Redetermined crystal structure of α-dl-me­thio­nine at 340 K

Görbitz, C.H.; Qi, L.; Mai, N.T.K.; Kristiansen, H.

doi:10.1107/S1600536814022211

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 337-340

doi:10.1107/S1600536814022211

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Redetermined crystal structure of α-DL-methionine at 340 K

Carl Henrik Görbitz,^a ^* Lianglin Qi,^a Ngan Thi Kim Mai ^a and Håvard Kristiansen ^a

^aDepartment of Chemistry, University of Oslo, PO Box 1033 Blindern, N-0315 Oslo, Norway
^*Correspondence e-mail: c.h.gorbitz@kjemi.uio.no

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 September 2014; accepted 8 October 2014; online 15 October 2014)

Two forms, α and β, are known for the racemic amino acid DL-methionine, C₅H₁₁NO₂S. The phase transition between them, taking place around 326 K, is associated with sliding at the central interfaces of the hydrophobic regions in the crystal, leaving the hydrogen-bonding pattern unperturbed. For the high-temperature α phase, only a structure of rather low quality has been available [R factor = 0.118, no H-atom coordinates; Taniguchi et al. (1980 ). Bull. Chem. Soc. Jpn, 53, 803–804]. We here present accurate structural data for this polymorph [R(F) = 0.049], which are compared with other related amino acid structures with similar properties. We report for the first time that the side chain of this phase has a minor disorder component [occupancy 0.0491 (18)] with a gauche+ rather than a gauche− conformation for the N—C—C—C group. In the crystal of the title compound, N—H⋯O hydrogen bonds link the molecules into (100) sheets.

Keywords: crystal structure; hydrogen bonding; phase transition; disorder; zwitterions.

CCDC reference: 1028063

1. Chemical context

The racemates of amino acids with linear side chains display a series of unique phase transitions that involve sliding of neighboring molecular bilayers compared to each other. Such behavior has been observed for DL-aminobutyric acid (DL-Abu, R = –CH₂CH₃; Görbitz et al., 2012 ), DL-norvaline (DL-Nva, –CH₂CH₂CH₃; Görbitz, 2011 ), DL-norleucine (DL-Nle, –CH₂CH₂CH₂CH₃; Coles et al., 2009 ) and DL-methionine (DL-Met, –CH₂CH₂SCH₃). Two phase transitions have been found for each of the three nonstandard amino acids. For DL-Met, only a single transition is known < 400 K, occurring at approximately 326 K from the β (low T) to the α form (high T). Both phases were originally described by Mathieson (1952 ), with R factors > 0.20, and were subject to redeterminations by Taniguchi et al. (1980) at room temperature (R = 0.088) and 333 K (R = 0.118). The β form was subsequently redetermined at 105 K (R = 0.041; Alagar et al., 2005 ; refcode DLMETA05 in the Cambridge Structual Database, Version 5.35; Allen, 2002 ). α-DL-Met, (I), however, remained one of the few structures of the standard amino acids for which no high-precision experimental data were available (Görbitz, 2015 ). We here provide a detailed description of this polymorph, obtained from a single-crystal X-ray diffraction investigation at 340 K.

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1. Despite the above-room-temperature conditions, thermal vibrations are comparatively modest. A previously undetected minor conformation with χ¹(N1—C2B—C3B—C4B) in a gauche+ orientation (Table 1) has occupancy 0.0491 (18). If the presence of this rotamer is neglected, the refinement converges at R = 0.0586 rather than 0.0490. Disorder is extensive for all known phases of DL-Abu and DL-Nva, so it is not unexpected that it is observed here for DL-Met.

Table 1
Selected torsion angles (°)

N1—C2—C3—C4	−59.3 (4)	N1—C2B—C3B—C4B	73 (8)
C2—C3—C4—S1	176.7 (2)	C2B—C3B—C4B—S1B	178 (5)
C3—C4—S1—C5	69.4 (3)	C3B—C4B—S1B—C5B	60 (3)

Figure 1
The molecular structure of (I)

, with 50% probability displacement ellipsoids and atomic numbering indicated. The L-enantiomer was used as the asymmetric unit, D-enantiomers being generated by symmetry. The minor side-chain orientation [occupancy 0.0491 (18)], with N1—C2B—C3B—C4B in a gauche+ rather than a gauche− orientation (Table 1

), is shown in a lighter colour.

