Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005001/tk6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005001/tk6011Isup2.hkl |
CCDC reference: 162835
The title compound, (I), was prepared by condensation of 2-hydrazinotropone with cyclohexanone accompanied by cyclization. The single crystals of (I) were obtained by recrystallization from a mixture of ethyl acetate and hexane.
All C-bound H atoms were included in the refinement at calculated positions as riding models with C—H distances set to 0.93 Å for aromatic and 0.97 Å for CH2– bonds. The H atom of the NH group was located from a difference syntheses and both positional and displacement parameters were refined for this atom.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids (Johnson, 1976). | |
Fig. 2. Packing diagram of (I) viewed down the c axis. Dotted lines represent hydrogen bonds. |
C13H13NO | F(000) = 424 |
Mr = 199.24 | Dx = 1.267 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.7107 Å |
a = 8.778 (2) Å | Cell parameters from 16 reflections |
b = 15.3778 (19) Å | θ = 8.9–18.2° |
c = 8.442 (2) Å | µ = 0.08 mm−1 |
β = 113.590 (18)° | T = 296 K |
V = 1044.3 (4) Å3 | Prism, yellow |
Z = 4 | 0.23 × 0.13 × 0.13 mm |
Enraf-Nonius CAD-4 diffractometer | 828 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
Graphite monochromator | θmax = 28.0°, θmin = 2.6° |
ω–2θ scans | h = −11→0 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→20 |
Tmin = 0.962, Tmax = 0.999 | l = −10→11 |
2677 measured reflections | 3 standard reflections every 120 min |
2519 independent reflections | intensity decay: 0.6% |
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)] = 0.062 | Hydrogen site location: mixed |
wR(F2) = 0.194 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0777P)2] where P = (Fo2 + 2Fc2)/3 |
2519 reflections | (Δ/σ)max < 0.001 |
140 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C13H13NO | V = 1044.3 (4) Å3 |
Mr = 199.24 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 8.778 (2) Å | µ = 0.08 mm−1 |
b = 15.3778 (19) Å | T = 296 K |
c = 8.442 (2) Å | 0.23 × 0.13 × 0.13 mm |
β = 113.590 (18)° |
Enraf-Nonius CAD-4 diffractometer | 828 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.059 |
Tmin = 0.962, Tmax = 0.999 | 3 standard reflections every 120 min |
2677 measured reflections | intensity decay: 0.6% |
2519 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.194 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.20 e Å−3 |
2519 reflections | Δρmin = −0.24 e Å−3 |
140 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.8866 (3) | 0.47307 (18) | 0.6722 (3) | 0.0523 (7) | |
O1 | 0.8557 (3) | 0.58737 (16) | 0.4107 (3) | 0.0838 (9) | |
C1 | 0.7595 (4) | 0.5952 (2) | 0.4868 (4) | 0.0588 (9) | |
C2 | 0.7684 (4) | 0.5361 (2) | 0.6203 (4) | 0.0500 (8) | |
C3 | 0.6758 (4) | 0.5282 (2) | 0.7237 (4) | 0.0516 (8) | |
C4 | 0.5378 (4) | 0.5784 (3) | 0.7150 (5) | 0.0655 (10) | |
H4 | 0.4864 | 0.5609 | 0.7870 | 0.079* | |
C5 | 0.4711 (4) | 0.6489 (3) | 0.6148 (5) | 0.0689 (10) | |
H5 | 0.3799 | 0.6741 | 0.6268 | 0.083* | |
C6 | 0.5230 (4) | 0.6883 (2) | 0.4956 (4) | 0.0676 (10) | |
H6 | 0.4651 | 0.7386 | 0.4453 | 0.081* | |
C7 | 0.6434 (4) | 0.6659 (2) | 0.4407 (4) | 0.0653 (10) | |
H7 | 0.6521 | 0.7032 | 0.3580 | 0.078* | |
C8 | 0.8752 (4) | 0.4257 (2) | 0.8049 (4) | 0.0520 (8) | |
C9 | 0.7453 (4) | 0.4580 (2) | 0.8372 (4) | 0.0553 (9) | |
