(3R,5S)-5(3)-Carb­oxy-3,4,5,6-tetra­hydro-2H-1,4-thia­zin-4-ium-3(5)-carboxyl­ate

Portalone, G.; Cassetta, A.; Colapietro, M.; Plattner, S.H.

doi:10.1107/S1600536808005151

organic compounds

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(3R,5S)-5(3)-Carboxy-3,4,5,6-tetrahydro-2H-1,4-thiazin-4-ium-3(5)-carboxylate

Gustavo Portalone,^a ^* Alberto Cassetta,^b Marcello Colapietro ^a and Susanne Heidi Plattner ^a

^aChemistry Department, University of Rome I "La Sapienza", P.le A. Moro 5, I-00185 Rome, Italy, and ^bInstitute of Crystallography, CNR, Trieste Outstation, Area Science Park-Basovizza, S.S.14 Km 163.5, I-34012 Trieste, Italy
^*Correspondence e-mail: g.portalone@caspur.it

(Received 12 February 2008; accepted 22 February 2008; online 27 February 2008)

The molecule of the zwitterionic title compound, C₆H₉NO₄S, 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] intermolecular 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_r = 191.21
Orthorhombic, P b n m
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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.094
S = 1.07
1060 reflections
76 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻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) -x, -y-1, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

The detection of 1,4-thiomorpholine-3,5-dicarboxylic acid (THT) as normal component in bovin brain (Cavallini, Pecci et al., 1985) and human urine (Matarese et al., 1987) has stimulated the investigation of the biological role played by this unusual cyclic, sulfur containing imino acid (Cavallini et al., 1991). Here we report the x-ray structure determination of the (3R,5S) epymer (THTC). The asymmetric unit of the title compound comprises a half-zwitterion disposed about a mirror plane along the line joining atoms S1 and N4 and perpendicular to the plane formed by C2, C3, C2^ì and C3^ì [symmetry code: (i) x, y, -z + 1/2]. From Fig. 1 it appears that the six-membered ring adopts a puckered chair conformation with the carboxyl group in equatorial position. The hydrogen-bonding network (Fig. 2) includes very short O—-H···O and N—-H···S (Allen et al., 1997) intermolecular contacts (Table 1).

Related literature top

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) epymer of THT, see: Portalone et al. (1993). For related literature, see: Allen et al. (1997); Paglialunga Paradisi et al. (1990).

Experimental top

(3R,5S)-tetrahydro-2H-1,4-thiazine-3,5-dicarboxylic acid was obtained as described previously (Paglialunga Paradisi et al., 1990). Crystals were grown from a water solution (0.1 mmol in ca 6 ml) by slow evaporation of the solvent.

Computing details top

Data collection: XCS (Colapietro et al., 1992); cell refinement: XCS (Colapietro et al., 1992); data reduction: XCS (Colapietro et al., 1992); 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 (Farrugia, 1999).

Figures top

	Fig. 1. The molecular component in the title compound showing the zwitterion lying on a crystallographic mirror plane and the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Packing diagram of the title compound viewed approximately down the a axis. H atoms are shown as small spheres of arbitrary radii. For the sake of clarity, H21, H22, H41 and H42 are omitted. H bonding is indicated by dashed lines.

(3R,5S)-5(3)-carboxy-3,4,5,6-tetrahydro-2H-1,4-thiazin-4-ium- 3(5)-carboxylate top

Crystal data top

C₆H₉NO₄S	F(000) = 400
M_r = 191.21	D_x = 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 = 20–25°
b = 9.323 (1) Å	µ = 0.41 mm⁻¹
c = 12.760 (1) Å	T = 298 K
V = 733.29 (14) Å³	Block, colourless
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Huber CS four-circle diffractometer	998 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.02
Graphite monochromator	θ_max = 30.0°, θ_min = 3.2°
ω scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→13
T_min = 0.916, T_max = 0.958	l = 0→17
1840 measured reflections	3 standard reflections every 97 reflections
1060 independent reflections	intensity decay: 2%

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.064P)² + 0.2054P] where P = (F_o² + 2F_c²)/3
1060 reflections	(Δ/σ)_max < 0.001
76 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₆H₉NO₄S	V = 733.29 (14) Å³
M_r = 191.21	Z = 4
Orthorhombic, Pbnm	Mo Kα radiation
a = 6.1641 (8) Å	µ = 0.41 mm⁻¹
b = 9.323 (1) Å	T = 298 K
c = 12.760 (1) Å	0.20 × 0.15 × 0.10 mm

Data collection top

Huber CS four-circle diffractometer	998 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.02
T_min = 0.916, T_max = 0.958	3 standard reflections every 97 reflections
1840 measured reflections	intensity decay: 2%
1060 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.25 e Å⁻³
1060 reflections	Δρ_min = −0.28 e Å⁻³
76 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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱⁱ	1.24	1.24	2.4704 (19)	180 (1)
N4—H41···S1ⁱⁱⁱ	0.87 (3)	2.60 (3)	3.4713 (15)	179 (3)
N4—H42···S1^iv	0.80 (3)	2.72 (3)	3.4155 (16)	147 (3)

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

Experimental details

Crystal data
Chemical formula	C₆H₉NO₄S
M_r	191.21
Crystal system, space group	Orthorhombic, Pbnm
Temperature (K)	298
a, b, c (Å)	6.1641 (8), 9.323 (1), 12.760 (1)
V (Å³)	733.29 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Huber CS four-circle diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.916, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	1840, 1060, 998
R_int	0.02
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.094, 1.07
No. of reflections	1060
No. of parameters	76
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.28

Computer programs: XCS (Colapietro et al., 1992), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	1.24	1.24	2.4704 (19)	180.00 (9)
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) −x, −y−1, −z; (ii) −x+1/2, y−1/2, z; (iii) −x−1/2, y−1/2, z.

Acknowledgements

We thank MIUR (Rome) for 2006 financial support of the project `X-ray diffractometry and spectrometry'.

References

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CRYSTALLOGRAPHIC
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doi:10.1107/S1600536808005151

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

(3R,5S)-5(3)-Carb­­oxy-3,4,5,6-tetra­hydro-2H-1,4-thia­zin-4-ium-3(5)-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(3R,5S)-5(3)-Carboxy-3,4,5,6-tetrahydro-2H-1,4-thiazin-4-ium-3(5)-carboxylate