The crystal packing of (I) is shown in Fig. 2(a) and may be compared with the structure of β-DL-Met in Fig. 2(b) (Alagar et al., 2005). The difference between the two forms is not limited to the obvious conformational change for the C3—C4—S—C5 torsion angle, which is trans for the β form, but involves a large shift along the 9.8 Å axis and also the characteristic translation half a unit-cell length along the 4.7 Å axis. Notably, hydrogen bonding is virtually unaffected by these displacements. Compared to the 105 K data, N1⋯O2 distances in Table 1 are 0.03 Å longer, while N1⋯O1 is 0.01 Å shorter. All H⋯A distances surprisingly appear to get shorter at 340 K, but this is an artefact resulting from different ways of handling the amino group (Görbitz, 2014 ). In the refinement of β-DL-Met, this group was fixed with idealized geometry and a perfectly staggered orientation, while we find, upon relaxing the positional parameteres for all three H atoms, a 14° counterclockwise rotation (for the L-enantiomer) that serves to give three shorter and more linear interactions.

Figure 2
(a) The crystal packing of (I)

, viewed along the monoclinic b axis (top) and the c axis (bottom). The minor side-chain conformation is not shown, and H atoms bonded to C have been omitted for clarity. L-Met and D-Met molecules are shown with light- and dark-grey C atoms, respectively. The blue arrows show the directions of C2—N bond vectors within each of the two sheets constituting a hydrogen-bonded layer. (b) Corresponding views for β-DL-Met at 105 K (Alagar et al., 2005

3. Supramolecular features

Hydrogen-bond geometries are listed in Table 2. The hydrogen-bonding patterns of all compounds discussed here belong to the LD–LD type (Görbitz et al., 2009 ), normally observed for racemates and quasiracemates where at least one of the side chains (for the L- or the D-enantiomer) is linear and leucine, with an isobutyl side chain, is not involved (Görbitz et al., 2009). Apart from a weak C^α—H⋯O contact along the b axis, all intermolecular interactions within a single sheet involve amino acids of opposite chirality (Fig. 3); two N—H⋯O interactions between amino acids of the same chirality serve to link the adjacent antiparallel sheets that form a double-sheet hydrogen-bonded layer.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.88 (3)	1.95 (3)	2.812 (2)	164 (2)
N1—H2⋯O2ⁱⁱ	0.92 (3)	1.94 (3)	2.843 (2)	168 (2)
N1—H3⋯O1ⁱⁱⁱ	0.93 (3)	1.86 (3)	2.785 (2)	171 (2)
C2—H21⋯O1^iv	0.98	2.46	3.264 (3)	140
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x, y-1, z.

Figure 3
Hydrogen-bonded sheet of (I)

. Colour coding as in Fig. 2

, except that H3 atoms connecting sheets appear in yellow. The side chains are shown as small spheres. A single L-Met molecule of the adjacent sheet is shown in black wireframe representation. O2ⁱ is at (x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ), O2ⁱⁱ at (x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ) and O1ⁱⁱⁱ at (−x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ) (Table 2

). The blue arrow has the same meaning as in Fig. 2

4. Synthesis and crystallization

From a saturated solution of DL-Met in water (approximately 30 mg ml⁻¹) 50 µl was pipetted into a 40 × 8 mm test tube, which was then sealed with parafilm. A small hole was pricked in the parafilm and the tube placed inside a larger test tube filled with 2 ml of acetonitrile. The system was ultimately capped and left for 5 d at 293 K. Suitable single crystals in the shape of plates formed as the organic solvent diffused into the aqueous solution.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. U_iso values for CnB atoms (n = 3–5) belonging to the minor side-chain conformation with occupancy 0.0491 (18) were fixed at the U_eq values of the corresponding Cn atom of the major conformation, while S1B was constrained to have the same set of anisotropic displacement parameters as S1. A similar procedure was undertaken for C2B and C2. Coordinates were refined for amino H atoms; other H atoms were positioned with idealized geometry with fixed C—H = 0.96 (methyl), 0.97 (methylene) or 0.98 Å (methine). U_iso(H) values were set at 1.2U_eq of the carrier atom or at 1.5U_eq for methyl and amino groups.

