(E)-N-(4-Chloro­benzyl­idene)-5-(4-methyl­phen­yl)-1,3,4-thia­diazol-2-amine

Yu, P.; Wang, P.; Zhang, J.-Q.; He, Q.; Wan, R.

doi:10.1107/S1600536811008841

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o861

doi:10.1107/S1600536811008841

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(E)-N-(4-Chlorobenzylidene)-5-(4-methylphenyl)-1,3,4-thiadiazol-2-amine

Peng Yu,^a Peng Wang,^a Jian-Qiang Zhang,^a Qiu He ^a and Rong Wan ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 7 March 2011; accepted 8 March 2011; online 12 March 2011)

The title compound, C₁₆H₁₂ClN₃S, was synthesized by the reaction of 5-(4-methylphenyl)-1,3,4-thiadiazol-2-amine and 4-chlorobenzaldehyde. The thiadiazole ring is essentially planar with mean deviation of 0.0042 Å.

Related literature

For the biological activity of 1,3,4-thiadiazole derivatives, see: He et al. (2010 ); Nakagawa et al. (1996 ); Wang et al. (1999 ).

Experimental

Crystal data

C₁₆H₁₂ClN₃S
M_r = 313.80
Triclinic, $[P \overline 1]$
a = 5.7940 (12) Å
b = 8.7510 (18) Å
c = 14.965 (3) Å
α = 98.64 (3)°
β = 90.66 (3)°
γ = 99.45 (3)°
V = 739.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.891, T_max = 0.962
3001 measured reflections
2708 independent reflections
1816 reflections with I > 2σ(I)
R_int = 0.027
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.179
S = 1.00
2708 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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/S1600536811008841/hg5007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008841/hg5007Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996; Wang et al., 1999). These compounds are known to exhibit diverse biological effects, such as insecticidal, fungicidal activities (Wang et al., 1999).

We are focusing our synthetic and structural studies on thiadiazole derivatives and published the structure of 2-(4-Fluoro-benzylidene)-[5-(4-methoxy-phenyl)-[1,3,4]thiadiazol-2-yl]-amine (He et al., 2010). We report here the crystal structure of the titled compound,(I). The molecular structure of (I) is shown in Fig.1. In this structure, ring A (S/C8/N1/N2/C9/) is a planar five-membered ring and the mean deviation from plane is 0.0042 Å. In this plane, the standard deviations for the distances of S, C8, N1, N2 and C9 to mean plane are 0.0049, -0.0032, -0.0006, -0.0018, 0.0057 and -0.0068, respectively. Ring B(C2—C7) and Ring C(C11—C16) are, of course, planar. The dihedral angles between them are A/B=21.9 (2) Å, A/C= 22.6 (3) Å, B/C =44.3 (2) Å, respectively. The intramolecular C—H···S hydrogen bonds (Table 1) result in the formation of two planar five-membered rings D(S/C8/C5/C6/H6A) and E(S/C9/N3/C10/H10A) which oriented with respect to the adjacent ring A at dihedral angles of A/D=18.2 (4) Å, A/E= 6.0 (4) Å. So ring A and ring E are nearly coplanar.

Related literature top

For the biological activity of 1,3,4-thiadiazole derivatives, see: He et al. (2010); Nakagawa et al. (1996); Wang et al. (1999).

Experimental top

5-(4-methylphenyl)-1,3,4-thiadiazol-2-yl amine (5 mmol) and 4-chlorobenzaldehyde (50 ml) were added in toluene, refluxed until stoichiometric water was collected in a Dean-Stark water separator. The reaction mixture was left to cool to room temperature, filtered, and the filter cake was crystallized from acetone to give pure compound (I) (m.p. 415–416 K). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate intramolecular C—H···S hydrogen bonds.
	Fig. 2. A packing diagram for (I). Dashed lines indicate intramolecular C—H···S hydrogen bonds.

