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The mol­ecules of the title compound, C34H24N2S4, lie across centres of inversion in the space group P21/n. The spacer unit linking the benzene rings and carbazole units is effectively planar, while the carbazole unit itself is slightly folded. Mol­ecules are linked into sheets by a single C—H...π(arene) hydrogen bond and the hydrogen-bonded sheets are themselves linked into a three-dimensional framework structure by a single π–π stacking inter­action.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110053102/gg3251sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110053102/gg3251Isup2.hkl
Contains datablock I

CCDC reference: 817050

Comment top

Xanthate derivatives are versatile reagents for reversible addition–fragmentation chain transfer (RAFT) polymerization, capable of directing formation of a range of well controlled polymer architectures (Perrier et al., 2004; Wan et al., 2007), and we report here the structure of the title compound, (I) (Fig. 1), which was synthesized for use in such applications.

The molecules of (I) lie across inversion centres in the space group P21/n, with the reference molecule selected as that lying across (1/2, 1/2, 1/2) (Fig. 1). The carbazole unit deviates slightly from planarity, with dihedral angles between the central five-membered ring on the one hand, and, on the other hand, the outer rings containing atoms C1 and C8, respectively, of 4.9 (2) and 0.5 (2)°, while the dihedral angle between the two six-membered rings in this unit is 4.7 (2)°. This asymmetric folding may be contrasted with that observed in carbazole itself [Cambridge Structural Database (CSD; Allen, 2002) refcode CRBZOL04; Gerkin & Reppart, 1986], where the molecules lie across mirror planes in the space group Pnma, adopting a butterfly-type conformation with a dihedral angle of 2.5 (2)° between the two symmetry-related parts of the molecule. On the other hand, asymmetric folding has been reported in both N-methylcarbazole (CSD refcode NMCABZ; Popova & Chetkina, 1979) and in N-vinylcarbazole [CSD refcodes VINCBZ (Tsutsui et al., 1976) and VINCBZ01 (Tian et al., 2006)], in both of which Z' = 2. The spacer unit linking the carbazole and aryl ring systems, i.e. between atoms N9 and C21 (Fig. 1), adopts an effectively planar all-trans conformation: the maximum deviations from the mean plane through atoms N9/C10/S10/S11/C11/C21 are 0.037 (1) Å for atom S11 and 0.024 (3) Å for atom C11, to opposite sides of the mean plane. The overall molecular conformation can then be specified in terms of just two dihedral angles, those between the plane of the linker unit on the one hand, and the two ring systems on the other: for the aryl ring, this dihedral angle is 65.0 (2)°, while the corresponding value for the central ring of the carbazole unit is 29.0 (2)°.

The pattern of the bond distances in the carbazole unit (Table 1) is reminiscent of that in carbazole itself. Specifically, the bonds labelled here as C1—C2, C3—C4, C5—C6 and C7—C8 are the shortest bonds in the six-membered rings, while the bond C4A—C4B is the longest C—C bond in the carbazole unit; however, the two independent C—N bonds are longer than the corresponding bonds in carbazole. Overall the distances indicate that there is effectively no peripheral electronic delocalization. The C10—S10 bond is short for its type (Allen et al., 1987), while N9—C10 is long for its type, possibly indicative of rather little delocalization of the lone pair at N9 into the CS double bond as a consequence of the relative orientation of the carbazole and spacer units.

The centrosymmetric molecules of (I) are linked by a combination of C—H···π(arene) hydrogen bonds and ππ stacking interactions to form a three-dimensional framework structure, whose formation is readily analysed in terms of the substructures (Ferguson et al., 1998a,b; Gregson et al., 2000) formed by the two types of interaction.

