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Acta Cryst. (2013). E69, o771    [ doi:10.1107/S1600536813010349 ]

9H-Carbazole-9-carbothioic dithioperoxyanhydride

N. Uludag, M. Ates, N. Çaylak Delibas, Ö. Çelik and T. Hökelek

Abstract top

The whole molecule of the title compound, C26H16N2S4, is generated by twofold rotational symmetry. The carbazole skeleton is nearly planar [maximum deviation = 0.054 (5) Å]. In the crystal, aromatic [pi]-[pi] stacking is observed between parallel carbazole ring systems of adjacent molecules, the shortest centroid-centroid distances between pyrrole and benzene rings being 3.948 (3) and 3.751 (3) Å.

Comment top

Tetrahydrocarbazole systems are present in the framework of a number of indole-type alkaloids of biological interest (Saxton, 1983). The structures of tricyclic, tetracyclic and pentacyclic ring systems with dithiolane and other substituents of the tetrahydrocarbazole core, have been reported previously (Hökelek et al., 1994; Patır et al., 1997; Hökelek et al., 1998; Hökelek et al., 1999; Hökelek & Patır, 1999). Substituted carbazole based monomers exhibit good electroactive and photoactive properties which make them the most promising candidates for hole transporting mobility of charge carriers (Cloutet et al., 1999) and photoluminescence efficiencies (Zhenhong et al., 2006). Carbazole based heterocyclic polymer systems can be chemically or electrochemically polymerized to yield materials with interesting properties with a number of applications, such as electroluminescent (Tirapattur et al., 2003), photoactive devices (Taoudi et al., 2001), sensors and rechargable batteries (Saraswathi et al., 1999) and electrochromic displays (Sarac et al., 2000). The title compound, (I), may be considered as a synthetic precursor of tetracyclic indole alkaloids of biological interests. The present study was undertaken to ascertain its crystal structure.

The asymmetric unit of the title compound contains one half of the molecule, the whole molecule being generated by two-fold rotational symmetry (Fig. 1). It consists of a carbazole skeleton with a dithioperoxyanhydride group , where the bond lengths and angles are within normal ranges, and generally agree with those in the previously reported compounds (Hökelek et al., 1994; Patır et al., 1997; Hökelek et al., 1998; Hökelek et al., 1999; Hökelek & Patır, 1999) in all of which atom N9 is substituted.

An examination of the deviations from the mean planes through individual rings shows that rings A (C1-C4/C4a/C9a), B (C4a/C5a/C8a/N9/C9a) and C (C5a/C5-C8/C8a) are planar [symmetry code: (a) x, -y+1, -z]. The carbazole skeleton, containing rings A, B and C is also nearly coplanar [maximum deviation of -0.054 (5) Å for atom C8] with dihedral angles of A/B = 3.80 (15), A/C = 3.74 (17) and B/C = 3.21 (16) °. Atoms S1, S2 and C10 are displaced by 1.4738 (13), -0.5052 (15) and 0.2107 (42) Å from the mean plane of the carbazole skeleton.

In the crystal, molecules are stacked nearly parallel to (110) [Fig. 2]. The ππ contacts between the pyrrole and benzene rings, Cg1—Cg2i and Cg1···Cg3ii [symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z; where Cg1, Cg2 and Cg3 are centroids of the rings A (C1-C4/C4a/C9a), B (C4a/C5a/C8a/N9/C9a) and C (C5a/C5-C8/C8a), respectively] may stabilize the structure, with centroid-centroid distances of 3.948 (3) and 3.751 (3) Å, respectively.

Related literature top

For tetrahydrocarbazole systems present in the framework of a number of indole-type alkaloids of biological interest, see: Saxton (1983). For related structures, see: Hökelek et al. (1994, 1998, 1999); Patır et al. (1997); Hökelek & Patır (1999). For hole-transporting mobility of charge carriers, see: Cloutet et al. (1999). For photoluminescence efficiencies, see: Zhenhong et al. (2006). For electroluminescent applications, see: Tirapattur et al. (2003). For photoactive devices, see: Taoudi et al. (2001). For sensors and rechargable batteries, see: Saraswathi et al. (1999). For electrochromic displays, see: Sarac et al. (2000).

