The 4-(3-chloro-4-methyl­phen­yl)-1,2,3,5-dithia­diazol-3-yl radical

Cole, J.M.; Aherne, C.M.; Howard, J.A.K.; Banister, A.J.; Waddell, P.G.

doi:10.1107/S1600536811034751

organic compounds

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Volume 67| Part 9| September 2011| Page o2514

doi:10.1107/S1600536811034751

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The 4-(3-chloro-4-methylphenyl)-1,2,3,5-dithiadiazol-3-yl radical

Jacqueline M. Cole,^a ^*‡ Christine M. Aherne,^b Judith A. K. Howard,^b Arthur J. Banister ^b and Paul G. Waddell ^a §

^aCavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, England, and ^bDepartment of Chemistry, University of Durham, South Road, Durham, DH1 3LE, England
^*Correspondence e-mail: jmc61@cam.ac.uk

(Received 28 July 2011; accepted 24 August 2011; online 27 August 2011)

The asymmetric unit of the title compound, C₈H₆ClN₂S₂, comprises two molecules forming a dimer via π–π stacking interactions [centroid–centroid distance = 3.634 (10) Å] and intradimer S⋯S contacts [3.012 (4) and 3.158 (4) Å] between the two molecules in a cis-antarafacial arrangement.

Related literature

For the properties of the 4-methylphenyl dithiadiazolyl radical, see: Boeré et al. (1992 ). For similar phenyl dithiadiazolyl radical structures, see: Allen et al. (2009 ); Clarke et al. (2010 ). For notes on the configurations adopted by phenyl dithiadiazolyl radicals in their crystal structures, see: Aherne et al. (1993 ).

Experimental

Crystal data

C₈H₆ClN₂S₂
M_r = 229.72
Monoclinic, P 2₁
a = 5.937 (3) Å
b = 13.407 (3) Å
c = 11.573 (3) Å
β = 95.87 (4)°
V = 916.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 150 K
0.25 × 0.18 × 0.15 mm

Data collection

Rigaku AFC-6S diffractometer
1655 measured reflections
1499 independent reflections
1054 reflections with I > 2σ(I)
R_int = 0.103
θ_max = 24.0°
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.098
S = 1.09
1499 reflections
237 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.38 e Å⁻³
Absolute structure: Flack (1983 ), 169 Friedel pairs
Flack parameter: −0.16 (19)

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991 $[Molecular Structure Corporation (1991). MSC/AFC Diffractometer Control Software. MSC, The Woodlands, Texas, USA.]$ ); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989 ); 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: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034751/bt5594sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034751/bt5594Isup2.hkl

checkCIF report

Comment top

As observed in similar structures (Aherne et al. 1993; Allen et al. 2009 and Clarke et al. 2010), within the planar CS₂N₂ rings the C—N and S—N bonds distances exhibit intermediate values between those of standard single and double bonds indicating the delocalized nature of the radical about the N—C—N fragment. Though the S—S distance is unusually long it is comparable to similar phenyl dithiadiazolyl radical structures. Intradimer contacts include π-π stacking interactions between the aryl rings of the 3-chloro-4-methylphenyl dithiadiazolyl radicals with a centroid-to-centroid distance of 3.634 (10) Å, and two cis-antarafacial S···S contacts (S1···S3 = 3.012 (4) Å; S2···S4 = 3.158 (4) Å).

Related literature top

For the properties of the 4-methylphenyl dithiadiazolyl radical, see: Boeré et al. (1992). For similar phenyl dithiadiazolyl radical structures, see: Allen et al. (2009); Clarke et al. (2010). For notes on the configurations adopted by phenyl dithiadiazolyl radicals in their crystal structures, see: Aherne et al. (1993).

Experimental top

Lithium hexamethyldisilazane (1.67 g, 0.01 mol) was added to 3-chloro-4-methylbenzonitrile (1.51 g, 0.01 mol) in ethanol (40 ml) and stirred for 3 h. To the resulting yellow solution SCl₂ (1.27 ml, 0.02 mol) and diethyl ether (25 ml) was added producing a red solution containing the 3-chloro-4-methylphenyl dithiadiazolyl cation (yield: 91°). The radical was formed upon reduction of the cation (1.43 g, 5 mmol) with a Zn(Cu) couple (0.18 g, 2.8 mmol) as the reducing agent in THF (25 ml). Crystals suitable for X-ray crystallography were grown via sublimation of the product under vacuum at 373 K.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); 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: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level showing S···S contacts (dashed lines).

