organic compounds
H-carbazol-3-yl)-9H-carbazole
of 9-butyl-3-(9-butyl-9aDepartment of Chemistry, Kalasalingam University, Krishnankoil 626 126, India, bLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 067, India, and cDepartment of Physics & International Research Centre, Kalasalingam University, Krishnankoil 626 126, India
*Correspondence e-mail: s_selvanayagam@rediffmail.com
In the title carbazole derivative, C32H32N2, the molecule resides on a crystallographic twofold axis, which runs through the central C—C bond. The carbazole ring system is almost planar, with a maximum deviation of 0.041 (1) Å for one of the ring-junction C atoms. The crystal packing is stabilized by C—H⋯π interactions only, which form a C(7) chain-like arrangement along [110] in the unit cell.
Keywords: crystal structure; carbazole derivatives; C—H⋯π interactions.
CCDC reference: 1034987
1. Related literature
For general background to carbazole derivatives and their applications, see: Giraud et al. (2014); Bandgar et al. (2012); Gu et al. (2014); Wang et al. (2011); Thiratmatrakul et al. (2014); Shi et al. (2012); Tavasli et al. (2012); Kim et al. (2011); Zhuang et al. (2012). For the preparation of the title compound, see: Ramalingan et al. (2010).
2. Experimental
2.1. Crystal data
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2.2. Data collection
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2.3. Refinement
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Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 and PLATON.
Supporting information
CCDC reference: 1034987
10.1107/S1600536814025367/zq2229sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814025367/zq2229Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814025367/zq2229Isup3.cml
In a round-bottomed flask (250 ml), iron(III) chloride (44.80 mmol) in chloroform (100 ml) was taken under nitrogen atmosphere. Then, 9-butyl-9H-carbazole (11.20 mmol) (Ramalingan et al., 2010) in chloroform (50 ml) was added in a drop-wise fashion and was stirred at ambient temperature for 1 hour. After the addition of a sodium hydroxide solution (10%), the organic phase was separated and the aqueous phase was extracted with chloroform. The combined organic phases were dried and concentrated to obtain the crude product which was dissolved in chloroform (15 ml) and reprecipitated slowly using methanol (200 ml). The product, thus, obtained was filtered, dried under vacuum at ambient temperature. Single crystals of (I) were obtained by slow evaporation of ethanol solution of the title compound at room temperature.
H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H distances of 0.93-0.97 Å, and Uiso(H) = 1.5Ueq(methyl C) and Uiso(H) = 1.2Ueq for other C atoms.
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 2. Molecular packing of the title compound, viewed along the a axis; C—H···π interactions are shown as dashed lines.For the sake of clarity, H atoms, not involved in hydrogen bonds, have been omitted for clarity. |
C32H32N2 | F(000) = 476 |
Mr = 444.59 | Dx = 1.223 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6184 (4) Å | Cell parameters from 9858 reflections |
b = 11.0946 (7) Å | θ = 2.4–27.2° |
c = 19.4673 (13) Å | µ = 0.07 mm−1 |
β = 95.982 (1)° | T = 292 K |
V = 1206.86 (14) Å3 | Block, colourless |
