4-Chloro-N-[3-methyl-1-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)but­yl]benzamide

Abstract

In the title compound, C₁₄H₁₆ClN₃O₂S, the dihedral angle between the 4-chloro­phenyl and 1,3,4-oxadiazole rings is 67.1 (1)° and the orientation of the amide N—H and C=O bonds is anti. In the crystal, mol­ecules are linked by N—H⋯O and N—H⋯S hydrogen bonds.

Related literature

For the biological properties of thia­diazo­les, see: Tu et al. (2008 ▶). For details of the synthesis, see: Ginzel et al. (1989 ▶); Boland et al. (2006 ▶); Havaldar & Patil (2009 ▶); Shriner & Furrow (1955 ▶). For related structures, see: Du et al. (2004 ▶); Ziyaev et al. (1992 ▶); Zareef et al. (2006 ▶).

Experimental

Crystal data

• C₁₄H₁₆ClN₃O₂S

• M _r = 325.81

• Orthorhombic,

• a = 6.0171 (6) Å

• b = 15.3120 (15) Å

• c = 18.1493 (17) Å

• V = 1672.2 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 298 K

• 0.42 × 0.22 × 0.18 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.864, T _max = 0.938

• 7892 measured reflections

• 2951 independent reflections

• 1447 reflections with I > 2σ(I)

• R _int = 0.056

Refinement

• R[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 0.108

• S = 1.10

• 2951 reflections

• 193 parameters

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1219 Friedel pairs

• Flack parameter: −0.09 (14)

Data collection: SMART (Bruker, 2001 ▶); 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 (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	1.87	2.720 (6)	171
N3—H3⋯S1ii	0.86	2.78	3.495 (4)	142

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The present oxadiazole derivate is in continuation to our previous work of the thiadiazole scaffold compounds and their biological activity (Tu et al., 2008). The title compound (Figure 1) was synthesized according to literature procedures (Ginzel et al., 1989; Boland et al., 2006; Havaldar & Patil 2009). Here, we report the structure of the title compound.

The oxadiazole ring is essentially planar and is inclined at 67.1 (1)° with respect to the p-cholobenzene ring. The N2=C2 and S1=C1 double bonds agree with the corresponding distances in three structures containing similar systems (Du et al., 2004; Ziyaev et al., 1992; Zareef et al., 2006). The conformations of the N—H and C=O bonds are anti with respect to each other. The structure is stabilized by a network of intermolecular hydrogen bonds of the type N—H···S (Table 1, Figure 2).

Experimental

To a stirred solution of DL-leucine methyl ester hydrochloride (0.03 mol) in CH₂Cl₂ (20 ml) was added triethylamine (0.06 mol) at 273 K. After 0.5 h, a solution of p-chlorobenzoic acid chloride (0.03 mol) in CH₂Cl₂ (10 ml) was added. The mixture was stirred for 2 h at 273 K, then allowed to warm to r.t. for 24 h. Washed with 10% HCl, 1 N NaOH and water. The organic layer was evaporated in vacuo and the residue was recrystallized from methanol to give corresponding amides as a white solid.

A mixture of the amides (0.02 mol) and 80% hydrazine monohydrate (0.04 mol) in absolute methanol (20 ml) was heated under reflux over night. After cooling, a white solid was separated and recrystallized from methanol to give corresponding hydrazide.

A mixture of the hydrazide (0.01 mol), KOH (0.01 mol), CS₂ (0.05 mol), and ethanol (70 ml) was heated under reflux with stirring for 12 h. Ethanol was distilled off under reduced pressure and the residue was dissolved in water and then acidified with 10% HCl. The resulting precipitate was filtered, washed with water, and recrystallized from ethanol. Colourless blocks of (I) precipitated after several days.

Refinement

H atoms were positioned geometrically and refined using a riding model using SHELXL97 default values (Uiso(H) = 1.2 Ueq(C) for CH and CH₂ groups and Uiso(H) = 1.5 Ueq(C) for CH₃).

Figures

Fig. 1.

Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

The crystal packing of (I), viewed along the a axis with hydrogen bonds drawn as dashed lines.