Table 3
Experimental details

Crystal data
Chemical formula	C₅H₁₁NO₂S
M_r	149.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	340
a, b, c (Å)	16.811 (5), 4.7281 (14), 9.886 (3)
β (°)	101.950 (7)
V (Å³)	768.7 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.35
Crystal size (mm)	0.62 × 0.55 × 0.13

Data collection
Diffractometer	Bruker D8 Vantage single crystal CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.819, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15046, 1513, 1332
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.129, 1.07
No. of reflections	1513
No. of parameters	107
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS2013 and SHELXL2013 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1028063

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814022211/hb7288sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022211/hb7288Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814022211/hb7288Isup3.cml

checkCIF report

Chemical context top

The racemates of amino acids with linear side chains display a series of unique phase transitions that involve sliding of neighboring molecular bilayers compared to each other. Such behavior has been observed for DL-aminobutyric acid (DL-Abu, R = –CH₂CH₃; Görbitz et al., 2012), DL-norvaline (DL-Nva, –CH₂CH₂CH₃; Görbitz, 2011), DL-norleucine (DL-Nle, –CH₂CH₂CH₂CH₃; Coles et al., 2009) and DL-methionine (DL-Met, –CH₂CH₂SCH₃). Two phase transitions have been found for each of the three nonstandard amino acids. For DL-Met, only a single transition is known < 400 K, occurring at approximately 326 K from the β (low T) to the α form (high T). Both phases were originally described by Mathieson (1952), with R factors > 0.20, and were subject to redeterminations by Taniguchi et al. (1980) at room temperature (R = 0.088) and 333 K (R = 0.118). The β form was subsequently redetermined at 105 (R = 0.041; Alagar et al., 2005; refcode DLMETA05 in the Cambridge Structual Database, Version 5.35; Allen, 2002). α-DL-Met, (I), however, remained one of the few structures of the standard amino acids for which no high-precision experimental data were available (Görbitz, 2014a). We here provide a detailed description of this polymorph, obtained from a single-crystal X-ray diffraction investigation at 340 K.

Structural commentary top

The crystal packing of (I) is shown in Fig. 2(a) and may be compared with the structure of β-DL-Met in Fig. 2(b) (Alagar et al., 2005). The difference between the two forms is not limited to the obvious conformational change for the C3—C4—S—C5 torsion angle, which is trans for the β form, but involves a large shift along the 9.8 Å axis and also the characteristic translation half a unit-cell length along the 4.7 Å axis. Notably, hydrogen bonding is virtually unaffected by these displacements. Compared to the 105 K data, N1···O2 distances in Table 1 are 0.03 Å longer, while N1···O1 is 0.01 Å shorter. All H···A distances surprisingly appear to get shorter at 340 K, but this is an artefact resulting from different ways of handling the amino group (Görbitz, 2014b). In the refinement of β-DL-Met, this group was fixed with idealized geometry and a perfectly staggered orientation, while we find, upon relaxing the positional parameteres for all three H atoms, a ~14° counterclockwise rotation (for the L enantiomer) that serves to give three shorter and more linear interactions.

Supramolecular features top

Hydrogen-bond geometries are listed in Table 3. The hydrogen-bonding patterns of all compounds discussed here belong to the LD–LD type (Görbitz et al., 2009), normally observed for racemates and quasiracemates where at least one of the side chains (for the L or the D enantiomer) is linear and leucine, with an isobutyl side chain, is not involved (Görbitz et al., 2009). Apart from a weak C^α—H···O contact along the b axis, all intermolecular interactions within a single sheet involve amino acids of opposite chirality (Fig. 3); two N—H···O interactions between amino acids of the same chirality serve to link the adjacent antiparallel sheets that form a double-sheet hydrogen-bonded layer.

