Crystal structure of methyl (2R,3S)-3-[(tert-butyl-sulfin-yl)amino]-2-fluoro-3-phenyl-propano-ate.

The title compound, C14H20FNO3S, contains two chiral carbon centres and the absolute configuration has been confirmed as (2R,3S). In the crystal, adjacent mol-ecules are linked by weak C-H⋯O hydrogen bonds, generating zigzag chains along the a-axis direction.

Related literature

For the use of of fluorinated β-amino acids in organic synthesis, see: Marsh (2014 ▸); Niemz & Tirrell (2001 ▸); Chiu et al. (2006 ▸). For their synthesis, see: Shang et al. (2015 ▸); Yoshinari et al. (2011 ▸); Duggan et al. (2010 ▸); Peddie & Abell (2012 ▸); Jing et al. (2011 ▸); Pan et al. (2010 ▸).

Experimental

Crystal data

C14H20FNO3S

M = 301.37

Orthorhombic,

a = 9.1809 (14) Å

b = 9.2384 (15) Å

c = 18.577 (3) Å

V = 1575.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 296 K

0.13 × 0.11 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T min = 0.972, T max = 0.985

8176 measured reflections

2773 independent reflections

2542 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.088

S = 1.04

2773 reflections

186 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▸)

Absolute structure parameter: 0.05 (8)

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); 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 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015023580/su5256sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023580/su5256Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023580/su5256Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015023580/su5256fig1.tif

Mol­ecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015023580/su5256fig2.tif

A partial view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1).

CCDC reference: 1441329

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H20FNO3S	F(000) = 640
Mr = 301.37	Dx = 1.270 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3418 reflections
a = 9.1809 (14) Å	θ = 2.2–25.5°
b = 9.2384 (15) Å	µ = 0.22 mm−1
c = 18.577 (3) Å	T = 296 K
V = 1575.7 (4) Å3	Block, colorless
Z = 4	0.13 × 0.11 × 0.07 mm

Bruker APEXII CCD diffractometer	2773 independent reflections
Radiation source: fine-focus sealed tube	2542 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→10
Tmin = 0.972, Tmax = 0.985	k = −11→11
8176 measured reflections	l = −22→21

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033	w = 1/[σ2(Fo2) + (0.0505P)2 + 0.1714P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.088	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.27 e Å−3
2773 reflections	Δρmin = −0.29 e Å−3
186 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0117 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), ???? Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.05 (8)

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	0.45246 (5)	0.13512 (6)	1.04644 (3)	0.04566 (16)
C1	0.4525 (2)	0.0513 (2)	0.86771 (10)	0.0454 (5)
C2	0.4258 (3)	0.1407 (3)	0.80959 (13)	0.0645 (7)
H2	0.3412	0.1960	0.8085	0.077*
C3	0.5233 (3)	0.1489 (4)	0.75313 (14)	0.0799 (8)
H3	0.5032	0.2089	0.7142	0.096*
C4	0.6486 (3)	0.0701 (4)	0.75394 (14)	0.0790 (9)
H4	0.7134	0.0755	0.7156	0.095*
C5	0.6780 (3)	−0.0166 (3)	0.81134 (15)	0.0763 (8)
H5	0.7640	−0.0698	0.8124	0.092*
C6	0.5812 (3)	−0.0262 (3)	0.86807 (13)	0.0614 (6)
H6	0.6029	−0.0855	0.9070	0.074*
C7	0.3370 (2)	0.0338 (2)	0.92539 (10)	0.0412 (4)
H7	0.2837	0.1254	0.9288	0.049*
C8	0.2285 (2)	−0.0833 (2)	0.90203 (11)	0.0485 (5)
H8	0.1834	−0.0536	0.8566	0.058*
C9	0.1100 (2)	−0.1116 (2)	0.95639 (13)	0.0467 (5)
C10	0.3929 (3)	0.0729 (3)	1.13521 (12)	0.0606 (6)
C11	0.4604 (4)	0.1814 (4)	1.18744 (15)	0.0919 (10)
H11A	0.4255	0.1626	1.2352	0.138*
H11B	0.4337	0.2778	1.1734	0.138*
H11C	0.5646	0.1720	1.1865	0.138*
C12	0.4469 (5)	−0.0790 (3)	1.15008 (15)	0.1004 (11)
H12A	0.5481	−0.0858	1.1376	0.151*
H12B	0.3920	−0.1468	1.1218	0.151*
H12C	0.4347	−0.1008	1.2002	0.151*
C13	0.2279 (3)	0.0833 (4)	1.13551 (16)	0.0914 (10)
H13A	0.1880	0.0102	1.1045	0.137*
H13B	0.1989	0.1772	1.1186	0.137*
H13C	0.1924	0.0692	1.1836	0.137*
C14	−0.1016 (3)	−0.0130 (4)	1.00859 (19)	0.0961 (11)
H14A	−0.1445	−0.1076	1.0052	0.144*
H14B	−0.1733	0.0589	0.9969	0.144*
H14C	−0.0670	0.0026	1.0567	0.144*
F1	0.30213 (17)	−0.21153 (14)	0.89103 (8)	0.0696 (4)
N1	0.38966 (18)	−0.00242 (17)	0.99719 (8)	0.0410 (4)
H1	0.3884	−0.0897	1.0133	0.049*
O1	0.02014 (16)	−0.00250 (18)	0.95826 (11)	0.0748 (5)
O2	0.10015 (19)	−0.21952 (17)	0.99189 (10)	0.0648 (5)
O3	0.61290 (18)	0.1341 (2)	1.04867 (11)	0.0792 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0395 (3)	0.0456 (3)	0.0519 (3)	−0.0028 (2)	0.0025 (2)	−0.0062 (2)
C1	0.0440 (11)	0.0485 (11)	0.0438 (11)	−0.0090 (10)	0.0010 (10)	0.0042 (9)
C2	0.0517 (14)	0.0817 (17)	0.0600 (14)	−0.0088 (13)	−0.0025 (11)	0.0254 (13)
C3	0.0740 (19)	0.111 (2)	0.0545 (14)	−0.0187 (18)	0.0034 (13)	0.0315 (15)
C4	0.0731 (19)	0.101 (2)	0.0632 (17)	−0.0250 (17)	0.0232 (15)	0.0080 (16)
C5	0.0572 (15)	0.0885 (19)	0.0832 (18)	0.0025 (15)	0.0285 (13)	0.0076 (16)
C6	0.0578 (14)	0.0670 (14)	0.0595 (14)	0.0055 (12)	0.0115 (11)	0.0130 (12)
C7	0.0402 (10)	0.0416 (10)	0.0418 (10)	−0.0018 (8)	0.0021 (8)	0.0043 (9)
C8	0.0455 (12)	0.0540 (12)	0.0458 (11)	−0.0051 (10)	0.0000 (9)	0.0011 (10)
C9	0.0369 (10)	0.0445 (11)	0.0588 (12)	−0.0058 (8)	−0.0021 (10)	0.0024 (11)
C10	0.0636 (15)	0.0741 (16)	0.0440 (12)	−0.0009 (13)	0.0036 (11)	−0.0078 (11)
C11	0.094 (2)	0.121 (2)	0.0608 (16)	−0.006 (2)	−0.0073 (16)	−0.0322 (16)
C12	0.152 (3)	0.089 (2)	0.0602 (16)	0.007 (2)	−0.020 (2)	0.0179 (15)
C13	0.0664 (18)	0.133 (3)	0.0744 (18)	−0.0155 (18)	0.0280 (15)	−0.0240 (18)
C14	0.0490 (15)	0.0811 (18)	0.158 (3)	0.0062 (14)	0.0448 (19)	0.019 (2)
F1	0.0689 (9)	0.0569 (8)	0.0828 (10)	−0.0086 (7)	0.0215 (7)	−0.0240 (7)
N1	0.0477 (10)	0.0368 (8)	0.0385 (8)	−0.0010 (7)	0.0006 (7)	0.0035 (7)
O1	0.0440 (9)	0.0610 (10)	0.1193 (15)	0.0081 (8)	0.0214 (10)	0.0283 (10)
O2	0.0621 (10)	0.0489 (9)	0.0835 (12)	−0.0020 (7)	0.0163 (9)	0.0133 (9)
O3	0.0401 (8)	0.0993 (14)	0.0981 (13)	−0.0126 (9)	0.0054 (9)	−0.0301 (12)

S1—O3	1.4737 (17)	C8—H8	0.9800
S1—N1	1.6685 (17)	C9—O2	1.199 (2)
S1—C10	1.830 (2)	C9—O1	1.303 (3)
C1—C2	1.381 (3)	C10—C12	1.513 (4)
C1—C6	1.381 (3)	C10—C13	1.518 (4)
C1—C7	1.516 (3)	C10—C11	1.527 (4)
C2—C3	1.381 (4)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.361 (4)	C11—H11C	0.9600
C3—H3	0.9300	C12—H12A	0.9600
C4—C5	1.361 (4)	C12—H12B	0.9600
C4—H4	0.9300	C12—H12C	0.9600
C5—C6	1.382 (3)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—N1	1.458 (2)	C14—O1	1.460 (3)
C7—C8	1.533 (3)	C14—H14A	0.9600
C7—H7	0.9800	C14—H14B	0.9600
C8—F1	1.379 (3)	C14—H14C	0.9600
C8—C9	1.507 (3)	N1—H1	0.8600
O3—S1—N1	110.87 (10)	O1—C9—C8	109.95 (18)
O3—S1—C10	105.74 (12)	C12—C10—C13	112.7 (3)
N1—S1—C10	98.71 (10)	C12—C10—C11	111.1 (2)
C2—C1—C6	117.7 (2)	C13—C10—C11	111.2 (2)
C2—C1—C7	119.5 (2)	C12—C10—S1	111.0 (2)
C6—C1—C7	122.66 (17)	C13—C10—S1	106.35 (19)
C1—C2—C3	120.8 (3)	C11—C10—S1	104.17 (19)
C1—C2—H2	119.6	C10—C11—H11A	109.5
C3—C2—H2	119.6	C10—C11—H11B	109.5
C4—C3—C2	120.6 (3)	H11A—C11—H11B	109.5
C4—C3—H3	119.7	C10—C11—H11C	109.5
C2—C3—H3	119.7	H11A—C11—H11C	109.5
C3—C4—C5	119.4 (2)	H11B—C11—H11C	109.5
C3—C4—H4	120.3	C10—C12—H12A	109.5
C5—C4—H4	120.3	C10—C12—H12B	109.5
C4—C5—C6	120.5 (3)	H12A—C12—H12B	109.5
C4—C5—H5	119.8	C10—C12—H12C	109.5
C6—C5—H5	119.8	H12A—C12—H12C	109.5
C1—C6—C5	120.9 (2)	H12B—C12—H12C	109.5
C1—C6—H6	119.5	C10—C13—H13A	109.5
C5—C6—H6	119.5	C10—C13—H13B	109.5
N1—C7—C1	116.05 (17)	H13A—C13—H13B	109.5
N1—C7—C8	108.22 (16)	C10—C13—H13C	109.5
C1—C7—C8	109.24 (16)	H13A—C13—H13C	109.5
N1—C7—H7	107.7	H13B—C13—H13C	109.5
C1—C7—H7	107.7	O1—C14—H14A	109.5
C8—C7—H7	107.7	O1—C14—H14B	109.5
F1—C8—C9	107.71 (16)	H14A—C14—H14B	109.5
F1—C8—C7	109.26 (18)	O1—C14—H14C	109.5
C9—C8—C7	113.67 (17)	H14A—C14—H14C	109.5
F1—C8—H8	108.7	H14B—C14—H14C	109.5
C9—C8—H8	108.7	C7—N1—S1	116.21 (12)
C7—C8—H8	108.7	C7—N1—H1	121.9
O2—C9—O1	125.5 (2)	S1—N1—H1	121.9
O2—C9—C8	124.6 (2)	C9—O1—C14	116.76 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O3i	0.96	2.79	3.045 (4)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O3i	0.96	2.79	3.045 (4)	135

Symmetry code: (i) .