Experimental top

Carbazole (0.80 g, 5 mmol) was added to a suspension of KOH (0.28 g, 20 mmol) in DMSO (20 ml) under vigorous stirring. The reaction mixture was stirred overnight at room temperature under O2. Carbon disulfide (0.40 g, 5 mmol) was added drop wise, and then the mixture stirred for 10 h at room temperature. The resultant reaction mixture was poured into a large amount of deionized water. The solid obtained was filtered and purified by recrystallization from diethyl ether [yield: 1.30 g, 50%], yielding rod-shaped orange crystals.

Refinement top

The C-bound H-atoms were positioned geometrically and treated as riding atoms: C—H = 0.93 Å with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with atom numbering [symmetry code: (a) x, -y+1, -z]. Displacement ellipsoids are drawn at the 50% probability level
[Figure 2] Fig. 2. A view along the c-axis of the crystal packing of the title compound (a-axis horizontal; b-axis vertical). Hydrogen atoms have been omitted for clarity.
9H-Carbazole-9-carbothioic dithioperoxyanhydride top
Crystal data top
C26H16N2S4F(000) = 500
Mr = 484.69Dx = 1.514 Mg m3
Orthorhombic, P22121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2bc 2Cell parameters from 2694 reflections
a = 3.9207 (2) Åθ = 6.2–28.7°
b = 14.9355 (4) ŵ = 0.47 mm1
c = 18.1494 (5) ÅT = 294 K
V = 1062.79 (7) Å3Rod, orange
Z = 20.35 × 0.15 × 0.10 mm
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
4100 independent reflections
Radiation source: fine-focus sealed tube2471 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 35.1°, θmin = 6.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 66
Tmin = 0.920, Tmax = 0.954k = 2310
5384 measured reflectionsl = 2718
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)] = 0.072H-atom parameters constrained
wR(F2) = 0.156 w = 1/[σ2(Fo2) + (0.P)2 + 0.892P]
where P = (Fo2 + 2Fc2)/3
S = 1.41(Δ/σ)max < 0.001
4100 reflectionsΔρmax = 0.35 e Å3
145 parametersΔρmin = 0.47 e Å3
0 restraintsAbsolute structure: Flack (1983), 1548 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (18)
Crystal data top
C26H16N2S4V = 1062.79 (7) Å3
Mr = 484.69Z = 2
Orthorhombic, P22121Mo Kα radiation
a = 3.9207 (2) ŵ = 0.47 mm1
b = 14.9355 (4) ÅT = 294 K
c = 18.1494 (5) Å0.35 × 0.15 × 0.10 mm
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
4100 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
2471 reflections with I > 2σ(I)
Tmin = 0.920, Tmax = 0.954Rint = 0.036
5384 measured reflectionsθmax = 35.1°
Refinement top
R[F2 > 2σ(F2)] = 0.072H-atom parameters constrained
wR(F2) = 0.156Δρmax = 0.35 e Å3
S = 1.41Δρmin = 0.47 e Å3
4100 reflectionsAbsolute structure: Flack (1983), 1548 Friedel pairs
145 parametersFlack parameter: 0.04 (18)
0 restraints
Special details top

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.

