(4-Benzyl-2-oxo-1,3-oxazolidin-5-yl)methyl methane­sulfonate

Cunico, W.; Gomes, C.R.B.; Tiekink, E.R.T.; Vellasco Junior, W.T.; Wardell, J.L.; Wardell, S.M.S.V.

doi:10.1107/S1600536809055020

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages o267-o268

https://doi.org/10.1107/S1600536809055020

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(4-Benzyl-2-oxo-1,3-oxazolidin-5-yl)methyl methanesulfonate

Wilson Cunico,^a Claudia R. B. Gomes,^b Edward R. T. Tiekink,^c ^* Walcimar T. Vellasco Junior,^b James L. Wardell ^d ‡ and Solange M. S. V. Wardell ^e

^aDepartamento de Química Orgânica, Universidade Federal de Pelotas (UFPel), Campus Universitário, s/n°, Caixa Postal 354, 96010-900 Pelotas, RS, Brazil, ^bFundação Oswaldo Cruz, Instituto de Tecnologia em Fármacos–Farmanguinhos, R. Sizenando Nabuco 100, Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, ^dCentro de Desenvolvimento Tecnológico em Saúde (CDTS), Fundação Oswaldo Cruz (FIOCRUZ), Casa Amarela, Campus de Manguinhos, Av. Brasil 4365, 21040-900 Rio de Janeiro, RJ, Brazil, and ^eCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 21 December 2009; accepted 21 December 2009; online 9 January 2010)

The title compound, C₁₂H₁₅NO₅S, features an approximately planar five-membered oxazolidin ring (r.m.s. deviation = 0.045 Å) with the peripheral benzyl and methyl methanesulfonate residues lying to either side of the plane. In the crystal, N—H⋯O hydrogen bonds, involving one of the sulfur-bound oxo groups as acceptor, lead to the formation of supramolecular chains along the b axis. These chains are reinforced by C—H⋯O contacts with the carbonyl O atom accepting three such interactions. The structure was refined as a racemic twin, with the major component being present 89% of the time.

Related literature

For the use of 1,3-oxazolidin-2-ones as chiral auxiliaries in organic synthesis, see: Evans et al. (1981 ); Ager et al. (1996 , 1997 ); Hintermann & Seebach (1998 ). For their biological activity, see: Poce et al. (2008 ); Brickner et al. (2008 ); Means et al. (2006 ); Kaiser et al. (2007 ); Clemmet & Markham (2000 ); Ebner et al. (2008 ); Negwer & Scharnow (2007 ); Mai et al. (2003 ). For background to their syntheses, see: Ochoa-Terán & Rivero (2008 ); Zappia et al. (2007 ).

Experimental

Crystal data

C₁₂H₁₅NO₅S
M_r = 285.31
Monoclinic, P 2₁
a = 8.7332 (5) Å
b = 5.8757 (3) Å
c = 12.9650 (7) Å
β = 103.317 (3)°
V = 647.39 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 120 K
0.26 × 0.08 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.700, T_max = 1.000
6748 measured reflections
2587 independent reflections
2266 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.123
S = 1.11
2587 reflections
177 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.88 (2)	2.28 (2)	3.113 (5)	160 (4)
C1—H1B⋯O5ⁱⁱ	0.98	2.51	3.428 (6)	155
C2—H2A⋯O5ⁱⁱ	0.99	2.32	3.214 (5)	150
C5—H5⋯O5ⁱⁱⁱ	1.00	2.36	3.326 (6)	162
C6—H6B⋯O1^iv	0.99	2.59	3.528 (6)	158
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (iii) x, y-1, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; 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 DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809055020/hb5289sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055020/hb5289Isup2.hkl

checkCIF report

Comment top

1,3-Oxazolidin-2-ones have found use initially as chiral auxiliaries in organic synthesis (Evans et al., 1981; Ager et al., 1996, 1997; Hintermann & Seebach 1998) and more recently in various biological applications, e.g., as a class of synthetic antibacterial agents with potent activity against clinically important susceptible and resistant Gram-positive and anaerobic pathogens (Poce et al., 2008; Brickner et al., 2008; Means et al., 2006; Kaiser et al., 2007; Clemmet & Markham, 2000; Ebner et al., 2008), as interneuron blocking agents or depressants of central synaptic transmission, muscle relaxants, anticonvulsants, and tranquilizers (Negwer & Scharnow, 2007), and as potent and selective monoamine oxidase type A (MAO) inhibitors (Mai et al., 2003). The syntheses of 1,3-oxazolidin-2-ones have been variously reported (Ochoa-Terán & Rivero, 2008; Zappia et al., 2007).