Z = 2 | 0.21 × 0.19 × 0.17 mm |
Bruker SMART APEX CCD area-detector diffractometer | Rint = 0.026 |
Radiation source: fine-focus sealed tube | θmax = 28.3°, θmin = 2.1° |
ω scans | h = −7→7 |
13872 measured reflections | k = −14→14 |
2928 independent reflections | l = −25→25 |
2319 reflections with I > 2σ(I) |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.0782P)2 + 0.1445P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
2928 reflections | Δρmax = 0.24 e Å−3 |
155 parameters | Δρmin = −0.19 e Å−3 |
C32H32N2 | V = 1206.86 (14) Å3 |
Mr = 444.59 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.6184 (4) Å | µ = 0.07 mm−1 |
b = 11.0946 (7) Å | T = 292 K |
c = 19.4673 (13) Å | 0.21 × 0.19 × 0.17 mm |
β = 95.982 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 2319 reflections with I > 2σ(I) |
13872 measured reflections | Rint = 0.026 |
2928 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.24 e Å−3 |
2928 reflections | Δρmin = −0.19 e Å−3 |
155 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3407 (2) | 0.68730 (12) | 0.15991 (7) | 0.0515 (4) | |
C1 | 0.2740 (3) | 0.77442 (13) | 0.11101 (8) | 0.0453 (4) | |
C2 | 0.3743 (3) | 0.80464 (14) | 0.05125 (9) | 0.0520 (4) | |
H2 | 0.5112 | 0.7659 | 0.0395 | 0.062* | |
C3 | 0.2664 (3) | 0.89298 (14) | 0.00987 (8) | 0.0498 (4) | |
H3 | 0.3343 | 0.9134 | −0.0301 | 0.060* | |
C4 | 0.0581 (3) | 0.95478 (12) | 0.02450 (7) | 0.0432 (3) | |
C5 | −0.0317 (3) | 0.92638 (13) | 0.08650 (8) | 0.0464 (4) | |
H5 | −0.1644 | 0.9677 | 0.0991 | 0.056* | |
C6 | 0.0733 (3) | 0.83737 (14) | 0.12995 (7) | 0.0445 (4) | |
C7 | 0.0185 (3) | 0.78577 (14) | 0.19467 (8) | 0.0487 (4) | |
C8 | −0.1572 (3) | 0.80724 (17) | 0.23854 (9) | 0.0601 (5) | |
H8 | −0.2688 | 0.8685 | 0.2289 | 0.072* | |
C9 | −0.1633 (4) | 0.7361 (2) | 0.29660 (9) | 0.0711 (5) | |
H9 | −0.2801 | 0.7496 | 0.3263 | 0.085* | |
C10 | 0.0034 (4) | 0.64469 (19) | 0.31106 (10) | 0.0718 (6) | |
H10 | −0.0045 | 0.5980 | 0.3504 | 0.086* | |
C11 | 0.1792 (4) | 0.62115 (17) | 0.26904 (9) | 0.0627 (5) | |
H11 | 0.2900 | 0.5598 | 0.2793 | 0.075* | |
C12 | 0.1855 (3) | 0.69250 (14) | 0.21042 (8) | 0.0502 (4) | |
C13 | 0.5130 (3) | 0.59184 (15) | 0.15104 (9) | 0.0572 (4) | |
H13A | 0.5533 | 0.5518 | 0.1950 | 0.069* | |
H13B | 0.6584 | 0.6275 | 0.1372 | 0.069* | |
C14 | 0.4206 (3) | 0.49911 (16) | 0.09770 (9) | 0.0580 (4) | |
H14A | 0.3929 | 0.5386 | 0.0531 | 0.070* | |
H14B | 0.5439 | 0.4388 | 0.0944 | 0.070* | |
C15 | 0.1935 (3) | 0.43619 (18) | 0.11230 (10) | 0.0661 (5) | |
H15A | 0.0679 | 0.4957 | 0.1143 | 0.079* | |
H15B | 0.2191 | 0.3973 | 0.1571 | 0.079* | |
C16 | 0.1125 (4) | 0.3428 (2) | 0.05817 (12) | 0.0911 (7) | |
H16A | 0.0976 | 0.3797 | 0.0133 | 0.137* | |
H16B | −0.0396 | 0.3107 | 0.0674 | 0.137* | |
H16C | 0.2281 | 0.2789 | 0.0595 | 0.137* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0529 (7) | 0.0499 (8) | 0.0513 (8) | 0.0010 (6) | 0.0039 (6) | 0.0007 (6) |
C1 | 0.0430 (7) | 0.0437 (8) | 0.0487 (8) | −0.0055 (6) | 0.0015 (6) | −0.0043 (6) |
C2 | 0.0426 (8) | 0.0532 (9) | 0.0618 (10) | 0.0013 (7) | 0.0127 (7) | 0.0005 (7) |
C3 | 0.0476 (8) | 0.0525 (9) | 0.0511 (9) | −0.0050 (7) | 0.0130 (7) | 0.0015 (7) |
C4 | 0.0439 (7) | 0.0388 (7) | 0.0468 (8) | −0.0065 (6) | 0.0050 (6) | −0.0071 (6) |