Crystal data

C14H16ClN3O2S	F(000) = 680
Mr = 325.81	Dx = 1.294 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2117 reflections
a = 6.0171 (6) Å	θ = 2.6–21.7°
b = 15.3120 (15) Å	µ = 0.36 mm−1
c = 18.1493 (17) Å	T = 298 K
V = 1672.2 (3) Å3	Block, colourless
Z = 4	0.42 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer	2951 independent reflections
Radiation source: fine-focus sealed tube	1447 reflections with I > 2σ(I)
graphite	Rint = 0.056
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.864, Tmax = 0.938	k = −18→11
7892 measured reflections	l = −21→16

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.050	w = 1/[σ2(Fo2) + (0.0147P)2 + 1.0529P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.31 e Å−3
2951 reflections	Δρmin = −0.32 e Å−3
193 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0034 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1219 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.09 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	1.2875 (3)	0.07537 (10)	−0.04447 (8)	0.1082 (7)
N1	0.4961 (8)	0.5638 (3)	0.2486 (2)	0.0653 (12)
H1	0.4553	0.6175	0.2515	0.078*
N2	0.6705 (8)	0.5299 (2)	0.2891 (2)	0.0679 (12)
N3	0.9177 (6)	0.3351 (2)	0.22952 (19)	0.0530 (10)
H3	1.0323	0.3577	0.2086	0.064*
O1	0.5141 (6)	0.4303 (2)	0.21792 (16)	0.0650 (10)
O2	0.6632 (6)	0.22820 (19)	0.23058 (17)	0.0672 (10)
S1	0.1860 (3)	0.51382 (10)	0.14928 (8)	0.0902 (5)
C1	0.3976 (8)	0.5066 (3)	0.2049 (2)	0.0601 (13)
C2	0.6745 (10)	0.4498 (3)	0.2683 (2)	0.0555 (13)
C3	0.8216 (9)	0.3780 (3)	0.2935 (2)	0.0572 (13)
H3A	0.7295	0.3352	0.3195	0.069*
C4	0.9999 (9)	0.4102 (3)	0.3469 (2)	0.0628 (14)
H4A	1.0827	0.4567	0.3233	0.075*
H4B	0.9271	0.4348	0.3898	0.075*
C5	1.1631 (10)	0.3406 (3)	0.3725 (3)	0.0793 (17)
H5	1.2452	0.3206	0.3290	0.095*
C6	1.3329 (10)	0.3803 (4)	0.4260 (3)	0.097 (2)
H6A	1.2604	0.3948	0.4715	0.145*
H6B	1.3955	0.4321	0.4046	0.145*
H6C	1.4490	0.3387	0.4353	0.145*
C7	1.0511 (12)	0.2623 (4)	0.4053 (3)	0.129 (3)
H7A	0.9645	0.2799	0.4471	0.193*