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 > 2sigma(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
S10.3301 (3)0.43540 (7)0.01656 (7)0.0393 (3)
S20.0207 (4)0.53764 (7)0.14312 (8)0.0452 (3)
C10.0287 (13)0.2527 (3)0.0425 (3)0.0379 (10)
H10.09160.29580.00820.046*
C20.0674 (12)0.1620 (3)0.0281 (3)0.0446 (12)
H20.15450.14400.01720.054*
C30.0206 (17)0.0976 (3)0.0796 (3)0.0511 (13)
H30.00770.03740.06830.061*
C40.1490 (13)0.1216 (3)0.1470 (3)0.0466 (12)
H40.20480.07810.18170.056*
C4A0.1946 (11)0.2119 (3)0.1629 (2)0.0335 (10)
C50.4408 (13)0.2274 (3)0.2947 (3)0.0437 (12)
H50.46600.16640.30340.052*
C5A0.3077 (12)0.2574 (3)0.2285 (2)0.0337 (10)
C60.5352 (14)0.2884 (3)0.3473 (3)0.0489 (13)
H60.62410.26860.39200.059*
C70.4988 (16)0.3796 (3)0.3344 (3)0.0493 (13)
H70.56210.42000.37090.059*
C80.3715 (13)0.4114 (3)0.2690 (3)0.0436 (12)
H80.35020.47260.26060.052*
C8A0.2759 (11)0.3501 (3)0.2160 (2)0.0313 (9)
N90.1597 (9)0.3628 (2)0.1418 (2)0.0331 (8)
C9A0.1079 (10)0.2763 (3)0.1103 (3)0.0306 (10)
C100.1482 (11)0.4442 (3)0.1066 (2)0.0316 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0498 (6)0.0332 (5)0.0351 (6)0.0087 (5)0.0081 (6)0.0058 (5)
S20.0588 (7)0.0339 (5)0.0428 (7)0.0065 (6)0.0051 (7)0.0033 (5)
C10.042 (2)0.035 (2)0.037 (3)0.001 (2)0.004 (2)0.0022 (19)
C20.050 (3)0.042 (2)0.042 (3)0.002 (2)0.008 (2)0.007 (2)
C30.070 (4)0.031 (2)0.052 (3)0.001 (3)0.003 (3)0.002 (2)
C40.060 (3)0.032 (2)0.048 (3)0.003 (2)0.004 (3)0.009 (2)
C4A0.033 (2)0.036 (2)0.032 (3)0.0024 (18)0.003 (2)0.0052 (18)
C50.045 (3)0.047 (3)0.038 (3)0.002 (2)0.001 (2)0.010 (2)
C5A0.032 (2)0.039 (2)0.029 (3)0.0000 (19)0.003 (2)0.0060 (19)
C60.048 (3)0.067 (3)0.031 (3)0.004 (3)0.008 (3)0.012 (3)
C70.054 (3)0.060 (3)0.034 (3)0.013 (3)0.003 (3)0.000 (2)
C80.053 (3)0.043 (2)0.035 (3)0.010 (2)0.003 (2)0.001 (2)
C8A0.029 (2)0.038 (2)0.027 (2)0.0021 (17)0.0025 (18)0.0039 (18)
N90.0412 (19)0.0308 (16)0.0272 (19)0.0019 (15)0.002 (2)0.0029 (16)
C9A0.032 (2)0.0288 (19)0.031 (2)0.0005 (15)0.0008 (18)0.0013 (18)
C100.031 (2)0.033 (2)0.031 (2)0.0012 (17)0.0003 (19)0.0034 (18)
Geometric parameters (Å, º) top
S1—S1i2.021 (2)C5—H50.9300
S1—C101.787 (4)C5A—C4A1.441 (6)
S2—C101.624 (4)C5A—C51.384 (6)
