2-(4-Methyl­phen­yl)-5-[({[5-(4-methyl­phen­yl)-1,3,4-thia­diazol-2-yl]sulfan­yl}meth­yl)sulfan­yl]-1,3,4-thia­diazole

doi:10.1107/S1600536812007520

Acta Crystallogr Sect E Struct Rep Online. 2012 March 1; 68(Pt 3): o851.

Published online 2012 February 24. doi: 10.1107/S1600536812007520

PMCID: PMC3297906

2-(4-Methylphenyl)-5-[({[5-(4-methylphenyl)-1,3,4-thiadiazol-2-yl]sulfanyl}methyl)sulfanyl]-1,3,4-thiadiazole

Yong Wang,^a^* Wen-ge Zhang,^b Yu-bo Wang,^c Jing-wen Yu,^a and Lin Zhou^a

^aSchool of Chemical Engineering, University of Science and Technology LiaoNing, Anshan 114051, People’s Republic of China

^bAnshan Normal University, Anshan 114005, People’s Republic of China

^cShengyang Agricultural University, Shengyang 116121, People’s Republic of China

Correspondence e-mail: wy2002866/at/126.com

Received February 8, 2012; Accepted February 20, 2012.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Abstract

In the title compound, C₁₉H₁₆N₄S₄, the molecules exhibit a butterfly conformation, where the thiadiazole and attached benzene rings in two wings are almost coplanar, with dihedral angles of 0.8 (3) and 0.9 (3)°, respectively, while the two thiadiazole rings form a dihedral angle of 46.3 (3)°.

Related literature

For the biological properties of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996

); Wang et al. (1999

); Carvalho et al. (2004

). For the crystal structures of related compounds, see: Li et al. (2011

); Wang et al. (2010

An external file that holds a picture, illustration, etc.
Object name is e-68-0o851-scheme1.jpg Object name is e-68-0o851-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₆N₄S₄
M _r = 428.60
Monoclinic,
a = 16.8944 (14) Å
b = 4.1959 (5) Å
c = 27.107 (2) Å
β = 96.084 (8)°
V = 1910.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 113 K
0.50 × 0.04 × 0.04 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T _min = 0.785, T _max = 0.980
14969 measured reflections
4535 independent reflections
2927 reflections with I > 2σ(I)
R _int = 0.094

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.142
S = 0.96
4535 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005

); cell refinement: CrystalClear; data reduction: CrystalClear; 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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812007520/cv5245sup1.cif

Click here to view.^{(20K, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007520/cv5245Isup2.hkl

Click here to view.^{(222K, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812007520/cv5245Isup3.cml

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

supplementary crystallographic information

Comment

1,3,4-Thiadiazole derivatives are important for medicinal chemistry due to their chemical and pharmaceutical properties (Nakagawa et al., 1996; Wang et al., 1999; Carvalho et al., 2004). Similar crystal structures of the 1,3,4-thiadiazole derivatives have been reported . As a part of our research, the title compound (I) has been synthesized, and herewith we present its crystal structure.

In (I) (Fig. 1), all geometric parameters are normal and comparable with those reported for related 1,3,4-thiadiazole derivatives (Li et al., 2011; Wang et al., 2010). Two thiadiazole rings form a dihedral angle of 46.3 (3)%. The dihedral angles between the benzene rings and attached thiadiazole rings are 0.8 (3) and 0.9 (3)° indicating the two rings are almost parallel. The same situation has been observed in the crystal structure of 1,4-bis(5-phenyl-1,3,4-thiadiazol-2-ylsulfanyl)butane (Li et al., 2011).

Experimental

The title compound was synthesized by the reaction of the 1,1-dibromomethane (1.0 mmol) and 5-tolyl-1,3,4-thiadiazol-2-thiol (2.0 mmol) in ethanol (20 ml) at room temperature. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-enthanol (1:1).

Figures

Fig. 1.

View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 60% probability level.

