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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o983.
Published online 2009 April 8. doi:  10.1107/S1600536809012471
PMCID: PMC2977678

Diethyl {[5-(2,4-dichloro­phen­yl)-1,3,4-thia­diazol-2-ylamino](4-methoxy­phenyl)methyl}­phospho­nate

Abstract

The title compound, C20H22Cl2N3O4PS, was synthesized by the reaction of N-(4-methoxy­benzyl­idene)-5-(2,4-dichloro­phenyl)-1,3,4-thia­diazol-2-amine and diethyl phosphite. In the crystal, inter­molecular C—H(...)O and N—H(...)O hydrogen bonds link the mol­ecules.

Related literature

For applications of thia­diazole ligands, see: Nakagawa et al. (1996 [triangle]); Omar et al. (1986 [triangle]); Sato et al. (1991 [triangle]); Wang et al. (1999 [triangle]). For related structures, see: Wan et al. (2007 [triangle]); Yin et al. (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o983-scheme1.jpg

Experimental

Crystal data

  • C20H22Cl2N3O4PS
  • M r = 502.34
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o983-efi1.jpg
  • a = 9.7100 (19) Å
  • b = 11.825 (2) Å
  • c = 11.845 (2) Å
  • α = 98.74 (3)°
  • β = 112.16 (3)°
  • γ = 103.05 (3)°
  • V = 1183.9 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.46 mm−1
  • T = 293 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.874, T max = 0.955
  • 4592 measured reflections
  • 4316 independent reflections
  • 2864 reflections with I > 2σ(I)
  • R int = 0.054
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.069
  • wR(F 2) = 0.157
  • S = 1.02
  • 4316 reflections
  • 277 parameters
  • H-atom parameters constrained
  • Δρmax = 0.56 e Å−3
  • Δρmin = −0.98 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks _global, I. DOI: 10.1107/S1600536809012471/ez2165sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012471/ez2165Isup2.hkl

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

Acknowledgments

The authors thank Professor Hua-qin Wang of the Analysis Centre, Nanjing University, for carrying out the X-ray crystallo­graphic analysis.

supplementary crystallographic information

Comment

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). They can also be widely used in the field of medicine (Sato et al., 1991), such as for anti-cancer drugs (Omar et al., 1986).

We report here the crystal structure of the title compound,(I). The molecular structure of (I) is shown in Fig.1. Bond lengths are in the normal ranges (Allen et al., 1987). The dihedral angle between the C15—C20 and S/C13/N2/N3/C14 is 32.4 (3)°, which shows that these two aromatic rings are not in the same plane. This dihedral angle is bigger than other phosphonate compounds, which is 7.54 (3)° (Wan et al., 2007) and 5.3 (2)° (Yin et al., 2008). There are intermolecular C—H···O and N—H···O hydrogen bonds (Fig. 2), which form chains along the b axis in the crystal.

Experimental

N-(4–methoxyphenyl)-5-(2,4-dichlorophenyl)-1,3,4-thiadiazol-2-amine (2 mmol) and diethyl phosphite (5 mmol) were mixed in a 25 ml flask, and kept in an oil bath at 90°C for 6 h. After cooling, the crude product (I) precipitated and was filtered. Pure compound (I) was obtained by crystallization from ethanol (20 ml). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Refinement

All H atoms bonded to the C atoms were placed geometrically at the distances of 0.93–0.97 Å and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.

Figures

Fig. 1.
A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular C—H···O and N—H···O hydrogen bonds.