The oxazolidin ring in (I), Fig. 1, is essentially planar with the maximum deviations of 0.036 (5) Å for atom C5 and -0.040 (4) Å for atom N1. The O5 atom lies 0.089 (3) Å out of the plane in the direction of the C2 atom, and the C6 atom is below the plane. The C2–C3–C5–C6 torsion angle of 124.6 (4) ° shows a significant twist consistent with the methanesulfonate residue being splayed out from the rest of the molecule. The methanesulfonate-methyl group is oriented towards the ring-O4 atom.

Supramolecular chains are formed in the crystal structure of (I) along the b direction. These are sustained by N—H···O hydrogen bonds where the oxygen acceptor is an sulfur-bound oxo group, Fig. 2 and Table 1. Three close C–H···O-carbonyl contacts, Table 1, provide additional stability to the chain. Chains are linked into supramolecular arrays in the bc plane via weaker C—H···O contacts and these stack along the a axis, Fig. 3 and Table 1.

Related literature top

For the use of 1,3-oxazolidin-2-ones as chiral auxiliaries in organic synthesis, see: Evans et al. (1981); Ager et al. (1996, 1997); Hintermann & Seebach (1998). For their biological activity, see: Poce et al. (2008); Brickner et al. (2008); Means et al. (2006); Kaiser et al. (2007); Clemmet & Markham (2000); Ebner et al. (2008); Negwer & Scharnow (2007); Mai et al. (2003). For background to their syntheses, see: Ochoa-Terán & Rivero (2008); Zappia et al. (2007).

Experimental top

A solution of (4S,5R)-4-benzyl-5-(hydroxymethyl)-1,3-oxazolidin-2-one (1.036 g, 5 mmol) and methanesulfonyl chloride (0.75 ml, 10 mmol) in triethylamine (10 ml) was stirred at room temperature for 2 h, HCl (20 ml, 15%) was added and the mixture was extracted with dichloromethane (5 x 20 ml). The combined organic layers were washed with brine, dried over anhydrous Na₂SO₄ and evaporated, giving (I) as a brown solid (0.62 g, 44%) which was recrystallized from aqueous ethanol. ¹H-NMR (MeOD, 400 MHz): δ 7.30 (m, 5H, Ph), 4.57 (m, 1H, CHO), 4.23 (dd, 1H, ¹J = 11.6; ²J = 3.0 Hz, CH₂O), 4.11 (dd, 1H, ¹J = 11.6; ²J = 4.9 Hz, CH₂O), 4.00 (m, 1H, CHN), 3.05 (s, 3H, CH₃), 2.92 (m, 2H, CH₂Ph) p.p.m.; NH not obs. ¹³C-NMR (MeOD, 100 MHz): 160.4 (C═O), 137.1–128.2 (Ph), 79.5 (CHO), 70.4 (CH2O), 56.3 (CHN), 41.7 (CH₂Ph), 37.4 (CH₃) p.p.m. MS (m/z): MH⁺ 286.2.

Structure description top

For the use of 1,3-oxazolidin-2-ones as chiral auxiliaries in organic synthesis, see: Evans et al. (1981); Ager et al. (1996, 1997); Hintermann & Seebach (1998). For their biological activity, see: Poce et al. (2008); Brickner et al. (2008); Means et al. (2006); Kaiser et al. (2007); Clemmet & Markham (2000); Ebner et al. (2008); Negwer & Scharnow (2007); Mai et al. (2003). For background to their syntheses, see: Ochoa-Terán & Rivero (2008); Zappia et al. (2007).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); 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 DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the supramolecular chain in (I) mediated by N–H···O hydrogen bonding and C–H···O contacts, shown as blue and orange dashed lines, respectively. Hydrogen atoms not involved in intermolecular contacts sustaining the chain are omitted for reasons of clarity. Colour code: S, yellow; O, red; N, blue; C, grey; and H, green.
	Fig. 3. A view of the stacking of layers in (I) with partial the interdigitation of the benzene rings. The N–H···O hydrogen bonding and C–H···O contacts stabilizing the supramolecular chains are shown as blue and orange dashed lines, respectively. The C–H···O contacts connecting the chains into layers are shown as green dashed lines. Colour code: S, yellow; O, red; N, blue; C, grey; and H, green.

