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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1198.
Published online 2009 May 7. doi:  10.1107/S1600536809016080
PMCID: PMC2969787

1-[9-Ethyl-6-(2-methyl­benzo­yl)-9H-carbazol-3-yl]ethanone

Abstract

In the title compound, C24H21NO2, the pendant benzene ring is inclined at a dihedral angle of 86.66 (18)° with respect to the adjacent aromatic ring of the carbozole unit. In the crystal structure, symmetry-related mol­ecules are linked via C—H(...)O and C—H(...)π inter­actions.

Related literature

For carbazole-containing compounds used as organic opto-electronic materials, see: Bai et al. (2007 [triangle]); Liu et al. (2009 [triangle]); Promarak et al. (2007 [triangle]). For the synthesis, see: Feng et al. (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o1198-scheme1.jpg

Experimental

Crystal data

  • C24H21NO2
  • M r = 355.42
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1198-efi1.jpg
  • a = 13.066 (3) Å
  • b = 13.416 (3) Å
  • c = 21.987 (4) Å
  • V = 3854.2 (13) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.977, T max = 0.992
  • 3492 measured reflections
  • 3492 independent reflections
  • 1733 reflections with I > 2σ(I)
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.068
  • wR(F 2) = 0.178
  • S = 1.06
  • 3492 reflections
  • 244 parameters
  • 7 restraints
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016080/su2106sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016080/su2106Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound is an important intermediate in the synthesis of carbazole-containing compounds used as organic optoelectronic materials, which have large π—π conjugated networks (Bai et al. 2007; Promarak et al. 2007; Liu et al. 2009). Our interest in this field of research lead us to synthesize, and to report here on the crystal structure of the title compound.

The molecular structure of the title compound is illustrated in Fig. 1. The geometrical parameters are within normal ranges (Allen et al., 1987). The carbozole moiety is slighty bowed with ring B (C9—C14) being inclined to ring D (C17—C22) by 3.04 (19)°. The central ring C (N1,C12,C13,C17,C22) is inclined to rings B and D by 2.76 (18) and 0.30 (18)°, respectively. Ring A (C2—C7) is inclined to ring B by 86.66 (18)°.

In the crystal structure symmetry related molecules are linked via C—H···O and C—H···π interactions (Table 1 and Fig. 2).

Experimental

The title compound was prepared by a slight modification of a method reported in the literature (Feng et al., 2007). That is, the title compound was recrystalized from a mixture of methanol and dichloromethane (V/V = 2:1). On solw evaporation of the solvent colourless block-like crystals appeared after ca 4 days.

Refinement

H atoms were positioned geometrically [C—H = 0.93 - 0.96 Å] and constrained to ride on their parent atoms [Uiso(H) = xUeq(C), where x = 1.2 for aromatic H, and = 1.5 for methyl H].

Figures

Fig. 1.
The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
Fig. 2.
A view along the c axis of the crystal structure of the title compound.

Crystal data

C24H21NO2F(000) = 1504
Mr = 355.42Dx = 1.225 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 13.066 (3) Åθ = 9–13°
b = 13.416 (3) ŵ = 0.08 mm1
c = 21.987 (4) ÅT = 298 K
V = 3854.2 (13) Å3Block, colorless
Z = 80.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer1733 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 25.3°, θmin = 1.9°
ω/2θ scansh = 0→15
Absorption correction: ψ scan (North et al., 1968)k = 0→16
Tmin = 0.977, Tmax = 0.992l = 0→26
3492 measured reflections3 standard reflections every 200 reflections
3492 independent reflections intensity decay: 1%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.178H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.07P)2 + P] where P = (Fo2 + 2Fc2)/3
3492 reflections(Δ/σ)max < 0.001
244 parametersΔρmax = 0.21 e Å3
7 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/Ueq
N10.0687 (2)0.16753 (19)0.42892 (12)0.0504 (8)
O10.0131 (2)−0.1722 (2)0.23132 (11)0.0875 (10)
O20.2544 (2)−0.1349 (2)0.61640 (11)0.0756 (9)
C10.2478 (3)−0.2480 (4)0.2692 (2)0.0959 (15)
H1A0.2169−0.18810.25390.144*
H1B0.2712−0.28790.23570.144*
H1C0.3047−0.23120.29480.144*
C20.1690 (3)−0.3066 (3)0.30595 (16)0.0585 (10)
C30.1953 (3)−0.3949 (3)0.33371 (19)0.0737 (12)
H3A0.2614−0.41970.32910.088*
C40.1260 (4)−0.4469 (3)0.3680 (2)0.0791 (13)
H4A0.1452−0.50650.38620.095*
C50.0289 (4)−0.4116 (3)0.37538 (19)0.0795 (13)
H5A−0.0184−0.44620.39890.095*
C60.0025 (3)−0.3240 (3)0.34747 (17)0.0634 (11)
H6A−0.0639−0.30010.35180.076*
C70.0713 (3)−0.2700 (2)0.31316 (14)0.0469 (9)
C80.0415 (3)−0.1750 (3)0.28459 (15)0.0506 (9)
C90.0412 (2)−0.0846 (2)0.32201 (14)0.0441 (8)
C100.0086 (3)0.0068 (3)0.29808 (14)0.0530 (9)
H10A−0.01530.00840.25820.064*
C110.0103 (3)0.0925 (3)0.33004 (15)0.0525 (9)
H11A−0.01600.15120.31380.063*
C120.0532 (2)0.0903 (2)0.38852 (14)0.0435 (8)
C130.0851 (2)−0.0001 (2)0.41460 (13)0.0398 (8)
C140.0809 (2)−0.0866 (2)0.38160 (13)0.0418 (8)
H14A0.1041−0.14610.39830.050*
C15−0.0522 (4)0.3030 (3)0.4458 (2)0.1066 (17)
H15A−0.06350.37240.43770.160*
H15B−0.05060.29220.48900.160*
H15C−0.10670.26450.42830.160*
C160.0474 (3)0.2716 (3)0.41870 (18)0.0673 (11)
H16A0.04600.28440.37530.081*
H16B0.10200.31130.43620.081*
C170.1146 (3)0.1274 (2)0.48129 (15)0.0462 (8)
C180.1455 (3)0.1773 (3)0.53372 (15)0.0561 (10)
H18A0.13790.24580.53820.067*
C190.1877 (3)0.1190 (3)0.57813 (16)0.0545 (10)
H19A0.21010.14990.61360.065*
C200.1989 (2)0.0176 (3)0.57334 (14)0.0477 (9)
C210.1685 (2)−0.0315 (2)0.52034 (14)0.0442 (8)
H21A0.1769−0.10000.51580.053*
C220.1251 (2)0.0261 (2)0.47458 (14)0.0439 (8)
C230.2439 (3)−0.0457 (3)0.62258 (16)0.0537 (9)
C240.2761 (3)0.0048 (3)0.68053 (16)0.0792 (13)
H24A0.3027−0.04390.70830.119*
H24B0.21810.03740.69850.119*
H24C0.32810.05330.67180.119*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.062 (2)0.0374 (16)0.0517 (16)0.0044 (14)−0.0039 (15)0.0025 (13)
O10.126 (3)0.0832 (19)0.0536 (16)0.0019 (17)−0.0341 (18)−0.0082 (14)
O20.092 (2)0.0652 (19)0.0696 (17)0.0159 (15)−0.0320 (16)−0.0102 (15)
C10.055 (3)0.126 (4)0.107 (3)0.009 (3)0.000 (3)0.025 (3)
C20.057 (3)0.061 (2)0.058 (2)−0.001 (2)−0.007 (2)0.0023 (19)
C30.063 (3)0.075 (3)0.083 (3)−0.003 (2)−0.014 (2)0.008 (2)
C40.088 (4)0.065 (3)0.084 (3)0.004 (3)−0.021 (3)0.014 (2)
C50.088 (4)0.082 (3)0.068 (3)−0.010 (3)0.000 (3)0.017 (2)
C60.062 (3)0.066 (3)0.062 (2)0.001 (2)0.001 (2)−0.005 (2)
C70.045 (2)0.058 (2)0.0376 (17)−0.0050 (18)−0.0094 (16)−0.0059 (16)
C80.047 (2)0.059 (2)0.045 (2)−0.0036 (17)−0.0077 (17)−0.0025 (17)
C90.040 (2)0.052 (2)0.0400 (18)−0.0051 (16)−0.0008 (15)−0.0030 (16)
C100.054 (2)0.067 (2)0.0377 (17)−0.0016 (19)−0.0066 (17)−0.0007 (18)
C110.050 (2)0.059 (2)0.048 (2)0.0083 (18)−0.0008 (18)0.0093 (18)
C120.039 (2)0.044 (2)0.0478 (19)−0.0004 (16)−0.0017 (16)−0.0002 (17)
C130.0384 (19)0.0406 (19)0.0406 (17)−0.0100 (15)−0.0022 (15)−0.0006 (16)
C140.0318 (18)0.051 (2)0.0429 (18)0.0050 (15)−0.0041 (15)0.0022 (16)
C150.109 (4)0.082 (3)0.129 (4)0.016 (3)−0.001 (4)−0.001 (3)
C160.082 (3)0.057 (2)0.063 (2)−0.008 (2)−0.010 (2)0.0046 (19)
C170.049 (2)0.037 (2)0.053 (2)0.0033 (15)0.0019 (18)−0.0017 (16)
C180.067 (3)0.045 (2)0.055 (2)0.0018 (18)−0.003 (2)−0.0111 (18)
C190.057 (3)0.053 (2)0.054 (2)−0.0043 (18)−0.006 (2)−0.0172 (18)
C200.035 (2)0.064 (3)0.0443 (18)0.0001 (17)−0.0045 (16)−0.0131 (17)
C210.043 (2)0.0440 (19)0.0459 (18)0.0038 (16)−0.0064 (16)−0.0024 (15)
C220.037 (2)0.052 (2)0.0425 (18)−0.0023 (16)0.0001 (16)−0.0041 (15)
C230.048 (2)0.051 (2)0.062 (2)−0.0021 (18)−0.0097 (19)−0.0116 (18)
C240.084 (3)0.095 (3)0.059 (2)0.006 (3)−0.024 (2)−0.019 (2)

Geometric parameters (Å, °)

N1—C121.380 (4)C11—H11A0.9300
N1—C171.406 (4)C12—C131.405 (4)
N1—C161.442 (4)C13—C141.369 (4)
O1—C81.229 (4)C13—C221.462 (4)
O2—C231.212 (4)C14—H14A0.9300
C1—C21.527 (5)C15—C161.492 (6)
C1—H1A0.9600C15—H15A0.9600
C1—H1B0.9600C15—H15B0.9600
C1—H1C0.9600C15—H15C0.9600
C2—C31.376 (5)C16—H16A0.9700
C2—C71.377 (5)C16—H16B0.9700
C3—C41.369 (5)C17—C221.373 (4)
C3—H3A0.9300C17—C181.393 (4)
C4—C51.365 (6)C18—C191.367 (5)
C4—H4A0.9300C18—H18A0.9300
C5—C61.370 (5)C19—C201.373 (5)
C5—H5A0.9300C19—H19A0.9300
C6—C71.379 (5)C20—C211.397 (4)
C6—H6A0.9300C20—C231.496 (5)
C7—C81.473 (5)C21—C221.390 (4)
C8—C91.466 (4)C21—H21A0.9300
C9—C101.399 (4)C23—C241.503 (5)
C9—C141.409 (4)C24—H24A0.9600
C10—C111.348 (5)C24—H24B0.9600
C10—H10A0.9300C24—H24C0.9600
C11—C121.403 (4)
C12—N1—C17107.6 (2)C12—C13—C22105.4 (3)
C12—N1—C16126.8 (3)C13—C14—C9119.4 (3)
C17—N1—C16125.5 (3)C13—C14—H14A120.3
C2—C1—H1A109.5C9—C14—H14A120.3
C2—C1—H1B109.5C16—C15—H15A109.5
H1A—C1—H1B109.5C16—C15—H15B109.5
C2—C1—H1C109.5H15A—C15—H15B109.5
H1A—C1—H1C109.5C16—C15—H15C109.5
H1B—C1—H1C109.5H15A—C15—H15C109.5
C3—C2—C7119.2 (4)H15B—C15—H15C109.5
C3—C2—C1120.6 (4)N1—C16—C15112.3 (3)
C7—C2—C1120.1 (3)N1—C16—H16A109.1
C4—C3—C2121.1 (4)C15—C16—H16A109.1
C4—C3—H3A119.4N1—C16—H16B109.1
C2—C3—H3A119.4C15—C16—H16B109.1
C5—C4—C3120.3 (4)H16A—C16—H16B107.9
C5—C4—H4A119.9C22—C17—C18122.4 (3)
C3—C4—H4A119.9C22—C17—N1109.5 (3)
C4—C5—C6118.6 (4)C18—C17—N1128.1 (3)
C4—C5—H5A120.7C19—C18—C17115.7 (3)
C6—C5—H5A120.7C19—C18—H18A122.1
C5—C6—C7122.1 (4)C17—C18—H18A122.1
C5—C6—H6A118.9C18—C19—C20123.7 (3)
C7—C6—H6A118.9C18—C19—H19A118.1
C2—C7—C6118.7 (3)C20—C19—H19A118.1
C2—C7—C8120.3 (3)C19—C20—C21120.1 (3)
C6—C7—C8121.0 (3)C19—C20—C23123.3 (3)
O1—C8—C9120.6 (3)C21—C20—C23116.6 (3)
O1—C8—C7120.8 (3)C22—C21—C20117.2 (3)
C9—C8—C7118.5 (3)C22—C21—H21A121.4
C10—C9—C14118.6 (3)C20—C21—H21A121.4
C10—C9—C8121.0 (3)C17—C22—C21120.9 (3)
C14—C9—C8120.3 (3)C17—C22—C13107.4 (3)
C11—C10—C9123.1 (3)C21—C22—C13131.6 (3)
C11—C10—H10A118.5O2—C23—C20121.6 (3)