Synthesis and crystallization top

From a saturated solution of DL-Met in water (approximately 30 mg ml^-1) 50 µl was pipetted into a 40 × 8 mm test tube, which was then sealed with parafilm. A small hole was pricked in the parafilm and the tube placed inside a larger test tube filled with 2 ml of acetonitrile. The system was ultimately capped and left for 5 d at 293 K. Suitable single crystals in the shape of plates formed as the organic solvent diffused into the aqueous solution.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. U_iso values for CnB atoms (n = 3–5) belonging to the minor side-chain conformation with occupancy 0.0491 (18) were fixed at the U_eq values of the corresponding Cn atom of the major conformation, while S1B was constrained to have the same set of anisotropic displacement parameters as S1. A similar procedure was taken for C2B and C2. Coordinates were refined for amino H atoms; other H atoms were positioned with idealized geometry with fixed C—H = 0.96 (methyl), 0.97 (methylene) or 0.98 Å (methine). U_iso(H) values were set at 1.2U_eq of the carrier atom or at 1.5U_eq for methyl and amino groups.

Related literature top

For related literature, see: Alagar et al. (2005); Allen (2002); Coles et al. (2009); Görbitz (2011, 2014a, 2014b); Görbitz et al. (2009, 2012); Mathieson (1952).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS2013 (Bruker, 2013); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures top

The molecular structure of (I), with 50% probability displacement ellipsoids and atomic numbering indicated. The L-enantiomer was used as the asymmetric unit, D-enantiomers being generated by symmetry. The minor side-chain orientation [occupancy 0.0491 (18)], with N1—C2B—C3B—C4B in a gauche+ rather than a gauche- orientation (Table 1), is shown in a lighter colour.

(a) The crystal packing of (I), viewed along the monoclinic b axis (top) and the c axis (bottom). The minor side-chain conformation is not shown, and H atoms bonded to C have been omitted for clarity. L-Met and D-Met molecules are shown with light- and dark-grey C atoms, respectively. The blue arrows show the directions of C2—N bond vectors within each of the two sheets constituting a hydrogen-bonded layer. (b) Corresponding views for β-DL-Met at 105 K (Alagar et al., 2005).

Hydrogen-bonded sheet of (I). Colour coding as in Fig. 2, except that H3 atoms connecting sheets appear in yellow. The side chains are shown as small spheres. A single L-Met molecule of the adjacent sheet is shown in black wireframe representation. O2ⁱ is at (x, -y+1/2, z-1/2), O2ⁱⁱ at (x, -y+3/2, z-1/2) and O1ⁱⁱⁱ at (-x+1, y-1/2, -z+1/2) (Table 3). The blue arrow has the same meaning as in Fig. 2.

2-Amino-4-(methylsulfanyl)butanoic acid top

Crystal data top

C₅H₁₁NO₂S	F(000) = 320
M_r = 149.21	D_x = 1.289 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.811 (5) Å	Cell parameters from 9952 reflections
b = 4.7281 (14) Å	θ = 2.5–28.3°
c = 9.886 (3) Å	µ = 0.35 mm⁻¹
β = 101.950 (7)°	T = 340 K
V = 768.7 (4) Å³	Plate, colourless
Z = 4	0.62 × 0.55 × 0.13 mm

Data collection top

Bruker D8 Vantage single crystal CCD diffractometer	1513 independent reflections
Radiation source: fine-focus sealed tube	1332 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 8.3 pixels mm^-1	θ_max = 26.0°, θ_min = 2.5°
Sets of exposures each taken over 0.5° ω rotation scans	h = −20→20
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −5→5
T_min = 0.819, T_max = 1.000	l = −12→12
15046 measured reflections

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.0499P)² + 0.5391P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1513 reflections	Δρ_max = 0.27 e Å⁻³
107 parameters	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₅H₁₁NO₂S	V = 768.7 (4) Å³
M_r = 149.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.811 (5) Å	µ = 0.35 mm⁻¹
b = 4.7281 (14) Å	T = 340 K
c = 9.886 (3) Å	0.62 × 0.55 × 0.13 mm
β = 101.950 (7)°