Crystal data

C₁₉H₁₆N₄S₄	F(000) = 888
M_r = 428.60	D_x = 1.490 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5461 reflections
a = 16.8944 (14) Å	θ = 1.4–27.8°
b = 4.1959 (5) Å	µ = 0.51 mm⁻¹
c = 27.107 (2) Å	T = 113 K
β = 96.084 (8)°	Prism, colourless
V = 1910.7 (3) Å³	0.50 × 0.04 × 0.04 mm
Z = 4

Data collection

Rigaku Saturn CCD area-detector diffractometer	4535 independent reflections
Radiation source: rotating anode	2927 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.094
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.8°, θ_min = 1.4°
and ω scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −5→4
T_min = 0.785, T_max = 0.980	l = −35→31
14969 measured reflections

Refinement

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0566P)²] where P = (F_o² + 2F_c²)/3
4535 reflections	(Δ/σ)_max = 0.001
246 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Special details

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)

	x	y	z	U_iso*/U_eq
S1	0.41711 (5)	0.77165 (19)	−0.01333 (3)	0.0266 (2)
S2	0.39123 (5)	1.1072 (2)	0.08165 (3)	0.0282 (2)
S3	0.26282 (5)	1.06832 (19)	0.15267 (3)	0.0270 (2)
S4	0.33462 (5)	1.07934 (19)	0.26002 (3)	0.0268 (2)
N1	0.26848 (16)	0.6479 (6)	−0.02748 (10)	0.0285 (6)
N2	0.27897 (16)	0.8187 (6)	0.01681 (10)	0.0288 (6)
N3	0.39960 (17)	1.3525 (6)	0.18983 (10)	0.0292 (6)
N4	0.44931 (16)	1.4137 (6)	0.23312 (10)	0.0289 (6)
C1	0.3546 (2)	−0.0838 (8)	−0.23078 (12)	0.0349 (8)
H1A	0.3223	−0.2782	−0.2313	0.052*
H1B	0.4101	−0.1403	−0.2341	0.052*
H1C	0.3343	0.0547	−0.2584	0.052*
C2	0.3500 (2)	0.0891 (7)	−0.18231 (12)	0.0263 (7)
C3	0.4179 (2)	0.2240 (8)	−0.15616 (12)	0.0296 (8)
H3	0.4680	0.2007	−0.1687	0.036*
C4	0.4135 (2)	0.3902 (7)	−0.11251 (12)	0.0283 (7)
H4	0.4602	0.4807	−0.0955	0.034*
C5	0.34068 (19)	0.4251 (7)	−0.09335 (11)	0.0237 (7)
C6	0.27246 (19)	0.2897 (7)	−0.11872 (12)	0.0268 (7)
H6	0.2225	0.3126	−0.1060	0.032*
C7	0.2776 (2)	0.1227 (7)	−0.16224 (12)	0.0275 (7)
H7	0.2309	0.0289	−0.1788	0.033*
C8	0.33463 (19)	0.6019 (7)	−0.04729 (11)	0.0242 (7)
C9	0.35275 (19)	0.8994 (7)	0.02832 (11)	0.0255 (7)
C10	0.2996 (2)	1.2661 (7)	0.10072 (12)	0.0277 (7)
H10A	0.3080	1.4939	0.1092	0.033*
H10B	0.2581	1.2551	0.0721	0.033*
C11	0.33781 (19)	1.1814 (7)	0.19861 (12)	0.0247 (7)
C12	0.42392 (18)	1.2861 (7)	0.27270 (12)	0.0258 (7)
C13	0.46511 (19)	1.3186 (7)	0.32295 (12)	0.0262 (7)
C14	0.43531 (19)	1.1764 (8)	0.36363 (12)	0.0278 (7)
H14	0.3872	1.0580	0.3591	0.033*
C15	0.4755 (2)	1.2068 (8)	0.41067 (12)	0.0292 (7)
