(1R,2S)-3-Methyl-2-(p-methyl­phenyl­sulfonyl­amino)-1-phenyl­butan-1-ol

In the crystal structure of the title compound, C₁₈H₂₃NO₃, the mol­ecules are linked by intermolecular N—H...O and O—H...O hydrogen bonds to form sheet-like structures perpendicular to the c cell direction.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.089
• Data-to-parameter ratio = 19.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.55
         From the CIF: _reflns_number_total               3952
         Count of symmetry unique reflns         2308
         Completeness (_total/calc)            171.23%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1644
         Fraction of Friedel pairs measured     0.712
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

S1. Comment

Chiral sulfonamides, derived from amino alcohols, have been investigated as chiral ligands for the reduction of prochiral ketones (Hu et al., 2001; Otsuka et al., 1995), enantioselective copper catalyzed 1,4-addition of diethylzinc to cyclohexenone (Wendisch & Sewald, 1997), asymmetric trialkylaluminum and diethylzinc addition to aldehydes catalyzed by titanium complexes (You et al., 2001; Ito et al., 1992), ruthenium-catalyzed asymmetric transfer hydrogenation of functionlized ketones (Everaere et al., 2001), and enantioselective trimethylsilylcyanation of aldehydes (You et al., 2000). It is known that the differences in ligand structures strongly influence the enantioselectivity of the reaction. For amino alcohols and their derivatives, the ligands with two stereocenters usually give better enantioselectivity than the ligands with one stereocenter. Further more, the ligands with R,S configuration are more effective for asymmetric reaction than the S,S diastereomers (You et al., 2000, 2001). As there is only one stereocenter in most amino alcohols derived from natural amino acids, it is of interest to develop new amino alcohols and their derivatives with two stereo centers for studying their structure and application in asymmetric reaction. Herein we report the preparation and crystal structure of (1R,2S)-3-methyl-2-(p-methylphenylsulfonylamino)-1-phenylbutan-1-ol, (I).

The structure observed for (I) is shown in Fig 1. As the starting material used for the synthesis of (I) is L-valine, it is reasonable that the configuration of C1 is S. The new chiral carbon atom C2 is in the R configuration. An intramolecular C—H···π contact is noted in the structure so that C17—H17A is 2.74 Å from the ring centroid of C3–C8 with an angle at H17A of 127°. In the crystal, the molecules translated along the a-cell direction are linked through N—H···O hydrogen bonds (Table 1) to form infinite one-dimensional molecular chains and these are interlinked by O—H···O hydrogen bonds to form a two-dimensional molecular network (Fig. 2).

S2. Experimental

The mixture of (R,S)- and (S,S)-2-amino-3-methyl-1-phenyl-butan-1-ol were prepared by using the route described in literature (Reetz et al., 1987) and were used without separation (the ratio of R,S to S,S is 87 to 13, estimated by 1HNMR analysis). p-Toluenesulfonyl chloride (0.21 g, 1.1 mmol) and triethylamine (1.5 mmol) were added to the solution of amino alcohol (0.18 g, 1 mmol) in 30 ml of dichloromethane. After the mixture was stirred at 273 K for 2 h and then at room temperature for 6 h, water (15 ml) was added and the organic layer was separated. The aqueous layer was extracted with dichloromethane (3 × 15 ml). The combined organic phase was washed with brine, dried over Na₂SO₄ and the solvents were removed in reduced pressure. The crude products were purified by flash chromatography and crystallized in dichloromethane and hexane to afford the (R,S)-2-amino-3-methyl-1-phenyl-butan-1-ol (0.21 g, 63% yield).

S3. Refinement

All H atoms were geometrically fixed and allowed to ride on the atoms to which they are attached.

Computing details

Data collection: SMART (Bruker, 1995); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Packing of the molecules viewed down the c axis.

(1R,2S)-3-Methyl-2-(p-methylphenylsulfonylamino)-1-phenylbutan-1-ol

Crystal data

C18H23NO3S	Dx = 1.290 Mg m^−3
Mr = 333.43	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3782 reflections
a = 5.7407 (6) Å	θ = 1–27.5°
b = 13.0939 (14) Å	µ = 0.20 mm^−1
c = 22.846 (2) Å	T = 294 K
V = 1717.3 (3) Å^3	Block, colorless
Z = 4	0.24 × 0.20 × 0.12 mm
F(000) = 712

Data collection

Bruker CCD Area Detector diffractometer	3952 independent reflections
Radiation source: fine-focus sealed tube	2225 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
ϕ and ω scans	θmax = 27.6°, θmin = 3.1°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.953, Tmax = 0.976	k = −16→17
11860 measured reflections	l = −24→29

