(2S)-Ethyl 2-[(S(s))-benzyl-sulfinyl-amino]-3,3-dimethylbutanoate.

The title compound, C(15)H(23)NO(3)S, is an unexpected 1,3-migration product in the addition of benzyl-zinc bromide to N-tert-butane-sulfinyl imino-acetate. In the crystal structure, mol-ecules are linked by N-H⋯O hydrogen bonds and weak C-H⋯O hydrogen bonds.

Related literature

For general background, see: Ellman et al. (2002 ▶); Lin et al. (2008 ▶); Daniel & Stockman (2006 ▶). For the synthesis of the titled compound, see: Sun et al. (2008 ▶).

Experimental

Crystal data

C15H23NO3S

M = 297.40

Monoclinic,

a = 11.166 (2) Å

b = 7.1917 (14) Å

c = 11.460 (2) Å

β = 115.473 (3)°

V = 830.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.20 mm−1

T = 293 (2) K

0.49 × 0.41 × 0.17 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.908, T max = 0.967

4782 measured reflections

3221 independent reflections

2661 reflections with I > 2σ(I)

R int = 0.120

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.134

S = 0.97

3221 reflections

189 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack (1983 ▶), 1295 Friedel pairs

Flack parameter: −0.09 (11)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028717/zl2133sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028717/zl2133Isup2.hkl

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

C15H23NO3S	F(000) = 320
Mr = 297.40	Dx = 1.189 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1845 reflections
a = 11.166 (2) Å	θ = 3.4–23.9°
b = 7.1917 (14) Å	µ = 0.20 mm−1
c = 11.460 (2) Å	T = 293 K
β = 115.473 (3)°	Prismatic, colorless
V = 830.8 (3) Å3	0.49 × 0.41 × 0.17 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	3221 independent reflections
Radiation source: fine-focus sealed tube	2661 reflections with I > 2σ(I)
graphite	Rint = 0.120
φ and ω scans	θmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→14
Tmin = 0.908, Tmax = 0.967	k = −8→9
4782 measured reflections	l = −14→13

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0662P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.001
3221 reflections	Δρmax = 0.43 e Å−3
189 parameters	Δρmin = −0.23 e Å−3
2 restraints	Absolute structure: Flack (1983), 1295 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.09 (11)

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	0.04167 (7)	0.26178 (12)	0.67424 (6)	0.0442 (2)
O1	0.3061 (3)	0.0339 (4)	0.5596 (3)	0.0741 (8)
O2	0.4124 (3)	0.2630 (5)	0.6946 (2)	0.0696 (7)
O3	0.0313 (3)	0.3869 (4)	0.5670 (2)	0.0665 (7)
N1	0.1252 (2)	0.0717 (4)	0.6804 (2)	0.0420 (6)
C1	0.2690 (3)	0.0814 (4)	0.7500 (3)	0.0397 (6)
H1	0.2901	0.1873	0.8094	0.048*
C2	0.3305 (3)	0.1206 (5)	0.6568 (3)	0.0501 (8)
C3	0.4801 (5)	0.3093 (8)	0.6131 (5)	0.0923 (17)
H3A	0.5348	0.2058	0.6108	0.111*
H3B	0.4155	0.3353	0.5255	0.111*
C4	0.5613 (6)	0.4705 (9)	0.6677 (5)	0.108 (2)
H4A	0.5056	0.5775	0.6547	0.162*
H4B	0.6189	0.4900	0.6263	0.162*
H4C	0.6136	0.4516	0.7586	0.162*
C5	0.3281 (3)	−0.0954 (5)	0.8332 (3)	0.0478 (7)
C6	0.4791 (4)	−0.0865 (6)	0.8887 (4)	0.0681 (10)
H6A	0.5167	−0.1912	0.9445	0.102*
H6B	0.5099	0.0264	0.9371	0.102*
H6C	0.5057	−0.0892	0.8194	0.102*
C7	0.2792 (4)	−0.2720 (5)	0.7539 (4)	0.0649 (10)
H7A	0.3185	−0.3781	0.8076	0.097*
H7B	0.3039	−0.2702	0.6833	0.097*
H7C	0.1844	−0.2791	0.7206	0.097*
C8	0.2833 (4)	−0.0948 (6)	0.9414 (3)	0.0653 (10)
H8A	0.1882	−0.0909	0.9048	0.098*
H8B	0.3191	0.0124	0.9952	0.098*
H8C	0.3145	−0.2055	0.9924	0.098*
C9	−0.1205 (3)	0.1504 (5)	0.6172 (3)	0.0513 (8)
H9A	−0.1880	0.2455	0.5975	0.062*
H9B	−0.1384	0.0834	0.5380	0.062*
C10	−0.1293 (3)	0.0198 (5)	0.7130 (3)	0.0494 (8)
C11	−0.1140 (4)	−0.1679 (6)	0.7036 (4)	0.0664 (10)
H11	−0.1014	−0.2145	0.6340	0.080*
C12	−0.1169 (5)	−0.2890 (6)	0.7960 (5)	0.0895 (15)
H12	−0.1062	−0.4161	0.7885	0.107*
C13	−0.1357 (5)	−0.2210 (10)	0.8991 (5)	0.0940 (15)
H13	−0.1374	−0.3023	0.9615	0.113*
C14	−0.1515 (5)	−0.0390 (8)	0.9098 (5)	0.0903 (16)
H14	−0.1651	0.0056	0.9794	0.108*
C15	−0.1479 (4)	0.0835 (6)	0.8193 (4)	0.0702 (11)
H15	−0.1579	0.2101	0.8289	0.084*
H1A	0.102 (3)	0.001 (3)	0.614 (2)	0.049 (7)*

