Mr = 171.19 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.931 (3) Å | µ = 0.08 mm−1 |
b = 6.174 (2) Å | T = 293 K |
c = 17.028 (5) Å | 0.52 × 0.28 × 0.14 mm |
β = 94.00 (2)° |
Oxford Diffraction Excalibur (TM) single-crystal X-ray diffractometer with Sapphire CCD detector | 815 reflections with I > 2σ(I) |
5481 measured reflections | Rint = 0.066 |
1803 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 1 restraint |
wR(F2) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.13 e Å−3 |
1803 reflections | Δρmin = −0.14 e Å−3 |
121 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. Mean-plane data from final SHELXL refinement run: Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 2.9924 (0.0090) x + 2.8321 (0.0046) y + 14.5824 (0.0084) z = 10.5556 (0.0085) * −0.0070 (0.0022) C1 * −0.0130 (0.0024) C2 * 0.0078 (0.0025) C3 * 0.0068 (0.0024) C4 * −0.0034 (0.0025) C5 * −0.0134 (0.0026) C6 * 0.0017 (0.0024) C7 * 0.0095 (0.0023) C8 * 0.0092 (0.0023) C9 * 0.0018 (0.0024) C10 − 0.0039 (0.0036) C11 − 0.0506 (0.0036) N11 − 0.0125 (0.0047) O11 Rms deviation of fitted atoms = 0.0084 |
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 | ||
C1 | 0.81777 (15) | −0.2035 (4) | 0.59510 (16) | 0.0523 (8) | |
C2 | 0.86254 (17) | −0.3869 (5) | 0.62111 (19) | 0.0678 (9) | |
H2 | 0.9158 | −0.4081 | 0.6132 | 0.081* | |
C3 | 0.81635 (18) | −0.5287 (5) | 0.65957 (19) | 0.0684 (9) | |
H3 | 0.8335 | −0.6588 | 0.6824 | 0.082* | |
C4 | 0.67554 (19) | −0.5457 (5) | 0.69167 (17) | 0.0639 (9) | |
H4 | 0.6868 | −0.6782 | 0.7159 | 0.077* | |
C5 | 0.59747 (18) | −0.4760 (5) | 0.69347 (19) | 0.0717 (10) | |
H5 | 0.5635 | −0.5680 | 0.7183 | 0.086* | |
C6 | 0.56442 (18) | −0.2881 (6) | 0.66306 (19) | 0.0718 (9) | |
H6 | 0.5107 | −0.2719 | 0.6696 | 0.086* | |
C7 | 0.59873 (17) | −0.1188 (5) | 0.62419 (19) | 0.0705 (9) | |
H7 | 0.5648 | −0.0052 | 0.6095 | 0.085* | |
C8 | 0.67591 (16) | −0.0935 (5) | 0.60397 (16) | 0.0584 (8) | |
H8 | 0.6865 | 0.0338 | 0.5775 | 0.070* | |
C9 | 0.73988 (15) | −0.2334 (4) | 0.61798 (15) | 0.0473 (7) | |
C10 | 0.73862 (16) | −0.4461 (5) | 0.65905 (16) | 0.0531 (8) | |
C11 | 0.84635 (16) | −0.0184 (5) | 0.55349 (16) | 0.0566 (8) | |
H11 | 0.8120 | 0.0959 | 0.5409 | 0.068* | |
N11 | 0.91781 (13) | −0.0081 (4) | 0.53362 (14) | 0.0616 (7) | |
O11 | 0.93267 (11) | 0.1898 (4) | 0.49475 (14) | 0.0763 (7) | |
H11O | 0.9787 (12) | 0.168 (5) | 0.4808 (19) | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0514 (17) | 0.0573 (18) | 0.0485 (18) | 0.0087 (15) | 0.0053 (14) | −0.0002 (15) |
C2 | 0.0526 (19) | 0.076 (2) | 0.075 (2) | 0.0178 (17) | 0.0090 (16) | 0.003 (2) |
C3 | 0.072 (2) | 0.061 (2) | 0.073 (2) | 0.0147 (18) | 0.0120 (17) | 0.0080 (18) |
C4 | 0.080 (2) | 0.0551 (19) | 0.057 (2) | −0.0070 (17) | 0.0051 (16) | −0.0009 (16) |
C5 | 0.062 (2) | 0.078 (2) | 0.076 (2) | −0.0146 (19) | 0.0142 (17) | 0.003 (2) |
C6 | 0.0479 (18) | 0.089 (3) | 0.079 (2) | −0.0009 (19) | 0.0069 (16) | 0.003 (2) |
C7 | 0.0509 (19) | 0.077 (2) | 0.084 (2) | 0.0124 (17) | 0.0064 (17) | 0.009 (2) |
C8 | 0.0533 (18) | 0.0608 (18) | 0.061 (2) | 0.0034 (15) | 0.0051 (14) | 0.0022 (17) |
C9 | 0.0496 (17) | 0.0505 (17) | 0.0418 (17) | 0.0070 (14) | 0.0034 (13) | −0.0044 (14) |
C10 | 0.0576 (19) | 0.0542 (18) | 0.0477 (19) | 0.0038 (15) | 0.0041 (14) | −0.0025 (15) |
C11 | 0.0504 (18) | 0.062 (2) | 0.058 (2) | 0.0106 (15) | 0.0076 (15) | −0.0015 (16) |
N11 | 0.0511 (15) | 0.0637 (17) | 0.0714 (19) | 0.0034 (12) | 0.0137 (12) | 0.0062 (14) |
O11 | 0.0603 (14) | 0.0758 (15) | 0.0952 (18) | 0.0054 (12) | 0.0239 (12) | 0.0206 (13) |
C1—C9 | 1.413 (3) | C6—C7 | 1.386 (4) |
C1—C2 | 1.416 (3) | C6—H6 | 0.9300 |
C1—C11 | 1.446 (3) | C7—C8 | 1.383 (4) |
C2—C3 | 1.371 (4) | C7—H7 | 0.9300 |
