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In the mol­ecule of the title compound, C19H20Cl2N3O3PS, intra­molecular C—H...N hydrogen bonding results in the formation of a nearly planar five-membered ring. In the crystal structure, inter­molecular N—H...O and C—H...N hydrogen bonds link the mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056632/hk2370sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056632/hk2370Isup2.hkl
Contains datablock I

CCDC reference: 674085

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.085
  • wR factor = 0.154
  • Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for P - O1 .. 5.57 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for O3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C17 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.12 PLAT322_ALERT_2_C Check Hybridisation of S in Main Residue . ? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 10 PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C1 - C2 ... 1.39 Ang. PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C3 - C4 ... 1.42 Ang.
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C5 = ... R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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 and fungicidal activities (Wang et al., 1999).

In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (C6—C11), B (S/N2/N3/C12/C13) and C (C14—C19) are, of course, planar and the dihedral angles between them are A/B = 74.19 (3)°, A/C = 75.91 (3)° and B/C = 10.69 (3)°. The intramolecular C—H···N hydrogen bond (Table 1) results in the formation of a nearly planar five-membered ring; D (N3/C13—C15/H7A), which is oriented with respect to the adjacent rings B and C, at dihedral angles of B/D = 10.93 (2)° and C/D = 5.632 (3)°.

In the crystal structure, intermolecular N—H···O and C—H···N hydrogen bonds (Table 1, Fig. 2)) link the molecules, in which they seem to be effective in the stabilization of the structure.

Related literature top

For related literature, see: Nakagawa et al. (1996); Wang et al. (1999). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, N-benzylidene-5-(2,4-dichlorophenyl) -1,3,4-thiadiazol-2-amine (2 mmol) and diethyl phosphite (5 mmol) were added in a flask (25 ml) and reacted in an oil bath (363 K) for 6 h. After cooling and filtering, crude compound (I) was obtained, and recrystallized from ethanol. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.

Refinement top

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.98, 0.97 and 0.96 Å for methine, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
(R,S)-Diethyl {[5-(2,4-dichlorophenyl)-1,3,4-thiadiazol-2-ylamino](phenyl)methyl}phosphonate top
Crystal data top
C19H20Cl2N3O3PSF(000) = 976
Mr = 472.31Dx = 1.428 Mg m3
Monoclinic, P21/nMelting point = 453–454 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.4870 (17) ÅCell parameters from 25 reflections
b = 16.530 (3) Åθ = 10–12°
c = 15.703 (3) ŵ = 0.49 mm1
β = 94.47 (3)°T = 298 K
V = 2196.3 (7) Å3Needle, colorless
Z = 40.40 × 0.10 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
3145 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.052
Graphite monochromatorθmax = 26.0°, θmin = 1.8°
ω/2θ scansh = 1010
Absorption correction: ψ scan
(North et al., 1968)
k = 020
Tmin = 0.828, Tmax = 0.953l = 019
4609 measured reflections3 standard reflections every 200 reflections
4312 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.085H-atom parameters constrained
wR(F2) = 0.154 w = 1/[σ2(Fo2) + (0.1265P)2 + 1.3578P]
where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max < 0.001
4312 reflectionsΔρmax = 0.31 e Å3
250 parametersΔρmin = 0.70 e Å3
Primary atom site location: structure-invariant direct methods
Crystal data top
C19H20Cl2N3O3PSV = 2196.3 (7) Å3
Mr = 472.31Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.4870 (17) ŵ = 0.49 mm1
b = 16.530 (3) ÅT = 298 K
c = 15.703 (3) Å0.40 × 0.10 × 0.10 mm
β = 94.47 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
3145 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.052
Tmin = 0.828, Tmax = 0.9533 standard reflections every 200 reflections
4609 measured reflections intensity decay: none
4312 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.085250 parameters
wR(F2) = 0.154H-atom parameters constrained
S = 1.17Δρmax = 0.31 e Å3
4312 reflectionsΔρmin = 0.70 e Å3
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
xyzUiso*/Ueq
Cl10.3460 (3)0.37335 (12)0.14352 (10)0.1114 (7)
Cl20.3666 (2)0.44309 (12)0.18670 (9)0.1133 (8)
S0.1558 (2)0.48605 (11)0.25006 (9)0.0806 (6)
P0.0393 (2)0.65490 (13)0.52266 (9)0.0760 (6)
O10.2180 (6)0.6788 (3)0.5237 (2)0.1143 (17)
O20.0005 (6)0.5841 (3)0.5707 (2)0.1010 (16)
O30.0427 (5)0.7339 (3)0.5529 (2)0.0810 (13)
N10.0476 (5)0.5763 (3)0.3769 (2)0.0743 (15)
H1A0.06970.53570.40990.089*
N20.0586 (6)0.6318 (3)0.2402 (3)0.0777 (15)
N30.1044 (6)0.6122 (3)0.1607 (3)0.0800 (16)
C10.3610 (7)0.6550 (4)0.6493 (4)0.100
H1B0.42660.67280.69830.150*
H1C0.41840.61700.61740.150*
H1D0.26790.62940.66780.150*
C20.3175 (8)0.7211 (4)0.5980 (4)0.104
H2C0.40900.74830.57800.125*
H2D0.25480.75960.62750.125*
C30.1313 (9)0.7382 (5)0.6870 (5)0.139 (3)
H3B0.21560.73630.72430.209*
H3C0.07860.78950.69290.209*
H3D0.05740.69560.70170.209*
C40.1941 (9)0.7282 (5)0.6014 (4)0.126 (3)
H4A0.26850.77080.58420.151*
H4B0.24540.67600.59280.151*
C50.0214 (6)0.6487 (4)0.4094 (3)0.0625 (16)
H5A0.02250.69540.38100.075*
C60.1952 (8)0.6534 (5)0.3975 (3)0.0728 (17)
C70.2645 (8)0.7291 (5)0.3791 (4)0.094 (2)
H7A0.20450.77520.37110.112*
C80.4350 (10)0.7307 (6)0.3735 (4)0.114 (3)
H8A0.48410.78050.36320.137*
C90.5298 (10)0.6650 (6)0.3820 (4)0.107 (2)
H9A0.63940.66890.37610.128*
C100.4547 (10)0.5930 (5)0.3999 (4)0.105 (2)
H10A0.51460.54700.40850.126*
C110.2943 (8)0.5873 (5)0.4053 (4)0.091 (2)
H11A0.24870.53660.41470.109*
C120.0776 (6)0.5735 (4)0.2916 (3)0.0647 (16)
C130.1598 (7)0.5399 (4)0.1552 (3)0.0660 (17)
C140.2134 (6)0.5107 (4)0.0727 (3)0.0646 (16)
C150.1763 (7)0.5587 (4)0.0007 (3)0.0771 (18)
H15A0.11720.60560.00580.092*
C160.2262 (7)0.5374 (4)0.0786 (3)0.0709 (17)
H16A0.20310.57020.12610.085*
C170.3105 (7)0.4667 (4)0.0856 (3)0.0694 (17)
C180.3452 (7)0.4183 (4)0.0185 (3)0.0785 (19)
H18A0.40530.37180.02390.094*
C190.2892 (7)0.4390 (4)0.0592 (3)0.0715 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.180 (2)0.0953 (15)0.0658 (11)0.0132 (14)0.0529 (11)0.0004 (10)
Cl20.1685 (18)0.1257 (18)0.0526 (9)0.0267 (15)0.0524 (10)0.0308 (10)
S0.1088 (13)0.0911 (14)0.0463 (8)0.0013 (11)0.0348 (8)0.0076 (9)
P0.0906 (14)0.0975 (16)0.0420 (9)0.0043 (12)0.0253 (8)0.0148 (10)
O10.119 (4)0.125 (5)0.061 (3)0.016 (4)0.025 (2)0.030 (3)
O20.168 (5)0.085 (4)0.056 (2)0.003 (3)0.043 (3)0.002 (2)
O30.094 (3)0.086 (4)0.056 (2)0.043 (3)0.043 (2)0.006 (2)
N10.096 (4)0.093 (4)0.038 (2)0.009 (3)0.028 (2)0.005 (3)
N20.101 (4)0.087 (4)0.051 (3)0.009 (3)0.039 (3)0.000 (3)
N30.115 (4)0.080 (4)0.050 (3)0.004 (3)0.039 (3)0.009 (3)
C10.100 (4)0.107 (3)0.100 (3)0.001 (2)0.008 (2)0.000 (3)
C20.104 (4)0.108 (4)0.104 (4)0.002 (2)0.007 (3)0.000 (3)
C30.149 (6)0.151 (7)0.118 (5)0.009 (6)0.015 (5)0.007 (5)
C40.156 (6)0.129 (6)0.099 (5)0.037 (5)0.040 (4)0.006 (5)
C50.065 (4)0.076 (4)0.050 (3)0.001 (3)0.028 (3)0.009 (3)
C60.081 (4)0.097 (5)0.042 (3)0.004 (4)0.018 (3)0.012 (3)
C70.090 (4)0.112 (5)0.080 (4)0.009 (4)0.013 (4)0.008 (4)
C80.109 (5)0.130 (6)0.104 (5)0.019 (5)0.014 (5)0.015 (5)
C90.105 (5)0.144 (6)0.074 (4)0.005 (4)0.022 (4)0.005 (5)
C100.104 (5)0.134 (6)0.079 (4)0.025 (5)0.029 (4)0.010 (5)
C110.096 (4)0.112 (5)0.069 (4)0.018 (4)0.032 (4)0.015 (4)
C120.061 (4)0.084 (4)0.052 (3)0.003 (3)0.027 (3)0.019 (3)
C130.075 (4)0.081 (4)0.043 (3)0.010 (4)0.020 (3)0.005 (3)
C140.066 (4)0.084 (4)0.046 (3)0.022 (3)0.017 (3)0.007 (3)
C150.100 (4)0.088 (5)0.045 (3)0.000 (4)0.019 (3)0.003 (3)
C160.085 (4)0.091 (5)0.038 (3)0.019 (4)0.014 (3)0.008 (3)
C170.089 (4)0.075 (5)0.047 (3)0.021 (4)0.016 (3)0.016 (3)
C180.096 (4)0.090 (5)0.053 (3)0.014 (4)0.030 (3)0.018 (3)
C190.087 (4)0.082 (4)0.050 (3)0.012 (4)0.031 (3)0.003 (3)
Geometric parameters (Å, º) top
Cl1—C191.751 (6)C4—H4A0.9700
Cl2—C171.737 (5)C4—H4B0.9700
S—C131.737 (6)C5—C61.475 (7)
S—C121.738 (6)C5—H5A0.9800
P—O21.444 (4)C6—C111.391 (8)
P—O11.567 (5)C6—C71.402 (9)
P—O31.570 (4)C7—C81.443 (9)
P—C51.815 (5)C7—H7A0.9300
O1—C21.552 (7)C8—C91.365 (10)
