(Z)-2-(2-Amino­thia­zol-1-ium-4-yl)-2-(tert-butoxy­carbonyl­methoxy­imino)acetate monohydrate

In the title compound, C₁₁H₁₅N₃O₅S·H₂O, the amino group is coplanar with the thia­zole ring. The dihedral angle between the thia­zole ring and the adjacent carboxyl­ate group is 74.19 (4)°. O—H...O and N—H...O hydrogen bonds link the mol­ecules into two-dimensional networks parallel to the (100) plane, and π–π inter­actions exist between the thia­zole rings of inversion-related mol­ecules, with a centroid–centroid separation of 3.5965 (6) Å.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.084
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.65 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.07 Ratio
PLAT430_ALERT_2_B Short Inter D...A Contact  S1     ..  O2      ..       2.86 Ang.

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.70 mm
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C4     -   C5     ...       1.53 Ang.

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

2-Aminothiazole compounds have been extensively studied because of their biological and industrial applications (Lynch et al., 1999; Toplak et al., 2003). A search of the Cambridge Structural Database (CSD, Version 5.28, May 2007; Allen, 2002) reveals that there are 127 crystal structures containing the 2-aminothiazole moiety. The title compound is an important intermediate of cefixime, which was the first oral third-generation cephalosporin available in Japan, The United States, Europe and other regions (Quintiliani, 1996). Crystal structures of some cephalosporin intermediates which contain a 2-aminothiazole group have been reported (Yoshida et al., 1989; Laurent et al., 1981).

In the title compound, the thiazole ring is planar to within 0.0047 (7) Å. The amino group and atom C4 are coplanar with the thiazole ring, with atoms N1 and C4 deviating from the thiazole plane by -0.0039 (3) and -0.075 (2)\ %A, respectively. The dihedral angle between the thiazole ring and the adjacent carboxylate group is 74.19 (4) °. The C3/C4/N2/O3 plane is twisted away from the thiazole plane by 3.20 (5) °, while the dihedral angle between the C3/C4/N2/O3 plane and adjacent carboxylate group is 77.39 (4) °.

The crystal structure is stabilized by intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) involving the O atoms of the water molecules, carboxylate groups and ester groups. These hydrogen bonds link the molecules into two-dimensional networks parallel to the (100) planes (Fig. 2). The thiazole rings of the inversion-related molecules at (x, y, z) and (2 - x, -y, 1 - z) are stacked with their centroids separated by a distance of 3.5965 (6) Å, indicating π-π interactions.

Related literature

For synthesis details, see: Furlenmeier et al. (1987). For general background, see: Quintiliani (1996); Lynch et al. (1999); Toplak et al. (2003). For related structures, see: Laurent et al. (1981); Yoshida et al. (1989). For related literature, see: Allen (2002).

S2. Experimental

The title compound was prepared according to the literature method (Furlenmeier et al., 1987). Crystals suitable for X-ray analysis were obtained by slow evaporation of an 2-propanol solution at 223 K

S3. Refinement

H atoms bound to N or O atoms were located from a difference Fourier map and refined freely. H atoms bound to C atoms were positioned geometrically (C—H = 0.94–0.98 Å) and refined using a riding model, with U_iso(H) = 1.2 or 1.5U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Molecular structure of the title compound, showing 30% probability displacement for non-H atoms. The dashed line denotes an O—H···O hydrogen bond.
	Fig. 2. Packing diagram. Dashed lines indicate intermolecular hydrogen bonds.

(Z)-(2-Aminothiazol-1-ium-4-yl)-2-(tert-butoxycarbonylmethoxyimino)acetate monohydrate

Crystal data

C11H15N3O5S·H2O	F(000) = 672
Mr = 319.34	Dx = 1.396 Mg m^−3
Monoclinic, P21/c	Melting point = 459–461 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4504 (2) Å	Cell parameters from 3446 reflections
b = 11.2896 (3) Å	θ = 2.0–27.5°
c = 13.0965 (3) Å	µ = 0.24 mm^−1
β = 100.407 (1)°	T = 223 K
V = 1519.72 (6) Å^3	Block, colourless
Z = 4	0.70 × 0.70 × 0.57 mm