(E)-N-(4-Chlorobenzylidene)-5-(4-methylphenyl)-1,3,4- thiadiazol-2-amine top

Crystal data top

C₁₆H₁₂ClN₃S	Z = 2
M_r = 313.80	F(000) = 324
Triclinic, P1	D_x = 1.409 Mg m⁻³
Hall symbol: -P 1	Melting point = 415–416 K
a = 5.7940 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7510 (18) Å	Cell parameters from 25 reflections
c = 14.965 (3) Å	θ = 9–12°
α = 98.64 (3)°	µ = 0.40 mm⁻¹
β = 90.66 (3)°	T = 293 K
γ = 99.45 (3)°	Plate, colorless
V = 739.5 (3) Å³	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 25.4°, θ_min = 1.4°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al.,1968)	k = −10→10
T_min = 0.891, T_max = 0.962	l = −18→18
3001 measured reflections	3 standard reflections every 200 reflections
2708 independent reflections	intensity decay: 1%

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.097P)²] where P = (F_o² + 2F_c²)/3
2708 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₆H₁₂ClN₃S	γ = 99.45 (3)°
M_r = 313.80	V = 739.5 (3) Å³
Triclinic, P1	Z = 2
a = 5.7940 (12) Å	Mo Kα radiation
b = 8.7510 (18) Å	µ = 0.40 mm⁻¹
c = 14.965 (3) Å	T = 293 K
α = 98.64 (3)°	0.30 × 0.10 × 0.10 mm
β = 90.66 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1816 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al.,1968)	R_int = 0.027
T_min = 0.891, T_max = 0.962	3 standard reflections every 200 reflections
3001 measured reflections	intensity decay: 1%
2708 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
2708 reflections	Δρ_min = −0.33 e Å⁻³
190 parameters

Special details top

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
S	0.23283 (16)	0.39838 (13)	0.35972 (7)	0.0476 (3)
Cl	−0.1368 (3)	−0.07874 (15)	0.83792 (8)	0.0817 (5)
N1	0.6673 (6)	0.4295 (4)	0.3257 (2)	0.0519 (9)
C1	0.3679 (10)	0.7600 (6)	−0.0164 (3)	0.0755 (15)
H1B	0.2081	0.7357	−0.0388	0.113*
H1C	0.4673	0.7212	−0.0622	0.113*
H1D	0.4125	0.8715	−0.0008	0.113*
N2	0.6450 (6)	0.3517 (4)	0.3990 (2)	0.0541 (9)
C2	0.3925 (8)	0.6843 (5)	0.0659 (3)	0.0514 (10)
N3	0.3694 (6)	0.2419 (4)	0.4943 (2)	0.0453 (8)
C3	0.6064 (8)	0.7020 (5)	0.1130 (3)	0.0549 (11)
H3B	0.7361	0.7632	0.0927	0.066*
C4	0.6334 (7)	0.6324 (5)	0.1885 (3)	0.0509 (10)
H4A	0.7784	0.6480	0.2188	0.061*
C5	0.4413 (6)	0.5384 (4)	0.2189 (2)	0.0411 (9)