Crystal data

C20H22Cl2N3O4PSF(000) = 520
Mr = 502.34Dx = 1.409 Mg m3
Triclinic, P1Melting point: 59365 K
a = 9.7100 (19) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.825 (2) ÅCell parameters from 25 reflections
c = 11.845 (2) Åθ = 9–13°
α = 98.74 (3)°µ = 0.46 mm1
β = 112.16 (3)°T = 293 K
γ = 103.05 (3)°Block, colorless
V = 1183.9 (4) Å30.30 × 0.20 × 0.10 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer2864 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.054
graphiteθmax = 25.3°, θmin = 1.8°
ω/2θ scansh = 0→11
Absorption correction: ψ scan (North et al., 1968)k = −14→13
Tmin = 0.874, Tmax = 0.955l = −14→13
4592 measured reflections3 standard reflections every 200 reflections
4316 independent reflections intensity decay: 1%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0281P)2 + 3.5816P] where P = (Fo2 + 2Fc2)/3
4316 reflections(Δ/σ)max < 0.001
277 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = −0.97 e Å3

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
Cl10.1915 (3)−0.0588 (2)0.04559 (17)0.1292 (9)
Cl20.60795 (15)0.19354 (15)0.51042 (15)0.0812 (5)
S0.45871 (13)0.26753 (10)0.68952 (11)0.0518 (3)
P0.28539 (13)0.35163 (11)1.04983 (12)0.0508 (3)
N10.4404 (4)0.3110 (3)0.9121 (3)0.0524 (10)
H1A0.49340.38430.92470.063*
O10.1252 (4)0.2999 (3)0.9312 (4)0.0754 (11)
C1−0.0855 (9)0.3620 (8)0.8045 (8)0.112
H1B−0.15500.28810.74270.168*
H1C−0.10080.42860.76940.168*
H1D−0.10690.36890.87770.168*
N20.2791 (5)0.1297 (3)0.7581 (3)0.0541 (10)
O20.2564 (4)0.2931 (3)1.1510 (3)0.0698 (10)
C20.0749 (9)0.3624 (9)0.8405 (8)0.123 (3)
H2A0.08510.32690.76580.148*
H2B0.14270.44510.87330.148*
O30.3460 (4)0.4837 (3)1.0857 (3)0.0621 (9)
N30.2468 (4)0.0703 (3)0.6370 (3)0.0541 (10)
C30.2866 (11)0.4070 (7)1.3512 (7)0.127 (3)
H3A0.35780.36671.39430.191*
H3B0.22850.42411.39810.191*
H3C0.34430.48081.34400.191*
O40.9613 (4)0.3317 (3)1.4496 (4)0.0826 (12)
C40.1777 (9)0.3289 (7)1.2240 (7)0.100 (2)
H4A0.11340.25771.23200.120*
H4B0.10910.37151.17960.120*
C50.4108 (5)0.2749 (4)1.0145 (4)0.0461 (10)
H5A0.35250.18880.98340.055*
C60.5616 (5)0.2897 (4)1.1290 (4)0.0454 (10)
C70.6196 (5)0.1950 (4)1.1435 (5)0.0572 (12)
H7A0.56710.12211.08210.069*
C80.7548 (5)0.2052 (4)1.2475 (5)0.0583 (12)
H8A0.79420.14061.25460.070*
C90.8308 (5)0.3130 (4)1.3412 (5)0.0569 (12)
C100.7780 (6)0.4085 (4)1.3276 (5)0.0735 (16)
H10A0.83000.48111.38960.088*
C110.6447 (6)0.3977 (4)1.2197 (5)0.0670 (15)
H11A0.61140.46471.20880.080*
C130.3876 (5)0.2336 (4)0.7974 (4)0.0441 (10)