(4-Benzyl-2-oxo-1,3-oxazolidin-5-yl)methyl methanesulfonate top

Crystal data top

C₁₂H₁₅NO₅S	F(000) = 300
M_r = 285.31	D_x = 1.464 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7909 reflections
a = 8.7332 (5) Å	θ = 2.9–27.5°
b = 5.8757 (3) Å	µ = 0.27 mm⁻¹
c = 12.9650 (7) Å	T = 120 K
β = 103.317 (3)°	Plate, colourless
V = 647.39 (6) Å³	0.26 × 0.08 × 0.02 mm
Z = 2

Data collection top

Nonius KappaCCD area-detector diffractometer	2587 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	2266 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.059
Detector resolution: 9.091 pixels mm^-1	θ_max = 26.5°, θ_min = 3.2°
φ and ω scans	h = −8→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −7→7
T_min = 0.700, T_max = 1.000	l = −16→14
6748 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + 1.5106P] where P = (F_o² + 2F_c²)/3
2587 reflections	(Δ/σ)_max < 0.001
177 parameters	Δρ_max = 0.33 e Å⁻³
2 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₂H₁₅NO₅S	V = 647.39 (6) Å³
M_r = 285.31	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.7332 (5) Å	µ = 0.27 mm⁻¹
b = 5.8757 (3) Å	T = 120 K
c = 12.9650 (7) Å	0.26 × 0.08 × 0.02 mm
β = 103.317 (3)°

Data collection top

Nonius KappaCCD area-detector diffractometer	2587 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	2266 reflections with I > 2σ(I)
T_min = 0.700, T_max = 1.000	R_int = 0.059
6748 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	2 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.33 e Å⁻³
2587 reflections	Δρ_min = −0.36 e Å⁻³
177 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.44667 (11)	0.00547 (18)	0.67229 (8)	0.0215 (2)
O1	0.6105 (3)	0.0327 (6)	0.7186 (2)	0.0284 (7)
O2	0.3629 (4)	−0.1750 (5)	0.7089 (2)	0.0283 (8)
O3	0.4391 (3)	−0.0275 (5)	0.5504 (2)	0.0210 (7)
O4	0.2132 (3)	0.2865 (5)	0.4405 (2)	0.0222 (7)
O5	0.0104 (3)	0.5267 (5)	0.4294 (2)	0.0233 (6)
N1	−0.0074 (4)	0.2084 (6)	0.3228 (3)	0.0223 (8)
H1N	−0.1104 (13)	0.208 (8)	0.305 (4)	0.027*
C1	0.3493 (6)	0.2628 (8)	0.6800 (4)	0.0278 (11)
H1A	0.3625	0.3063	0.7545	0.042*
H1B	0.2370	0.2448	0.6473	0.042*
H1C	0.3937	0.3815	0.6425	0.042*
C2	0.2907 (5)	−0.1031 (7)	0.4793 (3)	0.0207 (9)
H2A	0.2078	−0.1193	0.5196	0.025*