C6	0.2262 (7)	0.5216 (5)	0.1734 (3)	0.0484 (10)
H6A	0.0957	0.4613	0.1937	0.058*
C7	0.2041 (7)	0.5928 (5)	0.0990 (3)	0.0527 (10)
H7A	0.0580	0.5794	0.0698	0.063*
C8	0.4687 (6)	0.4610 (4)	0.2982 (2)	0.0393 (8)
C9	0.4290 (7)	0.3246 (4)	0.4246 (3)	0.0431 (9)
C10	0.1634 (7)	0.2334 (4)	0.5231 (3)	0.0453 (9)
H10A	0.0582	0.2843	0.4964	0.054*
C11	0.0852 (7)	0.1474 (4)	0.5959 (2)	0.0433 (9)
C12	0.2161 (7)	0.0438 (4)	0.6275 (3)	0.0455 (9)
H12A	0.3516	0.0236	0.5986	0.055*
C13	0.1470 (8)	−0.0277 (5)	0.7001 (3)	0.0536 (10)
H13A	0.2334	−0.0969	0.7207	0.064*
C14	−0.0557 (8)	0.0053 (5)	0.7428 (3)	0.0513 (10)
C15	−0.1919 (7)	0.1018 (5)	0.7109 (3)	0.0529 (10)
H15A	−0.3294	0.1195	0.7391	0.063*
C16	−0.1227 (7)	0.1715 (5)	0.6373 (3)	0.0481 (10)
H16A	−0.2153	0.2354	0.6148	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0299 (5)	0.0636 (7)	0.0531 (6)	0.0081 (4)	0.0042 (4)	0.0203 (5)
Cl	0.1063 (11)	0.0751 (9)	0.0674 (8)	0.0093 (8)	0.0292 (8)	0.0275 (7)
N1	0.0352 (18)	0.065 (2)	0.061 (2)	0.0123 (16)	0.0090 (16)	0.0222 (18)
C1	0.091 (4)	0.078 (3)	0.058 (3)	0.004 (3)	0.012 (3)	0.019 (2)
N2	0.0350 (19)	0.069 (2)	0.064 (2)	0.0163 (17)	0.0095 (16)	0.0223 (18)
C2	0.062 (3)	0.051 (2)	0.041 (2)	0.011 (2)	0.010 (2)	0.0053 (18)
N3	0.0394 (18)	0.0472 (18)	0.0524 (19)	0.0119 (15)	0.0037 (15)	0.0125 (15)
C3	0.049 (3)	0.057 (3)	0.057 (3)	0.000 (2)	0.016 (2)	0.013 (2)
C4	0.039 (2)	0.055 (2)	0.056 (2)	0.0050 (19)	0.0035 (18)	0.006 (2)
C5	0.040 (2)	0.039 (2)	0.042 (2)	0.0035 (17)	0.0042 (16)	0.0024 (16)
C6	0.038 (2)	0.058 (2)	0.047 (2)	−0.0003 (18)	0.0041 (17)	0.0078 (18)
C7	0.043 (2)	0.064 (3)	0.048 (2)	0.003 (2)	−0.0022 (18)	0.009 (2)
C8	0.0298 (19)	0.040 (2)	0.047 (2)	0.0063 (16)	0.0047 (16)	0.0023 (16)
C9	0.039 (2)	0.045 (2)	0.046 (2)	0.0113 (17)	0.0026 (17)	0.0051 (17)
C10	0.041 (2)	0.047 (2)	0.050 (2)	0.0121 (18)	0.0021 (18)	0.0084 (18)
C11	0.038 (2)	0.046 (2)	0.043 (2)	0.0069 (17)	−0.0031 (17)	0.0010 (17)
C12	0.037 (2)	0.044 (2)	0.056 (2)	0.0080 (17)	0.0081 (18)	0.0073 (18)
C13	0.056 (3)	0.049 (2)	0.058 (3)	0.013 (2)	0.005 (2)	0.0115 (19)
C14	0.060 (3)	0.043 (2)	0.048 (2)	0.000 (2)	0.005 (2)	0.0051 (18)
C15	0.038 (2)	0.054 (2)	0.064 (3)	0.0032 (19)	0.0130 (19)	0.003 (2)
C16	0.041 (2)	0.053 (2)	0.052 (2)	0.0108 (19)	0.0015 (18)	0.0098 (19)