C140.3304 (5)0.1296 (4)0.5888 (4)0.0418 (9)
C150.3017 (5)0.0854 (4)0.4561 (4)0.0468 (10)
C160.1499 (5)0.0152 (4)0.3671 (4)0.0515 (11)
H16A0.0708−0.00200.39390.062*
C170.1154 (7)−0.0281 (5)0.2443 (5)0.0700 (15)
H17A0.0133−0.07310.18820.084*
C180.2304 (8)−0.0064 (5)0.2005 (5)0.0770 (17)
C190.3822 (8)0.0635 (6)0.2868 (6)0.0856 (19)
H19A0.46080.08020.25950.103*
C200.4161 (6)0.1077 (4)0.4115 (5)0.0553 (12)
C121.0077 (7)0.2351 (6)1.4818 (7)0.089 (2)
H12A0.91750.16911.46380.133*
H12B1.07600.25711.57030.133*
H12C1.06190.21161.43390.133*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.1449 (18)0.1336 (17)0.0748 (11)−0.0205 (14)0.0628 (12)−0.0134 (10)
Cl20.0454 (7)0.0980 (11)0.0881 (10)0.0027 (7)0.0353 (7)0.0024 (8)
S0.0407 (6)0.0465 (6)0.0540 (6)−0.0047 (5)0.0178 (5)0.0081 (5)
P0.0381 (6)0.0437 (6)0.0588 (7)0.0023 (5)0.0147 (5)0.0120 (5)
N10.052 (2)0.0392 (19)0.045 (2)−0.0059 (16)0.0124 (17)0.0063 (16)
O10.0436 (19)0.071 (2)0.083 (3)0.0092 (17)0.0032 (18)0.017 (2)
C10.1120.1120.1120.0350.0480.029
N20.058 (2)0.043 (2)0.049 (2)−0.0044 (17)0.0235 (18)0.0071 (16)
O20.076 (2)0.061 (2)0.080 (2)0.0123 (19)0.045 (2)0.0251 (19)
C20.108 (6)0.143 (7)0.086 (5)0.030 (6)0.012 (4)0.030 (5)
O30.055 (2)0.0462 (18)0.077 (2)0.0073 (15)0.0238 (17)0.0175 (16)
N30.052 (2)0.046 (2)0.049 (2)−0.0017 (17)0.0170 (18)0.0078 (17)
C30.167 (9)0.098 (6)0.123 (7)0.036 (6)0.073 (7)0.027 (5)
O40.060 (2)0.057 (2)0.091 (3)0.0136 (18)−0.007 (2)0.019 (2)
C40.112 (6)0.104 (5)0.117 (6)0.041 (5)0.076 (5)0.037 (5)
C50.045 (2)0.037 (2)0.046 (2)−0.0004 (18)0.0152 (19)0.0106 (18)
C60.035 (2)0.040 (2)0.053 (2)0.0051 (18)0.0130 (19)0.0170 (19)
C70.049 (3)0.046 (3)0.068 (3)0.010 (2)0.023 (2)0.005 (2)
C80.042 (3)0.055 (3)0.073 (3)0.019 (2)0.017 (2)0.017 (2)
C90.037 (2)0.047 (3)0.071 (3)0.008 (2)0.010 (2)0.015 (2)
C100.060 (3)0.042 (3)0.077 (4)0.009 (2)−0.006 (3)0.005 (2)
C110.058 (3)0.042 (3)0.069 (3)0.015 (2)−0.003 (2)0.005 (2)
C130.031 (2)0.041 (2)0.049 (2)0.0038 (17)0.0097 (18)0.0123 (18)
C140.032 (2)0.038 (2)0.052 (2)0.0068 (17)0.0179 (18)0.0104 (18)
C150.044 (2)0.039 (2)0.055 (2)0.0091 (18)0.021 (2)0.0109 (19)
C160.045 (2)0.046 (2)0.051 (2)0.001 (2)0.018 (2)0.003 (2)
C170.072 (4)0.055 (3)0.059 (3)−0.008 (3)0.022 (3)0.005 (2)
C180.091 (4)0.062 (3)0.071 (3)0.001 (3)0.044 (3)0.008 (3)
C190.087 (4)0.081 (4)0.091 (4)0.002 (3)0.060 (4)0.006 (3)
C200.051 (3)0.052 (3)0.063 (3)0.006 (2)0.032 (2)0.008 (2)
C120.063 (4)0.073 (4)0.110 (5)0.027 (3)0.007 (3)0.037 (4)