H15	0.4540	1.1096	0.4380	0.035*
C16	0.54653 (19)	1.3758 (7)	0.41906 (12)	0.0285 (7)
C17	0.5753 (2)	1.5225 (8)	0.37799 (12)	0.0286 (7)
H17	0.6231	1.6434	0.3826	0.034*
C18	0.53548 (19)	1.4947 (8)	0.33077 (12)	0.0279 (7)
H18	0.5562	1.5961	0.3035	0.033*
C19	0.5928 (2)	1.3981 (9)	0.46959 (12)	0.0346 (8)
H19A	0.6398	1.2602	0.4708	0.052*
H19B	0.5590	1.3294	0.4949	0.052*
H19C	0.6096	1.6190	0.4760	0.052*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0174 (4)	0.0334 (5)	0.0289 (4)	−0.0015 (3)	0.0025 (3)	−0.0022 (4)
S2	0.0207 (4)	0.0359 (5)	0.0279 (4)	−0.0021 (3)	0.0019 (3)	−0.0029 (4)
S3	0.0204 (4)	0.0320 (5)	0.0285 (4)	−0.0002 (3)	0.0022 (3)	−0.0018 (3)
S4	0.0197 (4)	0.0329 (5)	0.0279 (4)	−0.0018 (3)	0.0022 (3)	0.0007 (3)
N1	0.0230 (15)	0.0343 (16)	0.0279 (14)	0.0008 (12)	0.0014 (12)	−0.0048 (12)
N2	0.0242 (15)	0.0342 (16)	0.0282 (14)	0.0000 (12)	0.0035 (12)	−0.0044 (12)
N3	0.0228 (15)	0.0352 (16)	0.0296 (14)	−0.0016 (12)	0.0026 (12)	0.0011 (12)
N4	0.0211 (15)	0.0357 (16)	0.0297 (15)	−0.0025 (12)	0.0013 (12)	0.0020 (12)
C1	0.034 (2)	0.037 (2)	0.0336 (19)	0.0041 (16)	0.0044 (16)	−0.0033 (16)
C2	0.0266 (18)	0.0262 (17)	0.0261 (16)	0.0032 (14)	0.0024 (14)	0.0034 (13)
C3	0.0204 (17)	0.0360 (19)	0.0332 (18)	0.0014 (14)	0.0064 (15)	0.0030 (15)
C4	0.0199 (17)	0.0312 (18)	0.0332 (18)	−0.0029 (14)	0.0003 (14)	−0.0010 (14)
C5	0.0209 (17)	0.0231 (16)	0.0262 (16)	0.0013 (13)	−0.0009 (13)	0.0034 (13)
C6	0.0203 (17)	0.0292 (17)	0.0311 (17)	0.0002 (13)	0.0035 (14)	0.0023 (14)
C7	0.0214 (17)	0.0306 (18)	0.0303 (17)	−0.0017 (14)	0.0012 (14)	−0.0005 (14)
C8	0.0196 (16)	0.0231 (16)	0.0290 (16)	0.0002 (13)	−0.0020 (13)	0.0030 (13)
C9	0.0230 (17)	0.0279 (17)	0.0261 (16)	0.0001 (14)	0.0045 (14)	0.0043 (14)
C10	0.0249 (18)	0.0283 (17)	0.0290 (17)	0.0051 (14)	−0.0019 (14)	−0.0024 (14)
C11	0.0185 (16)	0.0265 (17)	0.0291 (16)	0.0049 (13)	0.0034 (13)	0.0005 (13)
C12	0.0151 (16)	0.0272 (17)	0.0355 (18)	0.0012 (13)	0.0041 (14)	−0.0025 (14)
C13	0.0169 (16)	0.0276 (17)	0.0342 (18)	0.0044 (13)	0.0029 (14)	−0.0012 (14)
C14	0.0156 (16)	0.0309 (18)	0.0371 (18)	0.0004 (13)	0.0028 (14)	−0.0020 (15)
C15	0.0217 (17)	0.0355 (19)	0.0308 (17)	−0.0002 (14)	0.0044 (14)	−0.0010 (15)
C16	0.0193 (17)	0.0306 (18)	0.0350 (18)	0.0046 (14)	0.0001 (14)	−0.0035 (15)
C17	0.0169 (16)	0.0317 (18)	0.0373 (19)	0.0002 (14)	0.0027 (14)	−0.0037 (15)
C18	0.0210 (17)	0.0300 (17)	0.0329 (17)	0.0012 (14)	0.0043 (14)	−0.0028 (15)
C19	0.0221 (18)	0.046 (2)	0.0344 (18)	0.0029 (15)	−0.0023 (15)	−0.0011 (16)