4-(3-chloro-4-methylphenyl)-1,2,3,5-dithiadiazol-3-yl top

Crystal data top

C₈H₆ClN₂S₂	F(000) = 468
M_r = 229.72	D_x = 1.665 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 20 reflections
a = 5.937 (3) Å	θ = 3.0–11.0°
b = 13.407 (3) Å	µ = 0.82 mm⁻¹
c = 11.573 (3) Å	T = 150 K
β = 95.87 (4)°	Prism, colourless
V = 916.3 (6) Å³	0.25 × 0.18 × 0.15 mm
Z = 4

Data collection top

Rigaku AFC-6S diffractometer	θ_max = 24.0°, θ_min = 3.5°
Graphite monochromator	h = 0→6
ω scans	k = 0→15
1655 measured reflections	l = −13→13
1499 independent reflections	3 standard reflections every 200 reflections
1054 reflections with I > 2σ(I)	intensity decay: none
R_int = 0.103

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0132P)² + 2.2783P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1499 reflections	Δρ_max = 0.44 e Å⁻³
237 parameters	Δρ_min = −0.38 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 169 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.16 (19)

Crystal data top

C₈H₆ClN₂S₂	V = 916.3 (6) Å³
M_r = 229.72	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 5.937 (3) Å	µ = 0.82 mm⁻¹
b = 13.407 (3) Å	T = 150 K
c = 11.573 (3) Å	0.25 × 0.18 × 0.15 mm
β = 95.87 (4)°

Data collection top

Rigaku AFC-6S diffractometer	R_int = 0.103
1655 measured reflections	θ_max = 24.0°
1499 independent reflections	3 standard reflections every 200 reflections
1054 reflections with I > 2σ(I)	intensity decay: none

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.098	Δρ_max = 0.44 e Å⁻³
S = 1.09	Δρ_min = −0.38 e Å⁻³
1499 reflections	Absolute structure: Flack (1983), 169 Friedel pairs
237 parameters	Absolute structure parameter: −0.16 (19)
1 restraint

