organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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S-1,3-Benzo­thia­zol-2-yl (2Z)-2-(2-amino-1,3-thia­zol-4-yl)-2-(meth­oxy­imino)­ethane­thio­ate

aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore, Pakistan
*Correspondence e-mail: mnachemist@hotmail.com

(Received 19 June 2009; accepted 1 July 2009; online 11 July 2009)

The title compound, C13H10N4O2S3, is an acyl­ating agent which belongs to the thia­zole class of organic compounds. The dihedral angle between the benzene and thiazole rings, which are fused to each other, is 1.2 (2)° so the overall benzothiazole system is almost planar. Inter­molecular N—H⋯N inter­actions and weak C—H⋯O inter­actions between symmetry-related mol­ecules stabilize the crystal structure, forming three different ring motifs [R22(8), R22(10) and R22(16)] in three dimensions.

Related literature

For background literature, see: Khanna et al. (1999[Khanna, J. M., Handa, V. K., Dandala, R. & Aryan, R. C. (1999). US Patent No. 5 869 649.]). For related structures, see: Radha (1985[Radha, A. (1985). Z. Kristallogr. 171, 225-228.]); Laurent & Durant (1981[Laurent, G. & Durant, F. (1981). Cryst. Struct. Commun. 10, 1007-1014.]). For graph set notation, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C13H10N4O2S3

  • Mr = 350.43

  • Monoclinic, P 21 /c

  • a = 13.9725 (9) Å

  • b = 5.0156 (3) Å

  • c = 21.7664 (14) Å

  • β = 90.001 (3)°

  • V = 1525.40 (17) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.50 mm−1

  • T = 296 K

  • 0.31 × 0.11 × 0.07 mm

Data collection
  • Bruker Kappa APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.941, Tmax = 0.972

  • 16828 measured reflections

  • 3829 independent reflections

  • 2096 reflections with I > 2σ(I)

  • Rint = 0.054

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.145

  • S = 1.03

  • 3829 reflections

  • 200 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3A⋯N1i 0.86 2.29 3.106 (3) 158
N3—H3B⋯N4i 0.86 2.16 2.997 (3) 165
C12—H7⋯O1ii 0.93 2.51 3.198 (3) 131
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON.

Supporting information


Comment top

The title compound, (I), is a standard acylating agent for the synthesis of different cephalosporins derivatives (Khanna et al., 1999).

The title compound (Fig. 1) is composed of two components, a benzothiazole and an acyl group having 2-amino thiazole moiety. The N3 atoms of 2-aminothiazole moieties of molecules of (I) lying about inversion centers form intermolecular hydrogen bonds of the type N–H···N with N1 and N4 atoms resulting in dimers and form 8 and 10-membered rings which could be expressed in graph set notation as R22(8) and R22(10) motifs (Bernstein et al., 1995). In addition, there is a rather weak C–H···O type interaction, resulting in an R22(16) motif about inversion centers. The hydrogen bonding geometry is presented in Table 1 and Fig. 2. The crystal structures of compounds related to (I) have been reported (Radha, 1985; Laurent & Durant, 1981) .

Related literature top

For background literature, see: Khanna et al. (1999). For related structures, see: Radha (1985); Laurent & Durant (1981). For graph set notation, see: Bernstein et al. (1995).

Experimental top

The compound was dissolved in methanol and ethyl acetate mixture (20:80 v/v %). The light yellow prismatic crystals were obtained after two days.