Geometric parameters (Å, °)

Cl1—C181.709 (6)C4—H4A0.9700
Cl2—C201.736 (5)C4—H4B0.9700
S—C131.723 (4)C5—C61.526 (6)
S—C141.733 (4)C5—H5A0.9800
P—O31.469 (3)C6—C71.368 (6)
P—O21.553 (4)C6—C111.378 (6)
P—O11.559 (4)C7—C81.385 (7)
P—C51.803 (5)C7—H7A0.9300
N1—C131.354 (5)C8—C91.388 (7)
N1—C51.449 (5)C8—H8A0.9300
N1—H1A0.8600C9—C101.348 (7)
O1—C21.395 (9)C10—C111.398 (7)
C1—C21.450 (8)C10—H10A0.9300
C1—H1B0.9600C11—H11A0.9300
C1—H1C0.9600C14—C151.475 (6)
C1—H1D0.9600C15—C201.391 (6)
N2—C131.306 (5)C15—C161.408 (6)
N2—N31.380 (5)C16—C171.349 (7)
O2—C41.430 (7)C16—H16A0.9300
C2—H2A0.9700C17—C181.388 (8)
C2—H2B0.9700C17—H17A0.9300
N3—C141.301 (5)C18—C191.399 (8)
C3—C41.475 (7)C19—C201.373 (7)
C3—H3A0.9600C19—H19A0.9300
C3—H3B0.9600C12—H12A0.9600
C3—H3C0.9600C12—H12B0.9600
O4—C91.365 (6)C12—H12C0.9600
O4—C121.374 (7)
C13—S—C1487.0 (2)C11—C6—C5121.9 (4)
O3—P—O2116.2 (2)C6—C7—C8121.6 (5)
O3—P—O1113.2 (2)C6—C7—H7A119.2
O2—P—O1104.1 (2)C8—C7—H7A119.2
O3—P—C5115.3 (2)C7—C8—C9119.3 (5)
O2—P—C5101.5 (2)C7—C8—H8A120.4
O1—P—C5105.2 (2)C9—C8—H8A120.4
C13—N1—C5122.3 (3)C10—C9—O4115.6 (4)
C13—N1—H1A118.8C10—C9—C8120.2 (5)
C5—N1—H1A118.8O4—C9—C8124.2 (4)
C2—O1—P122.8 (4)C9—C10—C11119.6 (5)
C2—C1—H1B109.5C9—C10—H10A120.2
C2—C1—H1C109.5C11—C10—H10A120.2
H1B—C1—H1C109.5C6—C11—C10121.4 (5)
C2—C1—H1D109.5C6—C11—H11A119.3
H1B—C1—H1D109.5C10—C11—H11A119.3
H1C—C1—H1D109.5N2—C13—N1124.0 (4)
C13—N2—N3111.7 (4)N2—C13—S114.6 (3)
C4—O2—P126.3 (4)N1—C13—S121.4 (3)
O1—C2—C1113.6 (7)N3—C14—C15121.0 (4)
O1—C2—H2A108.8N3—C14—S113.4 (3)
C1—C2—H2A108.8C15—C14—S125.3 (3)
O1—C2—H2B108.8C20—C15—C16116.7 (4)
C1—C2—H2B108.8C20—C15—C14124.2 (4)
H2A—C2—H2B107.7C16—C15—C14119.1 (4)
C14—N3—N2113.4 (3)C17—C16—C15122.2 (5)
C4—C3—H3A109.5C17—C16—H16A118.9
C4—C3—H3B109.5C15—C16—H16A118.9
H3A—C3—H3B109.5C16—C17—C18120.8 (5)
C4—C3—H3C109.5C16—C17—H17A119.6
H3A—C3—H3C109.5C18—C17—H17A119.6
H3B—C3—H3C109.5C17—C18—C19118.2 (5)
C9—O4—C12119.5 (4)C17—C18—Cl1122.4 (5)
