4,5-Bis(isopropyl­sulfan­yl)benzene-1,2-dicarbonitrile

Wu, X.; Jiang, J.; Zhang, X.

doi:10.1107/S1600536810008755

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o795

doi:10.1107/S1600536810008755

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4,5-Bis(isopropylsulfanyl)benzene-1,2-dicarbonitrile

Xingcui Wu,^a Jianzhuang Jiang ^a ^* and Xiaomei Zhang ^a ^*

^aSchool of Chemistry & Chemical Technology, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: jianzhuang@ustb.edu.cn, zhangxiaomei@sdu.edu.cn

(Received 5 March 2010; accepted 8 March 2010; online 13 March 2010)

In the title compound, C₁₄H₁₆N₂S₂, the C atoms of the aromatic ring, the two cyanide groups and the two S atoms of the isopropylsulfanyl groups are almost coplanar [maximum deviation from the mean plane = 0.042 (7) Å]. In the crystal, inversion dimers linked by aromatic π–π stacking occur, with a centroid–centroid separation of 3.7543 (8) Å.

Related literature

For a related structure and background information on phthalocyanines, see: Zhang et al. (2009 ). For the synthesis, see: Rey et al. (1998 ).

Experimental

Crystal data

C₁₄H₁₆N₂S₂
M_r = 276.41
Monoclinic, P 2₁ /n
a = 10.4929 (7) Å
b = 9.3613 (6) Å
c = 15.4491 (11) Å
β = 96.467 (1)°
V = 1507.87 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 298 K
0.20 × 0.12 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.936, T_max = 0.983
7215 measured reflections
2653 independent reflections
2371 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.083
S = 1.05
2653 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008755/hb5352sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008755/hb5352Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of phthalocyanines (Zhang et al., 2009), we now report the synthesis and structure of the title compound, (I).

As shown in the Fig. 1, the aromatic carbon atoms, two nitrogen atoms and two carbon atoms of two cyanide groups, and two sulfur atoms in the substituted isopropylthio groups build the main skeleton for (I). The skeleton is almost planar with the maximum deviation from the mean plane of 0.042 (7) Å. The bond distances of cyanide groups are consistent with those in similar compounds (Zhang et al., 2009).

In the crystal, inversion dimers (–x, –y, 1–z) linked by aromatic π-π stacking occur, with a centroid-centroid separation of 3.7543 (8)Å.

Related literature top

For a related structure and background information on phthalocyanines, see: Zhang et al. (2009). For the synthesis, see: Rey et al. (1998).

Experimental top

The title compound was prepared according to the literature (Rey et al., 1998) and colourless plates of (I) were recrystallized from ethanol solution.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I) with displacement ellipsoids are drawn at the 30% probability level.

4,5-Bis(isopropylsulfanyl)benzene-1,2-dicarbonitrile top

Crystal data top

C₁₄H₁₆N₂S₂	F(000) = 584
M_r = 276.41	D_x = 1.218 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4590 reflections
a = 10.4929 (7) Å	θ = 2.5–27.4°
b = 9.3613 (6) Å	µ = 0.34 mm⁻¹
c = 15.4491 (11) Å	T = 298 K
β = 96.467 (1)°	Plate, colorless
V = 1507.87 (18) Å³	0.20 × 0.12 × 0.05 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2653 independent reflections
Radiation source: fine-focus sealed tube	2371 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 0 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −12→9
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −11→11
T_min = 0.936, T_max = 0.983	l = −17→18
7215 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0476P)² + 0.2613P] where P = (F_o² + 2F_c²)/3
2653 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₁₆N₂S₂	V = 1507.87 (18) Å³
M_r = 276.41	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.4929 (7) Å	µ = 0.34 mm⁻¹
b = 9.3613 (6) Å	T = 298 K
c = 15.4491 (11) Å	0.20 × 0.12 × 0.05 mm
β = 96.467 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2653 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2371 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.983	R_int = 0.016
7215 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.05	Δρ_max = 0.15 e Å⁻³
2653 reflections	Δρ_min = −0.20 e Å⁻³
163 parameters

