N,N′-[(1S,2S)-Cyclo­hexane-1,2-di­yl]bis­(4-methyl­benzene­sulfonamide)

Yi-Ling Hong; Hua-Jie Tan; Liang Shen

doi:10.1107/S1600536811012372

. 2011 Apr 13;67(Pt 5):o1121. doi: 10.1107/S1600536811012372

N,N′-[(1S,2S)-Cyclohexane-1,2-diyl]bis(4-methylbenzenesulfonamide)

Yi-Ling Hong ^a, Hua-Jie Tan ^a, Liang Shen ^a,^*

PMCID: PMC3089204 PMID: 21754435

Abstract

In the title compound, C₂₀H₂₆N₂O₄S₂, the cyclohexane ring has a chair conformation. The two chiral C atoms are in S configurations. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into chains propagating in [001]. Weak intermolecular C—H⋯O hydrogen bonds further stabilize the crystal packing.

Related literature

For the preparation of the title compound, see: Guo et al. (1997 ▶). For asymmetric catalysis, see: Ackermann et al. (2003 ▶); Bisai et al. (2005 ▶); Costa et al. (2005 ▶); Schwarz et al. (2010 ▶). For the crystal structures of racemates of the title compound, see: Nieger et al. (2004 ▶); Pritchett et al. (1999 ▶); Tasker et al. (2005 ▶).

Experimental

Crystal data

C₂₀H₂₆N₂O₄S₂
M _r = 422.55
Orthorhombic,
a = 11.5704 (14) Å
b = 12.2585 (15) Å
c = 15.3757 (19) Å
V = 2180.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 296 K
0.75 × 0.65 × 0.32 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.822, T _max = 0.918
9486 measured reflections
4196 independent reflections
3748 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.094
S = 1.00
4196 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 1706 Friedel pairs
Flack parameter: 0.07 (7)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia,1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012372/cv5062sup1.cif

e-67-o1121-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012372/cv5062Isup2.hkl

e-67-o1121-Isup2.hkl^{(201.5KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H101⋯O3ⁱ	0.96	2.02	2.971 (3)	171
N2—H102⋯O1ⁱⁱ	0.93	2.07	2.982 (3)	167
C11—H11⋯O4ⁱⁱⁱ	0.93	2.55	3.214 (3)	129
C9—H9⋯O1^iv	0.93	2.54	3.452 (3)	169

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We express our gratitude to the Zhejiang Provincial Natural Science Foundation of China for financial support through Project No. Y4090056.

supplementary crystallographic information

Comment

Chiral bis(sulfonamide)-based ligands have been successfully used in a variety of catalytic asymmetric transformations, such as asymmetric Diels-Alder cycloaddition, [2 + 2]cycloaddition, Claisen rearrangement, enolization-amination reactions, the cyclopropanation of allylic alcohols and the addition of alkyl groups to aldehydes. Among the above-mentioned reactions, the asymmetric addition of alkyl groups to aldehydes is one of the most efficient and highly enantioselective carbon-carbon bond forming processes (Ackermann et al., 2003; Costa et al., 2005). Bis(sulfonamide)-based ligands exhibit efficiency and enantioselectivity in the field of asymmetric synthesis, due to the robust nature of this linkage and bind well to some metals (Bisai et al., 2005; Schwarz et al., 2010). However, little was known about the structure of chiral bis(sulfonamide) ligands and, therefore, about the structure-catalytic activity relationships. Herein, we report the synthesis and crystal structure of the title compound (I) - a chiral bis(sulfonamide)-based ligand.

In (I) (Fig. 1), the C—C sigma single bond lengths in cyclohexane ring fall in the 1.478 (7) to 1.530 (3)Å range. The C1—C6 distance is 1.530 (3) Å, which is slightly longer than the corresponding distances of C1—C2 (1.508 (3) Å) and C5—C6 (1.524 (5) Å) resulting from the possible electron-withdrawing nature of the sulfonamide groups. The S1—O1 bond lengths of 1.4401 (16)Å is longer than other S1—O2 distances(1.4212 (17) Å), and S2—O3 distance (1.4376 Å) is also longer than S2—O4 bond lengths(1.4212 (19) Å). The disparity is a result of the forming of the hydrogen bonds involving O1 atom and O3. The bond lengths of S1—N1, S2—N2, S1—C7 and S2—C14 are 1.616 (19), 1.597 (2), 1.751 (3) and 1.769 (2) Å, which are comparable with these in racemic N,N'-cyclohexane-1,2-diylbis(4-methylbenzenesulfonamide) (Pritchett et al., 1999; Nieger et al., 2004; Tasker et al., 2005). The bond angles involving the O atoms involved in hydrogen-bonding, N1—S1—O1 and N2—S2—O3 are 104.81 (10) and 105.48 (11)°, respectively, while N1—S1—O2 and N2—S2—O4 are 108.82 (11) and 108.47 (12)°, respectively. The C—C—C bond angles within the cyclohexane rings are in the range 109.9 (3)–112.3 (3)°.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains propagated in [001]. Weak intermolecular C—H···O hydrogen bonds (Table 1) stabilize further the crystal packing.

Experimental

N,N'-(1S,2S)-Cyclohexane-1,2-diylbis(4- methylbenzenesulfonamide) was prepared according to literature method (Guo et al., 1997). To a stirred solution of (1S,2S)-1,2-diaminocyclohexane(1.2950 g, 11.36 mmol) in THF(100 mL) was added triethylamine(4.7 mL, 34 mmol) and the mixture was cooled to 0¯C and a solution of p-toluene sulfonyl chloride(4.3815 g, 22.72 mmol) in THF(10 mL) was added dropwise over 0.5–1 h. After the addition was complete, the mixture was allowed to warm to room temperature and stirred for 12 h. Then, the solvent removed under reduced pressure to obtain crude product. The crude product resolved in dichloromethane(10 mL), and washed with saturated sodium carbonate (13.5 mL). The aqueous solution was then extracted with dichloromethane(30 mL). The dichloromethane layers were combined, dried over anhydrous Na₂SO₄, filtered, and obtained title compound. The compound was characterized by elemental analysis, IR, 1H-NMR and MS. Yellow crystals suitable for X-ray diffraction were grown from hexane/ethyl acetate as a solvent.