A single C—H···π(arene) hydrogen bond (Table 2) links the reference molecule directly to four other molecules: thus the reference molecule centred at (1/2, 1/2, 1/2) acts as a hydrogen-bond donor to the two molecules centred at (0, 0, 0) and (1, 1, 1) and it acts as an acceptor of hydrogen bonds from the two molecules centred at (0, 1, 0) and (1, 0, 1). In this manner, the C—H···π(arene) hydrogen bond links the molecules into a sheet lying parallel to (101) (Fig. 2). The molecules of (I) are also weakly linked into chains by a ππ stacking interaction between the carbazole units of adjacent molecules. The aryl ring containing atom C4A in the reference molecule centred at (1/2, 1/2, 1/2) makes a dihedral angle of 4.7 (2)° with the aryl ring containing atom C4B at (-x, 2-y, 1-z) and forming part of the molecule centred at (-0.5, 1.5, 1/2): the ring-centroid separation is 3.872 (2) Å, with a ring-centroid offset of ca 1.32 Å. Propagation by inversion of this interaction generates a chain of π-stacked molecules running parallel to the [110] direction (Fig. 3) and this chain links the hydrogen-bonded sheets into a three-dimensional framework. It is interesting to note that while the central aryl ring acts as a twofold donor of hydrogen bonds, it neither accepts any hydrogen bonds nor participates in any ππ stacking interactions. By contrast, the carbazole unit both accepts a hydrogen bond and participates in the ππ stacking but, despite the large number of C—H bonds present, the carbazole unit does not act as a hydrogen-bond donor.

It is thus of interest briefly to compare the molecular aggregation in compound (I) with that in carbazole. which was not discussed in the original report (Gerkin & Reppart, 1986). While there are neither N—H···π(arene) hydrogen bonds nor aromatic ππ stacking interactions present in the crystal structure of carbazole, symmetry-related pairs of C—H···π(arene) hydrogen bonds link molecules related by a 21 screw axis along [100] into a chain of rings (Bernstein et al., 1995) running parallel to the [100] direction (Fig. 4), so that the mode of supramolecular aggregation in carbazole is very different from that found in compound (I).

Related literature top

For related literature, see: Allen et al. (1987); Ferguson et al. (1998a, 1998b); Gerkin & Reppart (1986); Gregson et al. (2000); Perrier et al. (2004); Popova & Chetkina (1979); Tian et al. (2006); Tsutsui et al. (1976); Wan et al. (2007).

Experimental top

For the synthesis of compound (I), a mixture of KOH (0.02 mol) and 9H-carbazole (0.02 mol) in dimethyl sulfoxide (50 ml) was stirred vigorously at room temperature for 2 h; carbon disulfide (0.02 mol) was then added dropwise over a period of 15 min, and the mixture was stirred for a further 3 h. 1,4-Bis(chloromethyl)benzene (0.01 mol) was added to the resulting mixture, forming a yellow solution. This solution was poured into a large excess of water, and the yellow precipitate which formed was collected by filtration. Recrystallization from a dichloromethane–methanol mixture (1:1 v/v) gave yellow crystals suitable for single-crystal X-ray diffraction (yield 32%, m.p 472–473 K).

