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The title compound, C15H11NO, exists in the crystal in its keto form as 3-phenyl­pyrrolo­[2,3-b]­tropone [systematic name: 3-phenyl­cyclo­hepta­[b]­pyrrol-8(1H)-one] rather than in the enol form as 8-hydroxy-3-phenyl-1-aza­azulene. The seven-membered ring shows pronounced bond alternation typical of tropone derivatives.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002021/ya6009sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002021/ya6009Isup2.hkl
Contains datablock I

CCDC reference: 159851

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](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




Comment top

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 However, our studies (yet unpublished) show that pyrrolo[b]tropones and their metal complexes do not have reasonable emitting properties.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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram viewed down the b axis.
3-Phenylpyrrolo[2,3-b]tropone top
Crystal data top
C15H11NOF(000) = 464
Mr = 221.25Dx = 1.309 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.2145 (10) ÅCell parameters from 25 reflections
b = 7.7681 (5) Åθ = 11.0–18.2°
c = 10.3928 (6) ŵ = 0.08 mm1
β = 101.980 (5)°T = 296 K
V = 1122.58 (13) Å3Prism, pale yellow
Z = 40.47 × 0.47 × 0.43 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
1921 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 28.0°, θmin = 2.9°
ω–2θ scansh = 1818
Absorption correction: ψ scan
(North et al., 1968)
k = 010
Tmin = 0.978, Tmax = 0.999l = 130
2851 measured reflections3 standard reflections every 120 min
2700 independent reflections intensity decay: 3.9%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: mixed
wR(F2) = 0.116H 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 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C15H11NOV = 1122.58 (13) Å3
Mr = 221.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.2145 (10) ŵ = 0.08 mm1
b = 7.7681 (5) ÅT = 296 K
c = 10.3928 (6) Å0.47 × 0.47 × 0.43 mm
β = 101.980 (5)°
Data collection top
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 = 0.9993 standard reflections every 120 min
2851 measured reflections intensity decay: 3.9%
2700 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.18 e Å3
2700 reflectionsΔρmin = 0.22 e Å3
158 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.11507 (8)0.24901 (15)0.12642 (11)0.0408 (3)
H10.0638 (12)0.229 (2)0.2009 (17)0.059 (5)*
O10.01425 (8)0.53883 (15)0.20816 (11)0.0581 (3)
C10.07444 (10)0.54791 (19)0.10252 (15)0.0429 (3)
C20.13198 (9)0.39801 (17)0.05691 (13)0.0367 (3)
C30.20964 (9)0.36788 (16)0.05017 (13)0.0345 (3)
C40.25393 (10)0.48854 (18)0.14654 (14)0.0423 (3)
H40.30870.45080.20510.051*
C50.22584 (12)0.6521 (2)0.16325 (15)0.0489 (4)
H50.26290.71200.23330.059*
C60.14712 (12)0.74387 (19)0.08764 (16)0.0512 (4)
H60.13700.85160.12130.061*
C70.08409 (11)0.70298 (19)0.02457 (16)0.0502 (4)
H70.03980.78880.05670.060*
C80.17702 (10)0.12603 (18)0.06909 (14)0.0398 (3)
H80.17830.01330.09880.048*
C90.23780 (9)0.19225 (17)0.03951 (13)0.0361 (3)
C100.31509 (9)0.09397 (17)0.12569 (13)0.0375 (3)
C110.32669 (10)0.09459 (19)0.26228 (14)0.0431 (3)
H110.28700.16340.30150.052*
C120.39655 (11)0.0060 (2)0.34035 (17)0.0539 (4)
H120.40320.00470.43130.065*
C130.45612 (11)0.1079 (2)0.28404 (19)0.0608 (5)
H130.50320.17480.33660.073*
C140.44574 (12)0.1101 (2)0.1495 (2)0.0619 (5)
H140.48580.17910.11120.074*
C150.37617 (11)0.0105 (2)0.07085 (17)0.0503 (4)
H150.37000.01320.02000.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0399 (6)0.0405 (6)0.0377 (6)0.0053 (5)0.0020 (5)0.0007 (5)
O10.0530 (6)0.0540 (7)0.0580 (7)0.0037 (5)0.0102 (5)0.0132 (5)
C10.0378 (7)0.0419 (8)0.0474 (8)0.0013 (6)0.0053 (6)0.0121 (6)
C20.0349 (6)0.0367 (7)0.0369 (7)0.0044 (5)0.0041 (5)0.0034 (5)
C30.0344 (6)0.0338 (6)0.0348 (7)0.0025 (5)0.0058 (5)0.0031 (5)
C40.0433 (7)0.0391 (7)0.0404 (7)0.0053 (6)0.0009 (6)0.0015 (6)
C50.0606 (9)0.0383 (7)0.0452 (8)0.0101 (7)0.0048 (7)0.0041 (6)