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)] = 0.045	Riding
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.03P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max < 0.001
3952 reflections	Δρmax = 0.22 e Å^−3
208 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (9)

Special details

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
S1	0.56193 (12)	0.64985 (5)	0.19743 (3)	0.03707 (18)
O1	1.1936 (3)	0.40088 (15)	0.23822 (8)	0.0510 (6)
H1A	1.2192	0.3487	0.2570	0.077*
O2	0.7680 (3)	0.71264 (13)	0.19693 (8)	0.0446 (5)
O3	0.3652 (3)	0.68540 (14)	0.23001 (8)	0.0504 (5)
N1	0.6395 (4)	0.53862 (15)	0.21918 (8)	0.0354 (6)
H1B	0.5389	0.4903	0.2162	0.042*
C1	0.8692 (4)	0.5123 (2)	0.24380 (10)	0.0344 (7)
H1C	0.9813	0.5619	0.2284	0.041*
C2	0.9494 (5)	0.40579 (19)	0.22344 (11)	0.0368 (6)
H2B	0.8664	0.3543	0.2465	0.044*
C3	0.9113 (5)	0.38307 (19)	0.15951 (12)	0.0374 (7)
C4	0.7096 (5)	0.3352 (2)	0.14207 (13)	0.0501 (8)
H4A	0.5978	0.3183	0.1699	0.060*
C5	0.6701 (6)	0.3117 (2)	0.08365 (14)	0.0616 (10)
H5A	0.5315	0.2806	0.0724	0.074*
C6	0.8363 (7)	0.3346 (3)	0.04267 (14)	0.0654 (10)
H6A	0.8118	0.3178	0.0036	0.078*
C7	1.0390 (6)	0.3822 (2)	0.05911 (14)	0.0615 (9)
H7A	1.1503	0.3988	0.0311	0.074*
C8	1.0778 (5)	0.4056 (2)	0.11738 (12)	0.0474 (7)
H8A	1.2166	0.4368	0.1284	0.057*
C9	0.8739 (5)	0.5215 (2)	0.31081 (11)	0.0462 (7)
H9A	1.0211	0.4914	0.3240	0.055*
C10	0.8732 (7)	0.6317 (3)	0.33145 (13)	0.0778 (11)
H10A	0.8758	0.6334	0.3735	0.117*
H10B	0.7351	0.6651	0.3175	0.117*
H10C	1.0081	0.6661	0.3164	0.117*
C11	0.6800 (6)	0.4621 (3)	0.34030 (13)	0.0755 (11)
H11A	0.6930	0.4693	0.3820	0.113*
H11B	0.6922	0.3913	0.3300	0.113*
H11C	0.5320	0.4882	0.3276	0.113*
C12	0.4688 (4)	0.63533 (19)	0.12435 (11)	0.0352 (6)
C13	0.2579 (5)	0.6742 (2)	0.10686 (12)	0.0453 (8)
H13A	0.1593	0.7051	0.1339	0.054*
C14	0.1937 (5)	0.6671 (2)	0.04886 (13)	0.0517 (8)
H14A	0.0510	0.6938	0.0372	0.062*
C15	0.3346 (6)	0.6217 (2)	0.00783 (12)	0.0503 (9)
C16	0.5444 (6)	0.5820 (2)	0.02646 (12)	0.0534 (8)