C10 | 0.6976 (5) | 0.4197 (3) | 0.9737 (4) | 0.0717 (10) | |
H10A | 0.5885 | 0.3933 | 0.9194 | 0.086* | |
H10B | 0.6907 | 0.4657 | 1.0491 | 0.086* | |
C11 | 0.8205 (6) | 0.3520 (3) | 1.0807 (5) | 0.0959 (14) | |
H11A | 0.9062 | 0.3812 | 1.1773 | 0.115* | |
H11B | 0.7631 | 0.3126 | 1.1280 | 0.115* | |
C12 | 0.9011 (6) | 0.3004 (3) | 0.9919 (5) | 0.1015 (15) | |
H12A | 0.8185 | 0.2625 | 0.9101 | 0.122* | |
H12B | 0.9839 | 0.2637 | 1.0763 | 0.122* | |
C13 | 0.9855 (4) | 0.3520 (2) | 0.8948 (4) | 0.0621 (9) | |
H13A | 1.0921 | 0.3738 | 0.9753 | 0.075* | |
H13B | 1.0042 | 0.3149 | 0.8114 | 0.075* | |
H1 | 0.963 (4) | 0.458 (2) | 0.629 (4) | 0.080 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0469 (16) | 0.0591 (17) | 0.0578 (17) | −0.0025 (15) | 0.0282 (14) | −0.0001 (15) |
O1 | 0.0821 (18) | 0.0977 (19) | 0.102 (2) | 0.0229 (15) | 0.0681 (17) | 0.0341 (16) |
C1 | 0.050 (2) | 0.066 (2) | 0.066 (2) | −0.0004 (19) | 0.0287 (18) | 0.0047 (19) |
C2 | 0.0423 (17) | 0.0536 (19) | 0.056 (2) | −0.0035 (18) | 0.0217 (15) | −0.0046 (17) |
C3 | 0.0502 (18) | 0.060 (2) | 0.052 (2) | −0.0061 (18) | 0.0279 (16) | −0.0071 (18) |
C4 | 0.059 (2) | 0.083 (3) | 0.066 (2) | −0.002 (2) | 0.0376 (19) | −0.010 (2) |
C5 | 0.064 (2) | 0.083 (3) | 0.068 (2) | 0.009 (2) | 0.035 (2) | −0.006 (2) |
C6 | 0.054 (2) | 0.074 (2) | 0.070 (2) | 0.0123 (19) | 0.020 (2) | 0.003 (2) |
C7 | 0.059 (2) | 0.067 (2) | 0.072 (2) | 0.006 (2) | 0.028 (2) | 0.015 (2) |
C8 | 0.054 (2) | 0.055 (2) | 0.0496 (19) | −0.0090 (17) | 0.0241 (16) | −0.0038 (17) |
C9 | 0.057 (2) | 0.066 (2) | 0.053 (2) | −0.0098 (19) | 0.0322 (17) | −0.0071 (18) |
C10 | 0.078 (3) | 0.087 (3) | 0.062 (2) | −0.005 (2) | 0.040 (2) | 0.001 (2) |
C11 | 0.114 (3) | 0.103 (3) | 0.087 (3) | 0.000 (3) | 0.057 (3) | 0.021 (3) |
C12 | 0.133 (4) | 0.095 (3) | 0.099 (3) | 0.021 (3) | 0.069 (3) | 0.032 (3) |
C13 | 0.056 (2) | 0.063 (2) | 0.064 (2) | −0.0055 (19) | 0.0216 (18) | −0.0009 (19) |
N1—C2 | 1.358 (4) | C7—H7 | 0.9300 |
N1—C8 | 1.374 (4) | C8—C9 | 1.367 (4) |
N1—H1 | 0.91 (3) | C8—C13 | 1.487 (4) |
O1—C1 | 1.254 (4) | C9—C10 | 1.495 (4) |
C1—C2 | 1.426 (4) | C10—C11 | 1.511 (5) |
C1—C7 | 1.432 (4) | C10—H10A | 0.9700 |
C2—C3 | 1.416 (4) | C10—H10B | 0.9700 |
C3—C4 | 1.414 (4) | C11—C12 | 1.455 (5) |
C3—C9 | 1.410 (4) | C11—H11A | 0.9700 |
C4—C5 | 1.356 (5) | C11—H11B | 0.9700 |
C4—H4 | 0.9300 | C12—C13 | 1.528 (5) |
C5—C6 | 1.398 (4) | C12—H12A | 0.9700 |
C5—H5 | 0.9300 | C12—H12B | 0.9700 |
C6—C7 | 1.358 (4) | C13—H13A | 0.9700 |
C6—H6 | 0.9300 | C13—H13B | 0.9700 |
C2—N1—C8 | 110.2 (3) | C8—C9—C3 | 108.1 (3) |
C2—N1—H1 | 130 (2) | C8—C9—C10 | 121.6 (3) |
C8—N1—H1 | 120 (2) | C3—C9—C10 | 130.3 (3) |
O1—C1—C2 | 120.5 (3) | C9—C10—C11 | 112.3 (3) |
O1—C1—C7 | 119.1 (3) | C9—C10—H10A | 109.2 |
C2—C1—C7 | 120.4 (3) | C11—C10—H10A | 109.2 |
N1—C2—C3 | 107.0 (3) | C9—C10—H10B | 109.2 |
N1—C2—C1 | 120.2 (3) | C11—C10—H10B | 109.2 |
C3—C2—C1 | 132.8 (3) | H10A—C10—H10B | 107.9 |
C9—C3—C4 | 125.6 (3) | C12—C11—C10 | 116.5 (3) |
C9—C3—C2 | 106.6 (3) | C12—C11—H11A | 108.2 |
C4—C3—C2 | 127.7 (3) | C10—C11—H11A | 108.2 |
C5—C4—C3 | 128.1 (3) | C12—C11—H11B | 108.2 |
C5—C4—H4 | 116.0 | C10—C11—H11B | 108.2 |
C3—C4—H4 | 116.0 | H11A—C11—H11B | 107.3 |
C4—C5—C6 | 127.7 (3) | C11—C12—C13 | 115.7 (3) |
C4—C5—H5 | 116.2 | C11—C12—H12A | 108.4 |
C6—C5—H5 | 116.2 | C13—C12—H12A | 108.4 |
C7—C6—C5 | 131.2 (3) | C11—C12—H12B | 108.4 |
C7—C6—H6 | 114.4 | C13—C12—H12B | 108.4 |