C5 | 0.0473 (8) | 0.0457 (8) | 0.0467 (8) | 0.0007 (6) | 0.0077 (6) | −0.0086 (6) |
C6 | 0.0469 (8) | 0.0437 (8) | 0.0428 (8) | −0.0066 (6) | 0.0049 (6) | −0.0089 (6) |
C7 | 0.0543 (9) | 0.0495 (8) | 0.0420 (8) | −0.0086 (7) | 0.0035 (6) | −0.0092 (7) |
C8 | 0.0673 (11) | 0.0648 (11) | 0.0494 (9) | −0.0063 (8) | 0.0124 (8) | −0.0130 (8) |
C9 | 0.0836 (13) | 0.0846 (14) | 0.0484 (10) | −0.0165 (11) | 0.0218 (9) | −0.0116 (9) |
C10 | 0.0935 (14) | 0.0744 (13) | 0.0483 (10) | −0.0190 (11) | 0.0109 (10) | 0.0034 (9) |
C11 | 0.0759 (12) | 0.0602 (10) | 0.0511 (10) | −0.0085 (9) | 0.0019 (8) | 0.0033 (8) |
C12 | 0.0558 (9) | 0.0498 (9) | 0.0441 (8) | −0.0093 (7) | 0.0015 (7) | −0.0056 (6) |
C13 | 0.0491 (9) | 0.0559 (10) | 0.0651 (10) | 0.0031 (7) | −0.0010 (7) | 0.0033 (8) |
C14 | 0.0574 (10) | 0.0579 (10) | 0.0594 (10) | 0.0074 (8) | 0.0090 (8) | 0.0012 (8) |
C15 | 0.0651 (11) | 0.0693 (11) | 0.0643 (11) | −0.0039 (9) | 0.0089 (9) | −0.0126 (9) |
C16 | 0.0988 (17) | 0.0948 (16) | 0.0795 (14) | −0.0229 (13) | 0.0083 (12) | −0.0273 (13) |
N1—C1 | 1.381 (2) | C9—C10 | 1.389 (3) |
N1—C12 | 1.382 (2) | C9—H9 | 0.9300 |
N1—C13 | 1.457 (2) | C10—C11 | 1.372 (3) |
C1—C2 | 1.385 (2) | C10—H10 | 0.9300 |
C1—C6 | 1.408 (2) | C11—C12 | 1.392 (2) |
C2—C3 | 1.369 (2) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | C13—C14 | 1.515 (2) |
C3—C4 | 1.411 (2) | C13—H13A | 0.9700 |
C3—H3 | 0.9300 | C13—H13B | 0.9700 |
C4—C5 | 1.392 (2) | C14—C15 | 1.507 (3) |
C4—C4i | 1.488 (3) | C14—H14A | 0.9700 |
C5—C6 | 1.391 (2) | C14—H14B | 0.9700 |
C5—H5 | 0.9300 | C15—C16 | 1.514 (3) |
C6—C7 | 1.446 (2) | C15—H15A | 0.9700 |
C7—C8 | 1.392 (2) | C15—H15B | 0.9700 |
C7—C12 | 1.409 (2) | C16—H16A | 0.9600 |
C8—C9 | 1.382 (3) | C16—H16B | 0.9600 |
C8—H8 | 0.9300 | C16—H16C | 0.9600 |
C1—N1—C12 | 108.37 (13) | C9—C10—H10 | 119.0 |
C1—N1—C13 | 124.27 (14) | C10—C11—C12 | 117.53 (19) |
C12—N1—C13 | 126.23 (14) | C10—C11—H11 | 121.2 |
N1—C1—C2 | 130.04 (14) | C12—C11—H11 | 121.2 |
N1—C1—C6 | 109.51 (13) | N1—C12—C11 | 129.16 (16) |
C2—C1—C6 | 120.44 (14) | N1—C12—C7 | 109.34 (14) |
C3—C2—C1 | 118.26 (14) | C11—C12—C7 | 121.50 (16) |
C3—C2—H2 | 120.9 | N1—C13—C14 | 112.98 (14) |
C1—C2—H2 | 120.9 | N1—C13—H13A | 109.0 |
C2—C3—C4 | 123.69 (15) | C14—C13—H13A | 109.0 |
C2—C3—H3 | 118.2 | N1—C13—H13B | 109.0 |
C4—C3—H3 | 118.2 | C14—C13—H13B | 109.0 |
C5—C4—C3 | 116.63 (14) | H13A—C13—H13B | 107.8 |
C5—C4—C4i | 122.27 (17) | C15—C14—C13 | 114.95 (15) |
C3—C4—C4i | 121.10 (17) | C15—C14—H14A | 108.5 |
C6—C5—C4 | 121.26 (14) | C13—C14—H14A | 108.5 |
C6—C5—H5 | 119.4 | C15—C14—H14B | 108.5 |
C4—C5—H5 | 119.4 | C13—C14—H14B | 108.5 |
C5—C6—C1 | 119.57 (13) | H14A—C14—H14B | 107.5 |
C5—C6—C7 | 134.08 (14) | C14—C15—C16 | 112.63 (16) |
C1—C6—C7 | 106.31 (14) | C14—C15—H15A | 109.1 |
C8—C7—C12 | 119.42 (15) | C16—C15—H15A | 109.1 |
C8—C7—C6 | 134.10 (16) | C14—C15—H15B | 109.1 |
C12—C7—C6 | 106.44 (14) | C16—C15—H15B | 109.1 |
C9—C8—C7 | 118.93 (18) | H15A—C15—H15B | 107.8 |
C9—C8—H8 | 120.5 | C15—C16—H16A | 109.5 |
C7—C8—H8 | 120.5 | C15—C16—H16B | 109.5 |
C8—C9—C10 | 120.59 (18) | H16A—C16—H16B | 109.5 |
C8—C9—H9 | 119.7 | C15—C16—H16C | 109.5 |
C10—C9—H9 | 119.7 | H16A—C16—H16C | 109.5 |
C11—C10—C9 | 122.02 (18) | H16B—C16—H16C | 109.5 |
C11—C10—H10 | 119.0 | ||
C12—N1—C1—C2 | 179.62 (16) | C1—C6—C7—C12 | −1.41 (16) |