Data collection top

Bruker D8 Vantage single crystal CCD diffractometer	1513 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1332 reflections with I > 2σ(I)
T_min = 0.819, T_max = 1.000	R_int = 0.041
15046 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	9 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.27 e Å⁻³
1513 reflections	Δρ_min = −0.29 e Å⁻³
107 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. Disorder, two side chain orientations.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.59254 (10)	0.4431 (4)	0.14177 (16)	0.0345 (4)
H1	0.6057 (14)	0.310 (5)	0.088 (2)	0.052*
H2	0.5958 (14)	0.614 (6)	0.099 (2)	0.052*
H3	0.5381 (16)	0.412 (5)	0.144 (2)	0.052*
O1	0.56499 (8)	0.8214 (3)	0.32823 (13)	0.0414 (4)
O2	0.62423 (10)	0.5530 (3)	0.50516 (13)	0.0492 (4)
C1	0.60684 (11)	0.6163 (4)	0.37937 (17)	0.0305 (4)
C2	0.64538 (12)	0.4338 (8)	0.2836 (3)	0.0307 (7)	0.9509 (18)
H21	0.6505	0.2385	0.3175	0.037*	0.9509 (18)
C3	0.73009 (12)	0.5543 (5)	0.2799 (2)	0.0423 (5)	0.9509 (18)
H31	0.7240	0.7509	0.2515	0.051*	0.9509 (18)
H32	0.7631	0.5497	0.3728	0.051*	0.9509 (18)
C4	0.77480 (16)	0.4004 (7)	0.1849 (3)	0.0697 (8)	0.9509 (18)
H41	0.7407	0.3955	0.0929	0.084*	0.9509 (18)
H42	0.7840	0.2067	0.2165	0.084*	0.9509 (18)
S1	0.87076 (5)	0.5570 (3)	0.17503 (10)	0.0907 (4)	0.9509 (18)
C5	0.9285 (2)	0.4833 (15)	0.3418 (5)	0.140 (2)	0.9509 (18)
H51	0.9820	0.5616	0.3507	0.211*	0.9509 (18)
H52	0.9324	0.2823	0.3552	0.211*	0.9509 (18)
H53	0.9025	0.5659	0.4100	0.211*	0.9509 (18)
C2B	0.6365 (12)	0.435 (16)	0.258 (10)	0.0307 (7)	0.0491 (18)
H22B	0.6223	0.2457	0.2854	0.037*	0.0491 (18)
C3B	0.7299 (13)	0.406 (8)	0.293 (4)	0.042*	0.0491 (18)
H33B	0.7467	0.3580	0.3903	0.050*	0.0491 (18)
H34B	0.7450	0.2491	0.2403	0.050*	0.0491 (18)
C4B	0.7757 (10)	0.665 (6)	0.265 (5)	0.069*	0.0491 (18)
H43B	0.7592	0.8227	0.3153	0.083*	0.0491 (18)
H44B	0.7602	0.7089	0.1669	0.083*	0.0491 (18)
S1B	0.8843 (9)	0.632 (5)	0.311 (2)	0.0907 (4)	0.0491 (18)
C5B	0.902 (2)	0.347 (12)	0.205 (7)	0.138*	0.0491 (18)
H54B	0.9590	0.3181	0.2150	0.207*	0.0491 (18)
H55B	0.8781	0.3901	0.1100	0.207*	0.0491 (18)
H56B	0.8770	0.1791	0.2319	0.207*	0.0491 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0413 (9)	0.0351 (9)	0.0287 (8)	−0.0045 (7)	0.0110 (7)	−0.0053 (7)
O1	0.0466 (8)	0.0371 (8)	0.0425 (8)	0.0092 (6)	0.0137 (6)	−0.0001 (6)
O2	0.0812 (11)	0.0411 (8)	0.0276 (7)	0.0022 (7)	0.0165 (7)	0.0011 (6)
C1	0.0359 (9)	0.0274 (8)	0.0306 (9)	−0.0060 (7)	0.0125 (7)	−0.0012 (7)
C2	0.0386 (10)	0.0273 (9)	0.0269 (19)	0.0018 (9)	0.0084 (9)	0.0009 (10)
C3	0.0366 (11)	0.0439 (12)	0.0478 (12)	−0.0009 (9)	0.0122 (9)	−0.0041 (10)
C4	0.0514 (14)	0.080 (2)	0.0857 (19)	−0.0088 (14)	0.0323 (14)	−0.0238 (16)
S1	0.0536 (5)	0.1247 (9)	0.1036 (7)	−0.0132 (5)	0.0393 (4)	−0.0009 (6)
C5	0.057 (2)	0.234 (6)	0.127 (4)	0.021 (3)	0.013 (2)	0.005 (4)
C2B	0.0386 (10)	0.0273 (9)	0.0269 (19)	0.0018 (9)	0.0084 (9)	0.0009 (10)
S1B	0.0536 (5)	0.1247 (9)	0.1036 (7)	−0.0132 (5)	0.0393 (4)	−0.0009 (6)

Geometric parameters (Å, º) top

N1—C2B	1.23 (8)	S1—C5	1.766 (5)
N1—C2	1.497 (3)	C5—H51	0.9600
N1—H1	0.88 (3)	C5—H52	0.9600
N1—H2	0.92 (3)	C5—H53	0.9600
N1—H3	0.93 (3)	C2B—C3B	1.542 (6)
O1—C1	1.242 (2)	C2B—H22B	0.9800
O2—C1	1.253 (2)	C3B—C4B	1.505 (6)
C1—C2	1.521 (4)	C3B—H33B	0.9700
C1—C2B	1.63 (10)	C3B—H34B	0.9700
C2—C3	1.541 (3)	C4B—S1B	1.794 (6)
C2—H21	0.9800	C4B—H43B	0.9700
C3—C4	1.506 (3)	C4B—H44B	0.9700
C3—H31	0.9700	S1B—C5B	1.765 (7)
C3—H32	0.9700	C5B—H54B	0.9600
C4—S1	1.796 (3)	C5B—H55B	0.9600
C4—H41	0.9700	C5B—H56B	0.9600
C4—H42	0.9700

C2B—N1—H1	112 (4)	C5—S1—C4	101.2 (2)
C2—N1—H1	111.8 (15)	S1—C5—H51	109.5
C2B—N1—H2	112 (3)	S1—C5—H52	109.5
C2—N1—H2	112.0 (14)	H51—C5—H52	109.5
H1—N1—H2	108 (2)	S1—C5—H53	109.5
C2B—N1—H3	112 (3)	H51—C5—H53	109.5
C2—N1—H3	111.9 (14)	H52—C5—H53	109.5
H1—N1—H3	106 (2)	N1—C2B—C3B	127 (6)
H2—N1—H3	107 (2)	N1—C2B—C1	117 (4)
O1—C1—O2	125.88 (17)	C3B—C2B—C1	110 (5)
O1—C1—C2	117.89 (17)	N1—C2B—H22B	98.6
O2—C1—C2	116.11 (18)	C3B—C2B—H22B	98.6
O1—C1—C2B	110 (2)	C1—C2B—H22B	98.6
O2—C1—C2B	124 (2)	C4B—C3B—C2B	114.8 (7)
N1—C2—C1	108.6 (2)	C4B—C3B—H33B	108.6
N1—C2—C3	109.8 (2)	C2B—C3B—H33B	108.6
C1—C2—C3	108.7 (2)	C4B—C3B—H34B	108.6
N1—C2—H21	109.9	C2B—C3B—H34B	108.6
C1—C2—H21	109.9	H33B—C3B—H34B	107.5
C3—C2—H21	109.9	C3B—C4B—S1B	114.5 (6)
C4—C3—C2	114.8 (3)	C3B—C4B—H43B	108.6
C4—C3—H31	108.6	S1B—C4B—H43B	108.6
C2—C3—H31	108.6	C3B—C4B—H44B	108.6
C4—C3—H32	108.6	S1B—C4B—H44B	108.6
C2—C3—H32	108.6	H43B—C4B—H44B	107.6
H31—C3—H32	107.5	C5B—S1B—C4B	101.5 (5)
C3—C4—S1	113.9 (2)	S1B—C5B—H54B	109.5
C3—C4—H41	108.8	S1B—C5B—H55B	109.5
S1—C4—H41	108.8	H54B—C5B—H55B	109.5
C3—C4—H42	108.8	S1B—C5B—H56B	109.5
S1—C4—H42	108.8	H54B—C5B—H56B	109.5
H41—C4—H42	107.7	H55B—C5B—H56B	109.5

