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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o2006.
Published online 2008 September 24. doi:  10.1107/S1600536808030353
PMCID: PMC2959416

(2R)-N-[5-(4-Chloro­phen­yl)-1,3,4-thia­diazol-2-yl]-2-(cinnamoylamino)propanamide

Abstract

In the title compound, C20H17ClN4O2S, the dihedral angle between the two benzene rings is 65.9 (1)°; the corresponding angle between the 4-chloro­phenyl and thia­diazole rings is 3.4 (8)°. The conformations of the N—H and C=O bonds are anti with respect to each other. The enone groups show a trans configuration. The structure displays intermolecular N—H(...)O, C—H(...)N, C—H(...)S and C—H(...)O hydrogen bonding.

Related literature

For 1,3,4-thia­diazole scaffold compounds and their biological activity, see: Tu et al. (2008 [triangle]). For the synthesis, see: Foroumadi et al. (1999 [triangle]); Levy & Palmer (1942 [triangle]); Song et al. (1992 [triangle]). For related structures, see: Fun et al. (2008 [triangle]); Gowda et al. (2008 [triangle]) Thiruvalluvar et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2006-scheme1.jpg

Experimental

Crystal data

  • C20H17ClN4O2S
  • M r = 412.89
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2006-efi1.jpg
  • a = 6.6324 (15) Å
  • b = 8.575 (2) Å
  • c = 34.367 (8) Å
  • V = 1954.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 296 (2) K
  • 0.41 × 0.17 × 0.07 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: none
  • 14721 measured reflections
  • 4706 independent reflections
  • 2807 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.099
  • S = 1.02
  • 4706 reflections
  • 254 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.20 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1876 Friedel pairs
  • Flack parameter: −0.12 (7)

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: APEX2; software used to prepare material for publication: APEX2 and publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030353/gw2052sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030353/gw2052Isup2.hkl

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

supplementary crystallographic information

Comment

In our previous work, 1,3,4-thiadiazole scaffold compounds and their biological activity have been studied (Tu et al., 2008). In view of the importance of these organic materials, the title compound (Fig. 1) was synthesized (Foroumadi et al., 1999; Levy & Palmer 1942; Song et al., 1992) and its crystal structure is reported here. The structure of title compound, C20H17ClN4O2S, has orthorhombic (P212121) symmetry. The dihedral angles between the p-cholobenzene and thiadiazol rings is 3.4 (8) °, the corresponding values between the two benzene rings are measured to 65.9 (1)°. The conformations of the N—H and C=O bonds are anti with respect to each other. The enone groups are trans configurated. Bond lengths and angles are in normal ranges and comparable to those in related structures (Gowda et al., 2008; Fun et al., 2008; Thiruvalluvar et al., 2008). In the crystal structure, molecules are linked through intermolecular hydrogen bonds forming a three-dimensional network (Table 1, Figure 2).

Experimental

N,N-Dicyclohexylcarbodiimide (5.7 mmol) was added to a cooled solution of N-cinnamoyl-D-alanine (5.6 mmol) and N-hydroxysuccinimide (5.6 mmol) in freshly distillation dioxane (30 ml). The reaction mixture was stirred overnight at room temperature. The insoluble material was filtered off and washed with cold dioxane. 2-Amino-5-(4-choloxyphenyl)-1,3,4-thiadiazole (5.5 mmol) was added to the filtrate and the reaction mixture was stirred for 48 hr at room temperature. The solvent was removed under reduced pressure. The residual was dissolved in EtOAc and the insoluble material was filtered off. The filtrate was washed successively with saturated Na2CO3 solution(20 ml, x 3), water(20 ml, x 1), 0.1 M HCl(20 ml, x 3) and water(20 ml, x 1). The organic layer evaporated in vacuo, the residual was recrystallized from methanol. Colorless block-shaped single crystals of the title compound suitable for X-ray diffraction analysis precipitated after several days.

Refinement

H atoms were positioned geometrically and refined using a riding model using SHELXL97 default values (Uĩso(H) = 1.2 Ueq(C) for CH and CH2 groups and Uĩso(H) = 1.5 Ueq(C) for CH3). Refinement with all data (Friedel opposites not merged) led to an unsuitably large error of the Flack parameter. The final refinement was therefore performed with a data set with merged Friedel pairs, hence the calculated Flack parameter is meaningless. The absolute configuration is nevertheless undoubtly as described since enantiomerically pure starting compounds were used and the reaction conditions are not condidered to lead to racemization or inversion.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
The crystal packing of title compound, viewed along the a axis with hydrogen bonds drawn as dashed lines.

