(1R,2S)-2-[N-Methyl-N-(4-toluene­sulfonyl)amino]-1-phenylpropan-1-ol

In the title compound, C₁₇H₂₁NO₃S, the S atom is in a distorted tetrahedral geometry and the N atom exhibits sp² character. The antiperiplanar conformation is observed for the N and hydroxyl-O atoms and the torsion angle around the N—C linkage is −136.3 (2)°. The mol­ecules are linked by O—H...O intermolecular hydrogen bonds to form an infinite one-dimensional chains along the c axis.

S1. Comment

The title compound is an N-tosyl derivative of (-)ephedrine. Generally ephedrine and its derivatives are used as sympathomimetic agents for allergic disorders, central nervous system stimulation, prophylaxis and treatment of hypotension and hypersensitive carotid sinusitis. The structure determination of the title compound, (I), was carried out in order to elucidate the molecular conformation and packing arrangements.

Scheme I

The S atom is in a distorted tetrahedral geometry with the maximum and minimum bond angles around this atom being 119.8 (1) and 106.4 (1)°, respectively. The sum of the bond angles around the N1 atom [354.6 (2)°] indicates the sp² character of this atom; the deviation of N1 from the S1—C8—C9 plane is 0.206 (2) Å. The S—N, S—O and C—S distances agree with those values reported for the toluenesulfonylamino derivatives (Urtiaga et al., 1994; Arriortua et al., 1995).

The N1—C9—C11—O3, torsion angle [164.6 (2)°] charaterizes the antiperiplanar conformation for the N1 and O3 atoms. The conformation observed across the S1—N1—C9—C11 linkage is -anti-clinal [torsion angle −136.3 (2)°]. The two phenyl ring planes form a dihedral angle of 59.3 (1)° between them (see Fig. 1).

In the solid state, the molecules translated along the c direction are linked through O3—H3B···O2ⁱ intermolecular hydrogen bonds (Table 2) to form infinite one-dimensional chains. Along the chain, the phenyl rings are stacked without any π-π interactions.

S2. Experimental

Ephedrine (1 g, 6.05 mmol), p-toluenesulfonyl chloride (1.73 g, 9.07 mmol) and tetra-n-butylammonium hydrogen sulfate (0.410 g, 1.21 mmol) in 50 ml of dry benzene was stirred with 10 ml of 50% NaOH at room temperature for 1 h. After completion of the reaction, the organic layer was separated, washed with water and dried over MgSO₄. After removal of the solvent, it gave a solid which was recrystallized from methyl alcohol. (yield 80%, m.p. 397–399 K).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997) PLATON (Spek, 1990).

Figures

Fig. 1. The structure of title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.

(1R,2S)-(2-N-methyl-N-4-toluenesulfonyl)amino-1-phenyl-1-propanol

Crystal data

C17H21NO3S	F(000) = 340
Mr = 319.41	Dx = 1.294 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2y1	Cell parameters from 4453 reflections
a = 6.0272 (2) Å	θ = 2.8–33.1°
b = 18.6624 (8) Å	µ = 0.21 mm^−1
c = 7.3642 (3) Å	T = 293 K
β = 98.148 (1)°	Parallelepiped, colourless
V = 819.98 (6) Å^3	0.50 × 0.34 × 0.26 mm
Z = 2

