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 March 1; 66(Pt 3): o571.
Published online 2010 February 10. doi:  10.1107/S1600536810004484
PMCID: PMC2983572

9-Ethyl-3,6-bis­(5-iodo-2-thien­yl)-9H-carbazole

Abstract

In the title compound, C22H15I2NS2, the two thio­phene rings are twisted out of the plane of the central pyrrole ring, making dihedral angles of 32.4 (2)° and 9.8 (2). In the crystal, neighboring mol­ecules are linked into centrosymmetric dimers by pairs of C—H(...)I inter­actions.

Related literature

For the crystal structures of related carbazole derivatives, see: Yang et al. (2005 [triangle]); Zhou et al. (2007 [triangle]); Zhou et al. (2008 [triangle]); Chen et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o571-scheme1.jpg

Experimental

Crystal data

  • C22H15I2NS2
  • M r = 611.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o571-efi1.jpg
  • a = 10.637 (3) Å
  • b = 7.814 (2) Å
  • c = 26.687 (7) Å
  • β = 107.313 (18)°
  • V = 2117.7 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.17 mm−1
  • T = 298 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.449, T max = 0.742
  • 17471 measured reflections
  • 3738 independent reflections
  • 3065 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.151
  • S = 1.16
  • 3738 reflections
  • 245 parameters
  • H-atom parameters constrained
  • Δρmax = 1.08 e Å−3
  • Δρmin = −0.79 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; 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/S1600536810004484/rk2188sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004484/rk2188Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant Nos. 50703001, 20771001), the Education Committee of Anhui Province (grant No. KJ2009A52), the Young Teacher Foundation of Institutions of Higher Education of An Hui Province (grant No. 2007jq1019), the Ministry of Education and the Person with Ability Foundation of Anhui University.

supplementary crystallographic information

Comment

Carbazole - based materials had been investigated for their electrical and optical properties. Especially, introduction of substituents on the 3- and 6-positions of carbazole represents a possible approach for designing carbazole-based photorefractive materials (Yang et al., 2005). The title molecule that we has designed and synthesized is a good intermediate and penetratingly investigated. In the title molecule (Fig.1), the bond lengths and angles show normal values (Chen et al., 2009; Zhou et al., 2007, 2008). Two thiophene rings are twisted out of the plane of the center pyrrole ring and the dihedral angles are 32.4 (2)° and 9.8 (2)°, respectively. In the crystal structure of title compound (Fig.2), the neighboring molecules form a centrosymmetric dimer by C17—H17···I1i (symmetry code: (i) -x, 3-y, 2-z). The neighboring dimers are stacked through weak π···π interaction and the face-to-face distance between two neighboring thiophene rings is 3.57 (4)Å.

Experimental

Preparation of 9-ethyl-3,6-diiodocarbazole: 9-ethylcarbazole (10 g, 51 mmol) and anhydrous ethanol (150 ml) were added to a three-necked flask equipped with a magnetic stirrer, a reflux condenser and an isobaric dropping funnel. ICl (20 g, 123 mmol)/ethanol (20 ml) was added to the mixture at 353 K. The reaction mixture was refluxed for 2 h, cooled to room temperature and filtered. The grey needle crystals (20.52 g, yield 90%) were obtained and washed with ethanol.

Preparation of 9-ethyl-3,6-di(2-thienyl)carbazole: a 80 ml three-necked round-bottomed flask was charged with of 9-ethyl-3,6-diiodocarbazole (3.00 g, 6 mmol), 10 ml of DMF, 10 ml of Et3N and thiophen-2-yl-boronic acid (2.55 g, 20 mmol). A catalytic amount of Pd(OAc)2 was added to the stirring solution at 343 K after 9-ethyl-3,6-diiodocarbazole was completely dissolved under nitrogen. The solution was refluxed for 6 h at 403 K. At the end of the reaction was judged by TLC analysis. The solution was cooled to room temperature and dissolved in 200 ml CH2Cl2, then washed with water (3× 200 ml), dried over anhydrous MgSO4, brown column crystals were obtained (2.00 g, yield 80% ).

