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

Hong, Y.-L.; Tan, H.-J.; Shen, L.

doi:10.1107/S1600536811012372

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1121

doi:10.1107/S1600536811012372

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

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

^aCollege of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, People's Republic of China
^*Correspondence e-mail: shenchem@hotmail.com

(Received 17 March 2011; accepted 3 April 2011; online 13 April 2011)

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, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.035
wR(F²) = 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)

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
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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).

Figures top

Fig. 1. Molecular structure of (I) showing 40% probability displacement ellipsoids.

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

Crystal data top

C₂₀H₂₆N₂O₄S₂	F(000) = 896
M_r = 422.55	D_x = 1.287 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5610 reflections
a = 11.5704 (14) Å	θ = 2.2–27.4°
b = 12.2585 (15) Å	µ = 0.27 mm⁻¹
c = 15.3757 (19) Å	T = 296 K
V = 2180.8 (5) Å³	Chunk, yellow
Z = 4	0.75 × 0.65 × 0.32 mm

Data collection top

Bruker SMART CCD diffractometer	4196 independent reflections
Radiation source: fine-focus sealed tube	3748 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.822, T_max = 0.918	k = −15→7
9486 measured reflections	l = −18→17

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0445P)² + 0.4906P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.18 e Å⁻³
4196 reflections	Δρ_min = −0.24 e Å⁻³
256 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0129 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1706 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.07 (7)

Crystal data top

C₂₀H₂₆N₂O₄S₂	V = 2180.8 (5) Å³
M_r = 422.55	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 11.5704 (14) Å	µ = 0.27 mm⁻¹
b = 12.2585 (15) Å	T = 296 K
c = 15.3757 (19) Å	0.75 × 0.65 × 0.32 mm

