(SS,2S,3S)-2-(2-Methyl­propan-2-sulfin­amido)-3-phenyl­butyronitrile

Harms, K.; Marsch, M.; Oberthür, M.; Schüler, P.

doi:10.1107/S1600536809041245

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2742

https://doi.org/10.1107/S1600536809041245

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(^SS,2S,3S)-2-(2-Methylpropan-2-sulfinamido)-3-phenylbutyronitrile

Klaus Harms,^a ^* Michael Marsch,^a Markus Oberthür ^a and Peter Schüler ^a

^aPhilipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Strasse, D-35032 Marburg, Germany
^*Correspondence e-mail: klaus.harms@chemie.uni-marburg.de

(Received 25 September 2009; accepted 9 October 2009; online 17 October 2009)

The absolute configuration has been determined for the title compound, C₁₄H₂₀N₂OS. There are two independent molecules in the asymmetric unit. Intermolecular N—H⋯O hydrogen bonds are observed in the crystal packing, forming infinite chains with the base vectors [100] and [010]. Each chain contains only one of the two independent molecules.

Related literature

For uses of tert-butanesulfinimines, see: Ferreira et al. (2009 ). For asymmetric Strecker reactions utilizing this auxiliary, see: Davis et al. (1994 ); Li et al. (2003 ). For natural sources of (2S,3S)-β-methylphenylalanine, see: Singh et al. (2003 ); Kaneda (1992 , 2002 ). For a related structure, see: Harms et al. (2009 ).

Experimental

Crystal data

C₁₄H₂₀N₂OS
M_r = 264.38
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.0344 (4) Å
b = 9.0617 (5) Å
c = 35.767 (3) Å
V = 2928.1 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.36 × 0.08 × 0.06 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.936, T_max = 1.041
15474 measured reflections
5160 independent reflections
3413 reflections with I > 2σ(I)
R_int = 0.093

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.074
S = 0.77
5160 reflections
342 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 2183 Friedel pairs
Flack parameter: −0.04 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.85 (2)	2.110 (17)	2.882 (3)	151 (3)
N21—H211⋯O21ⁱⁱ	0.85 (2)	2.23 (2)	2.995 (4)	149 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809041245/pv2213sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041245/pv2213Isup2.hkl

checkCIF report

Comment top

Chiral sulfinimines have proven to be powerful and versatile precursors for the synthesis of nonproteinogenic amino acids (Ferreira et al., 2008). They allow the stereoselective introduction of cyanide therefore representing an asymmetric modification of the Strecker reaction (Davis et al., 1994); Li et al., 2003). We have synthesized the title compound, (I), that can be hydrolyzed to give (2S,3S)-β-methylphenylalanine which is an amino acid found in the antibiotic families of the bottromycins and the mannopeptimycins (Singh et al., 2003); Kaneda, 1992; and Kaneda, 2002). In this paper we report the crystal structure and absolute configuration of (I).

The molecular structure of (I) is presented in Fig. 1. There are two independent molecules in the asymmetric unit. The structure exhibits intermolecular N—H···O hydrogen bonds resulting in infinite one dimensional chains with the base vectors [1 0 0] and [0 1 0], respectively (details have have been provided in Table 1 and Fig. 2). Each chain contains only one of the two independent molecules.

The crystal structure and absolute configuration of a closely related compound has just been reported (Harms et al., 2009).

Related literature top

For uses of tert-butanesulfinimines, see: Ferreira et al. (2009). For asymmetric Strecker reactions utilizing this auxiliary, see: Davis et al. (1994); Li et al. (2003). For natural sources of (2S,3S)-β-methylphenylalanine, see: Singh et al. (2003); Kaneda (1992, 2002). For a related structure, see: Harms et al. (2009).