H2B	0.3058	−0.2524	0.4478	0.025*
C3	0.2425 (5)	0.0726 (7)	0.3934 (3)	0.0208 (9)
H3	0.3280	0.0922	0.3544	0.025*
C4	0.0626 (5)	0.3548 (7)	0.3990 (3)	0.0209 (9)
C5	0.0868 (4)	0.0065 (9)	0.3147 (3)	0.0198 (8)
H5	0.0396	−0.1304	0.3410	0.024*
C6	0.1067 (5)	−0.0349 (8)	0.2020 (3)	0.0246 (10)
H6A	0.1506	0.1036	0.1763	0.030*
H6B	0.1824	−0.1607	0.2030	0.030*
C7	−0.0472 (5)	−0.0941 (8)	0.1270 (3)	0.0229 (9)
C8	−0.1231 (5)	0.0627 (8)	0.0526 (3)	0.0289 (11)
H8	−0.0773	0.2083	0.0492	0.035*
C9	−0.2646 (5)	0.0105 (11)	−0.0168 (3)	0.0333 (10)
H9	−0.3146	0.1199	−0.0674	0.040*
C10	−0.3333 (6)	−0.1999 (9)	−0.0126 (4)	0.0326 (11)
H10	−0.4308	−0.2360	−0.0597	0.039*
C11	−0.2577 (6)	−0.3580 (8)	0.0615 (4)	0.0301 (11)
H11	−0.3037	−0.5033	0.0653	0.036*
C12	−0.1161 (5)	−0.3054 (8)	0.1297 (4)	0.0267 (10)
H12	−0.0651	−0.4160	0.1792	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0215 (5)	0.0219 (5)	0.0206 (5)	−0.0014 (5)	0.0037 (4)	−0.0012 (5)
O1	0.0221 (14)	0.036 (2)	0.0237 (15)	−0.0046 (16)	−0.0008 (11)	−0.0039 (15)
O2	0.0333 (19)	0.0263 (18)	0.0235 (17)	−0.0045 (15)	0.0030 (14)	0.0029 (14)
O3	0.0161 (13)	0.0277 (18)	0.0178 (13)	−0.0015 (13)	0.0007 (10)	−0.0043 (13)
O4	0.0176 (15)	0.0207 (15)	0.0260 (16)	0.0016 (12)	0.0001 (12)	−0.0014 (13)
O5	0.0240 (14)	0.0174 (16)	0.0294 (15)	0.0013 (14)	0.0082 (12)	0.0000 (14)
N1	0.0172 (18)	0.026 (2)	0.024 (2)	0.0008 (15)	0.0046 (15)	−0.0014 (15)
C1	0.032 (3)	0.021 (2)	0.031 (3)	0.000 (2)	0.009 (2)	−0.005 (2)
C2	0.020 (2)	0.022 (2)	0.019 (2)	0.0003 (17)	0.0018 (17)	−0.0022 (17)
C3	0.020 (2)	0.014 (2)	0.028 (2)	−0.0019 (15)	0.0052 (17)	−0.0025 (16)
C4	0.022 (2)	0.021 (2)	0.021 (2)	−0.0033 (18)	0.0066 (17)	0.0057 (17)
C5	0.0181 (17)	0.0195 (19)	0.0217 (19)	0.001 (2)	0.0041 (14)	0.006 (2)
C6	0.022 (2)	0.026 (3)	0.025 (2)	0.0009 (18)	0.0060 (17)	0.0007 (18)
C7	0.027 (2)	0.026 (2)	0.017 (2)	0.0023 (18)	0.0080 (18)	−0.0022 (17)
C8	0.035 (2)	0.029 (3)	0.024 (2)	−0.001 (2)	0.0093 (19)	0.0006 (18)
C9	0.041 (2)	0.035 (3)	0.020 (2)	0.004 (3)	0.0000 (18)	−0.003 (3)
C10	0.027 (2)	0.043 (3)	0.027 (3)	0.003 (2)	0.003 (2)	−0.007 (2)
C11	0.033 (3)	0.024 (3)	0.034 (3)	−0.005 (2)	0.008 (2)	−0.003 (2)
C12	0.029 (2)	0.028 (2)	0.022 (2)	−0.001 (2)	0.0024 (18)	0.0016 (19)