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
S2	0.5244 (5)	0.3269 (2)	−0.1014 (2)	0.0271 (7)
S1	0.2324 (4)	0.3359 (2)	−0.0142 (2)	0.0263 (7)
N2	0.6580 (15)	0.4154 (7)	−0.0244 (7)	0.025 (2)
N1	0.3323 (14)	0.4260 (6)	0.0724 (7)	0.024 (2)
C1	0.5430 (17)	0.4558 (8)	0.0533 (9)	0.024 (2)
C2	0.6477 (16)	0.5355 (8)	0.1287 (8)	0.017 (2)
C6	0.9463 (14)	0.6549 (7)	0.1743 (7)	0.019 (2)
H6	1.0823	0.6826	0.1567	0.023*
C7	0.8533 (15)	0.5770 (8)	0.1066 (8)	0.021 (2)
H7	0.9289	0.5524	0.046	0.025*
C3	0.5398 (15)	0.5719 (7)	0.2224 (8)	0.020 (2)
H3	0.4034	0.5447	0.2401	0.024*
C5	0.8434 (15)	0.6933 (8)	0.2681 (8)	0.021 (2)
C8	0.9427 (16)	0.7782 (8)	0.3392 (8)	0.026 (2)
H8A	1.061	0.8085	0.3007	0.039*
H8B	1.004	0.7542	0.414	0.039*
H8C	0.827	0.8267	0.3488	0.039*
C4	0.6413 (15)	0.6499 (7)	0.2885 (7)	0.018 (2)
Cl1	0.5049 (4)	0.6884 (2)	0.4074 (2)	0.0278 (7)
S3	0.3937 (5)	0.1726 (2)	0.1531 (2)	0.0302 (7)
S4	0.7080 (4)	0.1669 (2)	0.0853 (2)	0.0293 (7)
Cl2	0.5678 (4)	0.47502 (19)	0.6289 (2)	0.0259 (6)
N4	0.8253 (12)	0.2511 (6)	0.1763 (7)	0.0208 (19)
C10	0.7757 (15)	0.3556 (7)	0.3403 (7)	0.018 (2)
C15	0.9878 (16)	0.4033 (8)	0.3377 (8)	0.025 (2)
H15	1.079	0.3871	0.2797	0.031*
C9	0.6891 (16)	0.2851 (8)	0.2539 (8)	0.021 (2)
C12	0.7250 (15)	0.4511 (7)	0.5142 (7)	0.014 (2)
C11	0.6480 (15)	0.3831 (7)	0.4301 (8)	0.022 (2)
H11	0.506	0.3544	0.4332	0.027*
C14	1.0611 (14)	0.4740 (8)	0.4206 (7)	0.023 (2)
H14	1.2004	0.5047	0.4161	0.027*
C13	0.9336 (16)	0.5008 (7)	0.5106 (8)	0.020 (2)
C16	1.0139 (17)	0.5799 (8)	0.6005 (9)	0.029 (3)
H16A	0.8912	0.6245	0.6114	0.043*
H16B	1.1369	0.6169	0.5738	0.043*
H16C	1.0639	0.5482	0.673	0.043*
N3	0.4777 (14)	0.2515 (7)	0.2537 (7)	0.025 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0299 (17)	0.0296 (16)	0.0226 (14)	−0.0059 (15)	0.0067 (12)	−0.0050 (12)
S1	0.0193 (14)	0.0277 (15)	0.0311 (15)	−0.0007 (13)	−0.0007 (12)	−0.0104 (14)
N2	0.031 (5)	0.025 (5)	0.022 (4)	0.001 (4)	0.012 (4)	0.001 (4)
N1	0.019 (5)	0.026 (5)	0.026 (5)	0.000 (4)	0.001 (4)	−0.011 (4)
C1	0.018 (5)	0.022 (6)	0.031 (6)	−0.013 (5)	−0.005 (4)	0.006 (5)
C2	0.015 (5)	0.019 (6)	0.018 (5)	0.007 (4)	0.002 (4)	0.001 (4)
C6	0.008 (4)	0.025 (7)	0.023 (5)	−0.002 (4)	−0.001 (4)	0.004 (4)
C7	0.022 (6)	0.027 (6)	0.014 (5)	0.007 (5)	−0.002 (4)	0.007 (5)
C3	0.015 (5)	0.012 (5)	0.032 (6)	0.001 (4)	−0.005 (5)	0.007 (5)
C5	0.015 (5)	0.018 (6)	0.030 (5)	0.003 (5)	−0.007 (4)	0.008 (5)
C8	0.022 (5)	0.031 (6)	0.024 (5)	−0.001 (5)	−0.002 (5)	−0.004 (5)
C4	0.016 (5)	0.026 (7)	0.012 (5)	0.013 (5)	0.000 (4)	−0.003 (5)
Cl1	0.0259 (13)	0.0279 (17)	0.0310 (14)	−0.0008 (13)	0.0090 (10)	−0.0078 (13)
S3	0.0353 (15)	0.0314 (17)	0.0242 (13)	−0.0117 (14)	0.0047 (11)	−0.0063 (13)
S4	0.0318 (15)	0.0270 (17)	0.0287 (14)	0.0049 (14)	0.0005 (12)	−0.0049 (13)
Cl2	0.0266 (13)	0.0286 (16)	0.0240 (13)	−0.0004 (14)	0.0094 (10)	−0.0073 (13)
N4	0.019 (4)	0.019 (5)	0.025 (5)	0.005 (4)	0.003 (4)	−0.011 (4)
C10	0.015 (5)	0.031 (7)	0.008 (4)	0.008 (5)	−0.003 (4)	0.006 (4)
C15	0.028 (6)	0.028 (6)	0.022 (5)	0.005 (5)	0.010 (4)	0.008 (5)
C9	0.019 (5)	0.027 (6)	0.017 (5)	−0.003 (5)	0.001 (4)	0.010 (5)
C12	0.018 (5)	0.012 (5)	0.012 (5)	0.009 (4)	0.000 (4)	0.002 (4)
C11	0.013 (5)	0.026 (6)	0.026 (5)	0.001 (5)	−0.008 (4)	0.005 (5)
C14	0.012 (5)	0.034 (6)	0.022 (5)	−0.004 (5)	0.001 (4)	0.002 (5)
C13	0.023 (6)	0.013 (5)	0.024 (6)	−0.003 (4)	−0.003 (4)	0.002 (4)
C16	0.029 (6)	0.021 (6)	0.037 (6)	−0.005 (5)	0.008 (5)	−0.012 (5)
N3	0.023 (5)	0.030 (5)	0.024 (4)	−0.013 (4)	0.011 (4)	−0.008 (4)