Preparation of 9-ethyl-3,6-di{2-[(5-iodo)thiophene]-yl}carbazole: a 50 ml round-bottomed flask was charged with 9-ethyl-3,6-di(2-thienyl)carbazole (0.13 g, 0.3 mmol) and 9 ml of acetone. A N-iodosuccinimide (0.42 g, 1.9 mmol) dissolved in 4 ml acetone and was added to the stirring solution at room temperature after 9-ethyl-3,6-di(2-thienyl)carbazole was completely dissolved. At the end of the reaction was judged by TLC analysis after 4 h. The solution was dissolved in 100 ml CH2Cl2, then washed with water (3× 200 ml), dried over anhydrous MgSO4. The organic layer was concentrated in vacuum, the orange suspended solution was decanted out of the flask after 3 ml ethanol was added, green crystals were obtained (0.14 g, yield 54%).

Refinement

All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97Å and Uiso(H) = 1.2–1.5 Ueq(C). At the end of the refinement, the highest peak in the electron–density map was 0.93Å from I2 and the deepest hole was 0.73 Å from I2.

Figures

Fig. 1.
The molecular structure of the title compound withb the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The H atoms are presented as a small spheres of arbitrary radius.
Fig. 2.
The packing diagram of the title compound. Dashed lines indicate a centrosymmetric dimer C17—H17···I1i. Symmetry code: (i) -x, 3-y, 2-z). H atoms not involved in hydrogen bonds are omitted for clarity.

Crystal data

C22H15I2NS2F(000) = 1168
Mr = 611.29Dx = 1.917 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 7193 reflections
a = 10.637 (3) Åθ = 2.4–27.4°
b = 7.814 (2) ŵ = 3.17 mm1
c = 26.687 (7) ÅT = 298 K
β = 107.313 (18)°Prism, green
V = 2117.7 (10) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3738 independent reflections
Radiation source: fine-focus sealed tube3065 reflections with I > 2σ(I)
graphiteRint = 0.022
[var phi]– and ω–scansθmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.449, Tmax = 0.742k = −9→9
17471 measured reflectionsl = −31→30