O3—C41.547 (7)C8—H8A0.9300
N1—C121.383 (6)C9—C101.368 (10)
N1—C51.443 (6)C9—H9A0.9300
N1—H1A0.8600C10—C111.361 (9)
N2—C121.260 (7)C10—H10A0.9300
N2—N31.376 (5)C11—H11A0.9300
N3—C131.289 (7)C13—C141.487 (6)
C1—C21.391 (7)C14—C191.372 (8)
C1—H1B0.9600C14—C151.397 (7)
C1—H1C0.9600C15—C161.392 (7)
C1—H1D0.9600C15—H15A0.9300
C2—H2C0.9700C16—C171.379 (8)
C2—H2D0.9700C16—H16A0.9300
C3—C41.416 (8)C17—C181.338 (8)
C3—H3B0.9600C18—C191.387 (7)
C3—H3C0.9600C18—H18A0.9300
C3—H3D0.9600
C13—S—C1286.0 (3)P—C5—H5A108.2
O2—P—O1117.3 (3)C11—C6—C7118.2 (7)
O2—P—O3113.1 (2)C11—C6—C5123.5 (7)
O1—P—O3103.8 (3)C7—C6—C5118.2 (7)
O2—P—C5114.0 (3)C6—C7—C8115.6 (8)
O1—P—C5103.0 (2)C6—C7—H7A122.2
O3—P—C5104.2 (3)C8—C7—H7A122.2
C2—O1—P126.2 (4)C9—C8—C7125.1 (9)
C4—O3—P120.2 (4)C9—C8—H8A117.4
C12—N1—C5118.8 (5)C7—C8—H8A117.4
C12—N1—H1A120.6C8—C9—C10116.3 (8)
C5—N1—H1A120.6C8—C9—H9A121.8
C12—N2—N3111.7 (5)C10—C9—H9A121.8
C13—N3—N2114.1 (5)C11—C10—C9121.4 (8)
C2—C1—H1B109.5C11—C10—H10A119.3
C2—C1—H1C109.5C9—C10—H10A119.3
H1B—C1—H1C109.5C10—C11—C6123.2 (8)
C2—C1—H1D109.5C10—C11—H11A118.4
H1B—C1—H1D109.5C6—C11—H11A118.4
H1C—C1—H1D109.5N2—C12—N1124.8 (6)
C1—C2—O1100.7 (6)N2—C12—S115.4 (4)
C1—C2—H2C111.6N1—C12—S119.7 (5)
O1—C2—H2C111.6N3—C13—C14119.7 (5)
C1—C2—H2D111.6N3—C13—S112.7 (4)
O1—C2—H2D111.6C14—C13—S127.5 (5)
H2C—C2—H2D109.4C19—C14—C15116.3 (5)
C4—C3—H3B109.5C19—C14—C13126.4 (6)
C4—C3—H3C109.5C15—C14—C13117.2 (6)
H3B—C3—H3C109.5C16—C15—C14121.0 (6)
C4—C3—H3D109.5C16—C15—H15A119.5
H3B—C3—H3D109.5C14—C15—H15A119.5
H3C—C3—H3D109.5C17—C16—C15118.8 (6)
C3—C4—O3101.2 (6)C17—C16—H16A120.6
C3—C4—H4A111.5C15—C16—H16A120.6
O3—C4—H4A111.5C18—C17—C16121.9 (6)
C3—C4—H4B111.5C18—C17—Cl2121.7 (6)
O3—C4—H4B111.5C16—C17—Cl2116.4 (5)
H4A—C4—H4B109.3C17—C18—C19118.4 (6)
N1—C5—C6115.4 (5)C17—C18—H18A120.8
N1—C5—P107.6 (4)C19—C18—H18A120.8
C6—C5—P109.0 (3)C14—C19—C18123.2 (6)
N1—C5—H5A108.2C14—C19—Cl1121.5 (4)
C6—C5—H5A108.2C18—C19—Cl1114.8 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.092.815 (7)141
C4—H4A···N3ii0.972.563.321 (11)134
C15—H15A···N30.932.452.783 (7)101
Symmetry codes: (i) x, y+1, z+1; (ii) x1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC19H20Cl2N3O3PS
Mr472.31
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)8.4870 (17), 16.530 (3), 15.703 (3)
β (°) 94.47 (3)
V3)2196.3 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.40 × 0.10 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.828, 0.953
No. of measured, independent and
observed [I > 2σ(I)] reflections
4609, 4312, 3145
Rint0.052
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.085, 0.154, 1.17
No. of reflections4312
No. of parameters250
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.70

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.092.815 (7)141
C4—H4A···N3ii0.972.563.321 (11)134
C15—H15A···N30.932.452.783 (7)101
Symmetry codes: (i) x, y+1, z+1; (ii) x1/2, y+3/2, z+1/2.
 

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