5-(4-Methyl-phenyl-sulfon-yl)-1,3-dithiolo[4,5-c]pyrrole-2-thione.

The asymmetric unit of the title compound, C(12)H(9)NO(2)S(4), contains one half-mol-ecule with the N, two S amd four C atoms lying on a mirror plane. The mol-ecule exhibits a V-shaped conformation, with a dihedral angle of 87.00 (7)° between the benzene and dithiol-opyrrole 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 mol-ecules 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 = 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) 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[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.094

S = 1.19

1633 reflections

99 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812009622/cv5254sup1.cif

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

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

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

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

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 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)

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.

	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)

	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

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)

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

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) .