Experimental top

Trimethylsilyl cyanide (TMSCN) (706 µL, 5.64 mmol) was added dropwise to a solution of (^SS)-(2-phenylpropyliden)-2-methyl-2-propansulfinylimin (1.12 g, 4.70 mmol) and CsF (858 mg, 5.64 mmol) in 50 ml n-hexane at 243 K. The mixture was stirred at this temperature for 14 h and subsequently quenched with semisaturated aqueous NH₄Cl solution. Extraction with EtOAc (2×50 mL) and drying of the combined organic phases (MgSO₄) yielded the crude mixture of 3S / 3R epimers. Crystallization from petrolether/EtOAc yielded 370 mg (1.41 mmol, 35%) of a 1:1 mixture of the diastereomers. Flash column chromatography of the mother liquor yielded 80 mg (303 mmol, 6%) of the pure 3S isomer, which had a slightly higher R_f-value (R_f=0.30 in petrol ether/EtOAc 2:1) than the 3R isomer of which 60 mg (227 mmol, 5%) could be isolated. The remaining fractions afforded 400 mg (1.53 mmol, 32%) of a roughly 1:1 mixture of the epimers. (^SS,2S,3S)-(2-Methylpropansulfinyl)-2-amino-3-phenylbutyronitrile was crystallized from petrol ether/THF.

Structure description top

The crystal structure and absolute configuration of a closely related compound has just been reported (Harms et al., 2009).

For uses of tert-butanesulfinimines, see: Ferreira et al. (2009). For asymmetric Strecker reactions utilizing this auxiliary, see: Davis et al. (1994); Li et al. (2003). For natural sources of (2S,3S)-β-methylphenylalanine, see: Singh et al. (2003); Kaneda (1992, 2002). For a related structure, see: Harms et al. (2009).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. A view of the two molecules in the asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. Symmetry operations, (i): x-1/2, -y+3/2, -z; (ii): -x, y+1/2, -z+1/2.
	Fig. 2. Unit cell packing of (I) viewed down the b-axis. Dotted lines indicate hydrogen bonds.

(^SS,2S,3S)-2-(2-Methylpropane-2-sulfinamido)-3- phenylbutyronitrile top

Crystal data top

C₁₄H₂₀N₂OS	F(000) = 1136
M_r = 264.38	D_x = 1.199 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10131 reflections
a = 9.0344 (4) Å	θ = 2.3–25°
b = 9.0617 (5) Å	µ = 0.21 mm⁻¹
c = 35.767 (3) Å	T = 100 K
V = 2928.1 (3) Å³	Prism, colourless
Z = 8	0.36 × 0.08 × 0.06 mm

Data collection top

Stoe IPDS II diffractometer	5160 independent reflections
Radiation source: sealed tube	3413 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.093
area detetor, ω scans	θ_max = 25°, θ_min = 2.3°
Absorption correction: multi-scan (Blessing, 1995)	h = −10→10
T_min = 0.936, T_max = 1.041	k = −9→10
15474 measured reflections	l = −41→42

Refinement top

Refinement on F²	Hydrogen site location: CH inferred from neighbouring sites, NH located
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0105P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.074	(Δ/σ)_max < 0.001
S = 0.77	Δρ_max = 0.19 e Å⁻³
5160 reflections	Δρ_min = −0.24 e Å⁻³
342 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
2 restraints	Extinction coefficient: 0.0011 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2183 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.04 (9)

Crystal data top

C₁₄H₂₀N₂OS	V = 2928.1 (3) Å³
M_r = 264.38	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.0344 (4) Å	µ = 0.21 mm⁻¹
b = 9.0617 (5) Å	T = 100 K
c = 35.767 (3) Å	0.36 × 0.08 × 0.06 mm

Data collection top

Stoe IPDS II diffractometer	5160 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	3413 reflections with I > 2σ(I)
T_min = 0.936, T_max = 1.041	R_int = 0.093
15474 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.074	Δρ_max = 0.19 e Å⁻³
S = 0.77	Δρ_min = −0.24 e Å⁻³
5160 reflections	Absolute structure: Flack (1983), 2183 Friedel pairs
342 parameters	Absolute structure parameter: −0.04 (9)
2 restraints