O2—C4—C3112.8 (6)C19—C18—Cl1119.5 (4)
O2—C4—H4A109.0C20—C19—C18120.6 (5)
C3—C4—H4A109.0C20—C19—H19A119.7
O2—C4—H4B109.0C18—C19—H19A119.7
C3—C4—H4B109.0C19—C20—C15121.5 (5)
H4A—C4—H4B107.8C19—C20—Cl2116.8 (4)
N1—C5—C6112.2 (3)C15—C20—Cl2121.7 (4)
N1—C5—P109.5 (3)O4—C12—H12A109.5
C6—C5—P113.9 (3)O4—C12—H12B109.5
N1—C5—H5A106.9H12A—C12—H12B109.5
C6—C5—H5A106.9O4—C12—H12C109.5
P—C5—H5A106.9H12A—C12—H12C109.5
C7—C6—C11117.8 (4)H12B—C12—H12C109.5
C7—C6—C5120.3 (4)
O3—P—O1—C224.0 (6)C7—C6—C11—C10−4.4 (8)
O2—P—O1—C2151.1 (6)C5—C6—C11—C10176.5 (5)
C5—P—O1—C2−102.7 (6)C9—C10—C11—C62.9 (10)
O3—P—O2—C446.8 (6)N3—N2—C13—N1179.2 (4)
O1—P—O2—C4−78.3 (5)N3—N2—C13—S0.2 (5)
C5—P—O2—C4172.6 (5)C5—N1—C13—N215.7 (7)
P—O1—C2—C1−133.6 (6)C5—N1—C13—S−165.4 (3)
C13—N2—N3—C140.1 (6)C14—S—C13—N2−0.3 (4)
P—O2—C4—C3−98.2 (7)C14—S—C13—N1−179.3 (4)
C13—N1—C5—C6118.7 (4)N2—N3—C14—C15−174.2 (4)
C13—N1—C5—P−113.8 (4)N2—N3—C14—S−0.4 (5)
O3—P—C5—N1−58.4 (3)C13—S—C14—N30.4 (4)
O2—P—C5—N1175.2 (3)C13—S—C14—C15173.9 (4)
O1—P—C5—N167.0 (3)N3—C14—C15—C20−150.9 (5)
O3—P—C5—C668.1 (3)S—C14—C15—C2036.0 (7)
O2—P—C5—C6−58.3 (3)N3—C14—C15—C1628.6 (7)
O1—P—C5—C6−166.5 (3)S—C14—C15—C16−144.4 (4)
N1—C5—C6—C7−93.9 (5)C20—C15—C16—C17−0.5 (7)
P—C5—C6—C7141.0 (4)C14—C15—C16—C17180.0 (5)
N1—C5—C6—C1185.2 (6)C15—C16—C17—C181.0 (9)
P—C5—C6—C11−39.9 (6)C16—C17—C18—C19−1.2 (9)
C11—C6—C7—C81.9 (7)C16—C17—C18—Cl1−179.6 (5)
C5—C6—C7—C8−178.9 (4)C17—C18—C19—C200.9 (10)
C6—C7—C8—C91.9 (8)Cl1—C18—C19—C20179.3 (5)
C12—O4—C9—C10168.9 (6)C18—C19—C20—C15−0.4 (10)
C12—O4—C9—C8−12.1 (9)C18—C19—C20—Cl2−179.9 (5)
C7—C8—C9—C10−3.5 (8)C16—C15—C20—C190.2 (8)
C7—C8—C9—O4177.5 (5)C14—C15—C20—C19179.7 (5)
O4—C9—C10—C11−179.8 (5)C16—C15—C20—Cl2179.6 (4)
C8—C9—C10—C111.1 (9)C14—C15—C20—Cl2−0.8 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.862.002.805 (5)156
C10—H10A···O4ii0.932.533.431 (7)163

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2165).

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