Refinement top

All H atoms were located in difference maps, and then treated as riding atoms in geometrically idealized positions with C—H distances of 0.95 (aromatic) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atom-labelling scheme. Atoms marked 'a' are at the symmetry position (-x + 1, -y + 1, -z + 1). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a sheet parallel to (101) and built using a single C—H···π(arene) hydrogen bond. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a π-stacked chain parallel to [110]. For the sake of clarity, all H atoms have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of carbazole, showing the formation of a hydrogen-bonded chain of rings along [100]. The deposited atomic coordinates (CSD refcode CRBZOL04; Gerkin & Reppart, 1986) have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.
1,4-Phenylenebis(methylene) bis(9H-carbazole-9-carbodithioate) top
Crystal data top
C34H24N2S4F(000) = 612
Mr = 588.83Dx = 1.444 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3110 reflections
a = 10.296 (2) Åθ = 2.7–27.5°
b = 10.0793 (19) ŵ = 0.38 mm1
c = 13.137 (2) ÅT = 120 K
β = 96.646 (14)°Needle, colourless
V = 1354.2 (4) Å30.52 × 0.17 × 0.10 mm
Z = 2
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2520 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode1880 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
Detector resolution: 9.091 pixels mm-1θmax = 25.5°, θmin = 2.7°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1212
Tmin = 0.869, Tmax = 0.963l = 1515
15566 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0292P)2 + 1.0522P]
where P = (Fo2 + 2Fc2)/3
2520 reflections(Δ/σ)max = 0.001
181 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C34H24N2S4V = 1354.2 (4) Å3
Mr = 588.83Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.296 (2) ŵ = 0.38 mm1
b = 10.0793 (19) ÅT = 120 K
c = 13.137 (2) Å0.52 × 0.17 × 0.10 mm
β = 96.646 (14)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2520 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1880 reflections with I > 2σ(I)
Tmin = 0.869, Tmax = 0.963Rint = 0.062
15566 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.13Δρmax = 0.25 e Å3
2520 reflectionsΔρmin = 0.30 e Å3
181 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0071 (3)0.8142 (3)0.3388 (2)0.0286 (7)
H10.07560.75330.33080.034*
C20.1208 (3)0.7738 (3)0.3284 (2)0.0358 (8)
H20.14120.68350.31360.043*
C30.2211 (3)0.8627 (4)0.3392 (2)0.0407 (8)
H30.30890.83190.33350.049*
C40.1952 (3)0.9937 (3)0.3579 (2)0.0363 (8)
H40.26441.05450.36360.044*
C4A0.0674 (3)1.0365 (3)0.36824 (19)0.0284 (7)
C4B0.0104 (3)1.1665 (3)0.37977 (19)0.0302 (7)
C50.0658 (3)1.2915 (3)0.3878 (2)0.0391 (8)
H50.15781.30130.38620.047*
C60.0135 (4)1.3989 (3)0.3980 (2)0.0482 (10)
H60.02351.48470.40290.058*
C70.1470 (4)1.3856 (3)0.4014 (2)0.0456 (9)
H70.20061.46240.41100.055*
C80.2047 (3)1.2638 (3)0.3912 (2)0.0369 (8)
H80.29671.25550.39210.044*