Special details top

Experimental. ν_max/cm^-1 3232 (br), 2963 (w), 2930 (w), 2872(w), 1492 (w), 1454 (m), 1422 (m), 1364 (w), 1113 (w), 1085 (m), 1054 (s), 1016(m); δ_H(300 MHz; DMSO) 0.75 (s, 9H, tBu), 1.37 (d, 3H, ³J_Me,CH= 7.1 Hz, CH₃), 3.10 (dq, 1H, ³J_CH,CHN= 10.3, J_CH,Me= 7.1 Hz, CH), 4.51 (pt, 1H, ³J_CHN,CH= 10.3 Hz, CHN), 6.24 (d, 1H, ³J_NH,CHN= 10.5 Hz, NH), 7.14 – 7.32 (m, 5H, CH_arom); δ_C(75 MHz; DMSO-d₆)18.4 (CH₃), 21.9 (C(CH₃)₃), 43.2 (CH), 52.8 (CHN), 55.9 (C(CH₃)₃), 120.2 (CN), 126.7 (p-CH_arom), 127.7 (CH_arom), 128.2 (CH_arom), 141.9 (i-C_arom); [α]_D²³ -1.0 (c 1.00 in CHCl₃).

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
C21	0.2714 (4)	0.3582 (4)	0.27085 (9)	0.0236 (9)
H21	0.36	0.2946	0.2662	0.028*
C22	0.3222 (4)	0.5196 (4)	0.27258 (10)	0.0270 (9)
H22	0.232	0.5812	0.2769	0.032*
C23	0.2020 (4)	0.3113 (5)	0.30640 (10)	0.0288 (9)
C24	0.4285 (4)	0.5485 (5)	0.30544 (10)	0.0336 (10)
H24A	0.5189	0.4903	0.302	0.05*
H24B	0.3805	0.5198	0.3289	0.05*
H24C	0.4537	0.6536	0.3063	0.05*
C25	0.3851 (4)	0.5647 (4)	0.23521 (10)	0.0251 (9)
C26	0.3155 (4)	0.6706 (4)	0.21346 (10)	0.0310 (9)
H26	0.229	0.7179	0.2227	0.037*
C27	0.3702 (4)	0.7092 (4)	0.17816 (10)	0.0332 (10)
H27	0.3217	0.783	0.1638	0.04*
C28	0.4935 (4)	0.6406 (4)	0.16434 (11)	0.0354 (11)
H28	0.5303	0.6659	0.1403	0.042*
C29	0.5647 (4)	0.5341 (4)	0.18560 (10)	0.0308 (9)
H29	0.6501	0.4861	0.176	0.037*
C210	0.5117 (4)	0.4971 (4)	0.22081 (11)	0.0265 (9)
H210	0.5622	0.425	0.2353	0.032*
C211	0.0856 (4)	0.2374 (4)	0.17447 (11)	0.0281 (9)
C212	−0.0540 (4)	0.3289 (5)	0.17864 (10)	0.0370 (10)
H21A	−0.1007	0.3413	0.1541	0.056*
H21B	−0.0287	0.4259	0.1889	0.056*
H21C	−0.1227	0.2785	0.1956	0.056*
C213	0.0538 (5)	0.0964 (5)	0.15275 (11)	0.0448 (11)
H21D	−0.0214	0.0386	0.166	0.067*
H21E	0.1449	0.0383	0.1505	0.067*
H21F	0.0175	0.1216	0.1277	0.067*
C214	0.2103 (4)	0.3255 (5)	0.15608 (10)	0.0322 (9)
H21G	0.3006	0.2657	0.1556	0.048*
H21H	0.2283	0.4158	0.1704	0.048*
H21I	0.1817	0.3514	0.1305	0.048*
N21	0.1689 (3)	0.3395 (3)	0.23975 (7)	0.0228 (7)
N22	0.1415 (4)	0.2754 (4)	0.33308 (9)	0.0399 (9)
O21	0.0331 (3)	0.0854 (3)	0.23728 (7)	0.0316 (6)