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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 1.16w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
3738 reflections(Δ/σ)max = 0.002
245 parametersΔρmax = 1.08 e Å3
0 restraintsΔρmin = −0.79 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
I10.25459 (4)1.46648 (5)1.073693 (15)0.0711 (2)
I2−0.70485 (4)0.47106 (5)0.685869 (19)0.0818 (2)
S10.28672 (13)1.0941 (2)1.02087 (5)0.0797 (5)
S2−0.39715 (12)0.45973 (15)0.75996 (5)0.0589 (3)
N10.2462 (4)0.3710 (7)0.87990 (17)0.0768 (13)
C10.3499 (4)0.6105 (8)0.94135 (18)0.0651 (13)
H10.43370.56260.95230.078*
C20.3241 (4)0.7652 (8)0.96071 (18)0.0631 (12)
H20.39250.82280.98470.076*
C30.1979 (4)0.8397 (7)0.94558 (16)0.0550 (11)
C40.0960 (4)0.7564 (6)0.90838 (16)0.0532 (10)
H40.01250.80500.89740.064*
C5−0.0883 (5)0.4929 (6)0.81521 (18)0.0513 (11)
H5−0.14400.58160.81820.062*
C6−0.1344 (4)0.3655 (6)0.77807 (17)0.0543 (11)
C7−0.0498 (5)0.2311 (7)0.7748 (2)0.0721 (14)
H7−0.08120.14500.75020.087*
C80.0776 (5)0.2224 (8)0.8067 (2)0.0792 (16)
H80.13260.13320.80350.095*
C90.1219 (5)0.3487 (7)0.8434 (2)0.0674 (13)
C100.0396 (5)0.4886 (6)0.84774 (19)0.0526 (11)
C110.1197 (4)0.6004 (6)0.88770 (16)0.0504 (10)
C120.2465 (5)0.5279 (7)0.9049 (2)0.0612 (13)
C130.3602 (6)0.2581 (11)0.8866 (3)0.101 (2)
H13A0.42070.27050.92170.121*
H13B0.33180.13970.88170.121*
C140.4210 (8)0.3038 (11)0.8499 (3)0.120 (3)
H14A0.43960.42430.85250.180*
H14B0.36410.27810.81540.180*
H14C0.50180.24110.85600.180*
C150.1743 (5)1.0054 (6)0.96736 (18)0.0521 (11)
C160.0690 (6)1.1130 (8)0.9511 (3)0.0900 (19)
H16−0.00441.08890.92270.108*
C170.0809 (6)1.2599 (9)0.9803 (3)0.098 (2)
H170.01651.34450.97320.117*
C180.1926 (4)1.2712 (6)1.01974 (17)0.0570 (11)
C19−0.2682 (4)0.3707 (6)0.74207 (17)0.0520 (10)
C20−0.3136 (5)0.3054 (7)0.69241 (19)0.0640 (13)
H20−0.25920.25280.67540.077*
C21−0.4518 (5)0.3255 (7)0.6691 (2)0.0672 (13)
H21−0.49720.28720.63560.081*
C22−0.5089 (4)0.4058 (6)0.7009 (2)0.0599 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.0604 (3)0.0777 (3)0.0697 (3)0.00741 (16)0.0107 (2)−0.00697 (16)
I20.0464 (3)0.0720 (3)0.1149 (4)0.00143 (15)0.0054 (2)−0.02046 (19)
S10.0533 (8)0.1005 (10)0.0672 (8)0.0256 (8)−0.0095 (6)−0.0250 (8)
S20.0444 (7)0.0653 (8)0.0655 (8)0.0031 (5)0.0137 (6)−0.0110 (5)
N10.047 (2)0.089 (3)0.086 (3)0.019 (2)0.007 (2)−0.025 (2)
C10.041 (2)0.091 (4)0.059 (3)0.017 (3)0.007 (2)−0.006 (3)
C20.038 (2)0.093 (4)0.050 (2)0.009 (2)0.0012 (18)−0.001 (2)
C30.041 (2)0.080 (3)0.043 (2)0.007 (2)0.0110 (18)0.003 (2)
C40.041 (2)0.071 (3)0.047 (2)0.004 (2)0.0113 (18)0.005 (2)
C50.040 (2)0.058 (2)0.059 (3)0.0080 (19)0.020 (2)0.005 (2)
C60.044 (2)0.064 (3)0.058 (3)−0.003 (2)0.0201 (19)−0.004 (2)
C70.053 (3)0.073 (3)0.089 (4)0.001 (3)0.020 (3)−0.025 (3)
C80.055 (3)0.081 (4)0.097 (4)0.018 (3)0.016 (3)−0.027 (3)
C90.042 (2)0.080 (3)0.077 (3)0.015 (3)0.012 (2)−0.008 (3)
C100.042 (3)0.060 (2)0.057 (3)0.005 (2)0.018 (2)−0.001 (2)
C110.040 (2)0.068 (3)0.045 (2)0.010 (2)0.0170 (18)0.004 (2)
C120.040 (3)0.081 (3)0.062 (3)0.011 (2)0.013 (2)−0.004 (2)
C130.070 (4)0.129 (6)0.107 (5)0.007 (4)0.032 (4)−0.041 (5)
C140.100 (5)0.111 (6)0.141 (7)−0.020 (5)0.023 (5)−0.026 (5)
C150.038 (2)0.068 (3)0.045 (2)0.004 (2)0.0054 (19)0.0058 (19)
C160.060 (3)0.079 (4)0.101 (4)0.018 (3)−0.023 (3)−0.016 (3)
C170.070 (4)0.077 (4)0.116 (5)0.023 (3)−0.019 (3)−0.015 (4)
C180.044 (2)0.065 (3)0.056 (3)0.004 (2)0.0054 (19)0.004 (2)
C190.043 (2)0.051 (2)0.063 (3)−0.003 (2)0.0174 (19)−0.005 (2)
C200.055 (3)0.076 (3)0.064 (3)−0.004 (3)0.022 (2)−0.017 (2)
C210.053 (3)0.069 (3)0.074 (3)−0.008 (3)0.011 (2)−0.025 (3)
C220.044 (2)0.050 (2)0.080 (3)−0.005 (2)0.010 (2)−0.008 (2)

