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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1990.
Published online 2008 September 24. doi:  10.1107/S1600536808028948
PMCID: PMC2959308

(±)-N-(3-Hydr­oxy-1,2-diphenyl­prop­yl)-4-methyl­benzene­sulfonamide

Abstract

In the title compound, C22H23NO3S, the relative stereochemistry of the two stereogenic centres is anti with respect to the H atoms. The mol­ecular packing of the crystal shows a double-strand arrangement, consisting of one strand of (S*,S*) enanti­omers and one strand of (R*,R*) enanti­omers. Both strands lie parallel to each other along the a axis. Each strand is made up of dimers in which the mol­ecules are connected to each other via an inter­molecular O—H(...)O hydrogen bond between the hydroxyl groups and an O—H(...)π inter­action with the aromatic ring. These units are then connected to neighbouring dimers via N—H(...)O hydrogen bonds and C—H(...)O interactions. Intramolecular C—H(...)O interactions are also observed.

Related literature

For a similar organocatalytic α-oxdiation of ketones, see: Engqvist et al. (2005 [triangle]). For a related structure, see: Chinnakali et al. (2007 [triangle]).

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Object name is e-64-o1990-scheme1.jpg

Experimental

Crystal data

  • C22H23NO3S
  • M r = 381.47
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1990-efi1.jpg
  • a = 39.4702 (16) Å
  • b = 5.4270 (2) Å
  • c = 17.4287 (7) Å
  • β = 91.028 (2)°
  • V = 3732.7 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 90 (2) K
  • 0.4 × 0.16 × 0.14 mm

Data collection

  • Bruker SMART diffractometer with APEXII CCD detector
  • Absorption correction: none
  • 22582 measured reflections
  • 4478 independent reflections
  • 3763 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.193
  • S = 1.13
  • 4478 reflections
  • 245 parameters
  • 15 restraints
  • H-atom parameters constrained
  • Δρmax = 1.06 e Å−3
  • Δρmin = −0.64 e Å−3

Data collection: SMART (Siemens, 1995 [triangle]); cell refinement: SAINT (Siemens, 1995 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028948/pv2094sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028948/pv2094Isup2.hkl

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

Acknowledgments

The authors thank Tania Groutso for the data collection. The awards of an International Doctoral Scholarship from the University of Auckland and a New Zealand International Doctoral Research Scholarship from Education New Zealand (to STT) are greatly appreciated.

supplementary crystallographic information

Comment

The title racemic sulfonamide was obtained unintentionally as a product from the study of the organocatalytic α-oxidation of phenylacetaldehyde catalysed by (S)-proline. The relative stereochemistry of the two stereogenic centres was established by X-ray crystallography as anti with respect to the H atoms of C8 and C15 (Fig. 1).

The molecular packing of the crystal shows a double strand arrangement, which consists of one strand of (8S*,15S*) enantiomers and one strand of (8R*,15R*) enantiomers. Both strands lie parallel to each other along the a axis and a number of hydrogen bonds has been observed throughtout the crystal lattice.

Each strand is made up of homodimeric units in which the sulfonamide molecules are connected to each other by intermolecular hydrogen bonds between the hydroxyl groups (O3—H3···O3) as well as the O—H···π interaction with the aromatic ring. The dimer is, in turn, linked to the next dimer along the strand via non-conventional hydrogen bonds (C1—H1A···O2—S1 and C1—H1B···O2—S1). Finally, neighbouring strand of the same stereochemistry are connected to each other via conventional (N1—H1···O1—S1) and non-conventional (C1—H1A···O2—S1 and C1—H1B···O2—S1) hydrogen bonds (Fig. 2).

Non-conventional intramolecular hydrogen interactions (C4—H4···O1—S1 and C8—H8···O1—S1) are also observed with a distance of 2.55 and 2.61 Å between the hydrogen and the acceptor oxygen (Table 1).

