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The molecule of the title compound, C11H14ClN2O2PS2, is essentially planar, the ethoxy groups being on opposite sides of the plane. Two mol­ecules related by an inversion center are connected through N—H...N hydrogen bonds, resulting in a dimeric structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008237/dn6062sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008237/dn6062IIsup2.hkl
Contains datablock II

CCDC reference: 214852

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.043
  • wR factor = 0.112
  • Data-to-parameter ratio = 17.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Owing to their biological activities (Li et al., 1998; Schuster, 1989), benzothiazoles have attracted considerable interests. In order to look for biologically active compounds containing both benzothiazolyl and dialkyl thiophosphate groups, we have designed and synthesized the title compound, (II).

A perspective view of (II) with the atom labeling scheme is shown in Fig. 1. It can be seen that the title compound results for the substitution of one H atom of the amino group of the starting 2-amino-6-chlorobenzothiazole by the dialkyl thiophosphate group and migration of the second one to the N1 atom in the benzothiazole ring.

The benzothiazolyl group, atoms N2 and Cl1 make a nearly perfect plane with the largest deviation, 0.018 (2) Å, at N2. Atoms S1 and P1 are slightly out of this plane by 0.589 (1) and 0.204 (1) Å, respectively. The ethoxy groups are located on each side of the plane, atoms O1 and O2 being, respectively, 1.261 (3) and −1.141 (3) Å above and below this plane.

The P1—N2 bond length, 1.629 (2) Å, is shorter than the value observed for a normal P—N single bond (1.76 Å; Ress, 1986; Chi & Chen, 2002), indicative of electron delocalization between N2 and P1. In addition, the N2—C7 bond length, 1.300 (3) Å, is close to that of a NC double bond (1.280 Å; Gao, 1982), whereas N1—C4 [1.389 (3) Å] and N1—C7 [1.348 (3) Å] are both longer than a double bond but significantly shorter than a N—C single bond (1.470 Å; Gao, 1982).

The sum of the three bond angles around N1 and C7 close to 360°, and the P1—N2—C7 angle of 126.75 (18)° indicate that N2, C7 and N1 have an sp2 hybridization. So, electron delocalization on the whole thiazole ring may be considered.

Two molecules related by an inversion center are connected through N—H···N hydrogen bonds (Table 2). The packing in the cell results from the stacking of these dimers (Fig. 2).