C8A0.1239 (3)1.1541 (3)0.37956 (19)0.0281 (7)
N90.1537 (2)1.0175 (2)0.37045 (16)0.0248 (5)
C9A0.0337 (3)0.9463 (3)0.36135 (19)0.0248 (6)
C100.2786 (3)0.9660 (3)0.37496 (19)0.0250 (6)
S100.40383 (8)1.04443 (8)0.33861 (6)0.0349 (2)
S110.29150 (7)0.80717 (7)0.42721 (6)0.0298 (2)
C110.4588 (3)0.7648 (3)0.4178 (2)0.0263 (6)
H11A0.47670.76710.34540.032*
H11B0.51800.82850.45740.032*
C210.4797 (3)0.6278 (3)0.46062 (19)0.0225 (6)
C220.5133 (3)0.5255 (3)0.3993 (2)0.0278 (7)
H220.52270.54230.32940.033*
C230.5334 (3)0.3994 (3)0.4378 (2)0.0276 (7)
H230.55660.33020.39430.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0285 (17)0.0339 (17)0.0226 (14)0.0009 (14)0.0006 (12)0.0006 (13)
C20.036 (2)0.0424 (19)0.0286 (16)0.0085 (15)0.0017 (14)0.0003 (14)
C30.0262 (18)0.066 (2)0.0302 (17)0.0075 (17)0.0063 (13)0.0001 (17)
C40.0313 (19)0.053 (2)0.0251 (15)0.0132 (16)0.0079 (13)0.0026 (15)
C4A0.0327 (18)0.0387 (18)0.0143 (13)0.0072 (14)0.0046 (12)0.0021 (12)
C4B0.0414 (19)0.0347 (18)0.0150 (13)0.0112 (14)0.0048 (13)0.0052 (12)
C50.054 (2)0.040 (2)0.0247 (15)0.0231 (18)0.0128 (14)0.0063 (14)
C60.082 (3)0.031 (2)0.0326 (18)0.022 (2)0.0139 (18)0.0062 (15)
C70.072 (3)0.0261 (18)0.0379 (18)0.0050 (18)0.0036 (18)0.0001 (15)
C80.047 (2)0.0286 (17)0.0334 (17)0.0047 (15)0.0024 (14)0.0034 (14)
C8A0.0413 (19)0.0222 (15)0.0198 (14)0.0052 (13)0.0003 (13)0.0022 (12)
N90.0267 (14)0.0233 (13)0.0240 (12)0.0012 (11)0.0014 (10)0.0011 (10)
C9A0.0260 (16)0.0311 (16)0.0166 (13)0.0004 (13)0.0002 (11)0.0009 (12)
C100.0308 (17)0.0257 (15)0.0183 (13)0.0002 (13)0.0017 (12)0.0004 (12)
S100.0370 (5)0.0305 (4)0.0388 (4)0.0045 (4)0.0119 (3)0.0054 (4)
S110.0241 (4)0.0278 (4)0.0386 (4)0.0034 (3)0.0091 (3)0.0098 (3)
C110.0215 (16)0.0308 (16)0.0270 (15)0.0009 (13)0.0053 (12)0.0005 (13)
C210.0164 (15)0.0291 (16)0.0217 (13)0.0011 (12)0.0018 (11)0.0003 (12)
C220.0332 (17)0.0314 (17)0.0193 (13)0.0032 (14)0.0056 (12)0.0001 (12)
C230.0298 (17)0.0312 (17)0.0220 (14)0.0073 (13)0.0032 (12)0.0040 (12)
Geometric parameters (Å, º) top
C1—C21.371 (4)C4—H40.9500
C2—C31.386 (4)C5—H50.9500
C3—C41.364 (5)C6—H60.9500
C4—C4A1.377 (4)C7—H70.9500
C4A—C4B1.437 (4)C8—H80.9500
C4B—C51.392 (4)N9—C101.381 (3)
C5—C61.353 (5)C10—S101.630 (3)
C6—C71.376 (5)C10—S111.741 (3)
C7—C81.378 (4)S11—C111.793 (3)
C8—C8A1.382 (4)C11—C211.497 (4)
C8A—N91.419 (3)C11—H11A0.9900
N9—C9A1.422 (3)C11—H11B0.9900
C9A—C11.384 (4)C21—C221.377 (4)
C4A—C9A1.393 (4)C21—C23i1.384 (4)
C4B—C8A1.389 (4)C22—C231.375 (4)
C1—H10.9500C22—H220.9500
C2—H20.9500C23—H230.9500
C3—H30.9500
C2—C1—C9A118.1 (3)C8A—C8—H8121.2
C2—C1—H1121.0C8—C8A—C4B120.9 (3)
C9A—C1—H1121.0C8—C8A—N9130.8 (3)
C1—C2—C3121.1 (3)C4B—C8A—N9108.3 (3)
C1—C2—H2119.4C10—N9—C8A124.8 (2)
C3—C2—H2119.4C10—N9—C9A127.6 (2)
C4—C3—C2120.7 (3)C8A—N9—C9A107.6 (2)
C4—C3—H3119.6C1—C9A—C4A120.7 (3)
C2—C3—H3119.6C1—C9A—N9130.7 (3)
C3—C4—C4A119.1 (3)C4A—C9A—N9108.3 (2)
C3—C4—H4120.5N9—C10—S10124.7 (2)
C4A—C4—H4120.5N9—C10—S11112.99 (19)