Experimental

To a solution of 3-phenyl-2-tosyl-1,2-oxaziridine (551 mg, 2.00 mmol) in distilled THF (8 ml) was added under ambient atmosphere (S)-proline (69.1 mg, 0.600 mmol). After 5 minutes, phenylacetaldehyde (0.450 ml, 4.00 mmol) was added. After 1 h, sodium borohydride (151 mg, 4.00 mmol) was added to the mixture at 273 K and the mixture was stirred overnight. The mixture was then poured onto a biphasic mixture of HCl (1 mol l-1) and EtOAc (1:1, 8 ml) at 273 K and vigorously stirred for 10 minutes. The organic phase was separated and the aqueous phase was extracted with EtOAc (8 ml x 4). The combined organic extracts were washed with brine, dried over MgSO4 and concentrated in vacuo to afford a yellow oil. Purification by flash chromatography using hexane–EtOAc (2:1 to 1:1) as eluent yielded the title sulfonamide as a white solid (6%). Recrystallization of the title sulfonamide in hexane–CH2Cl2 (4:1) afforded colourless needles.

Refinement

Hydrogen atoms attached to carbon and nitrogen atoms were placed in calculated positions and refined using the riding model (N—H = 0.86 Å & C—H 0.93–0.97 Å), with Uiso(H) = 1.2 and 1.5Ueq(parent atom) for the nonmethyl and methyl groups, respectively. The hydroxyl H-atom was disordered over two sites involved in either O—H···O hydrogen bonding to a neighboring alcohol or O—H···π interactions with a neighboring phenyl ring. In the final refinement these two hydrogen atoms were included, fixed in these two positions. After the final refinement a peak of electron density of 1.05 e Å-3, distanced 0.82 Å from the sulfonamide oxygen O2, was observed. No evidence of disorder could be discerned. This peak was also present in an alternate refinement using data that had been corrected for absorption. This refinement was indistinguishable from structure presented here.

Figures

Fig. 1.
The molecular structure and atom numbering scheme of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms.
Fig. 2.
The unit cell packing of the title compound showing double strands of (8S*,15S*) and (8R*,15R*) enantiomers. A third strand of (8S*,15S*) sulfonamide (dimmed) which is positioned below the unit cell is also depicted in the figure to show the hydrogen ...

Crystal data

C22H23NO3SDx = 1.358 Mg m3
Mr = 381.47Melting point: 426.7(8) K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 39.4702 (16) ÅCell parameters from 6191 reflections
b = 5.4270 (2) Åθ = 1.0–28.0°
c = 17.4287 (7) ŵ = 0.20 mm1
β = 91.028 (2)°T = 90 K
V = 3732.7 (3) Å3Needle, colourless
Z = 80.4 × 0.16 × 0.14 mm
F(000) = 1616

Data collection

Bruker SMART diffractometer with APEXII CCD detector3763 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
graphiteθmax = 28.0°, θmin = 1.0°
ω scansh = −51→51
22582 measured reflectionsk = −7→7
4478 independent reflectionsl = −22→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.193H-atom parameters constrained
S = 1.13w = 1/[σ2(Fo2) + (0.0794P)2 + 19.2449P] where P = (Fo2 + 2Fc2)/3
4478 reflections(Δ/σ)max < 0.001
245 parametersΔρmax = 1.06 e Å3
15 restraintsΔρmin = −0.64 e Å3