Refinement top

The H-atoms were refined geometrically and treated as riding atoms with C—H distances, 0.93 and 0.96 Å for aryl and methyl groups, respectively, and N–H = 0.86 Å with Uiso(H) = 1.2 times aromatic C and N atoms and Uiso(H) = 1.5 times methyl C atoms.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
[Figure 2] Fig. 2. Unit cell packing for (I) showing hydrogen bonds drawn as dashed lines.
S-1,3-Benzothiazol-2-yl (2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-(methoxyimino)ethanethioate top
Crystal data top
C13H10N4O2S3F(000) = 720
Mr = 350.43Dx = 1.526 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2744 reflections
a = 13.9725 (9) Åθ = 2.4–22.8°
b = 5.0156 (3) ŵ = 0.50 mm1
c = 21.7664 (14) ÅT = 296 K
β = 90.001 (3)°Prism, light yellow
V = 1525.40 (17) Å30.31 × 0.11 × 0.07 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3829 independent reflections
Radiation source: fine-focus sealed tube2096 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
ϕ and ω scansθmax = 28.4°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1818
Tmin = 0.941, Tmax = 0.972k = 66
16828 measured reflectionsl = 2928
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0695P)2]
where P = (Fo2 + 2Fc2)/3
3829 reflections(Δ/σ)max = 0.001
200 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C13H10N4O2S3V = 1525.40 (17) Å3
Mr = 350.43Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.9725 (9) ŵ = 0.50 mm1
b = 5.0156 (3) ÅT = 296 K
c = 21.7664 (14) Å0.31 × 0.11 × 0.07 mm
β = 90.001 (3)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3829 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
2096 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.972Rint = 0.054
16828 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.145H-atom parameters constrained
S = 1.03Δρmax = 0.35 e Å3
3829 reflectionsΔρmin = 0.34 e Å3
200 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
S11.09909 (5)0.53325 (15)0.33403 (3)0.0473 (2)
S20.82219 (5)1.20705 (16)0.47275 (4)0.0481 (2)
S30.62042 (6)1.30442 (19)0.51641 (4)0.0658 (3)
O10.73807 (14)0.7981 (4)0.41758 (10)0.0515 (6)
O20.76884 (15)1.2729 (4)0.32595 (10)0.0599 (6)
N10.97196 (15)0.6544 (4)0.41510 (10)0.0342 (5)
N20.85575 (16)1.1371 (5)0.31772 (11)0.0457 (6)
N31.07870 (17)0.3179 (5)0.44609 (11)0.0508 (7)
H3A1.05150.30010.48130.061*
H3B1.12730.22090.43680.061*
N40.73303 (16)0.9626 (5)0.56704 (11)0.0468 (6)
C11.04521 (18)0.4975 (5)0.40561 (12)0.0352 (6)
C21.0159 (2)0.7693 (5)0.31617 (13)0.0428 (7)
H11.01290.85980.27890.051*
C30.95521 (18)0.8065 (5)0.36329 (12)0.0340 (6)
C40.87134 (19)0.9811 (5)0.36324 (12)0.0370 (6)
C50.80041 (19)0.9594 (5)0.41574 (13)0.0379 (7)
C60.72758 (19)1.1345 (6)0.52336 (14)0.0427 (7)
C70.5768 (2)1.1236 (6)0.57791 (14)0.0516 (8)
C80.6472 (2)0.9518 (6)0.59907 (14)0.0451 (7)
C90.6272 (2)0.7821 (7)0.64769 (16)0.0641 (10)
H100.67330.66390.66220.077*
