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Acta Cryst. (2009). E65, o1198    [ doi:10.1107/S1600536809016080 ]

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

Y.-C. Hang, J.-X. Ji and M.-D. Chen

Abstract top

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...[pi] interactions.

Comment top

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).

Related literature top

For carbazole-containing compounds used as organic opto-electronic materials, see: Bai et al. (2007); Liu et al. (2009); Promarak et al. (2007). For the synthesis, see: Feng et al. (2007). For bond-length data, see: Allen et al. (1987). CgB is the centroid of the C9–C14 ring.

Experimental top

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 top

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].

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. A view along the c axis of the crystal structure of the title compound.
1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone top
Crystal data top
C24H21NO2F000 = 1504
Mr = 355.42Dx = 1.225 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 13.066 (3) Åθ = 9–13º
b = 13.416 (3) ŵ = 0.08 mm−1
c = 21.987 (4) ÅT = 298 K
V = 3854.2 (13) Å3Block, colorless
Z = 80.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.0000
Radiation source: fine-focus sealed tubeθmax = 25.3º
Monochromator: graphiteθmin = 1.9º
T = 298 Kh = 0→15
ω/2θ scansk = 0→16
Absorption correction: ψ scan
(North et al., 1968)		l = 0→26
Tmin = 0.977, Tmax = 0.9923 standard reflections
3492 measured reflections every 200 reflections
3492 independent reflections intensity decay: 1%
1733 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.178  w = 1/[σ2(Fo2) + (0.07P)2 + P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3492 reflectionsΔρmax = 0.21 e Å−3
244 parametersΔρmin = −0.21 e Å−3
7 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C24H21NO2V = 3854.2 (13) Å3
Mr = 355.42Z = 8
Orthorhombic, PbcaMo Kα
a = 13.066 (3) ŵ = 0.08 mm−1
b = 13.416 (3) ÅT = 298 K
c = 21.987 (4) Å0.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1733 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.977, Tmax = 0.9923 standard reflections
3492 measured reflections every 200 reflections
3492 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.0687 restraints
wR(F2) = 0.178H-atom parameters constrained
S = 1.06Δρmax = 0.21 e Å−3
3492 reflectionsΔρmin = −0.21 e Å−3
244 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
N10.0687 (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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
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