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 > 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
S1	0.19579 (3)	−0.17837 (4)	0.39373 (3)	0.05107 (14)
S2	0.31036 (3)	0.05041 (4)	0.51139 (2)	0.04640 (14)
C1	−0.02406 (13)	0.23666 (15)	0.41156 (9)	0.0420 (3)
C4	0.10593 (12)	−0.02113 (15)	0.39674 (9)	0.0374 (3)
C5	0.16133 (12)	0.08841 (14)	0.45253 (8)	0.0362 (3)
C6	0.09506 (13)	0.21542 (15)	0.45910 (9)	0.0418 (3)
H6	0.1307	0.2873	0.4957	0.050*
C3	−0.01420 (13)	0.00042 (16)	0.35047 (9)	0.0416 (3)
H3	−0.0515	−0.0718	0.3148	0.050*
C2	−0.07884 (13)	0.12884 (16)	0.35707 (9)	0.0408 (3)
C13	0.35421 (14)	0.20982 (16)	0.57640 (9)	0.0448 (3)
H13	0.2780	0.2470	0.6001	0.054*
C7	−0.08952 (15)	0.37074 (18)	0.41839 (11)	0.0538 (4)
C14	0.45028 (15)	0.1574 (2)	0.65105 (10)	0.0583 (4)
H14A	0.4111	0.0850	0.6832	0.088*
H14B	0.4762	0.2360	0.6890	0.088*
H14C	0.5240	0.1184	0.6280	0.088*
N1	−0.14093 (17)	0.47715 (17)	0.42345 (12)	0.0778 (5)
C10	0.10888 (15)	−0.29469 (16)	0.31245 (10)	0.0471 (4)
H10	0.0191	−0.3013	0.3240	0.057*
C8	−0.20085 (14)	0.15434 (18)	0.30676 (10)	0.0507 (4)
N2	−0.29515 (14)	0.1806 (2)	0.26646 (11)	0.0752 (5)
C12	0.4102 (2)	0.3253 (2)	0.52361 (13)	0.0714 (5)
H12A	0.3471	0.3552	0.4773	0.107*
H12B	0.4840	0.2887	0.4995	0.107*
H12C	0.4349	0.4054	0.5605	0.107*
C11	0.1728 (2)	−0.43966 (18)	0.32843 (14)	0.0722 (5)
H11A	0.1680	−0.4681	0.3877	0.108*
H11B	0.2610	−0.4333	0.3179	0.108*
H11C	0.1296	−0.5090	0.2898	0.108*
C9	0.1141 (2)	−0.2436 (2)	0.22038 (12)	0.0700 (5)
H9A	0.0734	−0.1519	0.2130	0.105*
H9B	0.0702	−0.3106	0.1805	0.105*
H9C	0.2019	−0.2358	0.2091	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0376 (2)	0.0453 (2)	0.0673 (3)	0.00601 (15)	−0.00753 (17)	−0.01699 (17)
S2	0.0365 (2)	0.0456 (2)	0.0536 (2)	0.00658 (15)	−0.01006 (16)	−0.00971 (16)
C1	0.0399 (7)	0.0423 (8)	0.0430 (7)	0.0060 (6)	0.0014 (6)	0.0032 (6)
C4	0.0323 (7)	0.0402 (7)	0.0398 (7)	−0.0001 (5)	0.0044 (5)	−0.0015 (6)
C5	0.0315 (7)	0.0403 (7)	0.0363 (7)	0.0011 (5)	0.0020 (5)	−0.0001 (5)
C6	0.0409 (8)	0.0401 (8)	0.0426 (8)	0.0028 (6)	−0.0031 (6)	−0.0029 (6)
C3	0.0354 (7)	0.0453 (8)	0.0433 (7)	−0.0034 (6)	0.0005 (6)	−0.0035 (6)
C2	0.0320 (7)	0.0489 (8)	0.0406 (7)	0.0008 (6)	0.0005 (6)	0.0062 (6)
C13	0.0383 (7)	0.0513 (9)	0.0434 (8)	0.0002 (6)	−0.0017 (6)	−0.0117 (6)
C7	0.0507 (9)	0.0505 (9)	0.0569 (9)	0.0110 (7)	−0.0083 (7)	0.0004 (7)
C14	0.0425 (8)	0.0797 (12)	0.0499 (9)	0.0037 (8)	−0.0078 (7)	−0.0122 (8)
N1	0.0790 (11)	0.0594 (10)	0.0895 (12)	0.0271 (9)	−0.0150 (9)	−0.0073 (8)
C10	0.0425 (8)	0.0420 (8)	0.0561 (9)	−0.0071 (6)	0.0025 (6)	−0.0093 (7)
C8	0.0384 (8)	0.0609 (10)	0.0513 (9)	0.0004 (7)	−0.0022 (7)	0.0051 (7)
N2	0.0455 (8)	0.1017 (13)	0.0736 (10)	0.0064 (8)	−0.0150 (7)	0.0103 (9)
C12	0.0734 (13)	0.0612 (11)	0.0777 (13)	−0.0156 (9)	0.0006 (10)	0.0011 (9)
C11	0.0770 (13)	0.0440 (10)	0.0921 (14)	0.0008 (9)	−0.0066 (11)	−0.0183 (9)
C9	0.0839 (13)	0.0701 (12)	0.0574 (10)	−0.0124 (10)	0.0142 (9)	−0.0105 (9)