Data collection top

Bruker SMART CCD diffractometer	4196 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3748 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.918	R_int = 0.021
9486 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	Δρ_max = 0.18 e Å⁻³
S = 1.00	Δρ_min = −0.24 e Å⁻³
4196 reflections	Absolute structure: Flack (1983), 1706 Friedel pairs
256 parameters	Absolute structure parameter: 0.07 (7)
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
S2	0.67936 (6)	0.34616 (4)	0.33373 (4)	0.05778 (17)
S1	0.62809 (5)	0.40875 (4)	0.66645 (3)	0.05630 (16)
C14	0.54709 (19)	0.41739 (18)	0.34420 (13)	0.0522 (5)
O1	0.66322 (17)	0.40834 (14)	0.75630 (9)	0.0696 (5)
O4	0.6663 (2)	0.24457 (14)	0.37717 (13)	0.0815 (6)
C7	0.4973 (2)	0.48007 (17)	0.65910 (13)	0.0546 (5)
O3	0.70891 (17)	0.34735 (14)	0.24292 (10)	0.0691 (5)
N2	0.77908 (17)	0.41378 (18)	0.38123 (10)	0.0600 (5)
H102	0.8017	0.4755	0.3500	0.090*
N1	0.72602 (17)	0.47945 (16)	0.61697 (10)	0.0553 (5)
H101	0.7469	0.5406	0.6526	0.083*
O2	0.61429 (19)	0.30761 (13)	0.62249 (11)	0.0717 (5)
C1	0.71703 (19)	0.49569 (17)	0.52189 (12)	0.0486 (5)
H1	0.6373	0.4812	0.5038	0.058*
C10	0.2880 (2)	0.5933 (2)	0.65482 (15)	0.0641 (6)
C13	0.1751 (3)	0.6529 (3)	0.6547 (2)	0.0824 (8)
H13A	0.1154	0.6058	0.6764	0.124*
H13B	0.1565	0.6749	0.5964	0.124*
H13C	0.1808	0.7163	0.6911	0.124*
C19	0.5374 (2)	0.5203 (2)	0.30984 (16)	0.0624 (6)
H19	0.6004	0.5527	0.2825	0.075*
C11	0.2962 (2)	0.4872 (2)	0.62491 (19)	0.0752 (7)
H11	0.2306	0.4529	0.6030	0.090*
C8	0.4911 (2)	0.5865 (2)	0.68795 (18)	0.0765 (7)
H8	0.5567	0.6212	0.7093	0.092*
C2	0.7466 (3)	0.6124 (2)	0.50033 (16)	0.0815 (9)
H2A	0.6980	0.6607	0.5345	0.098*
H2B	0.7301	0.6258	0.4394	0.098*
C6	0.7972 (2)	0.4147 (2)	0.47615 (13)	0.0631 (6)
H6	0.7820	0.3414	0.4989	0.076*
C18	0.4338 (2)	0.5754 (2)	0.31602 (18)	0.0728 (7)
H18	0.4279	0.6455	0.2933	0.087*
C12	0.3992 (3)	0.4310 (2)	0.62680 (17)	0.0719 (7)
H12	0.4025	0.3597	0.6062	0.086*
C17	0.3394 (2)	0.5287 (2)	0.35501 (17)	0.0723 (7)
C15	0.4543 (3)	0.3685 (2)	0.38376 (17)	0.0733 (7)
H15	0.4605	0.2985	0.4067	0.088*
C20	0.2257 (3)	0.5907 (3)	0.3615 (2)	0.1059 (11)
H20A	0.2108	0.6088	0.4212	0.159*
H20B	0.1641	0.5460	0.3396	0.159*
H20C	0.2305	0.6564	0.3277	0.159*
C9	0.3878 (3)	0.6408 (2)	0.6850 (2)	0.0810 (8)
H9	0.3850	0.7128	0.7041	0.097*
C16	0.3510 (3)	0.4257 (3)	0.38880 (19)	0.0850 (8)
H16	0.2878	0.3933	0.4159	0.102*
C5	0.9229 (3)	0.4441 (5)	0.4944 (2)	0.1246 (19)
H5A	0.9394	0.4311	0.5554	0.149*
H5B	0.9727	0.3968	0.4604	0.149*
C4	0.9504 (3)	0.5625 (6)	0.4727 (2)	0.156 (3)
H4A	1.0295	0.5782	0.4892	0.187*
H4B	0.9435	0.5733	0.4104	0.187*
C3	0.8719 (4)	0.6387 (4)	0.5182 (2)	0.1297 (18)
H3A	0.8881	0.7126	0.4992	0.156*
H3B	0.8861	0.6348	0.5803	0.156*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0767 (4)	0.0523 (3)	0.0444 (3)	0.0109 (3)	0.0052 (3)	−0.0021 (2)
S1	0.0786 (4)	0.0508 (3)	0.0395 (2)	−0.0039 (3)	0.0075 (3)	0.0023 (2)
C14	0.0620 (13)	0.0541 (11)	0.0406 (10)	−0.0011 (10)	−0.0020 (9)	−0.0021 (10)
O1	0.0994 (13)	0.0680 (9)	0.0414 (8)	−0.0018 (10)	0.0051 (8)	0.0113 (7)
O4	0.1114 (16)	0.0534 (9)	0.0798 (12)	0.0169 (10)	0.0114 (11)	0.0073 (8)
C7	0.0707 (14)	0.0495 (10)	0.0437 (11)	−0.0136 (10)	0.0092 (11)	−0.0052 (9)
O3	0.0919 (13)	0.0705 (10)	0.0449 (8)	0.0055 (10)	0.0063 (8)	−0.0122 (7)
N2	0.0655 (12)	0.0763 (12)	0.0382 (9)	0.0112 (11)	0.0029 (8)	0.0005 (9)
N1	0.0646 (11)	0.0676 (11)	0.0337 (8)	−0.0030 (9)	0.0017 (8)	0.0045 (8)
O2	0.0989 (14)	0.0533 (8)	0.0631 (10)	0.0004 (9)	0.0087 (10)	−0.0038 (8)
C1	0.0517 (11)	0.0612 (11)	0.0330 (9)	0.0032 (9)	−0.0022 (8)	0.0039 (9)
C10	0.0732 (15)	0.0639 (13)	0.0551 (13)	−0.0078 (12)	0.0077 (11)	0.0031 (11)
C13	0.0744 (17)	0.0878 (18)	0.085 (2)	−0.0004 (15)	0.0022 (15)	0.0123 (16)
C19	0.0597 (13)	0.0589 (13)	0.0687 (15)	−0.0012 (11)	0.0004 (11)	0.0099 (11)
C11	0.0691 (17)	0.0690 (15)	0.0875 (18)	−0.0214 (14)	−0.0050 (15)	−0.0062 (14)
C8	0.0723 (17)	0.0602 (14)	0.097 (2)	−0.0060 (13)	−0.0110 (15)	−0.0275 (14)
C2	0.130 (3)	0.0718 (16)	0.0428 (12)	−0.0146 (16)	−0.0041 (14)	0.0086 (11)
C6	0.0666 (14)	0.0855 (15)	0.0373 (10)	0.0252 (13)	0.0002 (9)	0.0033 (11)
C18	0.0702 (16)	0.0680 (15)	0.0803 (18)	0.0080 (13)	−0.0010 (13)	0.0064 (13)
C12	0.0838 (18)	0.0548 (13)	0.0771 (16)	−0.0185 (13)	0.0036 (14)	−0.0131 (12)
C17	0.0653 (15)	0.0912 (18)	0.0604 (15)	0.0078 (14)	−0.0004 (12)	−0.0065 (13)
C15	0.0838 (19)	0.0674 (15)	0.0688 (16)	−0.0057 (14)	0.0116 (14)	0.0111 (12)
C20	0.0752 (19)	0.132 (3)	0.110 (2)	0.024 (2)	0.0081 (19)	−0.007 (2)
C9	0.0863 (19)	0.0603 (14)	0.096 (2)	−0.0028 (14)	−0.0098 (16)	−0.0269 (14)
C16	0.0695 (18)	0.110 (2)	0.0755 (18)	−0.0133 (17)	0.0182 (14)	0.0057 (17)
C5	0.063 (2)	0.257 (6)	0.0537 (16)	0.050 (3)	−0.0093 (14)	−0.016 (3)
C4	0.079 (2)	0.334 (8)	0.0541 (17)	−0.088 (4)	0.0068 (16)	−0.014 (3)
C3	0.168 (4)	0.169 (4)	0.0517 (16)	−0.107 (3)	0.013 (2)	−0.004 (2)