Geometric parameters (Å, °)

I1—C182.066 (5)C7—C81.371 (7)
I2—C222.066 (5)C7—H70.9300
S1—C181.703 (5)C8—C91.372 (7)
S1—C151.713 (5)C8—H80.9300
S2—C221.720 (5)C9—C101.427 (7)
S2—C191.727 (4)C10—C111.444 (7)
N1—C121.395 (7)C11—C121.408 (6)
N1—C91.400 (6)C13—C141.373 (9)
N1—C131.466 (8)C13—H13A0.9700
C1—C21.374 (8)C13—H13B0.9700
C1—C121.392 (7)C14—H14A0.9600
C1—H10.9300C14—H14B0.9600
C2—C31.407 (6)C14—H14C0.9600
C2—H20.9300C15—C161.364 (7)
C3—C41.394 (6)C16—C171.373 (9)
C3—C151.471 (7)C16—H160.9300
C4—C111.392 (7)C17—C181.336 (7)
C4—H40.9300C17—H170.9300
C5—C101.380 (7)C19—C201.367 (6)
C5—C61.387 (6)C20—C211.425 (7)
C5—H50.9300C20—H200.9300
C6—C71.403 (7)C21—C221.338 (7)
C6—C191.462 (6)C21—H210.9300
C18—S1—C1593.1 (2)C1—C12—C11121.5 (5)
C22—S2—C1992.1 (2)N1—C12—C11109.5 (4)
C12—N1—C9108.0 (4)C14—C13—N1107.7 (7)
C12—N1—C13125.9 (5)C14—C13—H13A110.2
C9—N1—C13125.8 (5)N1—C13—H13A110.2
C2—C1—C12117.8 (4)C14—C13—H13B110.2
C2—C1—H1121.1N1—C13—H13B110.2
C12—C1—H1121.1H13A—C13—H13B108.5
C1—C2—C3122.5 (5)C13—C14—H14A109.5
C1—C2—H2118.8C13—C14—H14B109.5
C3—C2—H2118.8H14A—C14—H14B109.5
C4—C3—C2119.0 (5)C13—C14—H14C109.5
C4—C3—C15120.3 (4)H14A—C14—H14C109.5
C2—C3—C15120.8 (4)H14B—C14—H14C109.5
C11—C4—C3119.8 (4)C16—C15—C3129.6 (5)
C11—C4—H4120.1C16—C15—S1108.6 (4)
C3—C4—H4120.1C3—C15—S1121.8 (3)
C10—C5—C6120.3 (4)C15—C16—C17114.0 (5)
C10—C5—H5119.9C15—C16—H16123.0
C6—C5—H5119.9C17—C16—H16123.0
C5—C6—C7119.0 (4)C18—C17—C16114.4 (5)
C5—C6—C19121.2 (4)C18—C17—H17122.8
C7—C6—C19119.8 (4)C16—C17—H17122.8
C8—C7—C6122.2 (5)C17—C18—S1109.9 (4)
C8—C7—H7118.9C17—C18—I1128.5 (4)
C6—C7—H7118.9S1—C18—I1121.6 (2)
C7—C8—C9118.2 (5)C20—C19—C6128.3 (4)
C7—C8—H8120.9C20—C19—S2109.8 (3)
C9—C8—H8120.9C6—C19—S2121.9 (3)
C8—C9—N1129.7 (5)C19—C20—C21113.7 (4)
C8—C9—C10121.4 (5)C19—C20—H20123.1
N1—C9—C10108.9 (4)C21—C20—H20123.1
C5—C10—C9118.8 (4)C22—C21—C20112.2 (4)
C5—C10—C11134.8 (4)C22—C21—H21123.9
C9—C10—C11106.4 (4)C20—C21—H21123.9
C4—C11—C12119.5 (4)C21—C22—S2112.1 (4)
C4—C11—C10133.3 (4)C21—C22—I2127.9 (4)
C12—C11—C10107.1 (4)S2—C22—I2120.0 (3)
C1—C12—N1129.1 (4)
C12—C1—C2—C31.0 (8)C13—N1—C12—C11178.7 (6)
C1—C2—C3—C4−2.0 (8)C4—C11—C12—C1−1.4 (7)
C1—C2—C3—C15179.8 (5)C10—C11—C12—C1176.1 (5)
C2—C3—C4—C111.3 (7)C4—C11—C12—N1178.6 (4)