H7B	1.1615	0.2208	0.4205	0.193*
H7C	0.9557	0.2360	0.3692	0.193*
C8	0.8305 (9)	0.2601 (3)	0.2021 (2)	0.0520 (12)
C9	0.9491 (9)	0.2185 (3)	0.1398 (3)	0.0518 (13)
C10	0.8393 (9)	0.1520 (3)	0.1025 (2)	0.0575 (13)
H10	0.6966	0.1359	0.1168	0.069*
C11	0.9413 (10)	0.1093 (3)	0.0440 (3)	0.0673 (15)
H11	0.8661	0.0660	0.0181	0.081*
C12	1.1541 (11)	0.1319 (3)	0.0247 (3)	0.0663 (15)
C13	1.2613 (9)	0.1986 (3)	0.0598 (3)	0.0681 (15)
H13	1.4027	0.2153	0.0446	0.082*
C14	1.1604 (9)	0.2411 (3)	0.1174 (3)	0.0639 (14)
H14	1.2355	0.2858	0.1416	0.077*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.1383 (16)	0.0987 (12)	0.0876 (10)	0.0156 (12)	0.0383 (11)	−0.0126 (9)
N1	0.069 (3)	0.046 (3)	0.081 (3)	0.002 (3)	−0.002 (3)	−0.005 (2)
N2	0.078 (3)	0.047 (3)	0.079 (3)	0.005 (3)	−0.012 (3)	−0.004 (2)
N3	0.050 (3)	0.044 (2)	0.066 (3)	−0.006 (2)	0.007 (2)	−0.0108 (19)
O1	0.079 (3)	0.045 (2)	0.071 (2)	0.002 (2)	−0.019 (2)	−0.0068 (17)
O2	0.069 (3)	0.046 (2)	0.086 (2)	−0.004 (2)	0.016 (2)	−0.0039 (17)
S1	0.0914 (12)	0.0756 (10)	0.1037 (11)	−0.0050 (10)	−0.0315 (10)	0.0091 (9)
C1	0.064 (4)	0.058 (3)	0.058 (3)	−0.009 (3)	−0.004 (3)	−0.002 (3)
C2	0.074 (4)	0.037 (3)	0.056 (3)	0.004 (3)	0.001 (3)	−0.005 (2)
C3	0.072 (4)	0.046 (3)	0.053 (3)	0.001 (3)	0.009 (3)	−0.002 (2)
C4	0.074 (4)	0.056 (3)	0.058 (3)	0.001 (3)	−0.007 (3)	−0.004 (3)
C5	0.088 (5)	0.075 (4)	0.074 (4)	0.001 (4)	−0.015 (4)	0.007 (3)
C6	0.094 (5)	0.109 (5)	0.088 (4)	0.010 (4)	−0.017 (4)	0.003 (3)
C7	0.140 (7)	0.092 (5)	0.154 (6)	−0.018 (5)	−0.040 (5)	0.056 (5)
C8	0.056 (3)	0.043 (3)	0.057 (3)	0.000 (3)	0.000 (3)	0.001 (2)
C9	0.057 (3)	0.037 (3)	0.062 (3)	−0.002 (3)	−0.006 (3)	−0.003 (2)
C10	0.062 (4)	0.044 (3)	0.067 (3)	−0.004 (3)	0.001 (3)	0.002 (2)
C11	0.097 (5)	0.048 (3)	0.056 (3)	0.001 (3)	−0.001 (3)	−0.001 (3)
C12	0.084 (5)	0.055 (3)	0.059 (3)	0.011 (4)	0.007 (3)	0.005 (3)
C13	0.063 (4)	0.068 (4)	0.074 (3)	0.005 (3)	0.014 (3)	0.006 (3)
C14	0.067 (4)	0.051 (3)	0.074 (3)	−0.003 (3)	−0.002 (3)	0.000 (3)