Experimental top

The title compound, (II), was synthesized as described (see Scheme). Firstly, a dichloromethane solution of 2-amino-6-chlorobenzothiazole, thiophosphoryl chloride and triethylamine was refluxed for 15 h. After the solvent was evaporated, the residue was purified by flash chromatography (petroleum–acetone 4:1) to give compound (I); m.p. 473–476 K. 1H NMR (CDCl3, δH): 7.42 (s, 2H, Ar—H), 7.60 (s, 1H, Ar—H); 31P NMR (CDCl3, 85% H3PO4 as external standard): δ 51.69. Secondly, a mixture of compound (I) and sodium ethoxide was stirred and refluxed in ethanol. After evaporating the ethanol, the residue was washed with water/ether and the ether layer was dried over MgSO4. Finally, ether was evaporated off and the product was recrystallized from the mixed solvent of petroleum and acetone (4:1). White prism crystals of compound (II) were obtained, m.p. 406–408 K. Analysis calculated for C11H14ClN2O2PS2: C39.23, H 4.19, N 8.32%; found: C 39.19, H 4.14, N 8.35%; 1H NMR (CDCl3, δH): 7.41–7.40 (m, 2H, Ar—H), 7.22–7.17 (m, 1H, Ar—H), 4.12–4.04 (m, 4H, CH2), 1.25–1.18 (m, 6H, CH3); 31P (CDCl3, 85% H3PO4 as external standard): δ 58.25.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the title compound. Ellipsoids are drawn at 50% probability.
[Figure 2] Fig. 2. View showing the packing of the dimer arrangement.
(II) top
Crystal data top
C11H14ClN2O2PS2Z = 2
Mr = 336.78F(000) = 348
Triclinic, P1Dx = 1.486 Mg m3
Hall symbol: -P 1Melting point: 134 K
a = 7.605 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.288 (4) ÅCell parameters from 749 reflections
c = 10.568 (4) Åθ = 2.9–26.3°
α = 78.311 (6)°µ = 0.64 mm1
β = 70.600 (6)°T = 293 K
γ = 77.163 (6)°Prism, white
V = 752.9 (5) Å30.32 × 0.20 × 0.18 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3051 independent reflections
Radiation source: fine-focus sealed tube2289 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ϕ and ω scansθmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan
SADABS
h = 79
Tmin = 0.780, Tmax = 0.892k = 1212
4506 measured reflectionsl = 813
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0465P)2 + 0.5081P]
where P = (Fo2 + 2Fc2)/3
3050 reflections(Δ/σ)max < 0.001
176 parametersΔρmax = 0.63 e Å3
48 restraintsΔρmin = 0.40 e Å3
Crystal data top
C11H14ClN2O2PS2γ = 77.163 (6)°
Mr = 336.78V = 752.9 (5) Å3
Triclinic, P1Z = 2
a = 7.605 (3) ÅMo Kα radiation
b = 10.288 (4) ŵ = 0.64 mm1
c = 10.568 (4) ÅT = 293 K
α = 78.311 (6)°0.32 × 0.20 × 0.18 mm
β = 70.600 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3051 independent reflections
Absorption correction: multi-scan
SADABS
2289 reflections with I > 2σ(I)
Tmin = 0.780, Tmax = 0.892Rint = 0.020
4506 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04348 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.02Δρmax = 0.63 e Å3
3050 reflectionsΔρmin = 0.40 e Å3
176 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
xyzUiso*/Ueq
Cl11.08352 (11)0.39873 (10)0.67323 (10)0.0723 (3)
S10.16674 (12)0.04667 (8)1.24178 (10)0.0654 (3)
S20.43263 (10)0.21408 (7)1.00051 (8)0.0471 (2)
O20.1518 (3)0.1477 (2)1.1279 (3)0.0701 (7)
N10.2657 (3)0.4508 (2)0.9345 (2)0.0374 (5)
H10.17980.51980.92800.045*
N20.0508 (3)0.3201 (2)1.0821 (2)0.0416 (5)
C10.8396 (4)0.4198 (3)0.7500 (3)0.0463 (7)
C20.7300 (4)0.5429 (3)0.7241 (3)0.0481 (7)
H2A0.78680.61340.66720.058*
C30.5358 (4)0.5610 (3)0.7829 (3)0.0444 (6)
H30.46080.64360.76700.053*
C40.4558 (4)0.4534 (2)0.8658 (2)0.0352 (5)
C50.5680 (4)0.3310 (2)0.8909 (3)0.0389 (6)
C60.7628 (4)0.3127 (3)0.8334 (3)0.0465 (7)
H60.83840.23090.85070.056*
C70.2237 (4)0.3340 (2)1.0121 (2)0.0357 (6)
C100.2034 (6)0.0163 (4)1.1551 (5)0.0852 (12)
H10A0.09130.05121.15340.102*
H10B0.25040.00581.08360.102*
C110.3449 (7)0.0078 (6)1.2834 (6)0.125 (2)
H11A0.29160.01431.35550.188*
H11B0.38790.09041.28920.188*
H11C0.44960.06531.29120.188*
P10.01728 (10)0.19160 (7)1.19238 (8)0.0450 (2)
O10.1606 (4)0.2647 (2)1.3113 (2)0.0857 (9)
C90.3680 (6)0.2947 (5)1.5277 (4)0.0920 (14)
H9A0.37910.39071.50390.138*
H9B0.38360.27121.62300.138*
H9C0.46390.26431.50620.138*
C80.1815 (6)0.2306 (5)1.4515 (3)0.0821 (12)
H8A0.08390.26111.47270.099*
