supplementary materials
(2Z)-Methyl 2-(2-amino-1,3-thiazol-4-yl)-2-(methoxyimino)ethanoate
In the title compound, C7H9N3O3S, the planes of the 2-amino-1,3-thiazol-4-yl and the methyl ester groups are oriented at a dihedral angle of 67.06 (7)°. In the crystal, inversion dimers linked by pairs of N-H
N hydrogen bonds occur, forming R22(8) ring motifs. The dimers are interlinked by N-HO hydrogen bonds, resulting in sheets propagating in the ac plane.
2-Mercapto-benzothiazolyl-(Z)-2-(2-aminothiazol-4-yl)-2-methoxyimino
acetate (0.2 g, 1.4 mmol) was dissolved in methanol (5 ml) and stirred for 1 h
at 303 K. Yellow prisms of (I) were obtained through slow
evaporation after five days.
The coordinates of H-atoms of NH2 group were refined. Other
H atoms were positioned
geometrically, with C—H = 0.93 and 0.96 Å for aryl and methyl H,
respectively and constrained to ride on their parent atoms, with
Uiso(H) = xUeq(C, N), where x = 1.5 for methyl and
1.2 for other H atoms.
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 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
(2
Z)-Methyl 2-(2-amino-1,3-thiazol-4-yl)-2-(methoxyimino)ethanoate
top
Crystal data top
| C7H9N3O3S | F(000) = 448 |
| Mr = 215.23 | Dx = 1.431 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2295 reflections |
| a = 7.8096 (4) Å | θ = 2.6–27.5° |
| b = 8.1994 (5) Å | µ = 0.31 mm−1 |
| c = 15.6247 (9) Å | T = 296 K |
| β = 92.936 (2)° | Prism, yellow |
| V = 999.20 (10) Å3 | 0.25 × 0.20 × 0.18 mm |
| Z = 4 | |
Data collection top
Bruker Kappa APEXII CCD
diffractometer | 2295 independent reflections |
| Radiation source: fine-focus sealed tube | 1696 reflections with I > 2σ(I) |
| graphite | Rint = 0.028 |
| Detector resolution: 7.50 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
| ω scans | h = −10→10 |
Absorption correction: multi-scan
(SADABS; Bruker, 2005) | k = −8→10 |
| Tmin = 0.931, Tmax = 0.945 | l = −20→20 |
| 9949 measured reflections | |
Refinement top
| 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.2265P]
where P = (Fo2 + 2Fc2)/3 |
| 2295 reflections | (Δ/σ)max < 0.001 |
| 135 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
| C7H9N3O3S | V = 999.20 (10) Å3 |
| Mr = 215.23 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 7.8096 (4) Å | µ = 0.31 mm−1 |
| b = 8.1994 (5) Å | T = 296 K |
| c = 15.6247 (9) Å | 0.25 × 0.20 × 0.18 mm |
| β = 92.936 (2)° | |
Data collection top
Bruker Kappa APEXII CCD
diffractometer | 2295 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2005) | 1696 reflections with I > 2σ(I) |
| Tmin = 0.931, Tmax = 0.945 | Rint = 0.028 |
| 9949 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.120 | Δρmax = 0.26 e Å−3 |
| S = 1.03 | Δρmin = −0.16 e Å−3 |
| 2295 reflections | Absolute structure: ? |
| 135 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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| | x | y | z | Uiso*/Ueq | |
| S1 | 0.41857 (6) | 0.20584 (8) | 0.43460 (3) | 0.0599 (2) | |
| O1 | 0.04763 (18) | 0.26609 (19) | 0.13478 (9) | 0.0637 (5) | |
| O2 | 0.25926 (17) | 0.08248 (18) | 0.14230 (9) | 0.0599 (5) | |
| O3 | −0.14991 (17) | −0.0224 (2) | 0.17911 (8) | 0.0606 (5) | |
