PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3194.
Published online 2010 November 17. doi:  10.1107/S1600536810046167
PMCID: PMC3011571

4-[(9-Ethyl-9H-carbazol-3-yl)imino­meth­yl]phenol

Abstract

In the title compound, C21H18N2O, the dihedral angle between the phenol ring and the carbazole system is 39.34 (2)°. Inter­molecular O—H(...)N hydrogen bonds and C—H(...)π and π–π inter­actions [centroid–centroid distances = 3.426 (2) and 3.768 (2) Å] stabilize the crystal structure.

Related literature

For polar organic mol­ecules as components of non-linear optical, electro-optical, photorefractive and optical-limiting materials, see: Nalwa & Miyata (1997 [triangle]); Kuzyk & Dirk (1998 [triangle]); Nesterov et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3194-scheme1.jpg

Experimental

Crystal data

  • C21H18N2O
  • M r = 314.37
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3194-efi1.jpg
  • a = 13.386 (6) Å
  • b = 9.247 (4) Å
  • c = 26.443 (10) Å
  • V = 3273 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 295 K
  • 0.25 × 0.20 × 0.15 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • 21605 measured reflections
  • 2878 independent reflections
  • 1615 reflections with I > 2σ(I)
  • R int = 0.081
  • 3 standard reflections every 100 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.140
  • S = 1.02
  • 2878 reflections
  • 218 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 [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: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810046167/vm2053sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046167/vm2053Isup2.hkl

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

Acknowledgments

The authors would like to thank the Jilin Province Science and Technology Development Plan for support.

supplementary crystallographic information

Comment

Polar organic molecules as components of NLO, electro-optical, photorefractive and optical-limiting materials have been under intensive investigation (Nalwa & Miyata, 1997; Kuzyk & Dirk, 1998; Nesterov et al., 2002). Many N-ethylcarbazole derivatives have been studied for this purpose. In this paper, we describe the synthesis and structure determination of the title compound.

In the title compound, atoms O1, C15, N2 lie in the plane of phenyl ring C16—C21 (p1) with the largest deviation of 0.002 (3) Å for C16. The atoms of the carbazole ring together with C2 and N2 form a plane (p2) for which the largest deviation is 0.068 (1) Å for C5. The fragment C11,N2, C15,C16,C17 is coplanar (p3). The dihedral angles formed by p1 with p2 and p3 are 39.34 (2) and 6.01 (2)°, respectively. The dihedral angle between p2 and p3 is 42.21 (3)°.

In the lattice, π–π and C—H···π interactions occur [Cg1···Cg1i = 3.426 (2), Cg2···Cg3i = 3.768 (2) Å, C1···Cg2ii = 3.698 (2) Å, H1A···Cg2ii = 2.77 Å, symmetry codes: i 1 - x, -y, 1 - z; ii 3/2 - x, -1/2 + y, z. Cg1, Cg2, Cg3 refer to ring N1—C3—C8—C9—C14 and phenyl rings C3—C8 and C9—C14, respectively]. In addition, an intermolecular hydrogen bond (Table 1) along with the C—H···π and π–π interactions stabilizes the crystal structure. The H-bond results in infinite chains along [010].

Experimental

The title compound was synthesized by reaction of 9-ethyl-carbazol-3-amine (0.420 g, 0.002 mol) and 4-hydroxybenzaldehyde (0.244 g, 0.002 mol) in ethanol (50 ml) under stirring for 5 h at room temperature. Single crystals suitable for x-ray measurements were obtained by recrystallization from ethyl acetate at room temperature.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances=0.93–0.96 Å, O—H distance=0.82 Å and with Uiso=1.2–1.5Ueq.

Figures

Fig. 1.
The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C21H18N2OF(000) = 1328
Mr = 314.37Dx = 1.276 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 13.386 (6) Åθ = 4–14°
b = 9.247 (4) ŵ = 0.08 mm1
c = 26.443 (10) ÅT = 295 K
V = 3273 (2) Å3Block, brown
Z = 80.25 × 0.20 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.081
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 1.5°
graphiteh = −15→15
ω scansk = −10→10
21605 measured reflectionsl = −31→28
2878 independent reflections3 standard reflections every 100 reflections
1615 reflections with I > 2σ(I) intensity decay: none

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.140w = 1/[σ2(Fo2) + (0.0568P)2 + 0.6129P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2878 reflectionsΔρmax = 0.18 e Å3
218 parametersΔρmin = −0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0037 (8)