Data collection

Bruker SMART CCD diffractometer	3446 independent reflections
Radiation source: fine-focus sealed tube	3253 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −13→13
Tmin = 0.848, Tmax = 0.874	k = −14→14
14426 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0414P)^2 + 0.4932P] where P = (Fo^2 + 2Fc^2)/3
3446 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N2	0.88830 (10)	0.35059 (8)	0.40598 (8)	0.0270 (2)
N1	0.76747 (12)	−0.00740 (10)	0.59144 (9)	0.0351 (2)
H1A	0.7563	0.0458	0.6371	0.042*
H1B	0.7510	−0.0815	0.6020	0.042*
C3	0.87952 (10)	0.14516 (10)	0.38807 (8)	0.0232 (2)
C4	0.90625 (10)	0.26202 (10)	0.34927 (9)	0.0233 (2)
C1	0.80927 (11)	0.02414 (10)	0.50659 (9)	0.0257 (2)
C2	0.88474 (11)	0.04012 (10)	0.34035 (9)	0.0259 (2)
H2	0.9114	0.0305	0.2760	0.031*
C5	0.94464 (12)	0.27073 (9)	0.24220 (9)	0.0259 (2)
C6	0.85040 (12)	0.55092 (11)	0.40047 (11)	0.0323 (3)
H6A	0.8892	0.6273	0.3879	0.039*
H6B	0.8586	0.5406	0.4757	0.039*
C7	0.70753 (12)	0.55079 (10)	0.35059 (10)	0.0296 (2)
C8	0.50370 (13)	0.66070 (13)	0.35446 (12)	0.0413 (3)
C9	0.41658 (16)	0.55500 (17)	0.35991 (16)	0.0568 (4)
H9A	0.4360	0.4940	0.3128	0.085*
H9B	0.3263	0.5789	0.3402	0.085*
H9C	0.4315	0.5242	0.4302	0.085*
C10	0.4928 (2)	0.7057 (2)	0.24477 (18)	0.0706 (6)
H10A	0.5100	0.6414	0.2000	0.106*
H10B	0.5557	0.7685	0.2431	0.106*
H10C	0.4058	0.7361	0.2207	0.106*
C11	0.47690 (19)	0.7585 (2)	0.4269 (2)	0.0842 (8)
H11A	0.4844	0.7273	0.4967	0.126*
H11B	0.3897	0.7889	0.4038	0.126*
H11C	0.5394	0.8219	0.4265	0.126*
O5	0.64267 (9)	0.62911 (8)	0.39814 (8)	0.0370 (2)
O3	0.91826 (9)	0.45830 (7)	0.35939 (7)	0.0317 (2)
O2	1.06094 (9)	0.28914 (9)	0.23883 (7)	0.0359 (2)
N3	0.83732 (9)	0.13513 (8)	0.48304 (7)	0.0244 (2)
H12	0.8441 (17)	0.1918 (17)	0.5299 (15)	0.047 (5)*
O1	0.85201 (10)	0.25782 (9)	0.16842 (7)	0.0384 (2)
O4	0.66198 (10)	0.48971 (9)	0.27812 (8)	0.0405 (2)
S1	0.83619 (3)	−0.07545 (2)	0.41203 (2)	0.02844 (9)
O1W	0.75233 (14)	0.75009 (10)	0.59734 (11)	0.0578 (3)
H1W	0.814 (2)	0.724 (2)	0.649 (2)	0.079 (7)*
H2W	0.726 (2)	0.704 (2)	0.551 (2)	0.075 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0313 (5)	0.0227 (5)	0.0287 (5)	0.0010 (4)	0.0097 (4)	0.0022 (4)
O1W	0.0694 (8)	0.0357 (6)	0.0586 (8)	0.0060 (5)	−0.0141 (6)	−0.0073 (5)
N1	0.0523 (6)	0.0284 (5)	0.0298 (5)	−0.0008 (5)	0.0208 (5)	0.0018 (4)
C3	0.0252 (5)	0.0252 (5)	0.0196 (5)	0.0024 (4)	0.0056 (4)	0.0022 (4)
C4	0.0245 (5)	0.0237 (5)	0.0220 (5)	0.0019 (4)	0.0052 (4)	0.0023 (4)
C1	0.0292 (5)	0.0256 (5)	0.0238 (5)	0.0021 (4)	0.0082 (4)	0.0009 (4)
C2	0.0335 (5)	0.0253 (5)	0.0204 (5)	0.0014 (4)	0.0090 (4)	0.0017 (4)
C5	0.0365 (6)	0.0191 (5)	0.0237 (5)	0.0025 (4)	0.0100 (4)	0.0036 (4)
C6	0.0349 (6)	0.0226 (5)	0.0409 (7)	0.0027 (4)	0.0111 (5)	−0.0054 (5)
C7	0.0368 (6)	0.0250 (5)	0.0292 (6)	0.0026 (4)	0.0117 (5)	0.0010 (4)
C8	0.0324 (6)	0.0432 (7)	0.0462 (8)	0.0099 (5)	0.0015 (6)	−0.0041 (6)
C9	0.0383 (8)	0.0649 (11)	0.0648 (11)	−0.0013 (7)	0.0029 (7)	0.0111 (9)
C10	0.0623 (11)	0.0748 (13)	0.0739 (13)	0.0211 (10)	0.0102 (9)	0.0350 (11)
C11	0.0440 (9)	0.0921 (16)	0.1097 (18)	0.0300 (10)	−0.0048 (10)	−0.0523 (14)
O5	0.0321 (4)	0.0375 (5)	0.0404 (5)	0.0081 (4)	0.0041 (4)	−0.0112 (4)
O3	0.0376 (4)	0.0201 (4)	0.0412 (5)	0.0025 (3)	0.0176 (4)	0.0016 (3)
O2	0.0363 (5)	0.0404 (5)	0.0350 (5)	0.0012 (4)	0.0166 (4)	0.0057 (4)
N3	0.0307 (5)	0.0231 (4)	0.0209 (5)	0.0015 (4)	0.0088 (4)	0.0002 (3)
O1	0.0459 (5)	0.0456 (5)	0.0228 (4)	−0.0057 (4)	0.0039 (4)	0.0057 (4)
O4	0.0448 (5)	0.0437 (5)	0.0334 (5)	0.0024 (4)	0.0075 (4)	−0.0098 (4)
S1	0.04030 (17)	0.02140 (14)	0.02611 (15)	−0.00018 (10)	0.01262 (12)	−0.00021 (10)