Geometric parameters (Å, º)

S1—C9	1.733 (3)	C4—H4	0.9500
S1—C8	1.739 (3)	C5—C6	1.398 (4)
S2—C9	1.753 (3)	C5—C8	1.465 (4)
S2—C10	1.810 (3)	C6—C7	1.383 (4)
S3—C11	1.745 (3)	C6—H6	0.9500
S3—C10	1.801 (3)	C7—H7	0.9500
S4—C11	1.725 (3)	C10—H10A	0.9900
S4—C12	1.743 (3)	C10—H10B	0.9900
N1—C8	1.304 (4)	C12—C13	1.469 (4)
N1—N2	1.393 (4)	C13—C14	1.394 (4)
N2—C9	1.297 (4)	C13—C18	1.397 (4)
N3—C11	1.310 (4)	C14—C15	1.386 (4)
N3—N4	1.393 (4)	C14—H14	0.9500
N4—C12	1.311 (4)	C15—C16	1.391 (4)
C1—C2	1.510 (4)	C15—H15	0.9500
C1—H1A	0.9800	C16—C17	1.403 (5)
C1—H1B	0.9800	C16—C19	1.506 (4)
C1—H1C	0.9800	C17—C18	1.386 (5)
C2—C7	1.398 (4)	C17—H17	0.9500
C2—C3	1.403 (4)	C18—H18	0.9500
C3—C4	1.382 (4)	C19—H19A	0.9800
C3—H3	0.9500	C19—H19B	0.9800
C4—C5	1.393 (4)	C19—H19C	0.9800

C9—S1—C8	87.06 (15)	S1—C9—S2	119.18 (19)
C9—S2—C10	99.51 (15)	S3—C10—S2	115.46 (17)
C11—S3—C10	98.52 (15)	S3—C10—H10A	108.4
C11—S4—C12	87.24 (15)	S2—C10—H10A	108.4
C8—N1—N2	113.2 (3)	S3—C10—H10B	108.4
C9—N2—N1	111.9 (3)	S2—C10—H10B	108.4
C11—N3—N4	111.6 (3)	H10A—C10—H10B	107.5
C12—N4—N3	113.2 (3)	N3—C11—S4	114.7 (2)
C2—C1—H1A	109.5	N3—C11—S3	123.5 (2)
C2—C1—H1B	109.5	S4—C11—S3	121.77 (18)
H1A—C1—H1B	109.5	N4—C12—C13	123.9 (3)
C2—C1—H1C	109.5	N4—C12—S4	113.2 (2)
H1A—C1—H1C	109.5	C13—C12—S4	123.0 (2)
H1B—C1—H1C	109.5	C14—C13—C18	118.6 (3)
C7—C2—C3	117.7 (3)	C14—C13—C12	121.2 (3)
C7—C2—C1	121.0 (3)	C18—C13—C12	120.1 (3)
C3—C2—C1	121.3 (3)	C15—C14—C13	120.3 (3)
C4—C3—C2	121.4 (3)	C15—C14—H14	119.8
C4—C3—H3	119.3	C13—C14—H14	119.8
C2—C3—H3	119.3	C14—C15—C16	121.9 (3)
C3—C4—C5	120.2 (3)	C14—C15—H15	119.1
C3—C4—H4	119.9	C16—C15—H15	119.1
C5—C4—H4	119.9	C15—C16—C17	117.3 (3)
C4—C5—C6	119.2 (3)	C15—C16—C19	122.4 (3)
C4—C5—C8	121.0 (3)	C17—C16—C19	120.3 (3)
C6—C5—C8	119.8 (3)	C18—C17—C16	121.4 (3)
C7—C6—C5	120.2 (3)	C18—C17—H17	119.3
C7—C6—H6	119.9	C16—C17—H17	119.3
C5—C6—H6	119.9	C17—C18—C13	120.4 (3)
C6—C7—C2	121.3 (3)	C17—C18—H18	119.8
C6—C7—H7	119.3	C13—C18—H18	119.8
C2—C7—H7	119.3	C16—C19—H19A	109.5
N1—C8—C5	124.5 (3)	C16—C19—H19B	109.5
N1—C8—S1	113.2 (2)	H19A—C19—H19B	109.5
C5—C8—S1	122.3 (2)	C16—C19—H19C	109.5
N2—C9—S1	114.6 (2)	H19A—C19—H19C	109.5
N2—C9—S2	126.2 (3)	H19B—C19—H19C	109.5