Geometric parameters (Å, º) top

S2—O4	1.4212 (19)	C11—H11	0.9300
S2—O3	1.4376 (16)	C8—C9	1.369 (4)
S2—N2	1.597 (2)	C8—H8	0.9300
S2—C14	1.769 (2)	C2—C3	1.511 (6)
S1—O2	1.4212 (17)	C2—H2A	0.9700
S1—O1	1.4401 (16)	C2—H2B	0.9700
S1—N1	1.6166 (19)	C6—C5	1.524 (5)
S1—C7	1.751 (3)	C6—H6	0.9800
C14—C15	1.372 (3)	C18—C17	1.371 (4)
C14—C19	1.372 (3)	C18—H18	0.9300
C7—C12	1.377 (3)	C12—H12	0.9300
C7—C8	1.380 (3)	C17—C16	1.371 (4)
N2—C6	1.475 (3)	C17—C20	1.523 (4)
N2—H102	0.9334	C15—C16	1.389 (4)
N1—C1	1.479 (2)	C15—H15	0.9300
N1—H101	0.9589	C20—H20A	0.9600
C1—C2	1.508 (3)	C20—H20B	0.9600
C1—C6	1.530 (3)	C20—H20C	0.9600
C1—H1	0.9800	C9—H9	0.9300
C10—C9	1.373 (4)	C16—H16	0.9300
C10—C11	1.384 (4)	C5—C4	1.523 (7)
C10—C13	1.497 (4)	C5—H5A	0.9700
C13—H13A	0.9600	C5—H5B	0.9700
C13—H13B	0.9600	C4—C3	1.478 (7)
C13—H13C	0.9600	C4—H4A	0.9700
C19—C18	1.379 (3)	C4—H4B	0.9700
C19—H19	0.9300	C3—H3A	0.9700
C11—C12	1.376 (4)	C3—H3B	0.9700