C100.5376 (3)0.7925 (8)0.67398 (17)0.0729 (11)
H90.52320.67980.70660.088*
C110.4697 (3)0.9652 (8)0.65302 (19)0.0755 (11)
H80.40990.96760.67190.091*
C120.4867 (2)1.1338 (8)0.60535 (19)0.0762 (11)
H70.44001.25160.59160.091*
C130.7520 (3)1.4460 (6)0.27606 (16)0.0641 (10)
H11A0.80781.55370.26910.096*
H11B0.69851.55900.28520.096*
H11C0.73841.34310.23990.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0469 (4)0.0640 (5)0.0309 (4)0.0148 (4)0.0129 (3)0.0034 (4)
S20.0494 (5)0.0563 (5)0.0387 (5)0.0072 (4)0.0129 (4)0.0009 (4)
S30.0557 (5)0.0812 (6)0.0605 (6)0.0223 (4)0.0143 (4)0.0168 (5)
O10.0441 (12)0.0557 (12)0.0547 (15)0.0042 (10)0.0139 (10)0.0033 (10)
O20.0565 (13)0.0793 (15)0.0439 (14)0.0303 (11)0.0118 (11)0.0226 (11)
N10.0349 (12)0.0442 (13)0.0236 (13)0.0022 (10)0.0041 (10)0.0040 (10)
N20.0469 (14)0.0550 (14)0.0353 (15)0.0137 (12)0.0067 (11)0.0056 (12)
N30.0567 (16)0.0613 (15)0.0342 (15)0.0246 (13)0.0114 (12)0.0107 (13)
N40.0419 (14)0.0621 (15)0.0363 (15)0.0042 (12)0.0108 (11)0.0046 (13)
C10.0354 (14)0.0429 (15)0.0274 (15)0.0001 (12)0.0043 (12)0.0033 (13)
C20.0465 (16)0.0536 (17)0.0283 (16)0.0077 (13)0.0091 (13)0.0076 (13)
C30.0369 (14)0.0399 (14)0.0251 (15)0.0006 (12)0.0031 (12)0.0006 (12)
C40.0399 (15)0.0444 (16)0.0266 (16)0.0013 (12)0.0046 (12)0.0021 (13)
C50.0359 (14)0.0439 (16)0.0339 (17)0.0095 (13)0.0040 (12)0.0060 (13)
C60.0391 (15)0.0539 (17)0.0351 (17)0.0019 (13)0.0079 (13)0.0053 (14)
C70.0427 (16)0.069 (2)0.043 (2)0.0017 (15)0.0105 (14)0.0055 (16)
C80.0426 (16)0.0606 (19)0.0320 (17)0.0018 (14)0.0081 (13)0.0045 (15)
C90.060 (2)0.084 (2)0.049 (2)0.0032 (18)0.0113 (17)0.0124 (19)
C100.077 (3)0.095 (3)0.046 (2)0.021 (2)0.020 (2)0.006 (2)
C110.052 (2)0.109 (3)0.066 (3)0.010 (2)0.0231 (19)0.011 (2)
C120.047 (2)0.109 (3)0.072 (3)0.013 (2)0.0178 (19)0.001 (2)
C130.075 (2)0.066 (2)0.052 (2)0.0228 (18)0.0030 (18)0.0160 (18)
Geometric parameters (Å, º) top
S1—C21.704 (3)C2—C31.344 (4)
S1—C11.740 (3)C2—H10.9300
S2—C61.759 (3)C3—C41.463 (4)
S2—C51.782 (3)C4—C51.517 (3)
S3—C71.728 (3)C7—C81.387 (4)
S3—C61.729 (3)C7—C121.394 (4)
O1—C51.190 (3)C8—C91.387 (4)
O2—N21.404 (3)C9—C101.378 (5)
O2—C131.410 (4)C9—H100.9300
N1—C11.308 (3)C10—C111.364 (5)
N1—C31.382 (3)C10—H90.9300
N2—C41.281 (3)C11—C121.360 (5)
N3—C11.344 (3)C11—H80.9300
N3—H3A0.8600C12—H70.9300
N3—H3B0.8600C13—H11A0.9600
N4—C61.286 (4)C13—H11B0.9600
N4—C81.388 (3)C13—H11C0.9600
C2—S1—C188.90 (13)N4—C6—S2123.9 (2)
C6—S2—C599.42 (13)S3—C6—S2119.61 (18)
C7—S3—C688.79 (15)C8—C7—C12121.4 (3)
N2—O2—C13110.1 (2)C8—C7—S3109.5 (2)
C1—N1—C3109.6 (2)C12—C7—S3129.1 (3)
C4—N2—O2110.2 (2)C9—C8—C7119.5 (3)
C1—N3—H3A120.0C9—C8—N4125.6 (3)
C1—N3—H3B120.0C7—C8—N4115.0 (3)
H3A—N3—H3B120.0C10—C9—C8118.5 (3)
C6—N4—C8110.3 (2)C10—C9—H10120.8
N1—C1—N3124.9 (2)C8—C9—H10120.8
N1—C1—S1114.7 (2)C11—C10—C9121.2 (4)
N3—C1—S1120.37 (19)C11—C10—H9119.4
C3—C2—S1110.7 (2)C9—C10—H9119.4
C3—C2—H1124.7C12—C11—C10121.9 (3)