Data collection

Siemens SMART CCD area detector diffractometer	3379 independent reflections
Radiation source: fine-focus sealed tube	3038 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8.33 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ω scans	h = −7→7
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996)	k = −24→24
Tmin = 0.903, Tmax = 0.948	l = 0→9
5485 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0586P)^2 + 0.0071P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3379 reflections	Δρmax = 0.40 e Å^−3
199 parameters	Δρmin = −0.34 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.13 (7)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.71634 (9)	0.52841 (3)	0.16550 (6)	0.03538 (14)
N1	0.6812 (3)	0.53064 (12)	0.38077 (19)	0.0332 (3)
O1	0.5257 (4)	0.49339 (10)	0.0678 (2)	0.0560 (5)
O2	0.9365 (3)	0.50049 (10)	0.1579 (2)	0.0492 (4)
O3	1.0979 (3)	0.50374 (11)	0.7841 (2)	0.0617 (6)
H3B	1.0922	0.5042	0.8947	0.093*
C1	0.7120 (4)	0.61742 (11)	0.0817 (3)	0.0341 (5)
C2	0.9060 (4)	0.65819 (14)	0.1082 (3)	0.0457 (6)
H2A	1.0395	0.6387	0.1662	0.055*
C3	0.8984 (6)	0.72823 (15)	0.0473 (4)	0.0578 (7)
H3A	1.0285	0.7557	0.0650	0.069*
C4	0.7016 (6)	0.75878 (14)	−0.0397 (3)	0.0549 (7)
C5	0.5118 (6)	0.71686 (16)	−0.0663 (4)	0.0581 (7)
H5A	0.3791	0.7362	−0.1262	0.070*
C6	0.5137 (5)	0.64620 (15)	−0.0058 (3)	0.0463 (6)
H6A	0.3836	0.6188	−0.0238	0.056*
C7	0.6968 (9)	0.83623 (17)	−0.1010 (5)	0.0926 (13)
H7A	0.8437	0.8566	−0.0714	0.139*	0.50
H7B	0.5927	0.8625	−0.0393	0.139*	0.50
H7C	0.6510	0.8387	−0.2311	0.139*	0.50
H7D	0.5479	0.8486	−0.1565	0.139*	0.50
H7E	0.7989	0.8427	−0.1885	0.139*	0.50
H7F	0.7406	0.8666	0.0032	0.139*	0.50
C8	0.4563 (5)	0.54798 (18)	0.4198 (4)	0.0591 (8)
H8A	0.4552	0.5477	0.5500	0.089*
H8B	0.3519	0.5130	0.3631	0.089*
H8C	0.4141	0.5946	0.3719	0.089*
C9	0.8738 (4)	0.54664 (11)	0.5219 (3)	0.0337 (5)
H9A	1.0101	0.5374	0.4673	0.040*
C10	0.8826 (6)	0.62448 (14)	0.5843 (4)	0.0595 (8)
H10A	0.8804	0.6553	0.4797	0.089*
H10B	1.0178	0.6326	0.6677	0.089*
H10C	0.7552	0.6347	0.6449	0.089*
C11	0.8771 (4)	0.49567 (13)	0.6867 (3)	0.0396 (5)
H11A	0.7686	0.5126	0.7643	0.048*
C12	0.8253 (4)	0.41887 (13)	0.6347 (3)	0.0387 (5)
C13	0.6351 (5)	0.38624 (15)	0.6823 (4)	0.0522 (6)
H13A	0.5402	0.4118	0.7476	0.063*
C14	0.5852 (6)	0.31557 (16)	0.6332 (4)	0.0613 (8)
H14A	0.4587	0.2938	0.6675	0.074*
C15	0.7223 (6)	0.27767 (15)	0.5340 (4)	0.0630 (8)
H15A	0.6873	0.2306	0.4994	0.076*
C16	0.9115 (6)	0.30947 (15)	0.4861 (4)	0.0618 (8)
H16A	1.0047	0.2836	0.4197	0.074*
C17	0.9643 (5)	0.37935 (15)	0.5355 (4)	0.0516 (6)
H17B	1.0930	0.4003	0.5026	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0435 (3)	0.0380 (2)	0.0233 (2)	0.0017 (3)	0.00025 (16)	−0.0016 (2)
N1	0.0292 (8)	0.0437 (8)	0.0267 (6)	0.0019 (9)	0.0037 (6)	0.0023 (8)
O1	0.0702 (13)	0.0519 (10)	0.0397 (8)	−0.0153 (9)	−0.0142 (8)	−0.0032 (7)
O2	0.0612 (12)	0.0588 (9)	0.0293 (7)	0.0238 (9)	0.0118 (7)	0.0017 (6)
O3	0.0586 (12)	0.0873 (14)	0.0333 (8)	−0.0071 (10)	−0.0142 (7)	−0.0011 (8)
C1	0.0379 (12)	0.0407 (11)	0.0237 (9)	0.0027 (9)	0.0044 (8)	0.0045 (8)
C2	0.0404 (14)	0.0582 (15)	0.0371 (11)	−0.0044 (11)	0.0007 (9)	0.0048 (10)
C3	0.076 (2)	0.0558 (16)	0.0424 (13)	−0.0187 (15)	0.0119 (12)	0.0002 (11)
C4	0.089 (2)	0.0414 (13)	0.0384 (12)	0.0064 (14)	0.0223 (13)	0.0007 (10)
C5	0.0650 (19)	0.0614 (17)	0.0484 (14)	0.0228 (15)	0.0103 (13)	0.0140 (12)
C6	0.0402 (13)	0.0574 (15)	0.0404 (12)	0.0045 (11)	0.0031 (9)	0.0080 (10)
C7	0.165 (4)	0.0467 (17)	0.072 (2)	0.012 (2)	0.037 (2)	0.0089 (15)
C8	0.0387 (14)	0.086 (2)	0.0552 (14)	0.0092 (13)	0.0138 (11)	0.0106 (13)
C9	0.0334 (11)	0.0430 (12)	0.0252 (9)	−0.0039 (8)	0.0056 (7)	−0.0026 (7)
C10	0.094 (2)	0.0464 (14)	0.0378 (13)	−0.0163 (15)	0.0085 (14)	−0.0067 (11)
C11	0.0462 (14)	0.0505 (12)	0.0220 (8)	−0.0013 (11)	0.0043 (8)	0.0009 (9)
C12	0.0461 (14)	0.0442 (12)	0.0254 (10)	0.0048 (10)	0.0041 (9)	0.0103 (9)
C13	0.0533 (16)	0.0621 (16)	0.0424 (13)	−0.0019 (13)	0.0113 (11)	0.0046 (11)
C14	0.065 (2)	0.0617 (17)	0.0564 (16)	−0.0144 (14)	0.0045 (14)	0.0138 (13)
C15	0.089 (2)	0.0410 (14)	0.0569 (16)	−0.0043 (14)	0.0019 (15)	0.0045 (12)
C16	0.075 (2)	0.0485 (15)	0.0647 (17)	0.0131 (14)	0.0193 (15)	0.0051 (12)
C17	0.0554 (17)	0.0483 (14)	0.0532 (14)	0.0079 (12)	0.0158 (12)	0.0073 (11)