Geometric parameters (Å, °)

Cl1—C12	1.723 (5)	C5—C6	1.535 (7)
N1—C1	1.321 (5)	C5—H5	0.9800
N1—N2	1.382 (5)	C6—H6A	0.9600
N1—H1	0.8600	C6—H6B	0.9600
N2—C2	1.283 (5)	C6—H6C	0.9600
N3—C8	1.357 (5)	C7—H7A	0.9600
N3—C3	1.454 (5)	C7—H7B	0.9600
N3—H3	0.8600	C7—H7C	0.9600
O1—C2	1.363 (5)	C8—C9	1.481 (6)
O1—C1	1.382 (5)	C9—C14	1.379 (6)
O2—C8	1.232 (5)	C9—C10	1.390 (6)
S1—C1	1.629 (5)	C10—C11	1.390 (6)
C2—C3	1.483 (6)	C10—H10	0.9300
C3—C4	1.527 (6)	C11—C12	1.372 (7)
C3—H3A	0.9800	C11—H11	0.9300
C4—C5	1.522 (6)	C12—C13	1.366 (6)
C4—H4A	0.9700	C13—C14	1.373 (6)
C4—H4B	0.9700	C13—H13	0.9300
C5—C7	1.498 (7)	C14—H14	0.9300
C1—N1—N2	114.3 (4)	C5—C6—H6B	109.5
C1—N1—H1	122.9	H6A—C6—H6B	109.5
N2—N1—H1	122.9	C5—C6—H6C	109.5
C2—N2—N1	102.5 (4)	H6A—C6—H6C	109.5
C8—N3—C3	121.5 (4)	H6B—C6—H6C	109.5
C8—N3—H3	119.3	C5—C7—H7A	109.5
C3—N3—H3	119.3	C5—C7—H7B	109.5
C2—O1—C1	106.8 (3)	H7A—C7—H7B	109.5
N1—C1—O1	103.3 (4)	C5—C7—H7C	109.5
N1—C1—S1	132.6 (4)	H7A—C7—H7C	109.5
O1—C1—S1	124.0 (4)	H7B—C7—H7C	109.5
N2—C2—O1	113.1 (5)	O2—C8—N3	119.8 (4)
N2—C2—C3	128.9 (5)	O2—C8—C9	122.9 (4)
O1—C2—C3	117.9 (4)	N3—C8—C9	117.2 (4)
N3—C3—C2	109.0 (3)	C14—C9—C10	118.6 (5)
N3—C3—C4	111.9 (4)	C14—C9—C8	124.2 (4)
C2—C3—C4	112.1 (4)	C10—C9—C8	117.3 (5)
N3—C3—H3A	107.9	C11—C10—C9	120.4 (5)
C2—C3—H3A	107.9	C11—C10—H10	119.8
C4—C3—H3A	107.9	C9—C10—H10	119.8
C5—C4—C3	114.9 (4)	C12—C11—C10	119.3 (5)
C5—C4—H4A	108.5	C12—C11—H11	120.4
C3—C4—H4A	108.5	C10—C11—H11	120.4
C5—C4—H4B	108.5	C13—C12—C11	120.7 (5)
C3—C4—H4B	108.5	C13—C12—Cl1	119.7 (5)
H4A—C4—H4B	107.5	C11—C12—Cl1	119.6 (5)
C7—C5—C4	113.0 (5)	C12—C13—C14	120.1 (5)
C7—C5—C6	111.4 (5)	C12—C13—H13	120.0
C4—C5—C6	110.2 (4)	C14—C13—H13	120.0
C7—C5—H5	107.3	C13—C14—C9	120.9 (5)
C4—C5—H5	107.3	C13—C14—H14	119.6
C6—C5—H5	107.3	C9—C14—H14	119.6
C5—C6—H6A	109.5
C1—N1—N2—C2	0.1 (6)	C3—C4—C5—C6	−179.7 (4)
N2—N1—C1—O1	0.3 (5)	C3—N3—C8—O2	1.7 (7)
N2—N1—C1—S1	178.2 (4)	C3—N3—C8—C9	−176.2 (4)
C2—O1—C1—N1	−0.5 (5)	O2—C8—C9—C14	−165.1 (4)
C2—O1—C1—S1	−178.7 (3)	N3—C8—C9—C14	12.7 (7)
N1—N2—C2—O1	−0.5 (5)	O2—C8—C9—C10	14.3 (7)
N1—N2—C2—C3	−178.1 (5)	N3—C8—C9—C10	−167.9 (4)
C1—O1—C2—N2	0.7 (5)	C14—C9—C10—C11	0.1 (7)
C1—O1—C2—C3	178.6 (4)	C8—C9—C10—C11	−179.3 (4)
C8—N3—C3—C2	−98.1 (5)	C9—C10—C11—C12	1.8 (7)
C8—N3—C3—C4	137.4 (4)	C10—C11—C12—C13	−3.5 (7)
N2—C2—C3—N3	−129.7 (5)	C10—C11—C12—Cl1	176.5 (3)
O1—C2—C3—N3	52.8 (6)	C11—C12—C13—C14	3.2 (8)
N2—C2—C3—C4	−5.2 (8)	Cl1—C12—C13—C14	−176.7 (4)
O1—C2—C3—C4	177.2 (4)	C12—C13—C14—C9	−1.2 (7)
N3—C3—C4—C5	−54.7 (6)	C10—C9—C14—C13	−0.4 (7)
C2—C3—C4—C5	−177.5 (4)	C8—C9—C14—C13	178.9 (4)
C3—C4—C5—C7	−54.3 (6)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.86	1.87	2.720 (6)	171
N3—H3···S1ii	0.86	2.78	3.495 (4)	142

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x+1, y, z.