Crystal data

C20H17ClN4O2SDx = 1.403 Mg m3
Mr = 412.89Melting point: 480 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3308 reflections
a = 6.6324 (15) Åθ = 2.4–21.0°
b = 8.575 (2) ŵ = 0.33 mm1
c = 34.367 (8) ÅT = 296 K
V = 1954.6 (8) Å3Bolck, colourless
Z = 40.41 × 0.18 × 0.07 mm
F(000) = 856

Data collection

Bruker SMART CCD area-detector diffractometer2807 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.046
graphiteθmax = 28.4°, θmin = 2.4°
[var phi] and ω scansh = −8→8
14721 measured reflectionsk = −11→11
4706 independent reflectionsl = −45→44

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.099w = 1/[σ2(Fo2) + (0.0226P)2 + 0.0747P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
4706 reflectionsΔρmax = 0.15 e Å3
254 parametersΔρmin = −0.20 e Å3
0 restraintsAbsolute structure: Flack (1983), 1876 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.12 (7)

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)

xyzUiso*/Ueq
C10.6789 (5)0.2710 (4)0.19355 (8)0.0782 (9)
H1B0.60670.20300.17770.094*
C20.6159 (6)0.2979 (4)0.23129 (10)0.0996 (13)
H2B0.50240.24680.24080.120*
C30.7184 (6)0.3981 (5)0.25465 (9)0.0977 (12)
H3B0.67450.41580.28000.117*
C40.8862 (6)0.4732 (4)0.24098 (8)0.0937 (12)
H4B0.95510.54340.25680.112*
C50.9526 (5)0.4443 (4)0.20360 (8)0.0756 (9)
H5A1.06920.49270.19470.091*
C60.8481 (5)0.3443 (3)0.17924 (7)0.0613 (8)
C70.9087 (5)0.3172 (3)0.13882 (7)0.0612 (8)
H7A0.82460.25330.12420.073*
C81.0669 (4)0.3722 (3)0.12100 (7)0.0584 (7)
H8A1.15790.43140.13530.070*
C91.1094 (4)0.3464 (3)0.07984 (7)0.0523 (7)
C101.3357 (4)0.4044 (3)0.02573 (6)0.0483 (6)
H10A1.34210.29340.01900.058*
C111.5445 (4)0.4755 (3)0.02035 (8)0.0626 (8)
H11A1.63840.42450.03740.094*
H11B1.53970.58470.02640.094*
H11C1.58700.4619−0.00610.094*
C121.1836 (4)0.4831 (3)−0.00072 (7)0.0494 (6)
C131.0385 (4)0.4721 (3)−0.06496 (7)0.0471 (6)
C140.7573 (4)0.5583 (3)−0.10172 (6)0.0494 (6)
C150.5693 (4)0.6256 (3)−0.11652 (7)0.0490 (6)
C160.4931 (5)0.5842 (3)−0.15249 (7)0.0639 (7)
H16A0.56250.5115−0.16750.077*
C170.3163 (5)0.6479 (3)−0.16687 (8)0.0669 (8)
H17A0.26790.6198−0.19130.080*
C180.2142 (4)0.7538 (3)−0.14421 (8)0.0589 (7)
C190.2848 (5)0.7959 (3)−0.10843 (8)0.0637 (8)
H19A0.21370.8676−0.09350.076*
C200.4600 (4)0.7328 (3)−0.09455 (8)0.0591 (7)
H20A0.50680.7619−0.07010.071*
Cl1−0.00738 (13)0.83679 (9)−0.16181 (2)0.0835 (3)