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 (Å2)

xyzUiso*/UeqOcc. (<1)
S10.158723 (16)0.06828 (12)0.28375 (4)0.01431 (19)
O10.14448 (5)−0.1745 (4)0.27404 (12)0.0186 (4)
O20.17401 (5)0.1376 (4)0.35572 (11)0.0209 (5)
O30.02222 (6)0.6152 (6)0.18428 (13)0.0382 (7)
H3A0.00920.61560.22290.057*0.50
H3B0.00080.59060.17990.057*0.50
N10.12844 (6)0.2624 (4)0.26835 (13)0.0150 (5)
H10.12830.39590.29490.018*
C50.19060 (7)0.1017 (5)0.21504 (15)0.0138 (5)
C150.07339 (7)0.4164 (5)0.23044 (15)0.0154 (5)
H150.08430.57880.23130.019*
C60.21262 (7)0.3020 (5)0.22046 (16)0.0178 (6)
H60.20900.42530.25640.021*
C210.06575 (7)0.5353 (6)0.36894 (17)0.0185 (6)
H210.07860.67530.35970.022*
C20.24609 (7)0.1333 (5)0.11774 (16)0.0170 (5)
C160.05938 (6)0.3698 (5)0.30955 (15)0.0150 (5)
C100.10495 (7)0.0475 (5)0.07735 (16)0.0182 (6)
H100.0919−0.08550.09280.022*
C220.04555 (7)0.4221 (6)0.16845 (16)0.0231 (6)
H22A0.05550.44870.11870.028*
H22B0.03380.26530.16720.028*
C170.04036 (7)0.1590 (5)0.32496 (17)0.0194 (6)
H170.03610.04510.28610.023*
C140.13191 (7)0.4350 (5)0.10406 (16)0.0176 (6)
H140.13690.56350.13770.021*
C80.10096 (6)0.2233 (5)0.21110 (14)0.0133 (5)
H80.09140.05910.21960.016*
C90.11285 (6)0.2352 (5)0.12954 (15)0.0142 (5)
C130.14347 (7)0.4453 (6)0.02985 (17)0.0200 (6)
H130.15630.57910.01410.024*
C30.22313 (8)−0.0595 (6)0.11139 (18)0.0235 (6)
H30.2263−0.17930.07400.028*
C40.19557 (7)−0.0777 (6)0.15959 (18)0.0213 (6)
H40.1806−0.20920.15470.026*
C110.11646 (8)0.0577 (6)0.00254 (17)0.0221 (6)
H110.1111−0.0685−0.03160.027*
C190.03415 (8)0.2868 (6)0.45638 (17)0.0235 (6)
H190.02570.26010.50510.028*
C70.24002 (7)0.3160 (6)0.17183 (16)0.0193 (6)
H70.25460.45020.17550.023*
C120.13588 (7)0.2554 (6)−0.02141 (16)0.0205 (6)
H120.14380.2611−0.07130.025*
C200.05321 (8)0.4953 (6)0.44183 (17)0.0230 (6)
H200.05760.60850.48080.028*
C180.02775 (7)0.1177 (6)0.39810 (18)0.0222 (6)
H180.0151−0.02290.40780.027*
C10.27747 (7)0.1382 (6)0.06967 (18)0.0231 (6)
H1A0.29450.03380.09260.035*