H16A	0.6416	0.5502	−0.0005	0.064*
C17	0.6132 (5)	0.5884 (2)	0.08412 (12)	0.0454 (8)
H17A	0.7555	0.5613	0.0959	0.055*
C18	0.2583 (6)	0.6113 (3)	−0.05538 (13)	0.0811 (12)
H18A	0.1086	0.6429	−0.0604	0.122*
H18B	0.2480	0.5403	−0.0655	0.122*
H18C	0.3698	0.6442	−0.0804	0.122*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0363 (4)	0.0354 (4)	0.0395 (4)	0.0024 (4)	−0.0007 (4)	−0.0023 (3)
O1	0.0383 (12)	0.0489 (13)	0.0660 (14)	0.0020 (10)	−0.0122 (11)	0.0113 (11)
O2	0.0450 (11)	0.0342 (11)	0.0546 (12)	−0.0062 (9)	−0.0091 (11)	−0.0013 (10)
O3	0.0488 (12)	0.0535 (14)	0.0490 (11)	0.0157 (10)	0.0062 (10)	−0.0082 (9)
N1	0.0318 (13)	0.0300 (12)	0.0443 (13)	−0.0027 (10)	−0.0062 (10)	−0.0005 (10)
C1	0.0307 (15)	0.0368 (16)	0.0356 (16)	−0.0030 (12)	−0.0020 (13)	0.0038 (12)
C2	0.0312 (15)	0.0344 (16)	0.0448 (17)	0.0010 (14)	−0.0033 (14)	0.0030 (13)
C3	0.0336 (17)	0.0311 (16)	0.0476 (17)	0.0045 (14)	0.0013 (16)	−0.0024 (12)
C4	0.0442 (19)	0.052 (2)	0.054 (2)	−0.0021 (17)	0.0048 (15)	−0.0114 (16)
C5	0.050 (2)	0.066 (2)	0.069 (2)	0.0006 (17)	−0.0057 (19)	−0.0276 (19)
C6	0.073 (3)	0.071 (3)	0.052 (2)	0.010 (2)	0.000 (2)	−0.0198 (18)
C7	0.064 (2)	0.063 (2)	0.058 (2)	0.012 (2)	0.013 (2)	−0.0052 (17)
C8	0.0416 (18)	0.0438 (17)	0.057 (2)	0.0009 (17)	0.0039 (18)	−0.0010 (14)
C9	0.0494 (19)	0.0530 (19)	0.0362 (17)	−0.0007 (15)	−0.0073 (15)	0.0047 (14)
C10	0.116 (3)	0.068 (3)	0.049 (2)	−0.014 (2)	−0.003 (2)	−0.0150 (16)
C11	0.086 (3)	0.092 (3)	0.049 (2)	−0.015 (2)	0.010 (2)	0.010 (2)
C12	0.0316 (15)	0.0358 (16)	0.0382 (16)	0.0004 (14)	−0.0025 (13)	0.0022 (12)
C13	0.0396 (17)	0.049 (2)	0.0477 (19)	0.0028 (15)	0.0019 (15)	0.0048 (14)
C14	0.0394 (18)	0.060 (2)	0.055 (2)	0.0081 (17)	−0.0106 (16)	0.0095 (17)
C15	0.054 (2)	0.055 (2)	0.0421 (19)	−0.0066 (17)	−0.0120 (17)	0.0039 (15)
C16	0.057 (2)	0.064 (2)	0.0390 (19)	0.009 (2)	0.0028 (17)	0.0003 (15)
C17	0.0405 (18)	0.0540 (19)	0.0417 (18)	0.0072 (16)	0.0003 (16)	0.0047 (14)
C18	0.083 (3)	0.109 (3)	0.051 (2)	0.000 (3)	−0.0253 (19)	−0.001 (2)

