Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008237/dn6062sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008237/dn6062IIsup2.hkl |
CCDC reference: 214852
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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.
Fig. 1. A view of the title compound. Ellipsoids are drawn at 50% probability. | |
Fig. 2. View showing the packing of the dimer arrangement. |
C11H14ClN2O2PS2 | Z = 2 |
Mr = 336.78 | F(000) = 348 |
Triclinic, P1 | Dx = 1.486 Mg m−3 |
Hall symbol: -P 1 | Melting point: 134 K |
a = 7.605 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.288 (4) Å | Cell parameters from 749 reflections |
c = 10.568 (4) Å | θ = 2.9–26.3° |
α = 78.311 (6)° | µ = 0.64 mm−1 |
β = 70.600 (6)° | T = 293 K |
γ = 77.163 (6)° | Prism, white |
V = 752.9 (5) Å3 | 0.32 × 0.20 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 3051 independent reflections |
Radiation source: fine-focus sealed tube | 2289 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.1° |
Absorption correction: multi-scan SADABS | h = −7→9 |
Tmin = 0.780, Tmax = 0.892 | k = −12→12 |
4506 measured reflections | l = −8→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-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 parameters | Δρmax = 0.63 e Å−3 |
48 restraints | Δρmin = −0.40 e Å−3 |
C11H14ClN2O2PS2 | γ = 77.163 (6)° |
Mr = 336.78 | V = 752.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.605 (3) Å | Mo Kα radiation |
b = 10.288 (4) Å | µ = 0.64 mm−1 |
c = 10.568 (4) Å | T = 293 K |
α = 78.311 (6)° | 0.32 × 0.20 × 0.18 mm |
β = 70.600 (6)° |
Bruker SMART CCD area-detector diffractometer | 3051 independent reflections |
Absorption correction: multi-scan SADABS | 2289 reflections with I > 2σ(I) |
Tmin = 0.780, Tmax = 0.892 | Rint = 0.020 |
4506 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 48 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.63 e Å−3 |
3050 reflections | Δρmin = −0.40 e Å−3 |
176 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 1.08352 (11) | 0.39873 (10) | 0.67323 (10) | 0.0723 (3) | |
S1 | 0.16674 (12) | 0.04667 (8) | 1.24178 (10) | 0.0654 (3) | |
S2 | 0.43263 (10) | 0.21408 (7) | 1.00051 (8) | 0.0471 (2) | |
O2 | −0.1518 (3) | 0.1477 (2) | 1.1279 (3) | 0.0701 (7) | |
N1 | 0.2657 (3) | 0.4508 (2) | 0.9345 (2) | 0.0374 (5) | |
H1 | 0.1798 | 0.5198 | 0.9280 | 0.045* | |
N2 | 0.0508 (3) | 0.3201 (2) | 1.0821 (2) | 0.0416 (5) | |
C1 | 0.8396 (4) | 0.4198 (3) | 0.7500 (3) | 0.0463 (7) | |
C2 | 0.7300 (4) | 0.5429 (3) | 0.7241 (3) | 0.0481 (7) | |
H2A | 0.7868 | 0.6134 | 0.6672 | 0.058* | |
C3 | 0.5358 (4) | 0.5610 (3) | 0.7829 (3) | 0.0444 (6) | |
H3 | 0.4608 | 0.6436 | 0.7670 | 0.053* | |
C4 | 0.4558 (4) | 0.4534 (2) | 0.8658 (2) | 0.0352 (5) | |
C5 | 0.5680 (4) | 0.3310 (2) | 0.8909 (3) | 0.0389 (6) | |
C6 | 0.7628 (4) | 0.3127 (3) | 0.8334 (3) | 0.0465 (7) | |
H6 | 0.8384 | 0.2309 | 0.8507 | 0.056* | |
C7 | 0.2237 (4) | 0.3340 (2) | 1.0121 (2) | 0.0357 (6) | |
