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

Zheng, N.-J.; Yin, B.-Z.

doi:10.1107/S1600536812009622

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1046

doi:10.1107/S1600536812009622

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

Ning-Juan Zheng ^a and Bing-Zhu Yin ^a ^*

^aKey Laboratory of Natural Resources of Changbai Mountain & Functional Molecules (Yanbian University), Ministry of Education, Yanji 133002, People's Republic of China
^*Correspondence e-mail: zqcong@ybu.edu.cn

(Received 28 February 2012; accepted 5 March 2012; online 14 March 2012)

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, C 2/m
a = 15.687 (10) Å
b = 10.485 (9) Å
c = 8.255 (4) Å
β = 96.19 (3)°
V = 1349.9 (16) Å³
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[F² > 2σ(F²)] = 0.029
wR(F²) = 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

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) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812009622/cv5254sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009622/cv5254Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009622/cv5254Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); 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 (Sheldrick, 2008).

Figures top

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].

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

Crystal data top

C₁₂H₉NO₂S₄	F(000) = 672
M_r = 327.44	D_x = 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 top

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

Refinement top

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(F_o²) + (0.053P)² + 0.4647P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max = 0.012
1633 reflections	Δρ_max = 0.31 e Å⁻³
99 parameters	Δρ_min = −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)

Crystal data top

C₁₂H₉NO₂S₄	V = 1349.9 (16) Å³
M_r = 327.44	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 15.687 (10) Å	µ = 0.70 mm⁻¹
b = 10.485 (9) Å	T = 290 K
c = 8.255 (4) Å	0.46 × 0.43 × 0.40 mm
β = 96.19 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1633 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1467 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.770	R_int = 0.020
6671 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.19	Δρ_max = 0.31 e Å⁻³
1633 reflections	Δρ_min = −0.31 e Å⁻³
99 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₁₂H₉NO₂S₄
M_r	327.44
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	290
a, b, c (Å)	15.687 (10), 10.485 (9), 8.255 (4)
β (°)	96.19 (3)
V (Å³)	1349.9 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.46 × 0.43 × 0.40

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.740, 0.770
No. of measured, independent and observed [I > 2σ(I)] reflections	6671, 1633, 1467
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.094, 1.19
No. of reflections	1633
No. of parameters	99
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.31

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC and Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.33	3.243 (3)	166.0

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

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 21062022) and the Open Project of the State Key Laboratory of Supramolecular Structure and Materials, Jilin Universty.

References

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