C15—C3—C4—C11179.5 (4)C10—C11—C12—N1−3.9 (6)
C10—C5—C6—C71.2 (7)C12—N1—C13—C14−90.0 (8)
C10—C5—C6—C19−178.0 (4)C9—N1—C13—C1483.0 (9)
C5—C6—C7—C8−0.9 (8)C4—C3—C15—C16−12.0 (8)
C19—C6—C7—C8178.3 (5)C2—C3—C15—C16166.2 (6)
C6—C7—C8—C91.2 (9)C4—C3—C15—S1168.4 (4)
C7—C8—C9—N1−179.2 (6)C2—C3—C15—S1−13.4 (6)
C7—C8—C9—C10−1.7 (9)C18—S1—C15—C16−0.7 (5)
C12—N1—C9—C8174.0 (6)C18—S1—C15—C3179.0 (4)
C13—N1—C9—C80.0 (11)C3—C15—C16—C17−178.9 (6)
C12—N1—C9—C10−3.7 (6)S1—C15—C16—C170.8 (8)
C13—N1—C9—C10−177.7 (6)C15—C16—C17—C18−0.5 (10)
C6—C5—C10—C9−1.8 (7)C16—C17—C18—S10.0 (8)
C6—C5—C10—C11176.5 (5)C16—C17—C18—I1179.7 (5)
C8—C9—C10—C52.1 (8)C15—S1—C18—C170.4 (5)
N1—C9—C10—C5180.0 (5)C15—S1—C18—I1−179.4 (3)
C8—C9—C10—C11−176.6 (5)C5—C6—C19—C20151.0 (5)
N1—C9—C10—C111.3 (6)C7—C6—C19—C20−28.1 (8)
C3—C4—C11—C120.4 (7)C5—C6—C19—S2−31.6 (6)
C3—C4—C11—C10−176.4 (5)C7—C6—C19—S2149.2 (4)
C5—C10—C11—C40.2 (9)C22—S2—C19—C200.6 (4)
C9—C10—C11—C4178.5 (5)C22—S2—C19—C6−177.3 (4)
C5—C10—C11—C12−176.8 (5)C6—C19—C20—C21177.0 (5)
C9—C10—C11—C121.5 (5)S2—C19—C20—C21−0.6 (6)
C2—C1—C12—N1−179.3 (5)C19—C20—C21—C220.4 (7)
C2—C1—C12—C110.7 (8)C20—C21—C22—S20.1 (6)
C9—N1—C12—C1−175.2 (6)C20—C21—C22—I2178.7 (4)
C13—N1—C12—C1−1.2 (10)C19—S2—C22—C21−0.4 (4)
C9—N1—C12—C114.7 (7)C19—S2—C22—I2−179.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C17—H17···I1i0.933.154.040 (9)161

Symmetry codes: (i) −x, −y+3, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2188).

References

  • Bruker (2002). SMART, SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, L., Cheng, W., Song, G.-L. & Zhu, H.-J. (2009). Acta Cryst. E65, o574. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Goumlttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yang, J. X., Tao, X. T., Yuan, C. X., Yan, Y. X., Wang, L., Liu, Zh., Ren, Y. & Jiang, M. H. (2005). J. Am. Chem. Soc.127, 3278–3279. [PubMed]
  • Zhou, H. P., Lv, L. F., Wang, P. & Hu, R. T. (2008). Acta Cryst. E64, o1075. [PMC free article] [PubMed]
  • Zhou, H. P., Wang, P., Hu, Z. J., Li, L., Chen, J. J., Cui, Y., Tian, Y. P., Wu, J. Y., Yang, J. X., Tao, X. T. & Jiang, M. H. (2007). Eur. J. Inorg. Chem.13, 1854–1866.

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