Geometric parameters (Å, º) top

S2—N2	1.639 (10)	S3—N3	1.613 (9)
S2—S1	2.096 (3)	S3—S4	2.098 (4)
S1—N1	1.641 (8)	S4—N4	1.648 (8)
N2—C1	1.302 (13)	Cl2—C12	1.728 (9)
N1—C1	1.352 (13)	N4—C9	1.348 (12)
C1—C2	1.476 (13)	C10—C11	1.398 (13)
C2—C7	1.388 (13)	C10—C15	1.415 (13)
C2—C3	1.403 (13)	C10—C9	1.432 (13)
C6—C7	1.387 (13)	C15—C14	1.387 (13)
C6—C5	1.397 (12)	C15—H15	0.93
C6—H6	0.93	C9—N3	1.333 (12)
C7—H7	0.93	C12—C11	1.377 (13)
C3—C4	1.395 (13)	C12—C13	1.411 (13)
C3—H3	0.93	C11—H11	0.93
C5—C4	1.375 (12)	C14—C13	1.396 (13)
C5—C8	1.491 (14)	C14—H14	0.93
C8—H8A	0.96	C13—C16	1.528 (13)
C8—H8B	0.96	C16—H16A	0.96
C8—H8C	0.96	C16—H16B	0.96
C4—Cl1	1.746 (8)	C16—H16C	0.96

N2—S2—S1	94.3 (3)	N3—S3—S4	94.2 (3)
N1—S1—S2	94.1 (3)	N4—S4—S3	94.0 (3)
C1—N2—S2	114.7 (7)	C9—N4—S4	114.5 (7)
C1—N1—S1	113.6 (7)	C11—C10—C15	116.6 (9)
N2—C1—N1	123.3 (10)	C11—C10—C9	120.6 (8)
N2—C1—C2	119.3 (9)	C15—C10—C9	122.7 (8)
N1—C1—C2	117.3 (9)	C14—C15—C10	120.7 (8)
C7—C2—C3	118.8 (9)	C14—C15—H15	119.6
C7—C2—C1	120.4 (9)	C10—C15—H15	119.6
C3—C2—C1	120.7 (9)	N3—C9—N4	120.9 (9)
C7—C6—C5	122.4 (9)	N3—C9—C10	119.7 (8)
C7—C6—H6	118.8	N4—C9—C10	119.4 (8)
C5—C6—H6	118.8	C11—C12—C13	121.4 (8)
C6—C7—C2	120.3 (9)	C11—C12—Cl2	119.9 (7)
C6—C7—H7	119.9	C13—C12—Cl2	118.7 (7)
C2—C7—H7	119.9	C12—C11—C10	122.3 (9)
C4—C3—C2	118.6 (9)	C12—C11—H11	118.9
C4—C3—H3	120.7	C10—C11—H11	118.9
C2—C3—H3	120.7	C15—C14—C13	122.4 (9)
C4—C5—C6	115.8 (9)	C15—C14—H14	118.8
C4—C5—C8	122.1 (9)	C13—C14—H14	118.8
C6—C5—C8	122.1 (9)	C14—C13—C12	116.5 (9)
C5—C8—H8A	109.5	C14—C13—C16	122.1 (9)
C5—C8—H8B	109.5	C12—C13—C16	121.4 (8)
H8A—C8—H8B	109.5	C13—C16—H16A	109.5
C5—C8—H8C	109.5	C13—C16—H16B	109.5
H8A—C8—H8C	109.5	H16A—C16—H16B	109.5
H8B—C8—H8C	109.5	C13—C16—H16C	109.5
C5—C4—C3	124.0 (8)	H16A—C16—H16C	109.5
C5—C4—Cl1	119.5 (7)	H16B—C16—H16C	109.5
C3—C4—Cl1	116.4 (7)	C9—N3—S3	116.4 (7)

Experimental details

Crystal data
Chemical formula	C₈H₆ClN₂S₂
M_r	229.72
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	150
a, b, c (Å)	5.937 (3), 13.407 (3), 11.573 (3)
β (°)	95.87 (4)
V (Å³)	916.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku AFC-6S diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1655, 1499, 1054
R_int	0.103
θ_max (°)	24.0
(sin θ/λ)_max (Å⁻¹)	0.573

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.098, 1.09
No. of reflections	1499
No. of parameters	237
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.38
Absolute structure	Flack (1983), 169 Friedel pairs
Absolute structure parameter	−0.16 (19)

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Footnotes

‡Other affiliation: Department of Chemistry, University of New Brunswick, Fredericton, Canada NB E3B 5A3

§Other affiliation: Department of Chemistry, University of New Brunswick, Fredericton, Canada NB E3B 5A3.

Acknowledgements

JMC thanks the Royal Society for a University Research Fellowship, the University of New Brunswick for the UNB Vice-Chancellor's Research Chair (JMC) and NSERC Discovery Grant 355708 (for PGW).

References

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