5-(4-Methyl­phenyl­sulfon­yl)-1,3-dithiolo[4,5-c]pyrrole-2-thione

Abstract

The asymmetric unit of the title compound, C₁₂H₉NO₂S₄, contains one half-mol­ecule with the N, two S amd four C atoms lying on a mirror plane. The mol­ecule exhibits a V-shaped conformation, with a dihedral angle of 87.00 (7)° between the benzene and dithiol­opyrrole rings. The methyl group was treated as rotationally disordered between two orientations in a 1:1 ratio. In the crystal, weak C—H⋯O hydrogen bonds link the mol­ecules into chains in [010].

Related literature  

For background to the applications and synthesis of pyrrolo-annulated tetra­thia­fulvalenes, see: Becher et al. (2004 ▶); Hou et al. (2010 ▶). For a related structure, see: Hou et al. (2009 ▶). For details of the synthesis, see: Jeppesen et al.(2000 ▶).

Experimental  

Crystal data  

• C₁₂H₉NO₂S₄

• M _r = 327.44

• Monoclinic,

• a = 15.687 (10) Å

• b = 10.485 (9) Å

• c = 8.255 (4) Å

• β = 96.19 (3)°

• V = 1349.9 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 0.70 mm⁻¹

• T = 290 K

• 0.46 × 0.43 × 0.40 mm

Data collection  

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.740, T _max = 0.770

• 6671 measured reflections

• 1633 independent reflections

• 1467 reflections with I > 2σ(I)

• R _int = 0.020

Refinement  

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.094

• S = 1.19

• 1633 reflections

• 99 parameters

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812009622/cv5254Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1i	0.93	2.33	3.243 (3)	166

Symmetry code: (i) .

supplementary crystallographic information

Comment

Pyrrolo-annulated tetrathiafulvalenes, an important class of electron-donors, are versatile building blocks in supramolecular and materials chemistry (Becher et al., 2004). As a key precursor to the pyrrolo-annulated tetrathiafulvalenes, 5-Tosyl-5H-[1,3]dithiolo[4,5-c]pyrrole-2-thione, has attracted great attention (Hou et al., 2010). In this paper, we report the crystal structure of the title compound (I).

The asymmetric unit of (I) contains a half of the molecule situated on a mirror plane (Fig. 1). All bond lengths and angles are in the normal ranges and comparable with the reported ones (Hou et al. 2009). Atom N1 has a flattened pyramidal environment with the sum of bond angles of 356.9 (2) °. The benzene ring and dithiolopyrrole ring form a dihedral angle of 87.00 (7) °. In the crystal, the intermolecular C—H···O hydrogen bonds link the molecules into chains along b direction.

Experimental

The title compound was prepared according to the literature (Jeppesen et al., 2000). Single crystals suitable for X-ray diffraction were prepared by slow evaporation a mixture of dichloromethane and petroleum (60–90 °C) at room temperature.

Refinement

C-bound H-atoms were placed in calculated positions (C—H 0.93 and 0.96 Å) and were included in the refinement in the riding model with U_iso(H) = 1.2 or 1.5 U_eq(C). The methyl group was treated as rotationally disordered between two orientations in a ratio 1:1.

Figures

Fig. 1.

The molecular structure of (I) with the atom numbering. Displacement ellipsoids are drawn at the 30% probalility level [symmetry code (A): x, -y, z].

Crystal data

C12H9NO2S4	F(000) = 672
Mr = 327.44	Dx = 1.611 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 6182 reflections
a = 15.687 (10) Å	θ = 3.3–27.5°
b = 10.485 (9) Å	µ = 0.70 mm−1
c = 8.255 (4) Å	T = 290 K
β = 96.19 (3)°	Block, yellow
V = 1349.9 (16) Å3	0.46 × 0.43 × 0.40 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	1633 independent reflections
Radiation source: fine-focus sealed tube	1467 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −20→16
Tmin = 0.740, Tmax = 0.770	k = −13→13
6671 measured reflections	l = −10→10

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.053P)2 + 0.4647P] where P = (Fo2 + 2Fc2)/3
S = 1.19	(Δ/σ)max = 0.012
1633 reflections	Δρmax = 0.31 e Å−3
99 parameters	Δρmin = −0.31 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0106 (12)

Special details

Experimental. (See detailed section in the paper)

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.40151 (14)	0.0000	0.3618 (3)	0.0381 (5)
C2	0.33159 (9)	0.06779 (14)	0.61983 (17)	0.0328 (3)
C3	0.29981 (10)	0.10896 (15)	0.75702 (18)	0.0360 (3)
H3	0.2918	0.1931	0.7875	0.043*
C4	0.11420 (15)	0.0000	0.8848 (2)	0.0352 (4)
C5	0.07509 (12)	0.11519 (17)	0.8411 (2)	0.0451 (4)
H5	0.1013	0.1919	0.8736	0.054*
C6	−0.00330 (12)	0.1139 (2)	0.7486 (2)	0.0509 (4)
H6	−0.0298	0.1908	0.7179	0.061*
C7	−0.04379 (16)	0.0000	0.7000 (3)	0.0472 (6)
C8	−0.12828 (19)	0.0000	0.5964 (3)	0.0635 (8)
H8A	−0.1210	−0.0344	0.4910	0.095*	0.50
H8B	−0.1495	0.0858	0.5846	0.095*	0.50
H8C	−0.1685	−0.0514	0.6473	0.095*	0.50
N1	0.28154 (13)	0.0000	0.8431 (2)	0.0356 (4)
O1	0.23189 (8)	0.11804 (11)	1.07477 (13)	0.0442 (3)
S1	0.21652 (4)	0.0000	0.99190 (6)	0.03409 (18)
S2	0.37336 (3)	0.14002 (4)	0.45643 (5)	0.04288 (17)
S3	0.45063 (5)	0.0000	0.19690 (8)	0.0555 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0321 (10)	0.0470 (13)	0.0348 (10)	0.000	0.0025 (8)	0.000
C2	0.0351 (7)	0.0290 (8)	0.0338 (7)	−0.0026 (6)	0.0018 (5)	0.0010 (6)
C3	0.0459 (9)	0.0255 (7)	0.0369 (8)	−0.0028 (6)	0.0061 (6)	−0.0007 (6)
C4	0.0448 (12)	0.0348 (11)	0.0273 (9)	0.000	0.0094 (8)	0.000
C5	0.0565 (10)	0.0380 (9)	0.0412 (9)	0.0012 (7)	0.0069 (7)	0.0031 (7)
C6	0.0521 (10)	0.0540 (11)	0.0472 (10)	0.0090 (8)	0.0080 (8)	0.0093 (8)
C7	0.0445 (13)	0.0660 (16)	0.0329 (11)	0.000	0.0123 (9)	0.000
C8	0.0496 (16)	0.095 (2)	0.0456 (14)	0.000	0.0063 (11)	0.000
N1	0.0482 (11)	0.0259 (9)	0.0334 (9)	0.000	0.0073 (7)	0.000
O1	0.0641 (8)	0.0342 (6)	0.0340 (6)	−0.0022 (5)	0.0046 (5)	−0.0071 (4)
S1	0.0498 (3)	0.0270 (3)	0.0257 (3)	0.000	0.0050 (2)	0.000
S2	0.0525 (3)	0.0367 (3)	0.0409 (3)	−0.00501 (17)	0.01189 (18)	0.00431 (15)
S3	0.0545 (4)	0.0717 (5)	0.0429 (4)	0.000	0.0168 (3)	0.000

Geometric parameters (Å, º)

C1—S3	1.635 (2)	C5—H5	0.9300
C1—S2	1.7423 (17)	C6—C7	1.391 (3)
C1—S2i	1.7423 (17)	C6—H6	0.9300
C2—C3	1.356 (2)	C7—C6i	1.391 (3)
C2—C2i	1.422 (3)	C7—C8	1.498 (4)
C2—S2	1.7359 (16)	C8—H8A	0.9600
C3—N1	1.391 (2)	C8—H8B	0.9600
C3—H3	0.9300	C8—H8C	0.9600
C4—C5i	1.385 (2)	N1—C3i	1.391 (2)
C4—C5	1.385 (2)	N1—S1	1.679 (2)
C4—S1	1.747 (3)	O1—S1	1.4221 (14)
C5—C6	1.376 (3)	S1—O1i	1.4221 (14)
S3—C1—S2	122.58 (7)	C6—C7—C8	120.86 (12)
S3—C1—S2i	122.58 (7)	C6i—C7—C8	120.86 (12)
S2—C1—S2i	114.85 (14)	C7—C8—H8A	109.5
C3—C2—C2i	108.56 (9)	C7—C8—H8B	109.5
C3—C2—S2	135.53 (13)	H8A—C8—H8B	109.5
C2i—C2—S2	115.87 (6)	C7—C8—H8C	109.5
C2—C3—N1	106.24 (15)	H8A—C8—H8C	109.5
C2—C3—H3	126.9	H8B—C8—H8C	109.5
N1—C3—H3	126.9	C3—N1—C3i	110.37 (18)
C5i—C4—C5	121.4 (2)	C3—N1—S1	123.26 (10)
C5i—C4—S1	119.27 (11)	C3i—N1—S1	123.26 (10)
C5—C4—S1	119.27 (11)	O1—S1—O1i	120.99 (11)
C6—C5—C4	118.71 (18)	O1—S1—N1	105.49 (7)
C6—C5—H5	120.6	O1i—S1—N1	105.49 (7)
C4—C5—H5	120.6	O1—S1—C4	110.02 (7)
C5—C6—C7	121.42 (19)	O1i—S1—C4	110.02 (7)
C5—C6—H6	119.3	N1—S1—C4	103.14 (10)
C7—C6—H6	119.3	C2—S2—C1	96.66 (9)
C6—C7—C6i	118.3 (2)

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ii	0.93	2.33	3.243 (3)	166

Symmetry code: (ii) −x+1/2, −y+1/2, −z+2.