Geometric parameters (Å, º)

N2—C4	1.2795 (15)	C6—H6A	0.980
N2—O3	1.4206 (12)	C6—H6B	0.980
O1W—H1W	0.89 (3)	C7—O4	1.1998 (16)
O1W—H2W	0.81 (3)	C7—O5	1.3347 (15)
N1—C1	1.3145 (15)	C8—O5	1.5046 (15)
N1—H1A	0.870	C8—C10	1.508 (3)
N1—H1B	0.870	C8—C9	1.510 (2)
C3—C2	1.3461 (16)	C8—C11	1.514 (2)
C3—N3	1.3973 (14)	C9—H9A	0.970
C3—C4	1.4589 (15)	C9—H9B	0.970
C4—C5	1.5297 (15)	C9—H9C	0.970
C1—N3	1.3355 (15)	C10—H10A	0.970
C1—S1	1.7328 (12)	C10—H10B	0.970
C2—S1	1.7358 (11)	C10—H10C	0.970
C2—H2	0.940	C11—H11A	0.970
C5—O2	1.2417 (15)	C11—H11B	0.970
C5—O1	1.2466 (15)	C11—H11C	0.970
C6—O3	1.4225 (14)	N3—H12	0.88 (2)
C6—C7	1.5177 (17)
C4—N2—O3	110.66 (9)	O5—C8—C9	110.08 (12)
H1W—O1W—H2W	117 (2)	C10—C8—C9	111.63 (15)
C1—N1—H1A	120.0	O5—C8—C11	102.11 (12)
C1—N1—H1B	120.0	C10—C8—C11	111.13 (18)
H1A—N1—H1B	120.0	C9—C8—C11	111.41 (16)
C2—C3—N3	112.81 (10)	C8—C9—H9A	109.5
C2—C3—C4	127.48 (10)	C8—C9—H9B	109.5
N3—C3—C4	119.64 (10)	H9A—C9—H9B	109.5
N2—C4—C3	116.56 (10)	C8—C9—H9C	109.5
N2—C4—C5	124.90 (10)	H9A—C9—H9C	109.5
C3—C4—C5	118.42 (9)	H9B—C9—H9C	109.5
N1—C1—N3	124.73 (11)	C8—C10—H10A	109.5
N1—C1—S1	123.37 (9)	C8—C10—H10B	109.5
N3—C1—S1	111.90 (8)	H10A—C10—H10B	109.5
C3—C2—S1	111.76 (8)	C8—C10—H10C	109.5
C3—C2—H2	124.1	H10A—C10—H10C	109.5
S1—C2—H2	124.1	H10B—C10—H10C	109.5
O2—C5—O1	128.32 (11)	C8—C11—H11A	109.5
O2—C5—C4	117.63 (10)	C8—C11—H11B	109.5
O1—C5—C4	114.05 (10)	H11A—C11—H11B	109.5
O3—C6—C7	110.82 (10)	C8—C11—H11C	109.5
O3—C6—H6A	109.5	H11A—C11—H11C	109.5
C7—C6—H6A	109.5	H11B—C11—H11C	109.5
O3—C6—H6B	109.5	C7—O5—C8	121.08 (10)
C7—C6—H6B	109.5	N2—O3—C6	107.65 (9)
H6A—C6—H6B	108.1	C1—N3—C3	113.53 (9)
O4—C7—O5	125.98 (12)	C1—N3—H12	121.0 (12)
O4—C7—C6	124.05 (11)	C3—N3—H12	124.2 (12)
O5—C7—C6	109.96 (10)	C1—S1—C2	89.99 (5)
O5—C8—C10	110.08 (13)
O3—N2—C4—C3	179.80 (9)	O4—C7—O5—C8	−8.4 (2)
O3—N2—C4—C5	−4.32 (15)	C6—C7—O5—C8	170.59 (11)
C2—C3—C4—N2	176.36 (11)	C10—C8—O5—C7	−56.72 (18)
N3—C3—C4—N2	−0.33 (15)	C9—C8—O5—C7	66.76 (17)
C2—C3—C4—C5	0.20 (17)	C11—C8—O5—C7	−174.82 (16)
N3—C3—C4—C5	−176.49 (9)	C4—N2—O3—C6	157.27 (10)
N3—C3—C2—S1	0.33 (13)	C7—C6—O3—N2	−77.04 (12)
C4—C3—C2—S1	−176.55 (9)	N1—C1—N3—C3	−179.79 (11)
N2—C4—C5—O2	79.82 (15)	S1—C1—N3—C3	0.87 (12)
C3—C4—C5—O2	−104.37 (12)	C2—C3—N3—C1	−0.79 (14)
N2—C4—C5—O1	−100.26 (13)	C4—C3—N3—C1	176.36 (10)
C3—C4—C5—O1	75.55 (13)	N1—C1—S1—C2	−179.92 (11)
O3—C6—C7—O4	−8.02 (18)	N3—C1—S1—C2	−0.57 (9)
O3—C6—C7—O5	172.96 (10)	C3—C2—S1—C1	0.12 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^i	0.87	2.28	2.8647 (15)	125
N1—H1A···O1^i	0.87	2.44	3.0683 (15)	130
N1—H1B···O1W^ii	0.87	1.90	2.7443 (16)	162
N3—H12···O1^i	0.88 (2)	1.89 (2)	2.6914 (13)	151 (2)
O1W—H1W···O2^iii	0.89 (3)	1.79 (3)	2.6637 (16)	166 (2)
O1W—H2W···O5	0.81 (3)	2.20 (3)	2.9840 (16)	162 (2)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) −x+2, −y+1, −z+1.