C60.0646 (10)0.0333 (7)0.0581 (9)0.0009 (7)0.0182 (8)0.0014 (6)
C70.0506 (8)0.0363 (7)0.0629 (10)0.0047 (6)0.0102 (7)0.0106 (7)
C80.0436 (7)0.0341 (7)0.0407 (7)0.0027 (6)0.0063 (6)0.0003 (6)
C90.0369 (6)0.0348 (6)0.0356 (7)0.0019 (5)0.0056 (5)0.0013 (5)
C100.0350 (6)0.0341 (6)0.0415 (7)0.0014 (5)0.0040 (5)0.0007 (6)
C110.0430 (7)0.0419 (7)0.0422 (7)0.0037 (6)0.0038 (6)0.0006 (6)
C120.0509 (9)0.0536 (9)0.0494 (9)0.0022 (7)0.0075 (7)0.0055 (7)
C130.0440 (8)0.0537 (10)0.0767 (12)0.0105 (7)0.0056 (8)0.0123 (9)
C140.0486 (9)0.0572 (10)0.0811 (13)0.0166 (8)0.0161 (9)0.0008 (9)
C150.0499 (8)0.0506 (9)0.0514 (9)0.0066 (7)0.0129 (7)0.0004 (7)
Geometric parameters (Å, º) top
N1—C21.3591 (17)C7—H70.9300
N1—C81.3510 (18)C8—C91.3712 (18)
N1—H10.959 (17)C8—H80.9300
O1—C11.2460 (17)C9—C101.4777 (18)
C1—C21.4452 (19)C10—C111.3948 (19)
C1—C71.442 (2)C10—C151.394 (2)
C2—C31.4149 (18)C11—C121.386 (2)
C3—C41.4199 (19)C11—H110.9300
C3—C91.4326 (19)C12—C131.375 (3)
C4—C51.354 (2)C12—H120.9300
C4—H40.9300C13—C141.375 (3)
C5—C61.419 (2)C13—H130.9300
C5—H50.9300C14—C151.382 (2)
C6—C71.353 (2)C14—H140.9300
C6—H60.9300C15—H150.9300
C8—N1—C2109.92 (11)N1—C8—C9109.84 (12)
C8—N1—H1123.7 (10)N1—C8—H8125.1
C2—N1—H1126.2 (10)C9—C8—H8125.1
O1—C1—C7120.67 (13)C8—C9—C3106.41 (11)
O1—C1—C2118.80 (14)C8—C9—C10124.56 (12)
C7—C1—C2120.49 (13)C3—C9—C10129.03 (12)
N1—C2—C3107.47 (11)C15—C10—C11117.78 (13)
N1—C2—C1119.09 (12)C15—C10—C9120.06 (13)
C3—C2—C1133.42 (12)C11—C10—C9122.08 (12)
C2—C3—C4127.22 (12)C12—C11—C10120.86 (14)
C2—C3—C9106.36 (11)C12—C11—H11119.6
C4—C3—C9126.38 (12)C10—C11—H11119.6
C5—C4—C3127.63 (14)C13—C12—C11120.33 (16)
C5—C4—H4116.2C13—C12—H12119.8
C3—C4—H4116.2C11—C12—H12119.8
C4—C5—C6128.33 (14)C12—C13—C14119.62 (15)
C4—C5—H5115.8C12—C13—H13120.2
C6—C5—H5115.8C14—C13—H13120.2
C7—C6—C5131.65 (15)C13—C14—C15120.47 (16)
C7—C6—H6114.2C13—C14—H14119.8
C5—C6—H6114.2C15—C14—H14119.8
C6—C7—C1130.47 (14)C14—C15—C10120.94 (15)
C6—C7—H7114.8C14—C15—H15119.5
C1—C7—H7114.8C10—C15—H15119.5
C8—N1—C2—C30.43 (16)N1—C8—C9—C30.99 (15)
C8—N1—C2—C1179.03 (12)N1—C8—C9—C10179.72 (12)
O1—C1—C2—N13.7 (2)C2—C3—C9—C80.71 (15)
C7—C1—C2—N1173.98 (13)C4—C3—C9—C8178.44 (14)
O1—C1—C2—C3174.47 (15)C2—C3—C9—C10179.96 (13)
C7—C1—C2—C37.9 (2)C4—C3—C9—C102.3 (2)
N1—C2—C3—C4177.89 (13)C8—C9—C10—C1545.5 (2)
C1—C2—C3—C40.4 (3)C3—C9—C10—C1148.0 (2)
N1—C2—C3—C90.18 (15)C3—C9—C10—C15135.37 (15)
C1—C2—C3—C9178.14 (14)C8—C9—C10—C11131.13 (15)
C2—C3—C4—C56.6 (2)C15—C10—C11—C120.2 (2)
C9—C3—C4—C5176.15 (15)C9—C10—C11—C12176.50 (13)
C3—C4—C5—C61.5 (3)C10—C11—C12—C130.3 (2)
C4—C5—C6—C75.9 (3)C11—C12—C13—C140.3 (3)
C5—C6—C7—C12.4 (3)C12—C13—C14—C150.2 (3)
O1—C1—C7—C6175.93 (16)C13—C14—C15—C100.1 (3)
C2—C1—C7—C66.4 (3)C11—C10—C15—C140.1 (2)
C2—N1—C8—C90.91 (16)C9—C10—C15—C14176.71 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.959 (17)1.968 (16)2.773 (2)140.38 (10)
Symmetry code: (i) x, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC15H11NO
Mr221.25
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)14.2145 (10), 7.7681 (5), 10.3928 (6)
β (°) 101.980 (5)
V3)1122.58 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.47 × 0.47 × 0.43
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.978, 0.999
No. of measured, independent and
observed [I > 2σ(I)] reflections
2851, 2700, 1921
Rint0.022
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.116, 1.03
No. of reflections2700
No. of parameters158
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
N1—C21.3591 (17)C5—C61.419 (2)
N1—C81.3510 (18)C6—C71.353 (2)
N1—H10.959 (17)C8—C91.3712 (18)
O1—C11.2460 (17)C9—C101.4777 (18)
C1—C21.4452 (19)C10—C111.3948 (19)
C1—C71.442 (2)C10—C151.394 (2)
C2—C31.4149 (18)C11—C121.386 (2)
C3—C41.4199 (19)C12—C131.375 (3)
C3—C91.4326 (19)C13—C141.375 (3)
C4—C51.354 (2)C14—C151.382 (2)
C3—C9—C10—C1148.0 (2)C3—C9—C10—C15135.37 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.959 (17)1.968 (16)2.773 (2)140.38 (10)
Symmetry code: (i) x, y1/2, z1/2.
 

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