N1—C2—C3—C4	−59.3 (4)	O1—C1—C2—N1	−29.4 (3)
C2—C3—C4—S1	176.7 (2)	O2—C1—C2—N1	154.35 (18)
C3—C4—S1—C5	69.4 (3)	O1—C1—C2—C3	90.0 (2)
N1—C2B—C3B—C4B	73 (8)	O2—C1—C2—C3	−86.2 (2)
C2B—C3B—C4B—S1B	178 (5)	C1—C2—C3—C4	−178.0 (2)
C3B—C4B—S1B—C5B	60 (3)	C1—C2B—C3B—C4B	−78 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.88 (3)	1.95 (3)	2.812 (2)	164 (2)
N1—H2···O2ⁱⁱ	0.92 (3)	1.94 (3)	2.843 (2)	168 (2)
N1—H3···O1ⁱⁱⁱ	0.93 (3)	1.86 (3)	2.785 (2)	171 (2)
C2—H21···O1^iv	0.98	2.46	3.264 (3)	140

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, y−1, z.

Selected torsion angles (º) top

N1—C2—C3—C4	−59.3 (4)	N1—C2B—C3B—C4B	73 (8)
C2—C3—C4—S1	176.7 (2)	C2B—C3B—C4B—S1B	178 (5)
C3—C4—S1—C5	69.4 (3)	C3B—C4B—S1B—C5B	60 (3)

Experimental details

Crystal data
Chemical formula	C₅H₁₁NO₂S
M_r	149.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	340
a, b, c (Å)	16.811 (5), 4.7281 (14), 9.886 (3)
β (°)	101.950 (7)
V (Å³)	768.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.62 × 0.55 × 0.13

Data collection
Diffractometer	Bruker D8 Vantage single crystal CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2013)
T_min, T_max	0.819, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15046, 1513, 1332
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.129, 1.07
No. of reflections	1513
No. of parameters	107
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS2013 (Bruker, 2013), SHELXL2013 (Sheldrick, 2008), Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.88 (3)	1.95 (3)	2.812 (2)	164 (2)
N1—H2···O2ⁱⁱ	0.92 (3)	1.94 (3)	2.843 (2)	168 (2)
N1—H3···O1ⁱⁱⁱ	0.93 (3)	1.86 (3)	2.785 (2)	171 (2)
C2—H21···O1^iv	0.98	2.46	3.264 (3)	140

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, y−1, z.

References

Alagar, M., Krishnakumar, R. V., Mostad, A. & Natarajan, S. (2005). Acta Cryst. E61, o1165–o1167. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (2013). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coles, S. J., Gelbrich, T., Griesser, U. J., Hursthouse, M. B., Pitak, M. & Threlfall, T. (2009). Cryst. Growth Des. 9, 4610–4612. Web of Science CSD CrossRef CAS Google Scholar
Görbitz, C. H. (2011). J. Phys. Chem. B, 115, 2447–2453. Web of Science PubMed Google Scholar
Görbitz, C. H. (2014). Acta Cryst. E70, 341–343. CSD CrossRef IUCr Journals Google Scholar
Görbitz, C. H. (2015). Cryst. Rev. In the press. Google Scholar
Görbitz, C. H., Alebachew, F. & Petříček, V. (2012). J. Phys. Chem. B, 116, 10715–10721. Web of Science PubMed Google Scholar
Görbitz, C. H., Vestli, K. & Orlando, R. (2009). Acta Cryst. B65, 393–400. Web of Science CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
McL Mathieson, A. (1952). Acta Cryst. 5, 332–341. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taniguchi, T., Takaki, Y. & Sakurai, K. (1980). Bull. Chem. Soc. Jpn, 53, 803–804. CrossRef CAS Web of Science Google Scholar

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Volume 70| Part 11| November 2014| Pages 337-340

doi:10.1107/S1600536814022211

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