S21	0.15503 (10)	0.17532 (11)	0.22032 (3)	0.0260 (2)
C1	0.8730 (4)	0.4752 (4)	−0.02331 (10)	0.0228 (8)
H1	0.9404	0.3911	−0.0171	0.027*
C2	0.7114 (3)	0.4153 (4)	−0.02369 (10)	0.0252 (8)
H2	0.6449	0.4999	−0.03	0.03*
C3	0.9145 (4)	0.5311 (4)	−0.06101 (11)	0.0268 (9)
C4	0.6885 (4)	0.2967 (4)	−0.05361 (10)	0.0325 (10)
H4A	0.7481	0.2097	−0.0475	0.049*
H4B	0.7189	0.3354	−0.078	0.049*
H4C	0.5836	0.2691	−0.0545	0.049*
C5	0.6698 (4)	0.3632 (4)	0.01507 (9)	0.0242 (9)
C6	0.5653 (4)	0.4409 (4)	0.03603 (10)	0.0283 (9)
H6	0.5181	0.5254	0.0258	0.034*
C7	0.5311 (4)	0.3941 (5)	0.07186 (10)	0.0320 (9)
H7	0.4586	0.4467	0.0857	0.038*
C8	0.5988 (4)	0.2738 (4)	0.08799 (11)	0.0333 (10)
H8	0.5752	0.2442	0.1128	0.04*
C9	0.7019 (4)	0.1975 (4)	0.06715 (11)	0.0317 (9)
H9	0.7496	0.1139	0.0777	0.038*
C10	0.7372 (4)	0.2407 (4)	0.03095 (11)	0.0297 (9)
H10	0.8079	0.1861	0.017	0.036*
C11	0.9830 (4)	0.6723 (4)	0.07127 (9)	0.0234 (8)
C12	0.8840 (4)	0.8074 (4)	0.06764 (10)	0.0320 (9)
H12A	0.7922	0.78	0.0548	0.048*
H12B	0.9355	0.8836	0.0532	0.048*
H12C	0.8606	0.8456	0.0926	0.048*
C13	0.9020 (4)	0.5441 (4)	0.08954 (11)	0.0317 (10)
H13A	0.8719	0.5721	0.1149	0.047*
H13B	0.9677	0.4582	0.0907	0.047*
H13C	0.814	0.5194	0.0748	0.047*
C14	1.1218 (4)	0.7103 (4)	0.09391 (10)	0.0326 (10)
H14A	1.0935	0.7347	0.1196	0.049*
H14B	1.1717	0.7951	0.0825	0.049*
H14C	1.189	0.6254	0.0941	0.049*
N1	0.8892 (3)	0.5844 (3)	0.00524 (8)	0.0215 (7)
N2	0.9438 (4)	0.5784 (4)	−0.08972 (9)	0.0397 (8)
O1	1.1317 (2)	0.7367 (3)	0.00919 (7)	0.0304 (6)
S1	1.05045 (10)	0.60907 (10)	0.02574 (3)	0.0241 (2)
H211	0.087 (2)	0.384 (4)	0.2437 (9)	0.031 (11)*
H1A	0.831 (3)	0.658 (2)	0.0059 (9)	0.027 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C21	0.0206 (18)	0.025 (2)	0.025 (2)	0.0023 (15)	−0.0032 (14)	0.0016 (16)
C22	0.023 (2)	0.027 (2)	0.031 (2)	0.0031 (16)	−0.0027 (16)	−0.0024 (17)
C23	0.029 (2)	0.030 (2)	0.027 (2)	0.0060 (18)	0.0026 (17)	0.001 (2)
C24	0.030 (2)	0.039 (3)	0.032 (2)	−0.0029 (19)	−0.0009 (18)	−0.0053 (18)
C25	0.027 (2)	0.021 (2)	0.0267 (19)	−0.0030 (16)	−0.0063 (16)	0.0001 (16)
C26	0.024 (2)	0.026 (2)	0.043 (2)	−0.0047 (18)	−0.0068 (16)	−0.002 (2)
C27	0.041 (2)	0.029 (2)	0.030 (2)	−0.0087 (19)	−0.0113 (19)	0.0050 (18)
C28	0.036 (2)	0.040 (3)	0.031 (2)	−0.0128 (19)	−0.0006 (17)	−0.0053 (19)
C29	0.026 (2)	0.026 (2)	0.041 (2)	−0.0049 (18)	0.0029 (19)	−0.0031 (18)
C210	0.019 (2)	0.022 (2)	0.038 (2)	−0.0009 (15)	−0.0020 (17)	0.0003 (19)
C211	0.025 (2)	0.029 (2)	0.031 (2)	−0.0043 (17)	0.0041 (16)	0.0008 (17)
C212	0.031 (2)	0.041 (2)	0.039 (2)	0.003 (2)	0.0036 (18)	0.015 (2)
C213	0.048 (2)	0.038 (3)	0.049 (3)	−0.016 (2)	−0.004 (2)	−0.002 (2)
C214	0.029 (2)	0.033 (2)	0.035 (2)	−0.0036 (19)	0.0043 (16)	0.004 (2)
N21	0.0181 (17)	0.0239 (17)	0.0263 (15)	0.0025 (14)	−0.0009 (13)	−0.0021 (14)
N22	0.039 (2)	0.038 (2)	0.043 (2)	0.0162 (17)	0.0033 (18)	0.0054 (17)
O21	0.0292 (14)	0.0269 (15)	0.0386 (15)	−0.0126 (12)	0.0023 (11)	0.0106 (13)
S21	0.0233 (5)	0.0241 (5)	0.0306 (5)	−0.0019 (4)	0.0000 (4)	0.0011 (4)
C1	0.0180 (18)	0.0209 (19)	0.030 (2)	0.0025 (14)	0.0008 (16)	0.0009 (17)
C2	0.0179 (18)	0.030 (2)	0.0282 (19)	−0.0001 (15)	−0.0006 (15)	−0.0043 (19)
C3	0.016 (2)	0.033 (2)	0.032 (2)	0.0072 (16)	−0.0033 (16)	−0.0015 (18)
C4	0.023 (2)	0.040 (3)	0.035 (2)	−0.0018 (17)	−0.0022 (16)	−0.005 (2)
C5	0.0168 (18)	0.026 (2)	0.030 (2)	−0.0042 (16)	−0.0004 (15)	−0.0012 (16)
C6	0.0199 (19)	0.027 (2)	0.038 (2)	−0.0019 (17)	−0.0033 (17)	−0.0041 (17)
C7	0.027 (2)	0.037 (2)	0.032 (2)	−0.010 (2)	0.0006 (17)	−0.002 (2)
C8	0.028 (2)	0.040 (3)	0.032 (2)	−0.0152 (18)	0.0005 (17)	0.004 (2)
C9	0.031 (2)	0.024 (2)	0.041 (2)	−0.0078 (17)	−0.0058 (17)	0.005 (2)
C10	0.0200 (19)	0.028 (2)	0.041 (2)	−0.0025 (16)	0.0004 (18)	−0.0013 (19)
C11	0.026 (2)	0.0224 (19)	0.0222 (19)	−0.0018 (16)	0.0003 (14)	−0.0002 (17)
C12	0.036 (2)	0.029 (2)	0.031 (2)	−0.0051 (18)	0.0019 (16)	−0.0009 (19)
C13	0.029 (2)	0.035 (2)	0.031 (2)	−0.0019 (17)	0.0029 (17)	0.0009 (19)
C14	0.026 (2)	0.035 (3)	0.037 (2)	−0.0069 (17)	−0.0029 (17)	−0.0021 (19)
N1	0.0145 (16)	0.0214 (18)	0.0287 (16)	0.0009 (13)	−0.0041 (12)	−0.0014 (14)
N2	0.0345 (19)	0.044 (2)	0.041 (2)	0.0121 (17)	0.0020 (17)	0.0041 (18)
O1	0.0252 (13)	0.0318 (15)	0.0342 (15)	−0.0099 (12)	0.0069 (12)	0.0021 (12)
S1	0.0194 (4)	0.0229 (5)	0.0300 (5)	−0.0018 (4)	−0.0001 (4)	−0.0006 (5)

