(2Z)-Methyl 2-(2-amino-1,3-thia­zol-4-yl)-2-(methoxy­imino)ethano­ate

Sharif, S.; Tahir, M.N.; Khan, I.U.; Salariya, M.A.; Ahmad, S.

doi:10.1107/S1600536809019643

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1455

doi:10.1107/S1600536809019643

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(2Z)-Methyl 2-(2-amino-1,3-thiazol-4-yl)-2-(methoxyimino)ethanoate

Shahzad Sharif,^a M. Nawaz Tahir,^b ^* Islam Ullah Khan,^a Manan Ayub Salariya ^c and Sarfraz Ahmad ^c

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cPharmagen Ltd, Lahore 54000, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 23 May 2009; accepted 23 May 2009; online 6 June 2009)

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—H⋯O hydrogen bonds, resulting in sheets propagating in the ac plane.

Related literature

For a related structure, see: Laurent et al. (1981 ). For background to the use of the title compound in organic synthesis, see: Khanna et al. (1999 ). For graph-set notation, see: Bernstein et al. (1995 );

Experimental

Crystal data

C₇H₉N₃O₃S
M_r = 215.23
Monoclinic, P 2₁ /n
a = 7.8096 (4) Å
b = 8.1994 (5) Å
c = 15.6247 (9) Å
β = 92.936 (2)°
V = 999.20 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.931, T_max = 0.945
9949 measured reflections
2295 independent reflections
1696 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 1.03
2295 reflections
135 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019643/hb2983sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019643/hb2983Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For a related structure, see: Laurent et al. (1981). For background to the use of the title compound in organic synthesis, see: Khanna et al. (1999). For graph-set notation, see: Bernstein et al. (1995);

Experimental top

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.

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 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small spheres of arbitrary radius.
	Fig. 2. The partial packing of (I) which shows that molecules form dimers and the dimers are interlinked forming two dimensional polymeric sheets.

(2Z)-Methyl 2-(2-amino-1,3-thiazol-4-yl)-2-(methoxyimino)ethanoate top

Crystal data top

C₇H₉N₃O₃S	F(000) = 448
M_r = 215.23	D_x = 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 monochromator	R_int = 0.028
Detector resolution: 7.50 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→10
T_min = 0.931, T_max = 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(F_o²) + (0.0635P)² + 0.2265P] where P = (F_o² + 2F_c²)/3
2295 reflections	(Δ/σ)_max < 0.001
135 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₇H₉N₃O₃S	V = 999.20 (10) Å³
M_r = 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)
T_min = 0.931, T_max = 0.945	R_int = 0.028
9949 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.26 e Å⁻³
2295 reflections	Δρ_min = −0.16 e Å⁻³
135 parameters

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	U_iso*/U_eq
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, º) 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, º) 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.

Experimental details

Crystal data
Chemical formula	C₇H₉N₃O₃S
M_r	215.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.8096 (4), 8.1994 (5), 15.6247 (9)
β (°)	92.936 (2)
V (Å³)	999.20 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.931, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	9949, 2295, 1696
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 1.03
No. of reflections	2295
No. of parameters	135
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.16

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

Hydrogen-bond geometry (Å, º) 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.

Acknowledgements

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.

References

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