C13—N1—C1—C2 | −11.9 (2) | C12—C7—C8—C9 | 0.0 (2) |
C12—N1—C1—C6 | 0.15 (16) | C6—C7—C8—C9 | 177.40 (16) |
C13—N1—C1—C6 | 168.63 (13) | C7—C8—C9—C10 | 0.1 (3) |
N1—C1—C2—C3 | 177.59 (14) | C8—C9—C10—C11 | 0.0 (3) |
C6—C1—C2—C3 | −3.0 (2) | C9—C10—C11—C12 | −0.1 (3) |
C1—C2—C3—C4 | −0.2 (2) | C1—N1—C12—C11 | 178.61 (16) |
C2—C3—C4—C5 | 3.2 (2) | C13—N1—C12—C11 | 10.4 (3) |
C2—C3—C4—C4i | −176.60 (16) | C1—N1—C12—C7 | −1.07 (17) |
C3—C4—C5—C6 | −2.9 (2) | C13—N1—C12—C7 | −169.27 (14) |
C4i—C4—C5—C6 | 176.86 (15) | C10—C11—C12—N1 | −179.47 (16) |
C4—C5—C6—C1 | −0.1 (2) | C10—C11—C12—C7 | 0.2 (2) |
C4—C5—C6—C7 | −177.52 (15) | C8—C7—C12—N1 | 179.62 (14) |
N1—C1—C6—C5 | −177.26 (13) | C6—C7—C12—N1 | 1.54 (17) |
C2—C1—C6—C5 | 3.2 (2) | C8—C7—C12—C11 | −0.1 (2) |
N1—C1—C6—C7 | 0.79 (16) | C6—C7—C12—C11 | −178.17 (14) |
C2—C1—C6—C7 | −178.73 (14) | C1—N1—C13—C14 | −69.5 (2) |
C5—C6—C7—C8 | −1.4 (3) | C12—N1—C13—C14 | 96.88 (19) |
C1—C6—C7—C8 | −179.08 (17) | N1—C13—C14—C15 | −58.5 (2) |
C5—C6—C7—C12 | 176.24 (15) | C13—C14—C15—C16 | −178.80 (17) |
Symmetry code: (i) −x, −y+2, −z. |
Cg is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15B···Cgii | 0.97 | 2.98 | 3.838 (2) | 148 |
Symmetry code: (ii) −x+1/2, y−1/2, −z+1/2. |
Cg is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15B···Cgi | 0.97 | 2.98 | 3.838 (2) | 148 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Acknowledgements
CR and SS thank the Vice Chancellor and management of Kalasalingam University, Krishnankoil, for their support and encouragement.
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Carbazole based materials play vital roles in various areas of research. Various carbazole based heterocycles exhibit a diverse range of biological activities including pim kinase inhibitory (Giraud et al., 2014), anti-inflammatory, antioxidant (Bandgar et al., 2012), antimicrobial (Gu et al., 2014), antitumor (Wang et al., 2011), and anti-Alzheimer (Thiratmatrakul et al., 2014) activities etc. On the other hand, this class of materials has been identified as potential ones for OLED applications (Shi et al., 2012.; Tavasli et al., 2012; Kim et al., 2011; Zhuang et al., 2012). As an intermediate for the development of new carbazole based materials for biological/OLED applications, a dibutylbicarbazole has been synthesized and single crystals were grown by slow evaporation in ethanol.
The X-ray study confirmed the molecular structure and atomic connectivity of the title compound, as illustrated in Fig. 1. The bond distance C4—C4i of 1.488 (3) Å [symmetry code: (i) -x,-y+2,-z] confirms the single bond character. The sum of the angles at N1 (358.9°) is in accordance with sp2 hybridization.
The carbazole ring system is planar with a maximum deviation of -0.041 (1) Å for atom C7. The atom C13 attached to the carbazole ring system deviates by 0.250 (1) Å from the best plane of the carbazole ring system.
In addition to the van der Waals interactions, the molecular packing is influenced by intermolecular C—H···π interactions, such that atom H15B is 2.98 Å from the centroid of the phenyl ring (C7-C12) at (1/2-x, -1/2+y, 1/2-z) with a C15—H15B···.centroid angle of 148° and a C15···centroid distance of 3.838 (2) Å. This interactions form a C(7) chain like arrangement in the unit cell (Fig. 2).