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
O10.61757 (15)0.7932 (2)0.83217 (7)0.0802 (7)
H10.56240.83160.83140.096*
N10.64140 (15)0.0252 (2)0.47293 (8)0.0538 (6)
N20.58786 (17)0.3455 (2)0.64785 (8)0.0580 (6)
C10.7978 (2)−0.0332 (4)0.42951 (13)0.0866 (10)
H1A0.8397−0.11230.41930.130*
H1B0.83430.02920.45190.130*
H1C0.77720.02020.40020.130*
C20.7074 (2)−0.0908 (3)0.45633 (11)0.0639 (8)
H2B0.6711−0.15470.43380.077*
H2C0.7285−0.14680.48550.077*
C30.57518 (18)0.0966 (3)0.44114 (10)0.0509 (7)
C40.5568 (2)0.0753 (3)0.39037 (11)0.0635 (8)
H4A0.58920.00240.37250.076*
C50.4897 (2)0.1644 (3)0.36707 (12)0.0710 (9)
H5A0.47670.15230.33280.085*
C60.4407 (2)0.2721 (3)0.39335 (12)0.0692 (8)
H6A0.39530.33100.37650.083*
C70.45795 (19)0.2937 (3)0.44390 (11)0.0605 (7)
H7A0.42410.36580.46140.073*
C80.52679 (18)0.2060 (3)0.46856 (10)0.0473 (6)
C90.56752 (17)0.2025 (3)0.51875 (9)0.0462 (6)
C100.55122 (17)0.2834 (3)0.56227 (10)0.0509 (7)
H10A0.50300.35580.56240.061*
C110.60673 (19)0.2563 (3)0.60528 (10)0.0518 (7)
C120.6761 (2)0.1429 (3)0.60559 (10)0.0576 (7)
H12A0.71220.12420.63490.069*
C130.69205 (19)0.0585 (3)0.56350 (11)0.0579 (7)
H13A0.7376−0.01740.56420.069*
C140.63826 (18)0.0899 (3)0.51982 (10)0.0492 (7)
C150.6605 (2)0.3883 (3)0.67601 (11)0.0613 (8)
H15A0.72440.35390.66920.074*
C160.6471 (2)0.4883 (3)0.71814 (10)0.0593 (7)
C170.7279 (2)0.5339 (3)0.74665 (11)0.0716 (9)
H17A0.79070.49470.74040.086*
C180.7171 (2)0.6370 (4)0.78447 (11)0.0741 (9)
H18A0.77240.66750.80290.089*
C190.6242 (2)0.6938 (3)0.79452 (10)0.0624 (8)
C200.5425 (2)0.6490 (3)0.76697 (11)0.0685 (8)
H20A0.47950.68660.77390.082*
C210.5548 (2)0.5481 (3)0.72916 (11)0.0684 (8)
H21A0.49940.51920.71050.082*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0871 (15)0.0854 (15)0.0680 (13)−0.0061 (12)0.0009 (11)−0.0171 (12)
N10.0561 (13)0.0473 (13)0.0581 (15)0.0069 (11)0.0047 (11)−0.0006 (11)
N20.0668 (15)0.0555 (14)0.0516 (14)0.0026 (12)0.0064 (12)0.0043 (12)
C10.0619 (19)0.094 (2)0.104 (3)0.0178 (18)0.0165 (18)0.007 (2)
C20.0691 (18)0.0502 (17)0.072 (2)0.0120 (15)0.0020 (15)−0.0050 (15)
C30.0504 (15)0.0465 (15)0.0558 (18)−0.0040 (13)0.0049 (14)0.0011 (14)
C40.0670 (18)0.0630 (19)0.061 (2)0.0038 (16)0.0000 (15)−0.0093 (16)
C50.074 (2)0.080 (2)0.0587 (19)0.0030 (18)−0.0070 (16)−0.0039 (17)
C60.0697 (19)0.073 (2)0.065 (2)0.0118 (16)−0.0099 (16)0.0089 (17)
C70.0571 (17)0.0580 (18)0.066 (2)0.0058 (14)0.0018 (15)0.0063 (16)
C80.0452 (14)0.0447 (15)0.0521 (17)−0.0003 (12)0.0060 (12)0.0034 (13)
C90.0459 (14)0.0403 (14)0.0524 (17)0.0001 (12)0.0066 (12)0.0055 (13)
C100.0479 (15)0.0446 (15)0.0601 (17)0.0040 (12)0.0078 (14)0.0049 (14)
C110.0564 (16)0.0490 (16)0.0499 (17)0.0001 (13)0.0109 (14)0.0028 (14)
C120.0619 (17)0.0568 (17)0.0540 (18)0.0030 (15)−0.0014 (14)0.0062 (15)
C130.0585 (17)0.0518 (16)0.0633 (19)0.0102 (13)−0.0003 (15)0.0057 (15)
C140.0484 (15)0.0434 (15)0.0557 (18)−0.0011 (13)0.0075 (13)0.0001 (14)
C150.0726 (19)0.0539 (17)0.0573 (18)0.0054 (16)0.0096 (16)0.0085 (15)
C160.0678 (19)0.0598 (18)0.0502 (18)0.0014 (15)0.0049 (15)0.0060 (14)
C170.063 (2)0.081 (2)0.071 (2)0.0010 (17)0.0020 (16)0.0031 (19)
C180.072 (2)0.087 (2)0.063 (2)−0.0078 (18)−0.0039 (16)−0.0078 (18)
C190.075 (2)0.0636 (18)0.0484 (17)−0.0049 (17)0.0060 (16)0.0014 (15)
C200.069 (2)0.075 (2)0.0622 (19)0.0049 (16)0.0005 (16)−0.0105 (17)
C210.068 (2)0.078 (2)0.0593 (19)0.0006 (17)0.0005 (15)−0.0099 (17)