Geometric parameters (Å, º)

S1—O3	1.4306 (18)	C9—C11	1.516 (4)
S1—O2	1.4408 (17)	C9—C10	1.517 (4)
S1—N1	1.602 (2)	C9—H9A	0.98
S1—C12	1.763 (3)	C10—H10A	0.96
O1—C2	1.443 (3)	C10—H10B	0.96
O1—H1A	0.82	C10—H10C	0.96
N1—C1	1.474 (3)	C11—H11A	0.96
N1—H1B	0.86	C11—H11B	0.96
C1—C9	1.536 (3)	C11—H11C	0.96
C1—C2	1.541 (3)	C12—C13	1.372 (3)
C1—H1C	0.98	C12—C17	1.382 (3)
C2—C3	1.506 (3)	C13—C14	1.379 (3)
C2—H2B	0.98	C13—H13A	0.93
C3—C4	1.376 (4)	C14—C15	1.373 (4)
C3—C8	1.388 (3)	C14—H14A	0.93
C4—C5	1.388 (4)	C15—C16	1.379 (4)
C4—H4A	0.93	C15—C18	1.515 (4)
C5—C6	1.370 (4)	C16—C17	1.378 (3)
C5—H5A	0.93	C16—H16A	0.93
C6—C7	1.373 (4)	C17—H17A	0.93
C6—H6A	0.93	C18—H18A	0.96
C7—C8	1.384 (4)	C18—H18B	0.96
C7—H7A	0.93	C18—H18C	0.96
C8—H8A	0.93
O3—S1—O2	117.84 (11)	C11—C9—C1	112.9 (2)
O3—S1—N1	110.74 (11)	C10—C9—C1	112.6 (2)
O2—S1—N1	107.03 (11)	C11—C9—H9A	106.9
O3—S1—C12	106.74 (12)	C10—C9—H9A	106.9
O2—S1—C12	107.64 (12)	C1—C9—H9A	106.9
N1—S1—C12	106.26 (11)	C9—C10—H10A	109.5
C2—O1—H1A	109.5	C9—C10—H10B	109.5
C1—N1—S1	125.41 (17)	H10A—C10—H10B	109.5
C1—N1—H1B	117.3	C9—C10—H10C	109.5
S1—N1—H1B	117.3	H10A—C10—H10C	109.5
N1—C1—C9	112.2 (2)	H10B—C10—H10C	109.5
N1—C1—C2	111.3 (2)	C9—C11—H11A	109.5
C9—C1—C2	111.5 (2)	C9—C11—H11B	109.5
N1—C1—H1C	107.2	H11A—C11—H11B	109.5
C9—C1—H1C	107.2	C9—C11—H11C	109.5
C2—C1—H1C	107.2	H11A—C11—H11C	109.5
O1—C2—C3	111.0 (2)	H11B—C11—H11C	109.5
O1—C2—C1	105.1 (2)	C13—C12—C17	120.0 (3)
C3—C2—C1	115.3 (2)	C13—C12—S1	120.2 (2)
O1—C2—H2B	108.4	C17—C12—S1	119.7 (2)
C3—C2—H2B	108.4	C12—C13—C14	119.4 (3)
C1—C2—H2B	108.4	C12—C13—H13A	120.3
C4—C3—C8	118.4 (3)	C14—C13—H13A	120.3
C4—C3—C2	119.5 (3)	C15—C14—C13	121.9 (3)
C8—C3—C2	122.0 (3)	C15—C14—H14A	119.1
C3—C4—C5	121.1 (3)	C13—C14—H14A	119.1
C3—C4—H4A	119.4	C14—C15—C16	117.8 (3)
C5—C4—H4A	119.4	C14—C15—C18	121.3 (3)
C6—C5—C4	119.6 (3)	C16—C15—C18	120.9 (3)
C6—C5—H5A	120.2	C17—C16—C15	121.5 (3)
C4—C5—H5A	120.2	C17—C16—H16A	119.2
C5—C6—C7	120.2 (3)	C15—C16—H16A	119.2
C5—C6—H6A	119.9	C16—C17—C12	119.4 (3)
C7—C6—H6A	119.9	C16—C17—H17A	120.3
C6—C7—C8	120.0 (3)	C12—C17—H17A	120.3
C6—C7—H7A	120.0	C15—C18—H18A	109.5
C8—C7—H7A	120.0	C15—C18—H18B	109.5
C7—C8—C3	120.6 (3)	H18A—C18—H18B	109.5
C7—C8—H8A	119.7	C15—C18—H18C	109.5
C3—C8—H8A	119.7	H18A—C18—H18C	109.5
C11—C9—C10	110.3 (3)	H18B—C18—H18C	109.5
O3—S1—N1—C1	−119.78 (19)	N1—C1—C9—C11	52.9 (3)
O2—S1—N1—C1	9.9 (2)	C2—C1—C9—C11	−72.8 (3)
C12—S1—N1—C1	124.67 (19)	N1—C1—C9—C10	−72.9 (3)
S1—N1—C1—C9	91.8 (2)	C2—C1—C9—C10	161.4 (3)
S1—N1—C1—C2	−142.43 (19)	O3—S1—C12—C13	11.6 (3)
N1—C1—C2—O1	166.25 (19)	O2—S1—C12—C13	−115.7 (2)
C9—C1—C2—O1	−67.6 (3)	N1—S1—C12—C13	129.9 (2)
N1—C1—C2—C3	43.6 (3)	O3—S1—C12—C17	−171.0 (2)
C9—C1—C2—C3	169.8 (2)	O2—S1—C12—C17	61.6 (2)
O1—C2—C3—C4	147.9 (2)	N1—S1—C12—C17	−52.8 (2)
C1—C2—C3—C4	−92.7 (3)	C17—C12—C13—C14	−0.9 (4)
O1—C2—C3—C8	−29.7 (3)	S1—C12—C13—C14	176.4 (2)
C1—C2—C3—C8	89.7 (3)	C12—C13—C14—C15	0.3 (5)
C8—C3—C4—C5	−1.3 (4)	C13—C14—C15—C16	0.5 (5)
C2—C3—C4—C5	−179.0 (3)	C13—C14—C15—C18	178.0 (3)
C3—C4—C5—C6	1.3 (5)	C14—C15—C16—C17	−0.8 (4)
C4—C5—C6—C7	−1.2 (5)	C18—C15—C16—C17	−178.2 (3)
C5—C6—C7—C8	1.2 (5)	C15—C16—C17—C12	0.2 (4)
C6—C7—C8—C3	−1.2 (5)	C13—C12—C17—C16	0.6 (4)
C4—C3—C8—C7	1.3 (4)	S1—C12—C17—C16	−176.7 (2)
C2—C3—C8—C7	178.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2^i	0.82	2.07	2.884 (3)	172
N1—H1B···O1^ii	0.86	2.36	3.162 (3)	156

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