C4—C4A—C9A120.1 (3)S10—C10—S11122.32 (17)
C4—C4A—C4B132.1 (3)C10—S11—C11102.82 (13)
C9A—C4A—C4B107.6 (3)C21—C11—S11106.91 (19)
C8A—C4B—C5119.9 (3)C21—C11—H11A110.3
C8A—C4B—C4A108.2 (3)S11—C11—H11A110.3
C5—C4B—C4A131.9 (3)C21—C11—H11B110.3
C6—C5—C4B118.9 (3)S11—C11—H11B110.3
C6—C5—H5120.5H11A—C11—H11B108.6
C4B—C5—H5120.5C22—C21—C23i118.3 (3)
C5—C6—C7121.0 (3)C22—C21—C11120.4 (2)
C5—C6—H6119.5C23i—C21—C11121.3 (2)
C7—C6—H6119.5C23—C22—C21121.0 (2)
C6—C7—C8121.6 (3)C23—C22—H22119.5
C6—C7—H7119.2C21—C22—H22119.5
C8—C7—H7119.2C22—C23—C21i120.7 (3)
C7—C8—C8A117.6 (3)C22—C23—H23119.6
C7—C8—H8121.2C21i—C23—H23119.6
C9A—C1—C2—C30.6 (4)C4B—C8A—N9—C9A2.0 (3)
C1—C2—C3—C41.7 (4)C2—C1—C9A—C4A3.1 (4)
C2—C3—C4—C4A1.4 (4)C2—C1—C9A—N9175.8 (3)
C3—C4—C4A—C9A1.0 (4)C4—C4A—C9A—C13.4 (4)
C3—C4—C4A—C4B174.3 (3)C4B—C4A—C9A—C1173.1 (2)
C4—C4A—C4B—C8A175.7 (3)C4—C4A—C9A—N9177.6 (2)
C9A—C4A—C4B—C8A0.1 (3)C4B—C4A—C9A—N91.2 (3)
C4—C4A—C4B—C52.6 (5)C10—N9—C9A—C111.5 (4)
C9A—C4A—C4B—C5178.5 (3)C8A—N9—C9A—C1171.5 (3)
C8A—C4B—C5—C61.7 (4)C10—N9—C9A—C4A175.1 (2)
C4A—C4B—C5—C6179.9 (3)C8A—N9—C9A—C4A2.0 (3)
C4B—C5—C6—C70.6 (5)C8A—N9—C10—S1030.1 (4)
C5—C6—C7—C82.2 (5)C9A—N9—C10—S10153.3 (2)
C6—C7—C8—C8A1.4 (5)C8A—N9—C10—S11148.4 (2)
C7—C8—C8A—C4B1.0 (4)C9A—N9—C10—S1128.2 (3)
C7—C8—C8A—N9177.9 (3)N9—C10—S11—C11177.53 (19)
C5—C4B—C8A—C82.5 (4)S10—C10—S11—C113.9 (2)
C4A—C4B—C8A—C8178.9 (2)C10—S11—C11—C21179.58 (18)
C5—C4B—C8A—N9179.9 (2)S11—C11—C21—C22117.4 (3)
C4A—C4B—C8A—N91.3 (3)S11—C11—C21—C23i63.0 (3)
C8—C8A—N9—C102.1 (4)C23i—C21—C22—C230.0 (5)
C4B—C8A—N9—C10175.1 (2)C11—C21—C22—C23179.6 (3)
C8—C8A—N9—C9A179.3 (3)C21—C22—C23—C21i0.0 (5)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C22—H22···Cgii0.952.893.666 (3)140
Symmetry code: (ii) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC34H24N2S4
Mr588.83
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)10.296 (2), 10.0793 (19), 13.137 (2)
β (°) 96.646 (14)
V3)1354.2 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.52 × 0.17 × 0.10
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.869, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
15566, 2520, 1880
Rint0.062
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.099, 1.13
No. of reflections2520
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.30

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
C1—C21.371 (4)C8A—N91.419 (3)
C2—C31.386 (4)N9—C9A1.422 (3)
C3—C41.364 (5)C9A—C11.384 (4)
C4—C4A1.377 (4)C4A—C9A1.393 (4)
C4A—C4B1.437 (4)C4B—C8A1.389 (4)
C4B—C51.392 (4)N9—C101.381 (3)
C5—C61.353 (5)C10—S101.630 (3)
C6—C71.376 (5)C10—S111.741 (3)
C7—C81.378 (4)S11—C111.793 (3)
C8—C8A1.382 (4)C11—C211.497 (4)
C9A—N9—C10—S1128.2 (3)C10—S11—C11—C21179.58 (18)
N9—C10—S11—C11177.53 (19)S11—C11—C21—C22117.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C22—H22···Cgi0.952.893.666 (3)140
Symmetry code: (i) x+1/2, y1/2, z+1/2.
 

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