Geometric parameters (Å, °)

O1—C191.358 (3)C8—C91.435 (3)
O1—H10.8200C9—C101.390 (3)
N1—C141.377 (3)C9—C141.407 (3)
N1—C31.389 (3)C10—C111.382 (3)
N1—C21.457 (3)C10—H10A0.9300
N2—C151.288 (3)C11—C121.401 (3)
N2—C111.418 (3)C12—C131.376 (3)
C1—C21.500 (4)C12—H12A0.9300
C1—H1A0.9600C13—C141.392 (3)
C1—H1B0.9600C13—H13A0.9300
C1—H1C0.9600C15—C161.459 (4)
C2—H2B0.9700C15—H15A0.9300
C2—H2C0.9700C16—C171.384 (4)
C3—C41.379 (3)C16—C211.385 (4)
C3—C81.403 (3)C17—C181.389 (4)
C4—C51.366 (4)C17—H17A0.9300
C4—H4A0.9300C18—C191.376 (4)
C5—C61.380 (4)C18—H18A0.9300
C5—H5A0.9300C19—C201.378 (4)
C6—C71.371 (4)C20—C211.377 (4)
C6—H6A0.9300C20—H20A0.9300
C7—C81.390 (3)C21—H21A0.9300
C7—H7A0.9300
C19—O1—H1109.5C14—C9—C8106.9 (2)
C14—N1—C3108.6 (2)C11—C10—C9120.0 (2)
C14—N1—C2127.6 (2)C11—C10—H10A120.0
C3—N1—C2123.7 (2)C9—C10—H10A120.0
C15—N2—C11120.2 (2)C10—C11—C12119.8 (2)
C2—C1—H1A109.5C10—C11—N2116.9 (2)
C2—C1—H1B109.5C12—C11—N2123.3 (2)
H1A—C1—H1B109.5C13—C12—C11121.5 (2)
C2—C1—H1C109.5C13—C12—H12A119.2
H1A—C1—H1C109.5C11—C12—H12A119.2
H1B—C1—H1C109.5C12—C13—C14118.2 (2)
N1—C2—C1111.7 (2)C12—C13—H13A120.9
N1—C2—H2B109.3C14—C13—H13A120.9
C1—C2—H2B109.3N1—C14—C13129.8 (2)
N1—C2—H2C109.3N1—C14—C9108.9 (2)
C1—C2—H2C109.3C13—C14—C9121.3 (2)
H2B—C2—H2C107.9N2—C15—C16122.9 (3)
C4—C3—N1129.4 (2)N2—C15—H15A118.5
C4—C3—C8121.6 (3)C16—C15—H15A118.5
N1—C3—C8109.0 (2)C17—C16—C21117.5 (3)
C5—C4—C3118.0 (3)C17—C16—C15120.8 (3)
C5—C4—H4A121.0C21—C16—C15121.6 (3)
C3—C4—H4A121.0C16—C17—C18121.3 (3)
C4—C5—C6121.4 (3)C16—C17—H17A119.4
C4—C5—H5A119.3C18—C17—H17A119.4
C6—C5—H5A119.3C19—C18—C17119.7 (3)
C7—C6—C5121.1 (3)C19—C18—H18A120.2
C7—C6—H6A119.5C17—C18—H18A120.2
C5—C6—H6A119.5O1—C19—C18117.3 (3)
C6—C7—C8118.9 (3)O1—C19—C20122.6 (3)
C6—C7—H7A120.5C18—C19—C20120.0 (3)
C8—C7—H7A120.5C21—C20—C19119.5 (3)
C7—C8—C3119.0 (3)C21—C20—H20A120.2
C7—C8—C9134.3 (2)C19—C20—H20A120.2
C3—C8—C9106.6 (2)C20—C21—C16122.0 (3)
C10—C9—C14119.2 (2)C20—C21—H21A119.0
C10—C9—C8133.9 (2)C16—C21—H21A119.0

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C3–C8 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1···N2i0.822.092.842 (3)153
C1—H1A···Cg2ii0.962.773.698 (2)162

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VM2053).

References

  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Kuzyk, M. C. & Dirk, C. W. (1998). Characterization Techniques and Tabulations for Organic Nonlinear Optical Materials, p. 894. New York: Marcel Dekker Inc.
  • Nalwa, H. S. & Miyata, S. (1997). Nonlinear Optics of Organic Molecules and Polymers, p. 885. Boca Raton: CRC Press.
  • Nesterov, V. N., Montoya, N. G., Antipin, M. Yu., Sanghadasa, M., Clark, R. D. & Timofeeva, T. V. (2002). Acta Cryst. C58, o72–o75. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography