(3R,5S)-5(3)-Carb-oxy-3,4,5,6-tetra-hydro-2H-1,4-thia-zin-4-ium-3(5)-carboxyl-ate.

The molecule of the zwitterionic title compound, C(6)H(9)NO(4)S, which lies on a mirror plane, shows a puckered chair conformation of the six-membered ring with the S and N atoms out of the mean plane of the other four C atoms by 0.929 (2) and 0.647 (2) Å, respectively. The ionized carboxyl group is equatorially oriented. The hydrogen-bonding network includes very short O-H⋯O [2.470 (2) Å] and N-H⋯S [3.471 (2) and 3.416 (2) Å] inter-molecular contacts.

Related literature

For the detection of 1,4-thio­morpholine-3,5-dicarboxylic acid (THT) as a normal component in bovine brains and human urine, see: Cavallini, Pecci et al. (1985 ▶); Cavallini, Matarese et al. (1985 ▶); Matarese et al. (1987 ▶); Cavallini et al. (1991 ▶). For the previous structure determination of the (3R,5R) epimer of THT, see: Portalone et al. (1993 ▶). For related literature, see: Allen et al. (1997 ▶); Paglialunga Paradisi et al. (1990 ▶).

Experimental

Crystal data

C6H9NO4S

M = 191.21

Orthorhombic,

a = 6.1641 (8) Å

b = 9.323 (1) Å

c = 12.760 (1) Å

V = 733.29 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 298 (2) K

0.20 × 0.15 × 0.10 mm

Data collection

Huber CS four-circle diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.916, T max = 0.958

1840 measured reflections

1060 independent reflections

998 reflections with I > 2σ(I)

R int = 0.02

3 standard reflections every 97 reflections intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.094

S = 1.07

1060 reflections

76 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.28 e Å−3

Data collection: XCS (Colapietro et al., 1992 ▶); cell refinement: XCS; data reduction: XCS; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: WinGX.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005151/rz2198sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005151/rz2198Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H9NO4S	F000 = 400
Mr = 191.21	Dx = 1.732 Mg m−3
Orthorhombic, Pbnm	Mo Kα radiation λ = 0.71069 Å
Hall symbol: -P 2c 2ab	Cell parameters from 87 reflections
a = 6.1641 (8) Å	θ = 20–25º
b = 9.323 (1) Å	µ = 0.41 mm−1
c = 12.760 (1) Å	T = 298 (2) K
V = 733.29 (14) Å3	Block, colourless
Z = 4	0.20 × 0.15 × 0.10 mm

Huber CS four-circle diffractometer	Rint = 0.02
Radiation source: fine-focus sealed tube	θmax = 30.0º
Monochromator: graphite	θmin = 3.2º
T = 298(2) K	h = 0→8
ω scans	k = 0→13
Absorption correction: ψ scan(North et al., 1968)	l = 0→17
Tmin = 0.916, Tmax = 0.958	3 standard reflections
1840 measured reflections	every 97 reflections
1060 independent reflections	intensity decay: 2%
998 reflections with I > 2σ(I)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.064P)2 + 0.2054P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
1060 reflections	Δρmax = 0.25 e Å−3
76 parameters	Δρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
S1	0.04543 (7)	0.05914 (4)	0.2500	0.01738 (15)
O1	−0.04198 (17)	−0.42620 (10)	0.07779 (8)	0.0235 (2)
H1	0.0000	−0.5000	0.0000	0.049*
O2	−0.04168 (16)	−0.23791 (11)	−0.03208 (7)	0.0233 (2)
N4	−0.0505 (2)	−0.27615 (15)	0.2500	0.0152 (3)
H41	0.077 (5)	−0.316 (4)	0.2500	0.046 (9)*
H42	−0.129 (5)	−0.344 (3)	0.2500	0.035 (7)*
C2	0.0797 (2)	−0.06777 (12)	0.14454 (10)	0.0191 (3)
H21	0.232 (3)	−0.105 (2)	0.1441 (12)	0.031 (4)*
H22	0.054 (3)	−0.012 (2)	0.0759 (16)	0.029 (5)*
C3	−0.08019 (18)	−0.19183 (12)	0.15032 (9)	0.0154 (2)
H3	−0.232 (3)	−0.1555 (18)	0.1489 (11)	0.019 (4)*
C7	−0.05172 (18)	−0.29148 (12)	0.05503 (10)	0.0167 (2)