Geometric parameters (Å, º) top

S—C8	1.718 (4)	C5—C6	1.389 (5)
S—C9	1.748 (4)	C5—C8	1.471 (5)
Cl—C14	1.734 (4)	C6—C7	1.369 (5)
N1—C8	1.303 (5)	C6—H6A	0.9300
N1—N2	1.371 (4)	C7—H7A	0.9300
C1—C2	1.500 (6)	C10—C11	1.451 (5)
C1—H1B	0.9600	C10—H10A	0.9300
C1—H1C	0.9600	C11—C16	1.393 (5)
C1—H1D	0.9600	C11—C12	1.402 (5)
N2—C9	1.308 (5)	C12—C13	1.366 (5)
C2—C7	1.386 (6)	C12—H12A	0.9300
C2—C3	1.392 (6)	C13—C14	1.394 (6)
N3—C10	1.268 (5)	C13—H13A	0.9300
N3—C9	1.372 (5)	C14—C15	1.376 (6)
C3—C4	1.381 (5)	C15—C16	1.371 (5)
C3—H3B	0.9300	C15—H15A	0.9300
C4—C5	1.395 (5)	C16—H16A	0.9300
C4—H4A	0.9300

C8—S—C9	86.66 (18)	N1—C8—C5	123.9 (3)
C8—N1—N2	112.6 (3)	N1—C8—S	114.6 (3)
C2—C1—H1B	109.5	C5—C8—S	121.4 (3)
C2—C1—H1C	109.5	N2—C9—N3	121.5 (3)
H1B—C1—H1C	109.5	N2—C9—S	113.3 (3)
C2—C1—H1D	109.5	N3—C9—S	125.2 (3)
H1B—C1—H1D	109.5	N3—C10—C11	122.6 (4)
H1C—C1—H1D	109.5	N3—C10—H10A	118.7
C9—N2—N1	112.7 (3)	C11—C10—H10A	118.7
C7—C2—C3	116.6 (4)	C16—C11—C12	119.0 (4)
C7—C2—C1	121.8 (4)	C16—C11—C10	119.1 (4)
C3—C2—C1	121.6 (4)	C12—C11—C10	121.9 (3)
C10—N3—C9	119.0 (3)	C13—C12—C11	120.8 (4)
C4—C3—C2	122.5 (4)	C13—C12—H12A	119.6
C4—C3—H3B	118.7	C11—C12—H12A	119.6
C2—C3—H3B	118.7	C12—C13—C14	118.6 (4)
C3—C4—C5	119.5 (4)	C12—C13—H13A	120.7
C3—C4—H4A	120.3	C14—C13—H13A	120.7
C5—C4—H4A	120.3	C15—C14—C13	121.6 (4)
C6—C5—C4	118.5 (4)	C15—C14—Cl	119.7 (3)
C6—C5—C8	121.4 (3)	C13—C14—Cl	118.7 (3)
C4—C5—C8	120.0 (3)	C16—C15—C14	119.3 (4)
C7—C6—C5	120.8 (4)	C16—C15—H15A	120.4
C7—C6—H6A	119.6	C14—C15—H15A	120.4
C5—C6—H6A	119.6	C15—C16—C11	120.5 (4)
C6—C7—C2	122.1 (4)	C15—C16—H16A	119.7
C6—C7—H7A	119.0	C11—C16—H16A	119.7
C2—C7—H7A	119.0

C8—N1—N2—C9	0.7 (5)	N1—N2—C9—N3	177.1 (3)
C7—C2—C3—C4	0.4 (6)	N1—N2—C9—S	−1.2 (5)
C1—C2—C3—C4	−179.5 (4)	C10—N3—C9—N2	172.4 (4)
C2—C3—C4—C5	0.9 (6)	C10—N3—C9—S	−9.6 (5)
C3—C4—C5—C6	−1.8 (6)	C8—S—C9—N2	1.0 (3)
C3—C4—C5—C8	178.8 (3)	C8—S—C9—N3	−177.2 (3)
C4—C5—C6—C7	1.5 (6)	C9—N3—C10—C11	179.5 (3)
C8—C5—C6—C7	−179.2 (3)	N3—C10—C11—C16	165.7 (4)
C5—C6—C7—C2	−0.1 (6)	N3—C10—C11—C12	−12.5 (6)
C3—C2—C7—C6	−0.8 (6)	C16—C11—C12—C13	−2.7 (6)
C1—C2—C7—C6	179.1 (4)	C10—C11—C12—C13	175.5 (4)
N2—N1—C8—C5	−177.7 (3)	C11—C12—C13—C14	−0.5 (6)
N2—N1—C8—S	0.1 (4)	C12—C13—C14—C15	3.0 (6)
C6—C5—C8—N1	157.1 (4)	C12—C13—C14—Cl	−177.2 (3)
C4—C5—C8—N1	−23.5 (6)	C13—C14—C15—C16	−2.2 (6)
C6—C5—C8—S	−20.5 (5)	Cl—C14—C15—C16	178.0 (3)
C4—C5—C8—S	158.9 (3)	C14—C15—C16—C11	−1.1 (6)
C9—S—C8—N1	−0.6 (3)	C12—C11—C16—C15	3.5 (6)
C9—S—C8—C5	177.2 (3)	C10—C11—C16—C15	−174.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···S	0.93	2.76	3.139 (5)	106
C10—H10A···S	0.93	2.56	3.019 (4)	111

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂ClN₃S
M_r	313.80
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.7940 (12), 8.7510 (18), 14.965 (3)
α, β, γ (°)	98.64 (3), 90.66 (3), 99.45 (3)
V (Å³)	739.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al.,1968)
T_min, T_max	0.891, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	3001, 2708, 1816
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.179, 1.00
No. of reflections	2708
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.33

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···S	0.93	2.76	3.139 (5)	106
C10—H10A···S	0.93	2.56	3.019 (4)	111

Acknowledgements

The authors would like to thank Professor Hua-qin Wang of Nanjing University for carrying out the X-ray crystallographic analysis.

References

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