Geometric parameters (Å, º)

S1—O1	1.425 (2)	C7—H7F	0.9600
S1—O2	1.434 (2)	C8—H8A	0.9600
S1—N1	1.629 (1)	C8—H8B	0.9600
S1—C1	1.771 (2)	C8—H8C	0.9600
N1—C8	1.461 (3)	C9—C10	1.522 (3)
N1—C9	1.475 (3)	C9—C11	1.540 (3)
O3—C11	1.427 (3)	C9—H9A	0.9800
O3—H3B	0.8200	C10—H10A	0.9600
C1—C6	1.383 (3)	C10—H10B	0.9600
C1—C2	1.386 (3)	C10—H10C	0.9600
C2—C3	1.381 (4)	C11—C12	1.505 (3)
C2—H2A	0.9300	C11—H11A	0.9800
C3—C4	1.388 (4)	C12—C13	1.386 (4)
C3—H3A	0.9300	C12—C17	1.398 (3)
C4—C5	1.377 (5)	C13—C14	1.389 (4)
C4—C7	1.513 (4)	C13—H13A	0.9300
C5—C6	1.391 (4)	C14—C15	1.374 (5)
C5—H5A	0.9300	C14—H14A	0.9300
C6—H6A	0.9300	C15—C16	1.375 (4)
C7—H7A	0.9600	C15—H15A	0.9300
C7—H7B	0.9600	C16—C17	1.379 (4)
C7—H7C	0.9600	C16—H16A	0.9300
C7—H7D	0.9600	C17—H17B	0.9300
C7—H7E	0.9600
O1—S1—O2	119.9 (1)	H7C—C7—H7F	141.1
O1—S1—N1	107.2 (1)	H7D—C7—H7F	109.5
O2—S1—N1	107.2 (1)	H7E—C7—H7F	109.5
O1—S1—C1	106.4 (1)	N1—C8—H8A	109.5
O2—S1—C1	107.2 (1)	N1—C8—H8B	109.5
N1—S1—C1	108.5 (1)	H8A—C8—H8B	109.5
C8—N1—C9	118.4 (2)	N1—C8—H8C	109.5
C8—N1—S1	116.7 (2)	H8A—C8—H8C	109.5
C9—N1—S1	119.5 (1)	H8B—C8—H8C	109.5
C11—O3—H3B	109.5	N1—C9—C10	113.3 (2)
C6—C1—C2	120.6 (2)	N1—C9—C11	110.56 (18)
C6—C1—S1	119.72 (18)	C10—C9—C11	110.83 (17)
C2—C1—S1	119.69 (17)	N1—C9—H9A	107.3
C3—C2—C1	119.1 (2)	C10—C9—H9A	107.3
C3—C2—H2A	120.5	C11—C9—H9A	107.3
C1—C2—H2A	120.5	C9—C10—H10A	109.5
C2—C3—C4	121.7 (3)	C9—C10—H10B	109.5
C2—C3—H3A	119.1	H10A—C10—H10B	109.5
C4—C3—H3A	119.1	C9—C10—H10C	109.5
C5—C4—C3	118.1 (2)	H10A—C10—H10C	109.5
C5—C4—C7	121.3 (3)	H10B—C10—H10C	109.5
C3—C4—C7	120.6 (3)	O3—C11—C12	111.9 (2)
C4—C5—C6	121.6 (3)	O3—C11—C9	103.75 (18)
C4—C5—H5A	119.2	C12—C11—C9	114.15 (16)
C6—C5—H5A	119.2	O3—C11—H11A	108.9
C1—C6—C5	119.0 (3)	C12—C11—H11A	108.9
C1—C6—H6A	120.5	C9—C11—H11A	108.9