S1—C2—H1124.7C12—C11—H8119.1
C2—C3—N1116.1 (2)C10—C11—H8119.1
C2—C3—C4126.0 (2)C11—C12—C7117.5 (4)
N1—C3—C4117.8 (2)C11—C12—H7121.2
N2—C4—C3120.2 (2)C7—C12—H7121.2
N2—C4—C5121.0 (2)O2—C13—H11A109.5
C3—C4—C5118.7 (2)O2—C13—H11B109.5
O1—C5—C4123.6 (3)H11A—C13—H11B109.5
O1—C5—S2125.2 (2)O2—C13—H11C109.5
C4—C5—S2111.29 (19)H11A—C13—H11C109.5
N4—C6—S3116.5 (2)H11B—C13—H11C109.5
C13—O2—N2—C4179.6 (3)C8—N4—C6—S30.8 (3)
C3—N1—C1—N3177.9 (3)C8—N4—C6—S2179.6 (2)
C3—N1—C1—S11.6 (3)C7—S3—C6—N40.9 (3)
C2—S1—C1—N11.1 (2)C7—S3—C6—S2179.7 (2)
C2—S1—C1—N3178.4 (2)C5—S2—C6—N487.6 (3)
C1—S1—C2—C30.3 (2)C5—S2—C6—S393.60 (19)
S1—C2—C3—N10.6 (3)C6—S3—C7—C80.7 (2)
S1—C2—C3—C4176.0 (2)C6—S3—C7—C12179.4 (4)
C1—N1—C3—C21.4 (3)C12—C7—C8—C91.4 (5)
C1—N1—C3—C4175.5 (2)S3—C7—C8—C9178.6 (3)
O2—N2—C4—C3176.5 (2)C12—C7—C8—N4179.6 (3)
O2—N2—C4—C50.7 (4)S3—C7—C8—N40.4 (3)
C2—C3—C4—N27.4 (4)C6—N4—C8—C9177.9 (3)
N1—C3—C4—N2176.1 (2)C6—N4—C8—C70.3 (4)
C2—C3—C4—C5168.5 (3)C7—C8—C9—C100.8 (5)
N1—C3—C4—C58.1 (4)N4—C8—C9—C10178.8 (3)
N2—C4—C5—O192.6 (3)C8—C9—C10—C110.0 (6)
C3—C4—C5—O183.3 (3)C9—C10—C11—C120.2 (6)
N2—C4—C5—S286.7 (3)C10—C11—C12—C70.4 (6)
C3—C4—C5—S297.4 (2)C8—C7—C12—C111.2 (6)
C6—S2—C5—O11.4 (3)S3—C7—C12—C11178.8 (3)
C6—S2—C5—C4177.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N1i0.862.293.106 (3)158
N3—H3B···N4i0.862.162.997 (3)165
C12—H7···O1ii0.932.513.198 (3)131
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC13H10N4O2S3
Mr350.43
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)13.9725 (9), 5.0156 (3), 21.7664 (14)
β (°) 90.001 (3)
V3)1525.40 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.50
Crystal size (mm)0.31 × 0.11 × 0.07
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.941, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
16828, 3829, 2096
Rint0.054
(sin θ/λ)max1)0.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.145, 1.03
No. of reflections3829
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.34

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N1i0.862.293.106 (3)158
N3—H3B···N4i0.862.162.997 (3)165
C12—H7···O1ii0.932.513.198 (3)131
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+2, z+1.
 

Acknowledgements

The authors acknowledge the Higher Education Commission of Pakistan for providing a grant to the Materials Chemistry Laboratory at GC University, Lahore, Pakistan. The title compound was kindly provided by Pharmagen Ltd, Lahore, Pakistan.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationKhanna, J. M., Handa, V. K., Dandala, R. & Aryan, R. C. (1999). US Patent No. 5 869 649.  Google Scholar
First citationLaurent, G. & Durant, F. (1981). Cryst. Struct. Commun. 10, 1007–1014.  CAS Google Scholar
First citationRadha, A. (1985). Z. Kristallogr. 171, 225–228.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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