C10 | −0.2034 (6) | 0.0163 (4) | 1.1551 (5) | 0.0852 (12) | |
H10A | −0.0913 | −0.0512 | 1.1534 | 0.102* | |
H10B | −0.2504 | 0.0058 | 1.0836 | 0.102* | |
C11 | −0.3449 (7) | −0.0078 (6) | 1.2834 (6) | 0.125 (2) | |
H11A | −0.2916 | −0.0143 | 1.3555 | 0.188* | |
H11B | −0.3879 | −0.0904 | 1.2892 | 0.188* | |
H11C | −0.4496 | 0.0653 | 1.2912 | 0.188* | |
P1 | −0.01728 (10) | 0.19160 (7) | 1.19238 (8) | 0.0450 (2) | |
O1 | −0.1606 (4) | 0.2647 (2) | 1.3113 (2) | 0.0857 (9) | |
C9 | −0.3680 (6) | 0.2947 (5) | 1.5277 (4) | 0.0920 (14) | |
H9A | −0.3791 | 0.3907 | 1.5039 | 0.138* | |
H9B | −0.3836 | 0.2712 | 1.6230 | 0.138* | |
H9C | −0.4639 | 0.2643 | 1.5062 | 0.138* | |
C8 | −0.1815 (6) | 0.2306 (5) | 1.4515 (3) | 0.0821 (12) | |
H8A | −0.0839 | 0.2611 | 1.4727 | 0.099* | |
H8B | −0.1686 | 0.1337 | 1.4763 | 0.099* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0415 (4) | 0.0783 (6) | 0.0827 (6) | −0.0111 (4) | −0.0026 (4) | −0.0061 (5) |
S1 | 0.0516 (5) | 0.0485 (4) | 0.0812 (6) | −0.0024 (4) | −0.0247 (4) | 0.0252 (4) |
S2 | 0.0406 (4) | 0.0309 (3) | 0.0576 (5) | 0.0010 (3) | −0.0095 (3) | 0.0045 (3) |
O2 | 0.0652 (15) | 0.0465 (12) | 0.1041 (19) | −0.0171 (11) | −0.0436 (14) | 0.0168 (12) |
N1 | 0.0387 (12) | 0.0298 (10) | 0.0373 (11) | 0.0002 (9) | −0.0106 (9) | 0.0019 (9) |
N2 | 0.0385 (12) | 0.0344 (11) | 0.0440 (13) | −0.0013 (9) | −0.0121 (10) | 0.0064 (9) |
C1 | 0.0382 (14) | 0.0532 (17) | 0.0449 (16) | −0.0088 (13) | −0.0070 (12) | −0.0091 (13) |
C2 | 0.0497 (16) | 0.0471 (16) | 0.0442 (16) | −0.0123 (13) | −0.0115 (13) | 0.0014 (12) |
C3 | 0.0475 (16) | 0.0370 (14) | 0.0435 (15) | −0.0045 (12) | −0.0131 (12) | 0.0023 (11) |
C4 | 0.0404 (14) | 0.0341 (13) | 0.0293 (12) | −0.0032 (11) | −0.0106 (10) | −0.0035 (10) |
C5 | 0.0441 (14) | 0.0347 (13) | 0.0343 (13) | −0.0027 (11) | −0.0108 (11) | −0.0029 (10) |
C6 | 0.0407 (15) | 0.0418 (15) | 0.0499 (16) | 0.0020 (12) | −0.0096 (12) | −0.0067 (12) |
C7 | 0.0409 (14) | 0.0301 (12) | 0.0339 (13) | 0.0006 (10) | −0.0137 (11) | −0.0025 (10) |
C10 | 0.080 (3) | 0.058 (2) | 0.123 (4) | −0.016 (2) | −0.047 (3) | 0.009 (2) |
C11 | 0.105 (4) | 0.135 (5) | 0.137 (5) | −0.071 (4) | −0.042 (3) | 0.040 (4) |
P1 | 0.0413 (4) | 0.0354 (4) | 0.0461 (4) | −0.0013 (3) | −0.0096 (3) | 0.0100 (3) |
O1 | 0.099 (2) | 0.0727 (16) | 0.0406 (12) | 0.0255 (14) | 0.0004 (12) | 0.0109 (11) |
C9 | 0.099 (3) | 0.123 (4) | 0.046 (2) | −0.032 (3) | −0.001 (2) | −0.017 (2) |
C8 | 0.093 (3) | 0.100 (3) | 0.046 (2) | −0.017 (2) | −0.0155 (19) | −0.0021 (19) |
Cl1—C1 | 1.744 (3) | C4—C5 | 1.386 (3) |
S1—P1 | 1.9228 (11) | C5—C6 | 1.387 (4) |
S2—C5 | 1.744 (3) | C6—H6 | 0.9300 |
S2—C7 | 1.767 (3) | C10—C11 | 1.439 (6) |
O2—C10 | 1.439 (4) | C10—H10A | 0.9700 |
O2—P1 | 1.583 (2) | C10—H10B | 0.9700 |
N1—C7 | 1.348 (3) | C11—H11A | 0.9600 |
N1—C4 | 1.389 (3) | C11—H11B | 0.9600 |
N1—H1 | 0.8600 | C11—H11C | 0.9600 |
N2—C7 | 1.300 (3) | P1—O1 | 1.563 (2) |
N2—P1 | 1.629 (2) | O1—C8 | 1.414 (4) |
C1—C6 | 1.372 (4) | C9—C8 | 1.461 (6) |