| N1 | 0.11714 (18) | 0.0792 (2) | 0.41045 (9) | 0.0475 (5) | |
| N2 | 0.2110 (2) | 0.0993 (3) | 0.55484 (11) | 0.0719 (8) | |
| N3 | −0.06554 (18) | −0.0011 (2) | 0.26002 (9) | 0.0482 (5) | |
| C1 | 0.1775 (2) | 0.1176 (2) | 0.33140 (11) | 0.0419 (5) | |
| C2 | 0.3342 (2) | 0.1859 (3) | 0.33191 (12) | 0.0519 (6) | |
| C3 | 0.2315 (2) | 0.1199 (3) | 0.47114 (12) | 0.0483 (6) | |
| C4 | 0.0712 (2) | 0.0836 (2) | 0.25360 (11) | 0.0412 (5) | |
| C5 | 0.1219 (2) | 0.1552 (2) | 0.17005 (11) | 0.0452 (6) | |
| C6 | 0.3165 (3) | 0.1371 (4) | 0.05994 (15) | 0.0826 (10) | |
| C7 | −0.3004 (3) | −0.1162 (4) | 0.18950 (16) | 0.0913 (12) | |
| H2 | 0.38901 | 0.21784 | 0.28319 | 0.0622* | |
| H2A | 0.288 (3) | 0.129 (3) | 0.5901 (17) | 0.0863* | |
| H2B | 0.124 (4) | 0.053 (3) | 0.5734 (17) | 0.0863* | |
| H6A | 0.24081 | 0.09504 | 0.01485 | 0.1240* | |
| H6B | 0.43070 | 0.09816 | 0.05256 | 0.1240* | |
| H6C | 0.31566 | 0.25411 | 0.05803 | 0.1240* | |
| H7A | −0.27198 | −0.21154 | 0.22295 | 0.1370* | |
| H7B | −0.34834 | −0.14852 | 0.13428 | 0.1370* | |
| H7C | −0.38262 | −0.05196 | 0.21829 | 0.1370* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| S1 | 0.0470 (3) | 0.0858 (4) | 0.0465 (3) | −0.0188 (3) | −0.0024 (2) | 0.0058 (3) |
| O1 | 0.0605 (9) | 0.0762 (10) | 0.0548 (9) | 0.0119 (8) | 0.0062 (7) | 0.0219 (8) |
| O2 | 0.0583 (8) | 0.0742 (10) | 0.0486 (8) | 0.0134 (7) | 0.0177 (6) | 0.0089 (7) |
| O3 | 0.0514 (7) | 0.0897 (11) | 0.0403 (7) | −0.0193 (7) | −0.0009 (5) | 0.0000 (7) |
| N1 | 0.0366 (7) | 0.0672 (10) | 0.0385 (8) | −0.0026 (7) | 0.0012 (6) | 0.0057 (7) |
| N2 | 0.0506 (10) | 0.1262 (19) | 0.0386 (9) | −0.0213 (11) | −0.0016 (7) | 0.0093 (10) |
| N3 | 0.0444 (8) | 0.0626 (10) | 0.0374 (8) | −0.0034 (7) | 0.0015 (6) | −0.0006 (7) |
| C1 | 0.0397 (8) | 0.0468 (10) | 0.0392 (9) | 0.0019 (7) | 0.0019 (7) | 0.0054 (8) |
| C2 | 0.0480 (10) | 0.0666 (12) | 0.0410 (9) | −0.0114 (9) | 0.0023 (8) | 0.0065 (9) |
| C3 | 0.0383 (8) | 0.0634 (12) | 0.0431 (10) | −0.0017 (8) | 0.0019 (7) | 0.0053 (9) |
| C4 | 0.0377 (8) | 0.0475 (10) | 0.0385 (9) | 0.0033 (7) | 0.0039 (6) | 0.0016 (8) |
| C5 | 0.0415 (9) | 0.0546 (11) | 0.0394 (9) | −0.0019 (8) | 0.0010 (7) | 0.0015 (8) |
| C6 | 0.0799 (16) | 0.112 (2) | 0.0588 (14) | 0.0138 (15) | 0.0323 (12) | 0.0181 (14) |
| C7 | 0.0640 (14) | 0.142 (3) | 0.0674 (15) | −0.0480 (16) | −0.0010 (12) | −0.0012 (16) |
Geometric parameters (Å, °) top
| S1—C2 | 1.7109 (19) | N2—H2B | 0.84 (3) |
| S1—C3 | 1.7442 (18) | C1—C2 | 1.346 (2) |
| O1—C5 | 1.198 (2) | C1—C4 | 1.463 (2) |
| O2—C5 | 1.320 (2) | C4—C5 | 1.503 (2) |
| O2—C6 | 1.454 (3) | C2—H2 | 0.9300 |
| O3—N3 | 1.4062 (19) | C6—H6A | 0.9600 |
| O3—C7 | 1.421 (3) | C6—H6B | 0.9600 |
| N1—C1 | 1.381 (2) | C6—H6C | 0.9600 |
| N1—C3 | 1.312 (2) | C7—H7A | 0.9600 |
| N2—C3 | 1.336 (3) | C7—H7B | 0.9600 |
| N3—C4 | 1.282 (2) | C7—H7C | 0.9600 |
| N2—H2A | 0.83 (3) | | |
| | | |
| C2—S1—C3 | 88.83 (9) | O1—C5—O2 | 125.06 (16) |
| C5—O2—C6 | 116.32 (17) | O1—C5—C4 | 123.60 (15) |
| N3—O3—C7 | 108.47 (15) | O2—C5—C4 | 111.32 (14) |
| C1—N1—C3 | 109.73 (15) | S1—C2—H2 | 125.00 |
| O3—N3—C4 | 110.53 (14) | C1—C2—H2 | 125.00 |
| H2A—N2—H2B | 118 (3) | O2—C6—H6A | 109.00 |