N11.2732 (3)0.4188 (2)0.06588 (5)0.0537 (5)
H1A1.34360.47580.08130.064*
N21.1824 (3)0.4305 (2)−0.03825 (5)0.0525 (5)
H2A1.27680.3681−0.04550.063*
N31.0265 (4)0.4021 (3)−0.09856 (6)0.0590 (6)
N40.8619 (4)0.4535 (2)−0.12001 (6)0.0585 (6)
O11.0027 (3)0.2679 (2)0.05768 (5)0.0672 (5)
O21.0712 (3)0.5869 (2)0.00979 (5)0.0638 (5)
S10.85258 (10)0.60793 (7)−0.056449 (17)0.05201 (18)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.081 (3)0.090 (2)0.0635 (18)−0.017 (2)0.0140 (18)−0.0047 (16)
C20.112 (4)0.116 (3)0.070 (2)−0.030 (3)0.029 (2)−0.004 (2)
C30.110 (3)0.124 (3)0.0594 (19)−0.021 (3)0.021 (2)−0.006 (2)
C40.113 (3)0.114 (3)0.0541 (18)−0.028 (3)0.0073 (19)−0.0090 (18)
C50.080 (2)0.093 (2)0.0539 (17)−0.0173 (19)0.0071 (16)−0.0014 (15)
C60.068 (2)0.0673 (18)0.0484 (14)−0.0030 (16)0.0023 (14)0.0034 (12)
C70.075 (2)0.0623 (16)0.0465 (15)−0.0090 (16)−0.0007 (15)0.0002 (13)
C80.0591 (19)0.0670 (17)0.0490 (15)−0.0077 (15)0.0026 (13)−0.0025 (13)
C90.0530 (19)0.0535 (15)0.0503 (14)−0.0074 (13)−0.0006 (13)0.0012 (12)
C100.0448 (15)0.0539 (14)0.0464 (13)−0.0036 (14)0.0008 (12)−0.0019 (11)
C110.0491 (19)0.0728 (18)0.0658 (17)−0.0078 (15)0.0092 (14)−0.0079 (14)
C120.0496 (18)0.0524 (15)0.0460 (14)−0.0044 (13)0.0050 (12)−0.0053 (11)
C130.0461 (16)0.0516 (13)0.0437 (13)0.0004 (12)0.0065 (12)−0.0024 (11)
C140.0524 (18)0.0529 (15)0.0428 (13)−0.0032 (13)0.0074 (12)−0.0003 (11)
C150.0502 (17)0.0516 (14)0.0453 (14)−0.0025 (13)0.0051 (12)0.0000 (12)
C160.067 (2)0.0747 (18)0.0499 (15)0.0125 (17)0.0012 (15)−0.0069 (13)
C170.065 (2)0.081 (2)0.0540 (15)0.0083 (17)−0.0075 (15)−0.0055 (14)
C180.0460 (18)0.0622 (17)0.0686 (18)0.0037 (14)−0.0010 (14)0.0109 (14)
C190.055 (2)0.0669 (18)0.0695 (18)0.0050 (15)0.0080 (15)−0.0077 (14)
C200.056 (2)0.0666 (17)0.0545 (16)0.0020 (16)0.0009 (14)−0.0103 (13)
Cl10.0582 (5)0.0923 (6)0.1001 (6)0.0079 (4)−0.0089 (5)0.0129 (4)
N10.0521 (14)0.0672 (13)0.0417 (11)−0.0115 (12)−0.0006 (10)−0.0046 (10)
N20.0508 (14)0.0629 (13)0.0439 (11)0.0086 (11)0.0030 (10)−0.0048 (9)
N30.0611 (16)0.0685 (13)0.0472 (12)0.0108 (13)0.0006 (11)−0.0074 (11)
N40.0591 (16)0.0676 (13)0.0488 (11)0.0069 (13)0.0014 (12)−0.0090 (10)
O10.0605 (13)0.0815 (12)0.0595 (11)−0.0230 (11)0.0052 (11)−0.0127 (10)
O20.0666 (13)0.0715 (12)0.0534 (10)0.0174 (11)−0.0024 (9)−0.0166 (9)
S10.0507 (4)0.0584 (4)0.0469 (3)0.0047 (3)0.0040 (3)−0.0059 (3)