C1—C2 | 1.383 (4) | C9—H9A | 0.9600 |
C2—C3 | 1.385 (4) | C9—H9B | 0.9600 |
C2—H2A | 0.9300 | C9—H9C | 0.9600 |
C3—C4 | 1.384 (3) | C8—H8A | 0.9700 |
C3—H3 | 0.9300 | C8—H8B | 0.9700 |
C5—S2—C7 | 90.80 (12) | C11—C10—H10A | 108.9 |
C10—O2—P1 | 125.2 (2) | O2—C10—H10B | 108.9 |
C7—N1—C4 | 116.2 (2) | C11—C10—H10B | 108.9 |
C7—N1—H1 | 121.9 | H10A—C10—H10B | 107.7 |
C4—N1—H1 | 121.9 | C10—C11—H11A | 109.5 |
C7—N2—P1 | 126.75 (18) | C10—C11—H11B | 109.5 |
C6—C1—C2 | 122.3 (3) | H11A—C11—H11B | 109.5 |
C6—C1—Cl1 | 118.5 (2) | C10—C11—H11C | 109.5 |
C2—C1—Cl1 | 119.2 (2) | H11A—C11—H11C | 109.5 |
C1—C2—C3 | 120.0 (3) | H11B—C11—H11C | 109.5 |
C1—C2—H2A | 120.0 | O1—P1—O2 | 102.66 (16) |
C3—C2—H2A | 120.0 | O1—P1—N2 | 100.67 (13) |
C4—C3—C2 | 118.4 (3) | O2—P1—N2 | 100.77 (12) |
C4—C3—H3 | 120.8 | O1—P1—S1 | 115.64 (10) |
C2—C3—H3 | 120.8 | O2—P1—S1 | 114.28 (10) |
C3—C4—C5 | 120.7 (2) | N2—P1—S1 | 120.19 (9) |
C3—C4—N1 | 127.5 (2) | C8—O1—P1 | 128.1 (2) |
C5—C4—N1 | 111.8 (2) | C8—C9—H9A | 109.5 |
C4—C5—C6 | 121.1 (2) | C8—C9—H9B | 109.5 |
C4—C5—S2 | 111.4 (2) | H9A—C9—H9B | 109.5 |
C6—C5—S2 | 127.5 (2) | C8—C9—H9C | 109.5 |
C1—C6—C5 | 117.5 (3) | H9A—C9—H9C | 109.5 |
C1—C6—H6 | 121.3 | H9B—C9—H9C | 109.5 |
C5—C6—H6 | 121.3 | O1—C8—C9 | 109.0 (3) |
N2—C7—N1 | 121.7 (2) | O1—C8—H8A | 109.9 |
N2—C7—S2 | 128.52 (19) | C9—C8—H8A | 109.9 |
N1—C7—S2 | 109.82 (18) | O1—C8—H8B | 109.9 |
O2—C10—C11 | 113.5 (4) | C9—C8—H8B | 109.9 |
O2—C10—H10A | 108.9 | H8A—C8—H8B | 108.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2i | 0.86 | 2.14 | 2.996 (3) | 175 |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H14ClN2O2PS2 |
Mr | 336.78 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 752.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.32 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS |
Tmin, Tmax | 0.780, 0.892 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4506, 3051, 2289 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.02 |
No. of reflections | 3050 |
No. of parameters | 176 |
No. of restraints | 48 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.40 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
Cl1—C1 | 1.744 (3) | N1—C4 | 1.389 (3) |
S1—P1 | 1.9228 (11) | N1—H1 | 0.8600 |
S2—C5 | 1.744 (3) | N2—C7 | 1.300 (3) |
S2—C7 | 1.767 (3) | N2—P1 | 1.629 (2) |
O2—P1 | 1.583 (2) | C4—C5 | 1.386 (3) |
N1—C7 | 1.348 (3) | P1—O1 | 1.563 (2) |
C5—S2—C7 | 90.80 (12) | N1—C7—S2 | 109.82 (18) |
C7—N1—C4 | 116.2 (2) | O1—P1—O2 | 102.66 (16) |
C7—N2—P1 | 126.75 (18) | O1—P1—N2 | 100.67 (13) |
C5—C4—N1 | 111.8 (2) | O2—P1—N2 | 100.77 (12) |
C4—C5—S2 | 111.4 (2) | O1—P1—S1 | 115.64 (10) |
C6—C5—S2 | 127.5 (2) | O2—P1—S1 | 114.28 (10) |
N2—C7—N1 | 121.7 (2) | N2—P1—S1 | 120.19 (9) |
N2—C7—S2 | 128.52 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2i | 0.86 | 2.14 | 2.996 (3) | 175 |
Symmetry code: (i) −x, −y+1, −z+2. |
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 N═C 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).