| C3—N2—H2B | 122.2 (18) | O2—C6—H6B | 109.00 |
| C3—N2—H2A | 119.5 (17) | O2—C6—H6C | 109.00 |
| C2—C1—C4 | 124.15 (16) | H6A—C6—H6B | 109.00 |
| N1—C1—C4 | 119.64 (14) | H6A—C6—H6C | 109.00 |
| N1—C1—C2 | 116.21 (16) | H6B—C6—H6C | 109.00 |
| S1—C2—C1 | 110.60 (14) | O3—C7—H7A | 109.00 |
| S1—C3—N1 | 114.63 (14) | O3—C7—H7B | 109.00 |
| S1—C3—N2 | 121.05 (14) | O3—C7—H7C | 109.00 |
| N1—C3—N2 | 124.33 (17) | H7A—C7—H7B | 109.00 |
| C1—C4—C5 | 118.93 (14) | H7A—C7—H7C | 109.00 |
| N3—C4—C1 | 118.53 (15) | H7B—C7—H7C | 109.00 |
| N3—C4—C5 | 122.49 (15) | | |
| | | |
| C3—S1—C2—C1 | −0.42 (17) | O3—N3—C4—C5 | 3.3 (2) |
| C2—S1—C3—N1 | 0.46 (18) | N1—C1—C2—S1 | 0.3 (2) |
| C2—S1—C3—N2 | −179.5 (2) | C4—C1—C2—S1 | −179.86 (13) |
| C6—O2—C5—O1 | −3.7 (3) | N1—C1—C4—N3 | −9.3 (2) |
| C6—O2—C5—C4 | 177.57 (17) | N1—C1—C4—C5 | 168.00 (15) |
| C7—O3—N3—C4 | −179.82 (18) | C2—C1—C4—N3 | 170.87 (19) |
| C3—N1—C1—C2 | 0.0 (2) | C2—C1—C4—C5 | −11.8 (3) |
| C3—N1—C1—C4 | −179.81 (17) | N3—C4—C5—O1 | 70.4 (2) |
| C1—N1—C3—S1 | −0.4 (2) | N3—C4—C5—O2 | −110.87 (18) |
| C1—N1—C3—N2 | 179.6 (2) | C1—C4—C5—O1 | −106.8 (2) |
| O3—N3—C4—C1 | −179.50 (14) | C1—C4—C5—O2 | 71.92 (19) |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O1i | 0.83 (3) | 2.28 (2) | 3.058 (2) | 156 (2) |
| N2—H2B···N1ii | 0.84 (3) | 2.20 (3) | 3.024 (2) | 166 (3) |
| Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O1i | 0.83 (3) | 2.28 (2) | 3.058 (2) | 156 (2) |
| N2—H2B···N1ii | 0.84 (3) | 2.20 (3) | 3.024 (2) | 166 (3) |
| Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x, −y, −z+1. |
The authors acknowledge the Higher Education Commission, Islamabad, Pakistan,
and Bana International, Karachi, Pakistan, for funding the purchase of the
diffractometer and for technical support, respectively.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Khanna, J. M., Handa, V. K., Dandala, R. & Aryan, R. C. (1999). US Patent No. 5 869 649, C07D50106. [What is the second number?]
Laurent, G., Durant, F. & Evrard, G. (1981). Acta Cryst. (1981). Acta Cryst. B37, 972–974.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
![[Figure 1]](./hb2983fig1thm.gif)
![[Figure 2]](./hb2983fig2thm.gif)
2-Mercapto-benzothiazolyl-(Z)-2-(2-aminothiazol-4-yl)-2-methoxyimino acetate (MAEM) is a standard acylating agent for the preparation of cephalosporins (Khanna et al., 1999). The title compound (I), (Fig 1), is prepared as an intermediate for derivitaziation.
The crystal structure of (II) Ethyl 2-amino-α-(E-methoxyimino)-4-thiazoleacetate (Laurent et al., 1981) has been published. (I) differs from (II) due to the methoxy group attached with carbonyl instead of ethoxy moiety.
The title compound is dimerized due to the intermolecular H-bonding of N—H···N type forming R22(8) ring motifs (Bernstein et al., 1995). The dimers are further linked with each other through the intermolecular H-bonding of N—H···O type (Table 1), (Fig. 2). The five membered ring along with NH2 A (C1/C2/S1/C3/N1/N2), methyl ester group B (O1/C5/O2/C6) and the group C (C4/N3/O3/C7) are planar. The dihedral angles between A/B, A/C and B/C have values of 67.06 (7), 9.21 (16) and 71.67 (11)°, respectively.