Geometric parameters (Å, º) top

S1—O1	1.427 (3)	C3—H3	1.0000
S1—O2	1.430 (3)	C5—C6	1.529 (5)
S1—O3	1.578 (3)	C5—H5	1.0000
S1—C1	1.749 (5)	C6—C7	1.507 (6)
O3—C2	1.475 (5)	C6—H6A	0.9900
O4—C4	1.362 (5)	C6—H6B	0.9900
O4—C3	1.445 (5)	C7—C12	1.383 (6)
O5—C4	1.210 (5)	C7—C8	1.387 (6)
N1—C4	1.346 (6)	C8—C9	1.385 (6)
N1—C5	1.462 (6)	C8—H8	0.9500
N1—H1N	0.875 (10)	C9—C10	1.381 (8)
C1—H1A	0.9800	C9—H9	0.9500
C1—H1B	0.9800	C10—C11	1.390 (7)
C1—H1C	0.9800	C10—H10	0.9500
C2—C3	1.506 (5)	C11—C12	1.379 (7)
C2—H2A	0.9900	C11—H11	0.9500
C2—H2B	0.9900	C12—H12	0.9500
C3—C5	1.550 (5)

O1—S1—O2	118.9 (2)	N1—C4—O4	109.6 (4)
O1—S1—O3	103.99 (16)	N1—C5—C6	112.8 (3)
O2—S1—O3	109.53 (18)	N1—C5—C3	99.9 (4)
O1—S1—C1	109.4 (2)	C6—C5—C3	113.2 (3)
O2—S1—C1	109.2 (2)	N1—C5—H5	110.2
O3—S1—C1	104.8 (2)	C6—C5—H5	110.2
C2—O3—S1	119.4 (2)	C3—C5—H5	110.2
C4—O4—C3	109.8 (3)	C7—C6—C5	111.9 (3)
C4—N1—C5	113.8 (4)	C7—C6—H6A	109.2
C4—N1—H1N	117 (3)	C5—C6—H6A	109.2
C5—N1—H1N	123 (3)	C7—C6—H6B	109.2
S1—C1—H1A	109.5	C5—C6—H6B	109.2
S1—C1—H1B	109.5	H6A—C6—H6B	107.9
H1A—C1—H1B	109.5	C12—C7—C8	118.2 (4)
S1—C1—H1C	109.5	C12—C7—C6	121.3 (4)
H1A—C1—H1C	109.5	C8—C7—C6	120.5 (4)
H1B—C1—H1C	109.5	C9—C8—C7	121.1 (5)
O3—C2—C3	108.1 (3)	C9—C8—H8	119.4
O3—C2—H2A	110.1	C7—C8—H8	119.4
C3—C2—H2A	110.1	C10—C9—C8	120.2 (5)
O3—C2—H2B	110.1	C10—C9—H9	119.9
C3—C2—H2B	110.1	C8—C9—H9	119.9
H2A—C2—H2B	108.4	C9—C10—C11	118.9 (4)
O4—C3—C2	109.3 (3)	C9—C10—H10	120.5
O4—C3—C5	106.4 (3)	C11—C10—H10	120.5
C2—C3—C5	111.6 (3)	C12—C11—C10	120.4 (5)
O4—C3—H3	109.8	C12—C11—H11	119.8
C2—C3—H3	109.8	C10—C11—H11	119.8
C5—C3—H3	109.8	C11—C12—C7	121.1 (4)
O5—C4—N1	129.1 (4)	C11—C12—H12	119.5
O5—C4—O4	121.3 (4)	C7—C12—H12	119.5

O1—S1—O3—C2	168.8 (3)	C2—C3—C5—N1	123.5 (4)
O2—S1—O3—C2	40.7 (4)	O4—C3—C5—C6	124.6 (4)
C1—S1—O3—C2	−76.4 (3)	C2—C3—C5—C6	−116.3 (4)
S1—O3—C2—C3	122.4 (3)	N1—C5—C6—C7	−66.3 (5)
C4—O4—C3—C2	−121.3 (4)	C3—C5—C6—C7	−178.9 (4)
C4—O4—C3—C5	−0.7 (4)	C5—C6—C7—C12	−73.9 (5)
O3—C2—C3—O4	−62.6 (4)	C5—C6—C7—C8	106.5 (5)
O3—C2—C3—C5	180.0 (3)	C12—C7—C8—C9	0.4 (6)
C5—N1—C4—O5	−174.4 (4)	C6—C7—C8—C9	−180.0 (4)
C5—N1—C4—O4	7.3 (5)	C7—C8—C9—C10	0.3 (7)
C3—O4—C4—O5	177.7 (4)	C8—C9—C10—C11	−0.5 (7)
C3—O4—C4—N1	−3.8 (5)	C9—C10—C11—C12	−0.1 (7)
C4—N1—C5—C6	−127.6 (4)	C10—C11—C12—C7	0.9 (7)
C4—N1—C5—C3	−7.1 (4)	C8—C7—C12—C11	−1.0 (7)
O4—C3—C5—N1	4.4 (4)	C6—C7—C12—C11	179.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.88 (2)	2.28 (2)	3.113 (5)	160 (4)
C1—H1B···O5ⁱⁱ	0.98	2.51	3.428 (6)	155
C2—H2A···O5ⁱⁱ	0.99	2.32	3.214 (5)	150
C5—H5···O5ⁱⁱⁱ	1.00	2.36	3.326 (6)	162
C6—H6B···O1^iv	0.99	2.59	3.528 (6)	158

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₅S
M_r	285.31
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	120
a, b, c (Å)	8.7332 (5), 5.8757 (3), 12.9650 (7)
β (°)	103.317 (3)
V (Å³)	647.39 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.26 × 0.08 × 0.02

Data collection
Diffractometer	Nonius KappaCCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.700, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6748, 2587, 2266
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.123, 1.11
No. of reflections	2587
No. of parameters	177
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.36

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.88 (2)	2.28 (2)	3.113 (5)	160 (4)
C1—H1B···O5ⁱⁱ	0.98	2.51	3.428 (6)	155
C2—H2A···O5ⁱⁱ	0.99	2.32	3.214 (5)	150
C5—H5···O5ⁱⁱⁱ	1.00	2.36	3.326 (6)	162
C6—H6B···O1^iv	0.99	2.59	3.528 (6)	158

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

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil).

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