	U11	U22	U33	U12	U13	U23
S1	0.0470 (4)	0.0432 (4)	0.0420 (3)	0.0052 (4)	0.0189 (3)	0.0057 (4)
O1	0.0850 (19)	0.095 (2)	0.0564 (14)	−0.0256 (17)	0.0441 (13)	−0.0240 (15)
O2	0.0750 (16)	0.0817 (16)	0.0677 (13)	−0.0294 (18)	0.0455 (12)	−0.0137 (18)
O3	0.0640 (16)	0.0639 (16)	0.0641 (15)	0.0019 (13)	0.0206 (12)	0.0255 (13)
N1	0.0404 (14)	0.0454 (15)	0.0379 (12)	−0.0008 (11)	0.0146 (11)	−0.0041 (11)
C1	0.0383 (15)	0.0425 (17)	0.0387 (14)	−0.0046 (13)	0.0168 (12)	−0.0055 (13)
C2	0.0424 (17)	0.060 (2)	0.0489 (18)	−0.0037 (16)	0.0205 (14)	−0.0013 (16)
C3	0.098 (4)	0.119 (5)	0.086 (3)	−0.040 (3)	0.065 (3)	−0.019 (3)
C4	0.105 (4)	0.132 (5)	0.112 (4)	−0.035 (4)	0.070 (3)	0.001 (3)
C5	0.0499 (18)	0.0452 (17)	0.0415 (16)	0.0018 (15)	0.0132 (13)	−0.0001 (14)
C6	0.048 (2)	0.073 (2)	0.064 (2)	0.0088 (19)	0.0065 (17)	0.002 (2)
C7	0.067 (2)	0.048 (3)	0.067 (2)	0.0015 (18)	0.0159 (17)	−0.0079 (17)
C8	0.080 (3)	0.067 (2)	0.0490 (19)	0.004 (2)	0.0276 (18)	0.0121 (18)
C9	0.0421 (17)	0.065 (2)	0.0451 (16)	0.0087 (16)	0.0174 (14)	0.0066 (15)
C10	0.0369 (17)	0.059 (2)	0.0522 (18)	−0.0030 (14)	0.0190 (14)	0.0005 (15)
C11	0.062 (2)	0.070 (3)	0.064 (2)	−0.0145 (19)	0.0243 (18)	−0.0035 (18)
C12	0.092 (4)	0.058 (3)	0.113 (4)	−0.018 (2)	0.038 (3)	0.011 (2)
C13	0.086 (3)	0.108 (4)	0.094 (3)	−0.021 (4)	0.044 (2)	0.033 (4)
C14	0.095 (4)	0.121 (5)	0.077 (3)	−0.006 (3)	0.057 (3)	0.012 (3)
C15	0.074 (3)	0.075 (3)	0.074 (2)	−0.001 (2)	0.043 (2)	−0.002 (2)

S1—O3	1.487 (2)	C6—H6C	0.9600
S1—N1	1.639 (3)	C7—H7A	0.9600
S1—C9	1.824 (4)	C7—H7B	0.9600
O1—C2	1.201 (4)	C7—H7C	0.9600
O2—C2	1.316 (4)	C8—H8A	0.9600
O2—C3	1.471 (4)	C8—H8B	0.9600
N1—C1	1.455 (4)	C8—H8C	0.9600
N1—H1A	0.859 (17)	C9—C10	1.480 (5)
C1—C2	1.523 (4)	C9—H9A	0.9700
C1—C5	1.555 (4)	C9—H9B	0.9700
C1—H1	0.9800	C10—C11	1.371 (5)
C3—C4	1.439 (7)	C10—C15	1.398 (5)
C3—H3A	0.9700	C11—C12	1.382 (6)
C3—H3B	0.9700	C11—H11	0.9300
C4—H4A	0.9600	C12—C13	1.375 (7)
C4—H4B	0.9600	C12—H12	0.9300
C4—H4C	0.9600	C13—C14	1.334 (8)
C5—C7	1.520 (5)	C13—H13	0.9300
C5—C8	1.524 (5)	C14—C15	1.374 (6)
C5—C6	1.526 (5)	C14—H14	0.9300
C6—H6A	0.9600	C15—H15	0.9300
C6—H6B	0.9600
O3—S1—N1	112.37 (15)	H6A—C6—H6C	109.5
O3—S1—C9	104.90 (15)	H6B—C6—H6C	109.5
N1—S1—C9	96.19 (15)	C5—C7—H7A	109.5
C2—O2—C3	116.2 (3)	C5—C7—H7B	109.5
C1—N1—S1	117.2 (2)	H7A—C7—H7B	109.5
C1—N1—H1A	111.1 (19)	C5—C7—H7C	109.5
S1—N1—H1A	120.2 (19)	H7A—C7—H7C	109.5
N1—C1—C2	110.4 (2)	H7B—C7—H7C	109.5
N1—C1—C5	111.9 (2)	C5—C8—H8A	109.5
C2—C1—C5	112.4 (3)	C5—C8—H8B	109.5
N1—C1—H1	107.3	H8A—C8—H8B	109.5
C2—C1—H1	107.3	C5—C8—H8C	109.5
C5—C1—H1	107.3	H8A—C8—H8C	109.5
O1—C2—O2	123.9 (3)	H8B—C8—H8C	109.5
O1—C2—C1	124.3 (3)	C10—C9—S1	112.7 (2)
O2—C2—C1	111.8 (3)	C10—C9—H9A	109.1
C4—C3—O2	107.8 (4)	S1—C9—H9A	109.1
C4—C3—H3A	110.1	C10—C9—H9B	109.1
O2—C3—H3A	110.1	S1—C9—H9B	109.1
C4—C3—H3B	110.1	H9A—C9—H9B	107.8
O2—C3—H3B	110.1	C11—C10—C15	117.5 (4)
H3A—C3—H3B	108.5	C11—C10—C9	121.1 (3)
C3—C4—H4A	109.5	C15—C10—C9	121.4 (3)
C3—C4—H4B	109.5	C10—C11—C12	121.0 (4)
H4A—C4—H4B	109.5	C10—C11—H11	119.5
C3—C4—H4C	109.5	C12—C11—H11	119.5
H4A—C4—H4C	109.5	C13—C12—C11	119.8 (4)
H4B—C4—H4C	109.5	C13—C12—H12	120.1
C7—C5—C8	109.2 (3)	C11—C12—H12	120.1
C7—C5—C6	109.4 (3)	C14—C13—C12	120.2 (4)
C8—C5—C6	110.6 (3)	C14—C13—H13	119.9
C7—C5—C1	111.6 (2)	C12—C13—H13	119.9
C8—C5—C1	107.2 (3)	C13—C14—C15	120.8 (5)
C6—C5—C1	108.8 (3)	C13—C14—H14	119.6
C5—C6—H6A	109.5	C15—C14—H14	119.6
C5—C6—H6B	109.5	C14—C15—C10	120.8 (4)
H6A—C6—H6B	109.5	C14—C15—H15	119.6
C5—C6—H6C	109.5	C10—C15—H15	119.6
O3—S1—N1—C1	84.8 (2)	N1—C1—C5—C6	172.6 (3)
C9—S1—N1—C1	−166.3 (2)	C2—C1—C5—C6	47.8 (3)
S1—N1—C1—C2	−95.2 (3)	O3—S1—C9—C10	−179.6 (3)
S1—N1—C1—C5	138.8 (2)	N1—S1—C9—C10	65.2 (3)
C3—O2—C2—O1	−2.6 (6)	S1—C9—C10—C11	−99.0 (4)
C3—O2—C2—C1	178.3 (4)	S1—C9—C10—C15	78.2 (4)
N1—C1—C2—O1	−51.2 (4)	C15—C10—C11—C12	0.1 (6)
C5—C1—C2—O1	74.6 (4)	C9—C10—C11—C12	177.4 (4)
N1—C1—C2—O2	128.0 (3)	C10—C11—C12—C13	0.1 (7)
C5—C1—C2—O2	−106.3 (3)	C11—C12—C13—C14	0.2 (8)
C2—O2—C3—C4	178.3 (4)	C12—C13—C14—C15	−0.7 (9)
N1—C1—C5—C7	51.8 (3)	C13—C14—C15—C10	0.9 (7)
C2—C1—C5—C7	−73.1 (4)	C11—C10—C15—C14	−0.5 (6)
N1—C1—C5—C8	−67.8 (3)	C9—C10—C15—C14	−177.8 (4)
C2—C1—C5—C8	167.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1	0.96	2.61	3.234 (5)	123.
C9—H9B···O3i	0.97	2.48	3.296 (5)	142.
N1—H1A···O3i	0.86 (2)	2.13 (2)	2.932 (3)	156 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1	0.96	2.61	3.234 (5)	123
C9—H9B⋯O3i	0.97	2.48	3.296 (5)	142
N1—H1A⋯O3i	0.859 (17)	2.13 (2)	2.932 (3)	156 (3)

Symmetry code: (i) .