C8—N1—N2—C9	1.0 (4)	C11—S3—C10—S2	67.8 (2)
C11—N3—N4—C12	0.4 (4)	C9—S2—C10—S3	104.05 (19)
C7—C2—C3—C4	−1.3 (5)	N4—N3—C11—S4	−0.1 (3)
C1—C2—C3—C4	178.2 (3)	N4—N3—C11—S3	178.8 (2)
C2—C3—C4—C5	0.4 (5)	C12—S4—C11—N3	−0.2 (3)
C3—C4—C5—C6	0.1 (5)	C12—S4—C11—S3	−179.1 (2)
C3—C4—C5—C8	−179.6 (3)	C10—S3—C11—N3	−2.0 (3)
C4—C5—C6—C7	0.2 (5)	C10—S3—C11—S4	176.80 (19)
C8—C5—C6—C7	179.9 (3)	N3—N4—C12—C13	−179.3 (3)
C5—C6—C7—C2	−1.0 (5)	N3—N4—C12—S4	−0.6 (3)
C3—C2—C7—C6	1.6 (5)	C11—S4—C12—N4	0.4 (2)
C1—C2—C7—C6	−177.9 (3)	C11—S4—C12—C13	179.2 (3)
N2—N1—C8—C5	178.9 (3)	N4—C12—C13—C14	−179.8 (3)
N2—N1—C8—S1	−0.9 (3)	S4—C12—C13—C14	1.6 (4)
C4—C5—C8—N1	179.1 (3)	N4—C12—C13—C18	0.3 (5)
C6—C5—C8—N1	−0.7 (5)	S4—C12—C13—C18	−178.3 (2)
C4—C5—C8—S1	−1.2 (4)	C18—C13—C14—C15	−0.8 (5)
C6—C5—C8—S1	179.1 (2)	C12—C13—C14—C15	179.3 (3)
C9—S1—C8—N1	0.4 (2)	C13—C14—C15—C16	−0.5 (5)
C9—S1—C8—C5	−179.4 (3)	C14—C15—C16—C17	1.5 (5)
N1—N2—C9—S1	−0.7 (3)	C14—C15—C16—C19	−177.1 (3)
N1—N2—C9—S2	−178.4 (2)	C15—C16—C17—C18	−1.3 (5)
C8—S1—C9—N2	0.2 (3)	C19—C16—C17—C18	177.4 (3)
C8—S1—C9—S2	178.1 (2)	C16—C17—C18—C13	0.0 (5)
C10—S2—C9—N2	−16.9 (3)	C14—C13—C18—C17	1.0 (5)
C10—S2—C9—S1	165.53 (19)	C12—C13—C18—C17	−179.1 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV5245).

References

Carvalho, S. A., da Silva, E. F., Santa-Rita, R. M., de Castro, S. L. & Fraga, C. A. M. (2004). Bioorg. Med. Chem. Lett. 14, 5967–5970. [PubMed]
Li, S., Zhang, J., Jia, X., Gao, Y. & Wang, W. (2011). Acta Cryst. E67, o681. [PMC free article] [PubMed]
Nakagawa, Y., Nishimura, K., Izumi, K., Kinoshita, K., Kimura, T. & Kurihara, N. (1996). J. Pestic. Sci. 21, 195–201.
Rigaku/MSC (2005). CrystalClear Molecular Structure Corporation, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
Wang, Y. G., Cao, L., Yan, J., Ye, W. F., Zhou, Q. C. & Lu, B. X. (1999). Chem. J. Chin. Univ. 20, 1903–1905.
Wang, H., Gao, Y. & Wang, W. (2010). Acta Cryst. E66, o3085. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of
International Union of Crystallography