	U11	U22	U33	U12	U13	U23
S1	0.0253 (2)	0.0108 (2)	0.0160 (2)	−0.00097 (13)	0.000	0.000
O1	0.0403 (6)	0.0134 (4)	0.0170 (4)	0.0028 (3)	0.0010 (4)	−0.0023 (3)
O2	0.0352 (5)	0.0204 (5)	0.0142 (4)	−0.0015 (4)	−0.0003 (3)	0.0006 (3)
N4	0.0220 (7)	0.0109 (6)	0.0127 (6)	−0.0010 (5)	0.000	0.000
C2	0.0275 (6)	0.0142 (5)	0.0156 (5)	−0.0037 (4)	0.0027 (4)	−0.0009 (4)
C3	0.0211 (5)	0.0126 (4)	0.0124 (5)	0.0003 (4)	−0.0012 (4)	0.0006 (4)
C7	0.0198 (5)	0.0156 (5)	0.0146 (5)	−0.0008 (4)	−0.0011 (4)	−0.0026 (4)

S1—C2	1.8043 (12)	N4—H41	0.87 (3)
S1—C2i	1.8043 (12)	N4—H42	0.80 (3)
O1—C7	1.2905 (14)	C2—C3	1.5211 (16)
O1—H1	1.2352	C2—H21	1.00 (2)
O2—C7	1.2201 (16)	C2—H22	1.03 (2)
N4—C3i	1.5064 (13)	C3—C7	1.5403 (16)
N4—C3	1.5064 (13)	C3—H3	0.997 (17)
C2—S1—C2i	96.46 (8)	S1—C2—H22	106.5 (11)
C7—O1—H1	111.77	H21—C2—H22	108.4 (13)
C3i—N4—C3	115.20 (12)	N4—C3—C2	111.04 (10)
C3i—N4—H41	109.5 (10)	N4—C3—C7	109.75 (9)
C3—N4—H41	109.5 (10)	C2—C3—C7	110.28 (9)
C3i—N4—H42	109.9 (9)	N4—C3—H3	107.9 (8)
C3—N4—H42	109.9 (9)	C2—C3—H3	110.5 (10)
H41—N4—H42	102 (3)	C7—C3—H3	107.3 (9)
C3—C2—S1	112.75 (8)	O2—C7—O1	126.95 (11)
C3—C2—H21	110.2 (12)	O2—C7—C3	118.55 (11)
S1—C2—H21	109.9 (10)	O1—C7—C3	114.50 (10)
C3—C2—H22	108.9 (10)
C2i—S1—C2—C3	56.74 (12)	N4—C3—C7—O2	−170.39 (11)
C3i—N4—C3—C2	59.40 (16)	C2—C3—C7—O2	−47.76 (14)
C3i—N4—C3—C7	−178.42 (8)	N4—C3—C7—O1	9.90 (14)
S1—C2—C3—N4	−61.40 (12)	C2—C3—C7—O1	132.53 (11)
S1—C2—C3—C7	176.73 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ii	1.24	1.24	2.4704 (19)	180.00 (9)
N4—H41···S1iii	0.87 (3)	2.60 (3)	3.4713 (15)	179 (3)
N4—H42···S1iv	0.80 (3)	2.72 (3)	3.4155 (16)	147 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1i	1.24	1.24	2.4704 (19)	180
N4—H41⋯S1ii	0.87 (3)	2.60 (3)	3.4713 (15)	179 (3)
N4—H42⋯S1iii	0.80 (3)	2.72 (3)	3.4155 (16)	147 (3)

Symmetry codes: (i) ; (ii) ; (iii) .