C9—C10—H10A118.5O2—C23—C24120.6 (4)
C10—C11—C12117.8 (3)C20—C23—C24117.9 (3)
C10—C11—H11A121.1C23—C24—H24A109.5
C12—C11—H11A121.1C23—C24—H24B109.5
N1—C12—C11129.3 (3)H24A—C24—H24B109.5
N1—C12—C13110.0 (3)C23—C24—H24C109.5
C11—C12—C13120.7 (3)H24A—C24—H24C109.5
C14—C13—C12120.2 (3)H24B—C24—H24C109.5
C14—C13—C22134.2 (3)
C7—C2—C3—C40.3 (6)C12—C13—C14—C9−2.1 (5)
C1—C2—C3—C4178.5 (4)C22—C13—C14—C9−176.2 (3)
C2—C3—C4—C5−0.2 (6)C10—C9—C14—C131.1 (5)
C3—C4—C5—C60.6 (6)C8—C9—C14—C13176.4 (3)
C4—C5—C6—C7−1.1 (6)C12—N1—C16—C1598.8 (4)
C3—C2—C7—C6−0.8 (5)C17—N1—C16—C15−84.8 (4)
C1—C2—C7—C6−178.9 (3)C12—N1—C17—C22−1.7 (4)
C3—C2—C7—C8179.2 (3)C16—N1—C17—C22−178.6 (3)
C1—C2—C7—C81.1 (5)C12—N1—C17—C18179.1 (3)
C5—C6—C7—C21.2 (5)C16—N1—C17—C182.1 (6)
C5—C6—C7—C8−178.8 (3)C22—C17—C18—C190.4 (5)
C2—C7—C8—O184.0 (4)N1—C17—C18—C19179.6 (3)
C6—C7—C8—O1−95.9 (4)C17—C18—C19—C20−0.8 (5)
C2—C7—C8—C9−99.3 (4)C18—C19—C20—C211.4 (5)
C6—C7—C8—C980.8 (4)C18—C19—C20—C23−179.1 (3)
O1—C8—C9—C100.0 (5)C19—C20—C21—C22−1.5 (5)
C7—C8—C9—C10−176.8 (3)C23—C20—C21—C22179.0 (3)
O1—C8—C9—C14−175.3 (3)C18—C17—C22—C21−0.5 (5)
C7—C8—C9—C148.0 (5)N1—C17—C22—C21−179.9 (3)
C14—C9—C10—C11−2.3 (5)C18—C17—C22—C13−180.0 (3)
C8—C9—C10—C11−177.6 (3)N1—C17—C22—C130.7 (4)
C9—C10—C11—C124.4 (5)C20—C21—C22—C171.1 (5)
C17—N1—C12—C11−179.7 (3)C20—C21—C22—C13−179.6 (3)
C16—N1—C12—C11−2.8 (6)C14—C13—C22—C17175.3 (3)
C17—N1—C12—C132.0 (4)C12—C13—C22—C170.5 (4)
C16—N1—C12—C13178.9 (3)C14—C13—C22—C21−4.1 (6)
C10—C11—C12—N1176.5 (3)C12—C13—C22—C21−178.8 (3)
C10—C11—C12—C13−5.3 (5)C19—C20—C23—O2−178.7 (4)
N1—C12—C13—C14−177.2 (3)C21—C20—C23—O20.8 (5)
C11—C12—C13—C144.3 (5)C19—C20—C23—C241.4 (5)
N1—C12—C13—C22−1.6 (4)C21—C20—C23—C24−179.2 (3)
C11—C12—C13—C22179.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11A···O1i0.932.573.447 (5)157
C16—H16A···O1i0.972.543.476 (5)163
C3—H3A···CgBii0.932.783.671 (5)161

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2106).

References

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