H1B0.28590.30390.06690.035*
H1C0.27200.08010.01890.035*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0145 (3)0.0139 (3)0.0144 (3)0.0006 (2)−0.0002 (2)0.0022 (2)
O10.0180 (9)0.0144 (10)0.0235 (10)−0.0022 (8)0.0015 (7)0.0024 (8)
O20.0228 (10)0.0240 (11)0.0157 (10)−0.0013 (8)−0.0030 (7)0.0036 (8)
O30.0277 (12)0.0627 (18)0.0240 (12)0.0281 (13)−0.0033 (9)−0.0032 (12)
N10.0165 (11)0.0146 (11)0.0137 (10)0.0022 (9)−0.0020 (8)−0.0027 (9)
C50.0145 (12)0.0117 (12)0.0152 (12)0.0015 (10)−0.0017 (9)0.0012 (10)
C150.0172 (12)0.0137 (13)0.0154 (12)0.0023 (10)0.0018 (9)0.0000 (10)
C60.0231 (13)0.0142 (13)0.0162 (12)−0.0019 (11)−0.0006 (10)−0.0021 (10)
C210.0176 (13)0.0172 (14)0.0206 (14)−0.0016 (11)−0.0003 (10)0.0011 (11)
C20.0156 (12)0.0180 (14)0.0174 (13)0.0015 (10)−0.0015 (9)0.0038 (11)
C160.0131 (11)0.0150 (13)0.0169 (13)0.0033 (10)0.0014 (9)0.0014 (10)
C100.0206 (13)0.0148 (13)0.0191 (13)−0.0010 (11)−0.0010 (10)−0.0024 (11)
C220.0188 (13)0.0355 (18)0.0152 (13)0.0079 (12)0.0006 (10)−0.0009 (12)
C170.0209 (13)0.0151 (14)0.0221 (14)0.0009 (11)0.0003 (10)−0.0006 (11)
C140.0187 (13)0.0177 (14)0.0165 (13)−0.0011 (11)0.0005 (10)−0.0034 (11)
C80.0151 (12)0.0125 (12)0.0123 (12)0.0001 (10)−0.0006 (9)−0.0012 (10)
C90.0124 (11)0.0144 (13)0.0158 (12)0.0021 (10)−0.0009 (9)−0.0016 (10)
C130.0189 (13)0.0205 (14)0.0206 (14)−0.0010 (11)0.0034 (10)0.0003 (11)
C30.0268 (15)0.0190 (15)0.0251 (15)−0.0022 (12)0.0069 (12)−0.0067 (12)
C40.0208 (14)0.0169 (14)0.0262 (15)−0.0059 (11)0.0034 (11)−0.0064 (12)
C110.0285 (15)0.0198 (15)0.0180 (14)0.0032 (12)−0.0019 (11)−0.0074 (11)
C190.0239 (14)0.0286 (17)0.0183 (13)0.0051 (12)0.0063 (11)0.0065 (12)
C70.0195 (13)0.0168 (14)0.0213 (14)−0.0057 (11)−0.0016 (10)0.0013 (11)
C120.0200 (13)0.0288 (16)0.0129 (12)0.0047 (12)0.0029 (10)−0.0011 (11)
C200.0304 (16)0.0231 (15)0.0155 (13)0.0014 (12)0.0008 (11)−0.0009 (12)
C180.0197 (14)0.0179 (14)0.0291 (15)0.0008 (11)0.0037 (11)0.0065 (12)
C10.0191 (13)0.0259 (16)0.0245 (15)0.0008 (12)0.0032 (11)0.0053 (13)