Geometric parameters (Å, °)

C1—C61.377 (4)C11—H11C0.9600
C1—C21.382 (4)C12—O21.216 (3)
C1—H1B0.9300C12—N21.367 (3)
C2—C31.359 (5)C13—N31.304 (3)
C2—H2B0.9300C13—N21.372 (3)
C3—C41.369 (5)C13—S11.721 (3)
C3—H3B0.9300C14—N41.298 (3)
C4—C51.380 (4)C14—C151.465 (3)
C4—H4B0.9300C14—S11.732 (2)
C5—C61.384 (4)C15—C161.382 (3)
C5—H5A0.9300C15—C201.393 (3)
C6—C71.465 (4)C16—C171.385 (4)
C7—C81.303 (4)C16—H16A0.9300
C7—H7A0.9300C17—C181.375 (4)
C8—C91.459 (3)C17—H17A0.9300
C8—H8A0.9300C18—C191.364 (4)
C9—O11.239 (3)C18—Cl11.741 (3)
C9—N11.340 (3)C19—C201.368 (4)
C10—N11.446 (3)C19—H19A0.9300
C10—C121.517 (3)C20—H20A0.9300
C10—C111.524 (3)N1—H1A0.8600
C10—H10A0.9800N2—H2A0.8600
C11—H11A0.9600N3—N41.389 (3)
C11—H11B0.9600
C6—C1—C2120.4 (3)H11B—C11—H11C109.5
C6—C1—H1B119.8O2—C12—N2121.2 (2)
C2—C1—H1B119.8O2—C12—C10123.8 (2)
C3—C2—C1120.6 (4)N2—C12—C10115.0 (2)
C3—C2—H2B119.7N3—C13—N2121.0 (2)
C1—C2—H2B119.7N3—C13—S1114.7 (2)
C2—C3—C4120.1 (3)N2—C13—S1124.11 (17)
C2—C3—H3B120.0N4—C14—C15124.0 (2)
C4—C3—H3B120.0N4—C14—S1114.2 (2)
C3—C4—C5119.6 (3)C15—C14—S1121.72 (18)
C3—C4—H4B120.2C16—C15—C20117.6 (2)
C5—C4—H4B120.2C16—C15—C14121.4 (2)
C4—C5—C6121.0 (3)C20—C15—C14121.0 (2)
C4—C5—H5A119.5C15—C16—C17121.8 (3)
C6—C5—H5A119.5C15—C16—H16A119.1
C1—C6—C5118.3 (3)C17—C16—H16A119.1
C1—C6—C7119.3 (3)C18—C17—C16118.4 (3)
C5—C6—C7122.3 (3)C18—C17—H17A120.8
C8—C7—C6127.5 (3)C16—C17—H17A120.8
C8—C7—H7A116.2C19—C18—C17121.1 (3)
C6—C7—H7A116.2C19—C18—Cl1119.6 (2)
C7—C8—C9123.8 (3)C17—C18—Cl1119.3 (2)
C7—C8—H8A118.1C18—C19—C20120.1 (3)
C9—C8—H8A118.1C18—C19—H19A120.0
O1—C9—N1119.7 (2)C20—C19—H19A120.0
O1—C9—C8124.6 (3)C19—C20—C15121.0 (3)
N1—C9—C8115.7 (2)C19—C20—H20A119.5
N1—C10—C12110.1 (2)C15—C20—H20A119.5
N1—C10—C11110.0 (2)C9—N1—C10122.3 (2)
C12—C10—C11110.7 (2)C9—N1—H1A118.8
N1—C10—H10A108.7C10—N1—H1A118.8
C12—C10—H10A108.7C12—N2—C13123.3 (2)
C11—C10—H10A108.7C12—N2—H2A118.3
C10—C11—H11A109.5C13—N2—H2A118.3
C10—C11—H11B109.5C13—N3—N4111.8 (2)
H11A—C11—H11B109.5C14—N4—N3112.5 (2)
C10—C11—H11C109.5C13—S1—C1486.70 (12)
H11A—C11—H11C109.5
C6—C1—C2—C30.7 (6)C16—C17—C18—C190.2 (4)
C1—C2—C3—C4−0.3 (6)C16—C17—C18—Cl1179.5 (2)
C2—C3—C4—C5−1.2 (6)C17—C18—C19—C200.1 (4)
C3—C4—C5—C62.2 (5)Cl1—C18—C19—C20−179.2 (2)
C2—C1—C6—C50.2 (5)C18—C19—C20—C150.2 (4)
C2—C1—C6—C7−178.4 (3)C16—C15—C20—C19−0.8 (4)
C4—C5—C6—C1−1.7 (5)C14—C15—C20—C19179.8 (2)
C4—C5—C6—C7176.8 (3)O1—C9—N1—C10−2.3 (4)
C1—C6—C7—C8−177.5 (3)C8—C9—N1—C10179.8 (2)
C5—C6—C7—C84.0 (5)C12—C10—N1—C967.6 (3)
C6—C7—C8—C9−176.3 (2)C11—C10—N1—C9−170.1 (2)
C7—C8—C9—O1−1.3 (4)O2—C12—N2—C13−9.9 (4)
C7—C8—C9—N1176.5 (3)C10—C12—N2—C13171.0 (2)
N1—C10—C12—O224.2 (3)N3—C13—N2—C12−170.0 (2)
C11—C10—C12—O2−97.7 (3)S1—C13—N2—C125.7 (3)
N1—C10—C12—N2−156.8 (2)N2—C13—N3—N4175.5 (2)
C11—C10—C12—N281.4 (3)S1—C13—N3—N4−0.5 (3)
N4—C14—C15—C16−2.3 (4)C15—C14—N4—N3−176.1 (2)
S1—C14—C15—C16−179.3 (2)S1—C14—N4—N31.1 (3)
N4—C14—C15—C20177.1 (2)C13—N3—N4—C14−0.4 (3)
S1—C14—C15—C200.1 (3)N3—C13—S1—C140.9 (2)
C20—C15—C16—C171.1 (4)N2—C13—S1—C14−175.0 (2)
C14—C15—C16—C17−179.5 (2)N4—C14—S1—C13−1.2 (2)
C15—C16—C17—C18−0.8 (4)C15—C14—S1—C13176.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.861.942.802 (3)175.
C7—H7A···O10.932.582.888 (3)100.
C7—H7A···N3ii0.932.543.446 (3)164.
C11—H11C···S1iii0.962.773.526 (3)136.
C20—H20A···S10.932.693.105 (3)108.
C20—H20A···O2iv0.932.483.380 (3)162.

Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z; (iii) x+1, y, z; (iv) x−1/2, −y+3/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GW2052).

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