Geometric parameters (Å, º) top

S1—C4	1.7515 (14)	C7—N1	1.140 (2)
S1—C10	1.8265 (15)	C14—H14A	0.9600
S2—C5	1.7545 (13)	C14—H14B	0.9600
S2—C13	1.8284 (15)	C14—H14C	0.9600
C1—C6	1.3909 (19)	C10—C9	1.507 (2)
C1—C2	1.396 (2)	C10—C11	1.521 (2)
C1—C7	1.440 (2)	C10—H10	0.9800
C4—C3	1.3920 (19)	C8—N2	1.135 (2)
C4—C5	1.4211 (19)	C12—H12A	0.9600
C5—C6	1.3868 (19)	C12—H12B	0.9600
C6—H6	0.9300	C12—H12C	0.9600
C3—C2	1.390 (2)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C2—C8	1.441 (2)	C11—H11C	0.9600
C13—C12	1.512 (2)	C9—H9A	0.9600
C13—C14	1.525 (2)	C9—H9B	0.9600
C13—H13	0.9800	C9—H9C	0.9600

C4—S1—C10	106.90 (7)	H14A—C14—H14B	109.5
C5—S2—C13	105.88 (7)	C13—C14—H14C	109.5
C6—C1—C2	119.97 (13)	H14A—C14—H14C	109.5
C6—C1—C7	119.57 (13)	H14B—C14—H14C	109.5
C2—C1—C7	120.46 (13)	C9—C10—C11	111.96 (15)
C3—C4—C5	119.46 (13)	C9—C10—S1	113.04 (11)
C3—C4—S1	124.56 (11)	C11—C10—S1	104.09 (11)
C5—C4—S1	115.97 (10)	C9—C10—H10	109.2
C6—C5—C4	119.26 (12)	C11—C10—H10	109.2
C6—C5—S2	124.12 (10)	S1—C10—H10	109.2
C4—C5—S2	116.61 (10)	N2—C8—C2	176.87 (19)
C5—C6—C1	120.80 (13)	C13—C12—H12A	109.5
C5—C6—H6	119.6	C13—C12—H12B	109.5
C1—C6—H6	119.6	H12A—C12—H12B	109.5
C2—C3—C4	120.59 (13)	C13—C12—H12C	109.5
C2—C3—H3	119.7	H12A—C12—H12C	109.5
C4—C3—H3	119.7	H12B—C12—H12C	109.5
C3—C2—C1	119.90 (12)	C10—C11—H11A	109.5
C3—C2—C8	121.00 (14)	C10—C11—H11B	109.5
C1—C2—C8	119.08 (13)	H11A—C11—H11B	109.5
C12—C13—C14	111.97 (14)	C10—C11—H11C	109.5
C12—C13—S2	112.10 (11)	H11A—C11—H11C	109.5
C14—C13—S2	104.90 (11)	H11B—C11—H11C	109.5
C12—C13—H13	109.3	C10—C9—H9A	109.5
C14—C13—H13	109.3	C10—C9—H9B	109.5
S2—C13—H13	109.3	H9A—C9—H9B	109.5
N1—C7—C1	179.6 (2)	C10—C9—H9C	109.5
C13—C14—H14A	109.5	H9A—C9—H9C	109.5
C13—C14—H14B	109.5	H9B—C9—H9C	109.5

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂S₂
M_r	276.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.4929 (7), 9.3613 (6), 15.4491 (11)
β (°)	96.467 (1)
V (Å³)	1507.87 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.20 × 0.12 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.936, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	7215, 2653, 2371
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.05
No. of reflections	2653
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.20

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Acknowledgements

This work was supported by the Postdoctoral Scientific Foundation of China (grant No. 20070411093), the Postdoctoral Scientific Foundation of Shandong Province (grant No. 200603070) and the Independent Innovation Foundation of Shandong University, IIFSDU.

References

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