Geometric parameters (Å, °)

S1—O21.432 (2)C22—H22A0.9700
S1—O11.441 (2)C22—H22B0.9700
S1—N11.612 (2)C17—C181.395 (4)
S1—C51.762 (3)C17—H170.9300
O3—C221.425 (4)C14—C131.381 (4)
O3—H3A0.8541C14—C91.397 (4)
O3—H3B0.8579C14—H140.9300
N1—C81.476 (3)C8—C91.506 (3)
N1—H10.8600C8—H80.9800
C5—C41.389 (4)C13—C121.393 (4)
C5—C61.394 (4)C13—H130.9300
C15—C161.516 (4)C3—C41.390 (4)
C15—C221.528 (4)C3—H30.9300
C15—C81.552 (4)C4—H40.9300
C15—H150.9800C11—C121.387 (4)
C6—C71.388 (4)C11—H110.9300
C6—H60.9300C19—C201.384 (5)
C21—C201.389 (4)C19—C181.389 (5)
C21—C161.390 (4)C19—H190.9300
C21—H210.9300C7—H70.9300
C2—C31.387 (4)C12—H120.9300
C2—C71.392 (4)C20—H200.9300
C2—C11.508 (4)C18—H180.9300
C16—C171.397 (4)C1—H1A0.9600
C10—C111.389 (4)C1—H1B0.9600
C10—C91.397 (4)C1—H1C0.9600
C10—H100.9300
O2—S1—O1120.01 (13)C13—C14—C9121.2 (3)
O2—S1—N1105.87 (13)C13—C14—H14119.4
O1—S1—N1106.94 (12)C9—C14—H14119.4
O2—S1—C5105.87 (12)N1—C8—C9113.2 (2)
O1—S1—C5107.24 (12)N1—C8—C15105.4 (2)
N1—S1—C5110.85 (12)C9—C8—C15114.1 (2)
C22—O3—H3A123.7N1—C8—H8108.0
C22—O3—H3B120.5C9—C8—H8108.0
H3A—O3—H3B57.6C15—C8—H8108.0
C8—N1—S1123.52 (19)C14—C9—C10118.3 (3)
C8—N1—H1118.2C14—C9—C8120.8 (2)
S1—N1—H1118.2C10—C9—C8120.9 (2)
C4—C5—C6119.9 (3)C14—C13—C12120.0 (3)
C4—C5—S1120.8 (2)C14—C13—H13120.0
C6—C5—S1119.1 (2)C12—C13—H13120.0
C16—C15—C22112.2 (2)C2—C3—C4121.5 (3)
C16—C15—C8110.7 (2)C2—C3—H3119.2
C22—C15—C8111.0 (2)C4—C3—H3119.2
C16—C15—H15107.6C5—C4—C3119.5 (3)
C22—C15—H15107.6C5—C4—H4120.2
C8—C15—H15107.6C3—C4—H4120.2
C7—C6—C5119.6 (3)C12—C11—C10120.3 (3)
C7—C6—H6120.2C12—C11—H11119.8
C5—C6—H6120.2C10—C11—H11119.8
C20—C21—C16121.2 (3)C20—C19—C18119.9 (3)
C20—C21—H21119.4C20—C19—H19120.1
C16—C21—H21119.4C18—C19—H19120.1
C3—C2—C7118.1 (3)C6—C7—C2121.3 (3)
C3—C2—C1120.7 (3)C6—C7—H7119.3
C7—C2—C1121.1 (3)C2—C7—H7119.3
C21—C16—C17118.5 (3)C11—C12—C13119.5 (3)
C21—C16—C15120.4 (3)C11—C12—H12120.2
C17—C16—C15121.2 (3)C13—C12—H12120.2
C11—C10—C9120.6 (3)C19—C20—C21119.9 (3)
C11—C10—H10119.7C19—C20—H20120.0
C9—C10—H10119.7C21—C20—H20120.0
O3—C22—C15109.7 (2)C19—C18—C17120.0 (3)
O3—C22—H22A109.7C19—C18—H18120.0
C15—C22—H22A109.7C17—C18—H18120.0
O3—C22—H22B109.7C2—C1—H1A109.5
C15—C22—H22B109.7C2—C1—H1B109.5
H22A—C22—H22B108.2H1A—C1—H1B109.5
C18—C17—C16120.6 (3)C2—C1—H1C109.5
C18—C17—H17119.7H1A—C1—H1C109.5
C16—C17—H17119.7H1B—C1—H1C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.453.122 (3)136.
O3—H3A···O3ii0.852.062.910 (5)179.7
C4—H4···O10.932.552.909 (4)104.
C8—H8···O10.982.612.958 (3)101.
C1—H1A···O2iii0.962.633.557 (4)161.
C1—H1B···O2iv0.962.743.552 (4)142.
O3—H3B···C16ii0.862.673.489 (4)160.1
O3—H3B···C17ii0.862.853.499 (4)133.7

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2094).

References

  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
  • Chinnakali, K., Poornachandran, M., Raghunathan, R. & Fun, H.-K. (2007). Acta Cryst. E63, o1030–o1031.
  • Engqvist, M., Casas, J., Sunden, H., Ibrahem, I. & Cordova, A. (2005). Tetrahedron Lett.46, 2053–2057.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1995). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography