Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002021/ya6009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002021/ya6009Isup2.hkl |
CCDC reference: 159851
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.002 Å
- R factor = 0.042
- wR factor = 0.116
- Data-to-parameter ratio = 17.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound, (I), was prepared by condensation of 2-hydrazinotropone with acetophenone accompanied by cyclization (Nozoe et al., 1954). Single crystals of (I) were obtained by recrystallization from ethyl acetate.
All H atoms were included in the refinement in geometrically calculated positions in the riding model approximation with C—H set to 0.93 Å, except for the NH group H atom, which was located in the difference synthesis and for which both positional and displacement parameters were refined.
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. | |
Fig. 2. Packing diagram viewed down the b axis. |
C15H11NO | F(000) = 464 |
Mr = 221.25 | Dx = 1.309 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.2145 (10) Å | Cell parameters from 25 reflections |
b = 7.7681 (5) Å | θ = 11.0–18.2° |
c = 10.3928 (6) Å | µ = 0.08 mm−1 |
β = 101.980 (5)° | T = 296 K |
V = 1122.58 (13) Å3 | Prism, pale yellow |
Z = 4 | 0.47 × 0.47 × 0.43 mm |
Enraf-Nonius CAD-4 diffractometer | 1921 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 28.0°, θmin = 2.9° |
ω–2θ scans | h = −18→18 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.978, Tmax = 0.999 | l = −13→0 |
2851 measured reflections | 3 standard reflections every 120 min |
2700 independent reflections | intensity decay: 3.9% |
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)] = 0.042 | Hydrogen site location: mixed |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0526P)2 + 0.2047P] where P = (Fo2 + 2Fc2)/3 |
2700 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C15H11NO | V = 1122.58 (13) Å3 |
Mr = 221.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.2145 (10) Å | µ = 0.08 mm−1 |
b = 7.7681 (5) Å | T = 296 K |
c = 10.3928 (6) Å | 0.47 × 0.47 × 0.43 mm |
β = 101.980 (5)° |
Enraf-Nonius CAD-4 diffractometer | 1921 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.978, Tmax = 0.999 | 3 standard reflections every 120 min |
2851 measured reflections | intensity decay: 3.9% |
2700 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.18 e Å−3 |
2700 reflections | Δρmin = −0.22 e Å−3 |
158 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 | 0.11507 (8) | 0.24901 (15) | −0.12642 (11) | 0.0408 (3) | |
H1 | 0.0638 (12) | 0.229 (2) | −0.2009 (17) | 0.059 (5)* | |
O1 | 0.01425 (8) | 0.53883 (15) | −0.20816 (11) | 0.0581 (3) | |
C1 | 0.07444 (10) | 0.54791 (19) | −0.10252 (15) | 0.0429 (3) | |
C2 | 0.13198 (9) | 0.39801 (17) | −0.05691 (13) | 0.0367 (3) | |
C3 | 0.20964 (9) | 0.36788 (16) | 0.05017 (13) | 0.0345 (3) | |
C4 | 0.25393 (10) | 0.48854 (18) | 0.14654 (14) | 0.0423 (3) | |
H4 | 0.3087 | 0.4508 | 0.2051 | 0.051* | |
C5 | 0.22584 (12) | 0.6521 (2) | 0.16325 (15) | 0.0489 (4) | |
H5 | 0.2629 | 0.7120 | 0.2333 | 0.059* | |
C6 | 0.14712 (12) | 0.74387 (19) | 0.08764 (16) | 0.0512 (4) | |
H6 | 0.1370 | 0.8516 | 0.1213 | 0.061* | |
C7 | 0.08409 (11) | 0.70298 (19) | −0.02457 (16) | 0.0502 (4) | |
H7 | 0.0398 | 0.7888 | −0.0567 | 0.060* | |
C8 | 0.17702 (10) | 0.12603 (18) | −0.06909 (14) | 0.0398 (3) | |
H8 | 0.1783 | 0.0133 | −0.0988 | 0.048* | |
C9 | 0.23780 (9) | 0.19225 (17) | 0.03951 (13) | 0.0361 (3) | |
C10 | 0.31509 (9) | 0.09397 (17) | 0.12569 (13) | 0.0375 (3) | |
C11 | 0.32669 (10) | 0.09459 (19) | 0.26228 (14) | 0.0431 (3) | |
H11 | 0.2870 | 0.1634 | 0.3015 | 0.052* | |
C12 | 0.39655 (11) | −0.0060 (2) | 0.34035 (17) | 0.0539 (4) | |
H12 | 0.4032 | −0.0047 | 0.4313 | 0.065* | |
C13 | 0.45612 (11) | −0.1079 (2) | 0.28404 (19) | 0.0608 (5) | |
H13 | 0.5032 | −0.1748 | 0.3366 | 0.073* | |
C14 | 0.44574 (12) | −0.1101 (2) | 0.1495 (2) | 0.0619 (5) | |
H14 | 0.4858 | −0.1791 | 0.1112 | 0.074* | |
C15 | 0.37617 (11) | −0.0105 (2) | 0.07085 (17) | 0.0503 (4) | |
H15 | 0.3700 | −0.0132 | −0.0200 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0399 (6) | 0.0405 (6) | 0.0377 (6) | −0.0053 (5) | −0.0020 (5) | 0.0007 (5) |
O1 | 0.0530 (6) | 0.0540 (7) | 0.0580 (7) | 0.0037 (5) | −0.0102 (5) | 0.0132 (5) |
C1 | 0.0378 (7) | 0.0419 (8) | 0.0474 (8) | −0.0013 (6) | 0.0053 (6) | 0.0121 (6) |
C2 | 0.0349 (6) | 0.0367 (7) | 0.0369 (7) | −0.0044 (5) | 0.0041 (5) | 0.0034 (5) |
C3 | 0.0344 (6) | 0.0338 (6) | 0.0348 (7) | −0.0025 (5) | 0.0058 (5) | 0.0031 (5) |
C4 | 0.0433 (7) | 0.0391 (7) | 0.0404 (7) | −0.0053 (6) | −0.0009 (6) | 0.0015 (6) |
C5 | 0.0606 (9) | 0.0383 (7) | 0.0452 (8) | −0.0101 (7) | 0.0048 (7) | −0.0041 (6) |
C6 | 0.0646 (10) | 0.0333 (7) | 0.0581 (9) | −0.0009 (7) | 0.0182 (8) | 0.0014 (6) |
C7 | 0.0506 (8) | 0.0363 (7) | 0.0629 (10) | 0.0047 (6) | 0.0102 (7) | 0.0106 (7) |
C8 | 0.0436 (7) | 0.0341 (7) | 0.0407 (7) | −0.0027 (6) | 0.0063 (6) | −0.0003 (6) |
C9 | 0.0369 (6) | 0.0348 (6) | 0.0356 (7) | −0.0019 (5) | 0.0056 (5) | 0.0013 (5) |
C10 | 0.0350 (6) | 0.0341 (6) | 0.0415 (7) | −0.0014 (5) | 0.0040 (5) | 0.0007 (6) |
C11 | 0.0430 (7) | 0.0419 (7) | 0.0422 (7) | 0.0037 (6) | 0.0038 (6) | −0.0006 (6) |
C12 | 0.0509 (9) | 0.0536 (9) | 0.0494 (9) | 0.0022 (7) | −0.0075 (7) | 0.0055 (7) |
C13 | 0.0440 (8) | 0.0537 (10) | 0.0767 (12) | 0.0105 (7) | −0.0056 (8) | 0.0123 (9) |
C14 | 0.0486 (9) | 0.0572 (10) | 0.0811 (13) | 0.0166 (8) | 0.0161 (9) | 0.0008 (9) |
C15 | 0.0499 (8) | 0.0506 (9) | 0.0514 (9) | 0.0066 (7) | 0.0129 (7) | −0.0004 (7) |
N1—C2 | 1.3591 (17) | C7—H7 | 0.9300 |
N1—C8 | 1.3510 (18) | C8—C9 | 1.3712 (18) |
N1—H1 | 0.959 (17) | C8—H8 | 0.9300 |
O1—C1 | 1.2460 (17) | C9—C10 | 1.4777 (18) |
C1—C2 | 1.4452 (19) | C10—C11 | 1.3948 (19) |
C1—C7 | 1.442 (2) | C10—C15 | 1.394 (2) |
C2—C3 | 1.4149 (18) | C11—C12 | 1.386 (2) |
C3—C4 | 1.4199 (19) | C11—H11 | 0.9300 |
C3—C9 | 1.4326 (19) | C12—C13 | 1.375 (3) |
C4—C5 | 1.354 (2) | C12—H12 | 0.9300 |
C4—H4 | 0.9300 | C13—C14 | 1.375 (3) |
C5—C6 | 1.419 (2) | C13—H13 | 0.9300 |
C5—H5 | 0.9300 | C14—C15 | 1.382 (2) |
C6—C7 | 1.353 (2) | C14—H14 | 0.9300 |
C6—H6 | 0.9300 | C15—H15 | 0.9300 |
C8—N1—C2 | 109.92 (11) | N1—C8—C9 | 109.84 (12) |
C8—N1—H1 | 123.7 (10) | N1—C8—H8 | 125.1 |
C2—N1—H1 | 126.2 (10) | C9—C8—H8 | 125.1 |
O1—C1—C7 | 120.67 (13) | C8—C9—C3 | 106.41 (11) |
O1—C1—C2 | 118.80 (14) | C8—C9—C10 | 124.56 (12) |
C7—C1—C2 | 120.49 (13) | C3—C9—C10 | 129.03 (12) |
N1—C2—C3 | 107.47 (11) | C15—C10—C11 | 117.78 (13) |
N1—C2—C1 | 119.09 (12) | C15—C10—C9 | 120.06 (13) |
C3—C2—C1 | 133.42 (12) | C11—C10—C9 | 122.08 (12) |
C2—C3—C4 | 127.22 (12) | C12—C11—C10 | 120.86 (14) |
C2—C3—C9 | 106.36 (11) | C12—C11—H11 | 119.6 |
C4—C3—C9 | 126.38 (12) | C10—C11—H11 | 119.6 |
C5—C4—C3 | 127.63 (14) | C13—C12—C11 | 120.33 (16) |
C5—C4—H4 | 116.2 | C13—C12—H12 | 119.8 |
C3—C4—H4 | 116.2 | C11—C12—H12 | 119.8 |
C4—C5—C6 | 128.33 (14) | C12—C13—C14 | 119.62 (15) |
C4—C5—H5 | 115.8 | C12—C13—H13 | 120.2 |
C6—C5—H5 | 115.8 | C14—C13—H13 | 120.2 |
C7—C6—C5 | 131.65 (15) | C13—C14—C15 | 120.47 (16) |
C7—C6—H6 | 114.2 | C13—C14—H14 | 119.8 |
C5—C6—H6 | 114.2 | C15—C14—H14 | 119.8 |
C6—C7—C1 | 130.47 (14) | C14—C15—C10 | 120.94 (15) |
C6—C7—H7 | 114.8 | C14—C15—H15 | 119.5 |
C1—C7—H7 | 114.8 | C10—C15—H15 | 119.5 |
C8—N1—C2—C3 | 0.43 (16) | N1—C8—C9—C3 | 0.99 (15) |
C8—N1—C2—C1 | 179.03 (12) | N1—C8—C9—C10 | −179.72 (12) |
O1—C1—C2—N1 | −3.7 (2) | C2—C3—C9—C8 | −0.71 (15) |
C7—C1—C2—N1 | 173.98 (13) | C4—C3—C9—C8 | −178.44 (14) |
O1—C1—C2—C3 | 174.47 (15) | C2—C3—C9—C10 | −179.96 (13) |
C7—C1—C2—C3 | −7.9 (2) | C4—C3—C9—C10 | 2.3 (2) |
N1—C2—C3—C4 | 177.89 (13) | C8—C9—C10—C15 | 45.5 (2) |
C1—C2—C3—C4 | −0.4 (3) | C3—C9—C10—C11 | 48.0 (2) |
N1—C2—C3—C9 | 0.18 (15) | C3—C9—C10—C15 | −135.37 (15) |
C1—C2—C3—C9 | −178.14 (14) | C8—C9—C10—C11 | −131.13 (15) |
C2—C3—C4—C5 | 6.6 (2) | C15—C10—C11—C12 | −0.2 (2) |
C9—C3—C4—C5 | −176.15 (15) | C9—C10—C11—C12 | 176.50 (13) |
C3—C4—C5—C6 | −1.5 (3) | C10—C11—C12—C13 | 0.3 (2) |
C4—C5—C6—C7 | −5.9 (3) | C11—C12—C13—C14 | −0.3 (3) |
C5—C6—C7—C1 | 2.4 (3) | C12—C13—C14—C15 | 0.2 (3) |
O1—C1—C7—C6 | −175.93 (16) | C13—C14—C15—C10 | −0.1 (3) |
C2—C1—C7—C6 | 6.4 (3) | C11—C10—C15—C14 | 0.1 (2) |
C2—N1—C8—C9 | −0.91 (16) | C9—C10—C15—C14 | −176.71 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.959 (17) | 1.968 (16) | 2.773 (2) | 140.38 (10) |
Symmetry code: (i) −x, y−1/2, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H11NO |
Mr | 221.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 14.2145 (10), 7.7681 (5), 10.3928 (6) |
β (°) | 101.980 (5) |
V (Å3) | 1122.58 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.47 × 0.47 × 0.43 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.978, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2851, 2700, 1921 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.116, 1.03 |
No. of reflections | 2700 |
No. of parameters | 158 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.22 |
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.
N1—C2 | 1.3591 (17) | C5—C6 | 1.419 (2) |
N1—C8 | 1.3510 (18) | C6—C7 | 1.353 (2) |
N1—H1 | 0.959 (17) | C8—C9 | 1.3712 (18) |
O1—C1 | 1.2460 (17) | C9—C10 | 1.4777 (18) |
C1—C2 | 1.4452 (19) | C10—C11 | 1.3948 (19) |
C1—C7 | 1.442 (2) | C10—C15 | 1.394 (2) |
C2—C3 | 1.4149 (18) | C11—C12 | 1.386 (2) |
C3—C4 | 1.4199 (19) | C12—C13 | 1.375 (3) |
C3—C9 | 1.4326 (19) | C13—C14 | 1.375 (3) |
C4—C5 | 1.354 (2) | C14—C15 | 1.382 (2) |
C3—C9—C10—C11 | 48.0 (2) | C3—C9—C10—C15 | −135.37 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.959 (17) | 1.968 (16) | 2.773 (2) | 140.38 (10) |
Symmetry code: (i) −x, y−1/2, −z−1/2. |
It is known that tris(8-quinolinolido)AlIII is widely used for electron-transporting materials (Tang & VanSlyke, 1987). Pyrrolo[b]tropones (Nozoe et al., 1954) are isoelectronic to 8-quinolinols, and so might have potentials to form emitting materials. However, our studies (yet unpublished) show that pyrrolo[b]tropones and their metal complexes do not have reasonable emitting properties. We now report the structure of 3-phenylpyrrolo[2,3-b]tropone, (I), to determine its major tautomer.
The pyrrolotropone moiety of molecule (I) is approximately planar, the deviations from the least-squares plane defined by C1—C9/O1/N1 do not exceed 0.1 Å. The dihedral angle between the pyrrolotropone and the phenyl susbtituent planes is 45.31 (5)°; which is much greater than the analogous angle formed by the phenyl and indolizine planes in 2-phenyl-6-nitroindolizine (6.1°; Tafeenko & Aslanov, 1980).
The C—C bond lengths of the seven-membered ring show bond alternation typical of tropone; the C1—O1 bond length [1.2460 (17) Å] is similar to that observed in the structure of unsubstituted tropone (1.259 Å; Barrow et al., 1973). The C—C and C—N bond lengths in the pyrrole ring are close to those found in pyrrole (Goddard et al., 1997). The objective location of the H1 atom bonded to N1, rather than O1 atom, as well as the tropone-like bond-length distribution, makes assignment of the keto form, (I), rather than the enol form, (I'), unambiguous.
The pyrrole NH group participates in the intermolecular hydrogen bond [N1—H1 0.959 (17), N1···O1i 2.773 (2) and H1···O1i 1.968 (16) Å; symmetry code: (i) -x, -1/2 + y, -1/2 - z] of the N–H···O type. This hydrogen bond links molecules (I) in crystal into infinite chains stretching along the b axis of the crystal.