Geometric parameters (Å, º) top

C21—N21	1.457 (4)	C1—N1	1.429 (4)
C21—C23	1.480 (5)	C1—C3	1.488 (5)
C21—C22	1.535 (5)	C1—C2	1.557 (4)
C21—H21	1	C1—H1	1
C22—C25	1.509 (5)	C2—C5	1.512 (5)
C22—C24	1.540 (5)	C2—C4	1.530 (5)
C22—H22	1	C2—H2	1
C23—N22	1.146 (4)	C3—N2	1.144 (4)
C24—H24A	0.98	C4—H4A	0.98
C24—H24B	0.98	C4—H4B	0.98
C24—H24C	0.98	C4—H4C	0.98
C25—C26	1.386 (5)	C5—C10	1.387 (5)
C25—C210	1.396 (5)	C5—C6	1.396 (5)
C26—C27	1.400 (5)	C6—C7	1.385 (5)
C26—H26	0.95	C6—H6	0.95
C27—C28	1.369 (5)	C7—C8	1.377 (5)
C27—H27	0.95	C7—H7	0.95
C28—C29	1.387 (5)	C8—C9	1.379 (5)
C28—H28	0.95	C8—H8	0.95
C29—C210	1.388 (5)	C9—C10	1.390 (5)
C29—H29	0.95	C9—H9	0.95
C210—H210	0.95	C10—H10	0.95
C211—C212	1.516 (5)	C11—C13	1.520 (5)
C211—C213	1.523 (5)	C11—C12	1.522 (5)
C211—C214	1.529 (5)	C11—C14	1.532 (4)
C211—S21	1.843 (4)	C11—S1	1.831 (3)
C212—H21A	0.98	C12—H12A	0.98
C212—H21B	0.98	C12—H12B	0.98
C212—H21C	0.98	C12—H12C	0.98
C213—H21D	0.98	C13—H13A	0.98
C213—H21E	0.98	C13—H13B	0.98
C213—H21F	0.98	C13—H13C	0.98
C214—H21G	0.98	C14—H14A	0.98
C214—H21H	0.98	C14—H14B	0.98
C214—H21I	0.98	C14—H14C	0.98
N21—S21	1.647 (3)	N1—S1	1.646 (3)
N21—H211	0.85 (2)	N1—H1A	0.85 (2)
O21—S21	1.498 (2)	O1—S1	1.493 (2)

N21—C21—C23	110.7 (3)	N1—C1—C3	112.7 (3)
N21—C21—C22	109.4 (3)	N1—C1—C2	110.1 (3)
C23—C21—C22	111.5 (3)	C3—C1—C2	110.3 (3)
N21—C21—H21	108.4	N1—C1—H1	107.9
C23—C21—H21	108.4	C3—C1—H1	107.9
C22—C21—H21	108.4	C2—C1—H1	107.9
C25—C22—C21	109.6 (3)	C5—C2—C4	112.8 (3)
C25—C22—C24	113.3 (3)	C5—C2—C1	109.5 (3)
C21—C22—C24	112.3 (3)	C4—C2—C1	112.2 (3)
C25—C22—H22	107.1	C5—C2—H2	107.3
C21—C22—H22	107.1	C4—C2—H2	107.3
C24—C22—H22	107.1	C1—C2—H2	107.3
N22—C23—C21	176.6 (4)	N2—C3—C1	177.7 (4)
C22—C24—H24A	109.5	C2—C4—H4A	109.5
C22—C24—H24B	109.5	C2—C4—H4B	109.5
H24A—C24—H24B	109.5	H4A—C4—H4B	109.5
C22—C24—H24C	109.5	C2—C4—H4C	109.5
H24A—C24—H24C	109.5	H4A—C4—H4C	109.5
H24B—C24—H24C	109.5	H4B—C4—H4C	109.5
C26—C25—C210	117.9 (4)	C10—C5—C6	118.7 (3)
C26—C25—C22	120.9 (3)	C10—C5—C2	121.1 (3)
C210—C25—C22	121.1 (3)	C6—C5—C2	120.2 (3)
C25—C26—C27	121.3 (4)	C7—C6—C5	119.6 (4)
C25—C26—H26	119.4	C7—C6—H6	120.2
C27—C26—H26	119.4	C5—C6—H6	120.2
C28—C27—C26	120.0 (4)	C8—C7—C6	122.1 (4)
C28—C27—H27	120	C8—C7—H7	119
C26—C27—H27	120	C6—C7—H7	119
C27—C28—C29	119.7 (4)	C7—C8—C9	118.1 (4)
C27—C28—H28	120.1	C7—C8—H8	121
C29—C28—H28	120.1	C9—C8—H8	121
C28—C29—C210	120.4 (4)	C8—C9—C10	121.1 (4)
C28—C29—H29	119.8	C8—C9—H9	119.4
C210—C29—H29	119.8	C10—C9—H9	119.4
C29—C210—C25	120.8 (4)	C5—C10—C9	120.4 (4)
C29—C210—H210	119.6	C5—C10—H10	119.8
C25—C210—H210	119.6	C9—C10—H10	119.8
C212—C211—C213	110.6 (3)	C13—C11—C12	111.6 (3)
C212—C211—C214	111.7 (3)	C13—C11—C14	109.8 (3)
C213—C211—C214	110.9 (3)	C12—C11—C14	110.2 (3)
C212—C211—S21	111.2 (2)	C13—C11—S1	107.7 (3)
C213—C211—S21	105.2 (3)	C12—C11—S1	111.8 (2)
C214—C211—S21	107.0 (2)	C14—C11—S1	105.5 (2)
C211—C212—H21A	109.5	C11—C12—H12A	109.5
C211—C212—H21B	109.5	C11—C12—H12B	109.5
H21A—C212—H21B	109.5	H12A—C12—H12B	109.5
C211—C212—H21C	109.5	C11—C12—H12C	109.5
H21A—C212—H21C	109.5	H12A—C12—H12C	109.5
H21B—C212—H21C	109.5	H12B—C12—H12C	109.5
C211—C213—H21D	109.5	C11—C13—H13A	109.5
C211—C213—H21E	109.5	C11—C13—H13B	109.5
H21D—C213—H21E	109.5	H13A—C13—H13B	109.5
C211—C213—H21F	109.5	C11—C13—H13C	109.5
H21D—C213—H21F	109.5	H13A—C13—H13C	109.5
H21E—C213—H21F	109.5	H13B—C13—H13C	109.5
C211—C214—H21G	109.5	C11—C14—H14A	109.5
C211—C214—H21H	109.5	C11—C14—H14B	109.5
H21G—C214—H21H	109.5	H14A—C14—H14B	109.5
C211—C214—H21I	109.5	C11—C14—H14C	109.5
H21G—C214—H21I	109.5	H14A—C14—H14C	109.5
H21H—C214—H21I	109.5	H14B—C14—H14C	109.5
C21—N21—S21	118.4 (2)	C1—N1—S1	120.2 (2)
C21—N21—H211	112 (2)	C1—N1—H1A	120 (2)
S21—N21—H211	115 (3)	S1—N1—H1A	115 (2)
O21—S21—N21	112.12 (15)	O1—S1—N1	111.33 (15)
O21—S21—C211	106.03 (15)	O1—S1—C11	105.92 (16)
N21—S21—C211	97.20 (16)	N1—S1—C11	98.29 (15)

N21—C21—C22—C25	−54.4 (4)	N1—C1—C2—C5	−53.4 (4)
C23—C21—C22—C25	−177.1 (3)	C3—C1—C2—C5	−178.3 (3)
N21—C21—C22—C24	178.7 (3)	N1—C1—C2—C4	−179.5 (3)
C23—C21—C22—C24	56.0 (4)	C3—C1—C2—C4	55.6 (4)
N21—C21—C23—N22	−17 (8)	N1—C1—C3—N2	−44 (10)
C22—C21—C23—N22	105 (7)	C2—C1—C3—N2	80 (10)
C21—C22—C25—C26	114.1 (4)	C4—C2—C5—C10	58.2 (4)
C24—C22—C25—C26	−119.7 (4)	C1—C2—C5—C10	−67.5 (4)
C21—C22—C25—C210	−63.4 (4)	C4—C2—C5—C6	−123.8 (3)
C24—C22—C25—C210	62.8 (4)	C1—C2—C5—C6	110.4 (3)
C210—C25—C26—C27	−0.1 (5)	C10—C5—C6—C7	−0.3 (5)
C22—C25—C26—C27	−177.7 (3)	C2—C5—C6—C7	−178.3 (3)
C25—C26—C27—C28	0.8 (5)	C5—C6—C7—C8	1.1 (5)
C26—C27—C28—C29	−0.6 (5)	C6—C7—C8—C9	−1.1 (5)
C27—C28—C29—C210	−0.2 (5)	C7—C8—C9—C10	0.2 (5)
C28—C29—C210—C25	0.9 (5)	C6—C5—C10—C9	−0.5 (5)
C26—C25—C210—C29	−0.8 (5)	C2—C5—C10—C9	177.5 (3)
C22—C25—C210—C29	176.8 (3)	C8—C9—C10—C5	0.5 (5)
C23—C21—N21—S21	−83.2 (3)	C3—C1—N1—S1	−85.7 (3)
C22—C21—N21—S21	153.6 (2)	C2—C1—N1—S1	150.7 (2)
C21—N21—S21—O21	93.0 (3)	C1—N1—S1—O1	98.6 (3)
C21—N21—S21—C211	−156.4 (2)	C1—N1—S1—C11	−150.6 (3)
C212—C211—S21—O21	59.6 (3)	C13—C11—S1—O1	−178.8 (2)
C213—C211—S21—O21	−60.2 (3)	C12—C11—S1—O1	58.2 (3)
C214—C211—S21—O21	−178.2 (2)	C14—C11—S1—O1	−61.6 (3)
C212—C211—S21—N21	−56.0 (3)	C13—C11—S1—N1	66.1 (3)
C213—C211—S21—N21	−175.7 (2)	C12—C11—S1—N1	−56.9 (3)
C214—C211—S21—N21	66.2 (3)	C14—C11—S1—N1	−176.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85 (2)	2.11 (2)	2.882 (3)	151 (3)
N21—H211···O21ⁱⁱ	0.85 (2)	2.23 (2)	2.995 (4)	149 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₂₀N₂OS
M_r	264.38
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	9.0344 (4), 9.0617 (5), 35.767 (3)
V (Å³)	2928.1 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.36 × 0.08 × 0.06

Data collection
Diffractometer	Stoe IPDS II
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.936, 1.041
No. of measured, independent and observed [I > 2σ(I)] reflections	15474, 5160, 3413
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.074, 0.77
No. of reflections	5160
No. of parameters	342
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)	0.19, −0.24
Absolute structure	Flack (1983), 2183 Friedel pairs
Absolute structure parameter	−0.04 (9)

Computer programs: X-AREA (Stoe & Cie, 2002), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85 (2)	2.110 (17)	2.882 (3)	151 (3)
N21—H211···O21ⁱⁱ	0.85 (2)	2.23 (2)	2.995 (4)	149 (3)

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

Acknowledgements

The authors gratefully acknowledge funding by the Philipps-Universität Marburg, the Deutsche Forschungsgemeinschaft (PS & MO) and the Ernst-Schering-Foundation (PS).

References

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