C5—C6—H6 | 114.4 | H12A—C12—H12B | 107.4 |
C6—C7—C1 | 131.8 (3) | C8—C13—C12 | 108.2 (3) |
C6—C7—H7 | 114.1 | C8—C13—H13A | 110.1 |
C1—C7—H7 | 114.1 | C12—C13—H13A | 110.1 |
C9—C8—N1 | 108.0 (3) | C8—C13—H13B | 110.1 |
C9—C8—C13 | 126.9 (3) | C12—C13—H13B | 110.1 |
N1—C8—C13 | 125.1 (3) | H13A—C13—H13B | 108.4 |
C8—N1—C2—C3 | −0.6 (3) | C2—N1—C8—C9 | 1.0 (3) |
C8—N1—C2—C1 | 178.2 (3) | C2—N1—C8—C13 | −179.4 (3) |
O1—C1—C2—N1 | 3.1 (5) | N1—C8—C9—C3 | −1.0 (3) |
C7—C1—C2—N1 | −175.2 (3) | C13—C8—C9—C3 | 179.5 (3) |
O1—C1—C2—C3 | −178.5 (3) | N1—C8—C9—C10 | 179.1 (3) |
C7—C1—C2—C3 | 3.2 (6) | C13—C8—C9—C10 | −0.4 (5) |
N1—C2—C3—C9 | 0.0 (3) | C4—C3—C9—C8 | 179.3 (3) |
C1—C2—C3—C9 | −178.6 (3) | C2—C3—C9—C8 | 0.6 (3) |
N1—C2—C3—C4 | −178.7 (3) | C4—C3—C9—C10 | −0.8 (6) |
C1—C2—C3—C4 | 2.8 (6) | C2—C3—C9—C10 | −179.5 (3) |
C9—C3—C4—C5 | 176.5 (3) | C8—C9—C10—C11 | 7.3 (5) |
C2—C3—C4—C5 | −5.1 (6) | C3—C9—C10—C11 | −172.6 (3) |
C3—C4—C5—C6 | 0.3 (6) | C9—C10—C11—C12 | −33.0 (5) |
C4—C5—C6—C7 | 4.1 (7) | C10—C11—C12—C13 | 52.8 (5) |
C5—C6—C7—C1 | −0.9 (6) | C9—C8—C13—C12 | 16.7 (5) |
O1—C1—C7—C6 | 177.4 (4) | N1—C8—C13—C12 | −162.8 (3) |
C2—C1—C7—C6 | −4.2 (6) | C11—C12—C13—C8 | −41.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.91 (3) | 1.89 (4) | 2.781 (4) | 166.53 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H13NO |
Mr | 199.24 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 296 |
a, b, c (Å) | 8.778 (2), 15.3778 (19), 8.442 (2) |
β (°) | 113.590 (18) |
V (Å3) | 1044.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.23 × 0.13 × 0.13 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.962, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2677, 2519, 828 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.194, 0.94 |
No. of reflections | 2519 |
No. of parameters | 140 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.24 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), Xtal_GX (Hall & du Boulay, 1995), SHELXL97.
Pyrrolo[b]tropones (Nozoe et al., 1954) are isoelectronic with 8-quinolinols. 3-Phenylpyrrolo[2,3-b]tropone (Kubo et al., 2001) gave a dark-purple coloration when treated with aqueous ferric chloride in methanol and the color fades upon addition of mineral acid. This suggests that pyrrolo[2,3-b]tropones can be used as an analytical reagent for metal cations. 3-Phenylpyrrolo[2,3-b]tropone exists as the keto tautomer the in solid state (Kubo et al., 2001) and we now report the structure of the title compound, (I), in order to determine its form.
In (I), the C—C, C—O and C—N bond lengths of the pyrrolotropone ring are similar to those found in unsubstituted tropone (Barrow et al., 1973), unsubstituted pyrrole (Goddard et al., 1997), and 3-phenylpyrrolo[2,3-b]tropone (Kubo et al., 2001). The objective location of the H1 atom bonded to N1, rather than to the O1 atom, as well as the tropone-like distribution of bonds, allows the unambiguous assignment of the keto form (I) rather than the enol form (I').
The pyrrole NH group participates in an intermolecular hydrogen bond of the N—H.·O type: N1—H1 0.91 (3), N1.·O1i 2.781 (4) and H1.·O1i 1.89 (4) Å; symmetry code: (i) 2 - x, 1 - y, 1 - z. The hydrogen-bonding scheme links molecules into infinite chains orientated along a bisector between the the b and c axes of the unit cell. A similar mode of association was found in the structure of 3-phenylpyrrolo[2,3-b]tropone (Kubo et al., 2001).