C1—C9A1.387 (6)C5A—C8A1.409 (6)
C1—H10.9300C6—H60.9300
C2—C11.388 (6)C7—C61.390 (7)
C2—C31.384 (7)C7—C81.373 (7)
C2—H20.9300C7—H70.9300
C3—H30.9300C8—H80.9300
C4—C31.371 (7)C8A—C81.380 (6)
C4—H40.9300N9—C8A1.433 (6)
C4A—C41.391 (6)N9—C9A1.428 (5)
C4A—C9A1.397 (6)N9—C101.375 (5)
C5—C61.370 (7)
C10—S1—S1i101.63 (15)C5—C6—C7120.4 (5)
C2—C1—H1121.4C5—C6—H6119.8
C9A—C1—C2117.2 (4)C7—C6—H6119.8
C9A—C1—H1121.4C6—C7—H7119.2
C1—C2—H2119.2C8—C7—C6121.5 (5)
C3—C2—C1121.6 (5)C8—C7—H7119.2
C3—C2—H2119.2C7—C8—C8A118.2 (5)
C2—C3—H3119.6C7—C8—H8120.9
C4—C3—C2120.9 (4)C8A—C8—H8120.9
C4—C3—H3119.6C5A—C8A—N9108.1 (4)
C3—C4—C4A119.0 (4)C8—C8A—N9130.8 (4)
C3—C4—H4120.5C8—C8A—C5A121.0 (4)
C4A—C4—H4120.5C9A—N9—C8A107.5 (3)
C4—C4A—C5A131.9 (4)C10—N9—C8A124.4 (3)
C4—C4A—C9A119.7 (4)C10—N9—C9A127.5 (4)
C9A—C4A—C5A108.3 (4)C1—C9A—N9129.8 (4)
C5A—C5—H5120.3C1—C9A—C4A121.7 (4)
C6—C5—C5A119.5 (4)C4A—C9A—N9108.4 (4)
C6—C5—H5120.3S2—C10—S1124.0 (2)
C5—C5A—C4A132.9 (4)N9—C10—S1110.3 (3)
C5—C5A—C8A119.4 (4)N9—C10—S2125.4 (3)
C8A—C5A—C4A107.6 (4)
S1i—S1—C10—S21.3 (3)C4A—C5A—C8A—N92.8 (5)
S1i—S1—C10—N9173.6 (3)C4A—C5A—C8A—C8178.8 (4)
C2—C1—C9A—C4A1.7 (7)C5—C5A—C8A—N9175.2 (4)
C2—C1—C9A—N9176.2 (5)C5—C5A—C8A—C80.8 (7)
C3—C2—C1—C9A1.1 (7)C8—C7—C6—C50.6 (9)
C1—C2—C3—C40.2 (9)C6—C7—C8—C8A0.7 (8)
C4A—C4—C3—C20.9 (9)N9—C8A—C8—C7175.0 (5)
C5A—C4A—C4—C3176.9 (5)C5A—C8A—C8—C70.0 (7)
C9A—C4A—C4—C30.3 (7)C9A—N9—C8A—C5A2.3 (5)
C4—C4A—C9A—C11.1 (7)C9A—N9—C8A—C8177.8 (5)
C4—C4A—C9A—N9176.6 (4)C10—N9—C8A—C5A169.8 (4)
C5A—C4A—C9A—C1176.3 (4)C10—N9—C8A—C85.7 (7)
C5A—C4A—C9A—N90.8 (5)C8A—N9—C9A—C1174.1 (4)
C5A—C5—C6—C70.2 (8)C8A—N9—C9A—C4A0.9 (5)
C5—C5A—C4A—C47.6 (10)C10—N9—C9A—C114.1 (7)
C5—C5A—C4A—C9A175.4 (5)C10—N9—C9A—C4A170.9 (4)
C8A—C5A—C4A—C4174.7 (5)C8A—N9—C10—S1132.7 (4)
C8A—C5A—C4A—C9A2.2 (5)C8A—N9—C10—S242.1 (6)
C4A—C5A—C5—C6178.3 (5)C9A—N9—C10—S137.7 (5)
C8A—C5A—C5—C60.9 (7)C9A—N9—C10—S2147.4 (4)
Symmetry code: (i) x, y+1, z.
Acknowledgements top

The authors are indebted to Dicle University Scientific and Technological Applied and Research Center, Diyarbakır, Turkey, for use of the X-ray diffractometer.

references
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