C5—C6—H6A	120.5	C13—C12—C17	118.6 (3)
C4—C7—H7A	109.5	C13—C12—C11	120.2 (2)
C4—C7—H7B	109.5	C17—C12—C11	121.2 (2)
H7A—C7—H7B	109.5	C12—C13—C14	120.5 (3)
C4—C7—H7C	109.5	C12—C13—H13A	119.8
H7A—C7—H7C	109.5	C14—C13—H13A	119.8
H7B—C7—H7C	109.5	C15—C14—C13	120.2 (3)
C4—C7—H7D	109.5	C15—C14—H14A	119.9
H7A—C7—H7D	141.1	C13—C14—H14A	119.9
H7B—C7—H7D	56.3	C14—C15—C16	119.8 (3)
H7C—C7—H7D	56.3	C14—C15—H15A	120.1
C4—C7—H7E	109.5	C16—C15—H15A	120.1
H7A—C7—H7E	56.3	C15—C16—C17	120.6 (3)
H7B—C7—H7E	141.1	C15—C16—H16A	119.7
H7C—C7—H7E	56.3	C17—C16—H16A	119.7
H7D—C7—H7E	109.5	C16—C17—C12	120.3 (3)
C4—C7—H7F	109.5	C16—C17—H17B	119.9
H7A—C7—H7F	56.3	C12—C17—H17B	119.9
H7B—C7—H7F	56.3
O1—S1—N1—C8	−41.8 (2)	C4—C5—C6—C1	−0.6 (4)
O2—S1—N1—C8	−171.7 (2)	C8—N1—C9—C10	−54.8 (3)
C1—S1—N1—C8	72.8 (2)	S1—N1—C9—C10	98.6 (2)
O1—S1—N1—C9	164.4 (2)	C8—N1—C9—C11	70.4 (3)
O2—S1—N1—C9	34.5 (2)	S1—N1—C9—C11	−136.3 (2)
C1—S1—N1—C9	−81.0 (2)	N1—C9—C11—O3	164.6 (2)
O1—S1—C1—C6	20.8 (2)	C10—C9—C11—O3	−68.9 (3)
O2—S1—C1—C6	150.15 (18)	N1—C9—C11—C12	42.5 (3)
N1—S1—C1—C6	−94.36 (19)	C10—C9—C11—C12	169.0 (2)
O1—S1—C1—C2	−160.79 (19)	O3—C11—C12—C13	126.5 (2)
O2—S1—C1—C2	−31.4 (2)	C9—C11—C12—C13	−116.0 (2)
N1—S1—C1—C2	84.08 (19)	O3—C11—C12—C17	−54.6 (3)
C6—C1—C2—C3	0.5 (3)	C9—C11—C12—C17	62.9 (3)
S1—C1—C2—C3	−177.94 (18)	C17—C12—C13—C14	0.4 (4)
C1—C2—C3—C4	0.0 (4)	C11—C12—C13—C14	179.4 (2)
C2—C3—C4—C5	−0.8 (4)	C12—C13—C14—C15	−1.1 (4)
C2—C3—C4—C7	178.5 (3)	C13—C14—C15—C16	1.1 (5)
C3—C4—C5—C6	1.1 (4)	C14—C15—C16—C17	−0.5 (5)
C7—C4—C5—C6	−178.2 (3)	C15—C16—C17—C12	−0.2 (4)
C2—C1—C6—C5	−0.2 (3)	C13—C12—C17—C16	0.2 (4)
S1—C1—C6—C5	178.24 (19)	C11—C12—C17—C16	−178.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2^i	0.82	2.27	3.047 (2)	158

Symmetry code: (i) x, y, z+1.