H8B0.16860.13371.47630.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0415 (4)0.0783 (6)0.0827 (6)0.0111 (4)0.0026 (4)0.0061 (5)
S10.0516 (5)0.0485 (4)0.0812 (6)0.0024 (4)0.0247 (4)0.0252 (4)
S20.0406 (4)0.0309 (3)0.0576 (5)0.0010 (3)0.0095 (3)0.0045 (3)
O20.0652 (15)0.0465 (12)0.1041 (19)0.0171 (11)0.0436 (14)0.0168 (12)
N10.0387 (12)0.0298 (10)0.0373 (11)0.0002 (9)0.0106 (9)0.0019 (9)
N20.0385 (12)0.0344 (11)0.0440 (13)0.0013 (9)0.0121 (10)0.0064 (9)
C10.0382 (14)0.0532 (17)0.0449 (16)0.0088 (13)0.0070 (12)0.0091 (13)
C20.0497 (16)0.0471 (16)0.0442 (16)0.0123 (13)0.0115 (13)0.0014 (12)
C30.0475 (16)0.0370 (14)0.0435 (15)0.0045 (12)0.0131 (12)0.0023 (11)
C40.0404 (14)0.0341 (13)0.0293 (12)0.0032 (11)0.0106 (10)0.0035 (10)
C50.0441 (14)0.0347 (13)0.0343 (13)0.0027 (11)0.0108 (11)0.0029 (10)
C60.0407 (15)0.0418 (15)0.0499 (16)0.0020 (12)0.0096 (12)0.0067 (12)
C70.0409 (14)0.0301 (12)0.0339 (13)0.0006 (10)0.0137 (11)0.0025 (10)
C100.080 (3)0.058 (2)0.123 (4)0.016 (2)0.047 (3)0.009 (2)
C110.105 (4)0.135 (5)0.137 (5)0.071 (4)0.042 (3)0.040 (4)
P10.0413 (4)0.0354 (4)0.0461 (4)0.0013 (3)0.0096 (3)0.0100 (3)
O10.099 (2)0.0727 (16)0.0406 (12)0.0255 (14)0.0004 (12)0.0109 (11)
C90.099 (3)0.123 (4)0.046 (2)0.032 (3)0.001 (2)0.017 (2)
C80.093 (3)0.100 (3)0.046 (2)0.017 (2)0.0155 (19)0.0021 (19)
Geometric parameters (Å, º) top
Cl1—C11.744 (3)C4—C51.386 (3)
S1—P11.9228 (11)C5—C61.387 (4)
S2—C51.744 (3)C6—H60.9300
S2—C71.767 (3)C10—C111.439 (6)
O2—C101.439 (4)C10—H10A0.9700
O2—P11.583 (2)C10—H10B0.9700
N1—C71.348 (3)C11—H11A0.9600
N1—C41.389 (3)C11—H11B0.9600
N1—H10.8600C11—H11C0.9600
N2—C71.300 (3)P1—O11.563 (2)
N2—P11.629 (2)O1—C81.414 (4)
C1—C61.372 (4)C9—C81.461 (6)
C1—C21.383 (4)C9—H9A0.9600
C2—C31.385 (4)C9—H9B0.9600
C2—H2A0.9300C9—H9C0.9600
C3—C41.384 (3)C8—H8A0.9700
C3—H30.9300C8—H8B0.9700
C5—S2—C790.80 (12)C11—C10—H10A108.9
C10—O2—P1125.2 (2)O2—C10—H10B108.9
C7—N1—C4116.2 (2)C11—C10—H10B108.9
C7—N1—H1121.9H10A—C10—H10B107.7
C4—N1—H1121.9C10—C11—H11A109.5
C7—N2—P1126.75 (18)C10—C11—H11B109.5
C6—C1—C2122.3 (3)H11A—C11—H11B109.5
C6—C1—Cl1118.5 (2)C10—C11—H11C109.5
C2—C1—Cl1119.2 (2)H11A—C11—H11C109.5
C1—C2—C3120.0 (3)H11B—C11—H11C109.5
C1—C2—H2A120.0O1—P1—O2102.66 (16)
C3—C2—H2A120.0O1—P1—N2100.67 (13)
C4—C3—C2118.4 (3)O2—P1—N2100.77 (12)
C4—C3—H3120.8O1—P1—S1115.64 (10)
C2—C3—H3120.8O2—P1—S1114.28 (10)
C3—C4—C5120.7 (2)N2—P1—S1120.19 (9)
C3—C4—N1127.5 (2)C8—O1—P1128.1 (2)
C5—C4—N1111.8 (2)C8—C9—H9A109.5
C4—C5—C6121.1 (2)C8—C9—H9B109.5
C4—C5—S2111.4 (2)H9A—C9—H9B109.5
C6—C5—S2127.5 (2)C8—C9—H9C109.5
C1—C6—C5117.5 (3)H9A—C9—H9C109.5
C1—C6—H6121.3H9B—C9—H9C109.5
C5—C6—H6121.3O1—C8—C9109.0 (3)
N2—C7—N1121.7 (2)O1—C8—H8A109.9
N2—C7—S2128.52 (19)C9—C8—H8A109.9
N1—C7—S2109.82 (18)O1—C8—H8B109.9
O2—C10—C11113.5 (4)C9—C8—H8B109.9
O2—C10—H10A108.9H8A—C8—H8B108.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.862.142.996 (3)175
Symmetry code: (i) x, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC11H14ClN2O2PS2
Mr336.78
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.605 (3), 10.288 (4), 10.568 (4)
α, β, γ (°)78.311 (6), 70.600 (6), 77.163 (6)
V3)752.9 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.64
Crystal size (mm)0.32 × 0.20 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
SADABS
Tmin, Tmax0.780, 0.892
No. of measured, independent and
observed [I > 2σ(I)] reflections
4506, 3051, 2289
Rint0.020
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.112, 1.02
No. of reflections3050
No. of parameters176
No. of restraints48
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.63, 0.40

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
Cl1—C11.744 (3)N1—C41.389 (3)
S1—P11.9228 (11)N1—H10.8600
S2—C51.744 (3)N2—C71.300 (3)
S2—C71.767 (3)N2—P11.629 (2)
O2—P11.583 (2)C4—C51.386 (3)
N1—C71.348 (3)P1—O11.563 (2)
C5—S2—C790.80 (12)N1—C7—S2109.82 (18)
C7—N1—C4116.2 (2)O1—P1—O2102.66 (16)
C7—N2—P1126.75 (18)O1—P1—N2100.67 (13)
C5—C4—N1111.8 (2)O2—P1—N2100.77 (12)
C4—C5—S2111.4 (2)O1—P1—S1115.64 (10)
C6—C5—S2127.5 (2)O2—P1—S1114.28 (10)
N2—C7—N1121.7 (2)N2—P1—S1120.19 (9)
N2—C7—S2128.52 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.862.142.996 (3)175
Symmetry code: (i) x, y+1, z+2.
 

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