C2—H2 | 0.9300 | C8—C9 | 1.393 (3) |
C3—C10 | 1.411 (3) | C8—H8 | 0.9300 |
C3—H3 | 0.9300 | C9—C10 | 1.489 (4) |
C4—C10 | 1.382 (3) | C11—N11 | 1.281 (3) |
C4—C5 | 1.392 (4) | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | N11—O11 | 1.420 (3) |
C5—C6 | 1.374 (4) | O11—H11O | 0.840 (17) |
C5—H5 | 0.9300 | ||
C9—C1—C2 | 107.4 (3) | C8—C7—C6 | 129.7 (3) |
C9—C1—C11 | 126.1 (2) | C8—C7—H7 | 115.2 |
C2—C1—C11 | 126.5 (3) | C6—C7—H7 | 115.2 |
C3—C2—C1 | 110.5 (3) | C7—C8—C9 | 128.6 (3) |
C3—C2—H2 | 124.8 | C7—C8—H8 | 115.7 |
C1—C2—H2 | 124.8 | C9—C8—H8 | 115.7 |
C2—C3—C10 | 109.2 (3) | C8—C9—C1 | 127.0 (3) |
C2—C3—H3 | 125.4 | C8—C9—C10 | 126.2 (2) |
C10—C3—H3 | 125.4 | C1—C9—C10 | 106.8 (2) |
C10—C4—C5 | 129.3 (3) | C4—C10—C3 | 125.7 (3) |
C10—C4—H4 | 115.4 | C4—C10—C9 | 128.2 (3) |
C5—C4—H4 | 115.4 | C3—C10—C9 | 106.1 (2) |
C6—C5—C4 | 128.0 (3) | N11—C11—C1 | 121.6 (3) |
C6—C5—H5 | 116.0 | N11—C11—H11 | 119.2 |
C4—C5—H5 | 116.0 | C1—C11—H11 | 119.2 |
C5—C6—C7 | 130.0 (3) | C11—N11—O11 | 111.6 (2) |
C5—C6—H6 | 115.0 | N11—O11—H11O | 101 (2) |
C7—C6—H6 | 115.0 | ||
C9—C1—C2—C3 | −0.4 (3) | C11—C1—C9—C10 | −179.9 (2) |
C11—C1—C2—C3 | 179.0 (3) | C5—C4—C10—C3 | −179.7 (3) |
C1—C2—C3—C10 | 1.1 (4) | C5—C4—C10—C9 | 1.2 (5) |
C10—C4—C5—C6 | −0.4 (6) | C2—C3—C10—C4 | 179.4 (3) |
C4—C5—C6—C7 | −1.0 (6) | C2—C3—C10—C9 | −1.4 (3) |
C5—C6—C7—C8 | 1.2 (6) | C8—C9—C10—C4 | −0.7 (4) |
C6—C7—C8—C9 | −0.3 (5) | C1—C9—C10—C4 | −179.7 (3) |
C7—C8—C9—C1 | 178.8 (3) | C8—C9—C10—C3 | −179.9 (3) |
C7—C8—C9—C10 | −0.1 (5) | C1—C9—C10—C3 | 1.1 (3) |
C2—C1—C9—C8 | −179.5 (3) | C9—C1—C11—N11 | −178.4 (3) |
C11—C1—C9—C8 | 1.1 (5) | C2—C1—C11—N11 | 2.3 (5) |
C2—C1—C9—C10 | −0.4 (3) | C1—C11—N11—O11 | −178.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11O···N11i | 0.84 (2) | 2.04 (2) | 2.841 (3) | 158 (3) |
Symmetry code: (i) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H9NO |
Mr | 171.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.931 (3), 6.174 (2), 17.028 (5) |
β (°) | 94.00 (2) |
V (Å3) | 1775.6 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.52 × 0.28 × 0.14 |
Data collection | |
Diffractometer | Oxford Diffraction Excalibur (TM) single-crystal X-ray diffractometer with Sapphire CCD detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5481, 1803, 815 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.149, 0.98 |
No. of reflections | 1803 |
No. of parameters | 121 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.13, −0.14 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2001), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2001) and ORTEPIII (Johnson & Burnett, 1998), SHELXL97 CIF and IUCr SHELXL97 template.
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11O···N11i | 0.840 (17) | 2.043 (19) | 2.841 (3) | 158 (3) |
Symmetry code: (i) −x+2, −y, −z+1. |
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Azulene-1-carboxaldehyde oxime was first obtained by Hafner (Hafner & Bernhard, 1959) as cystalline derivative of azulene-1-carbaldehyde. To determine the configuration of the oxime, the synthesis was optimized. The (E)-azulene-1-carboxaldehyde oxime, (I), could be separated from the isomer (Z)-azulene-1-carboxaldehyde and crystallized. No isomerization could be observed in solution in the absence of acids. The (E)-azulene-1-carboxaldehyde oxime shows the expected molecular geometry (see Fig. 1), viz. a planar azulene moiety with a delocalized 10π-electron perimeter [mean C—C distance 1.392 (4) Å] and a central bond length of 1.489 (4) Å. The crystal packing is determined by intermolecular hydrogen bonds and π-stacking as shown in Fig. 2. Hydrogen bonded centrosymmetric dimers are stacked along the z axis.