O4—S2—O3	119.38 (11)	C1—C2—H2B	109.1
O4—S2—N2	108.47 (12)	C3—C2—H2B	109.1
O3—S2—N2	105.48 (11)	H2A—C2—H2B	107.9
O4—S2—C14	107.31 (12)	N2—C6—C5	108.6 (2)
O3—S2—C14	106.81 (10)	N2—C6—C1	111.93 (17)
N2—S2—C14	109.09 (10)	C5—C6—C1	109.9 (3)
O2—S1—O1	119.01 (10)	N2—C6—H6	108.8
O2—S1—N1	108.82 (11)	C5—C6—H6	108.8
O1—S1—N1	104.81 (10)	C1—C6—H6	108.8
O2—S1—C7	107.92 (12)	C17—C18—C19	121.2 (3)
O1—S1—C7	107.91 (11)	C17—C18—H18	119.4
N1—S1—C7	107.92 (10)	C19—C18—H18	119.4
C15—C14—C19	120.6 (2)	C11—C12—C7	120.2 (2)
C15—C14—S2	120.10 (18)	C11—C12—H12	119.9
C19—C14—S2	119.28 (18)	C7—C12—H12	119.9
C12—C7—C8	119.1 (2)	C16—C17—C18	118.2 (3)
C12—C7—S1	121.16 (18)	C16—C17—C20	121.3 (3)
C8—C7—S1	119.76 (19)	C18—C17—C20	120.6 (3)
C6—N2—S2	124.00 (18)	C14—C15—C16	118.5 (2)
C6—N2—H102	117.6	C14—C15—H15	120.7
S2—N2—H102	112.8	C16—C15—H15	120.7
C1—N1—S1	119.21 (15)	C17—C20—H20A	109.5
C1—N1—H101	118.5	C17—C20—H20B	109.5
S1—N1—H101	109.1	H20A—C20—H20B	109.5
N1—C1—C2	109.21 (18)	C17—C20—H20C	109.5
N1—C1—C6	108.92 (17)	H20A—C20—H20C	109.5
C2—C1—C6	112.2 (2)	H20B—C20—H20C	109.5
N1—C1—H1	108.8	C8—C9—C10	122.6 (2)
C2—C1—H1	108.8	C8—C9—H9	118.7
C6—C1—H1	108.8	C10—C9—H9	118.7
C9—C10—C11	117.0 (3)	C17—C16—C15	121.9 (3)
C9—C10—C13	121.8 (2)	C17—C16—H16	119.1
C11—C10—C13	121.2 (3)	C15—C16—H16	119.1
C10—C13—H13A	109.5	C4—C5—C6	112.6 (3)
C10—C13—H13B	109.5	C4—C5—H5A	109.1
H13A—C13—H13B	109.5	C6—C5—H5A	109.1
C10—C13—H13C	109.5	C4—C5—H5B	109.1
H13A—C13—H13C	109.5	C6—C5—H5B	109.1
H13B—C13—H13C	109.5	H5A—C5—H5B	107.8
C14—C19—C18	119.6 (2)	C3—C4—C5	111.8 (3)
C14—C19—H19	120.2	C3—C4—H4A	109.3
C18—C19—H19	120.2	C5—C4—H4A	109.3
C12—C11—C10	121.5 (2)	C3—C4—H4B	109.3
C12—C11—H11	119.2	C5—C4—H4B	109.3
C10—C11—H11	119.2	H4A—C4—H4B	107.9
C9—C8—C7	119.6 (2)	C4—C3—C2	111.6 (3)
C9—C8—H8	120.2	C4—C3—H3A	109.3
C7—C8—H8	120.2	C2—C3—H3A	109.3
C1—C2—C3	112.3 (3)	C4—C3—H3B	109.3
C1—C2—H2A	109.1	C2—C3—H3B	109.3
C3—C2—H2A	109.1	H3A—C3—H3B	108.0

O4—S2—C14—C15	−4.0 (2)	C6—C1—C2—C3	−54.0 (3)
O3—S2—C14—C15	125.1 (2)	S2—N2—C6—C5	155.9 (3)
N2—S2—C14—C15	−121.3 (2)	S2—N2—C6—C1	−82.5 (3)
O4—S2—C14—C19	178.14 (19)	N1—C1—C6—N2	170.8 (2)
O3—S2—C14—C19	−52.7 (2)	C2—C1—C6—N2	−68.2 (3)
N2—S2—C14—C19	60.8 (2)	N1—C1—C6—C5	−68.4 (3)
O2—S1—C7—C12	8.9 (2)	C2—C1—C6—C5	52.6 (3)
O1—S1—C7—C12	−120.9 (2)	C14—C19—C18—C17	−0.9 (4)
N1—S1—C7—C12	126.37 (19)	C10—C11—C12—C7	0.1 (4)
O2—S1—C7—C8	−172.6 (2)	C8—C7—C12—C11	−1.1 (4)
O1—S1—C7—C8	57.6 (2)	S1—C7—C12—C11	177.3 (2)
N1—S1—C7—C8	−55.2 (2)	C19—C18—C17—C16	0.8 (4)
O4—S2—N2—C6	−37.9 (2)	C19—C18—C17—C20	179.9 (3)
O3—S2—N2—C6	−166.88 (18)	C19—C14—C15—C16	−0.5 (4)
C14—S2—N2—C6	78.7 (2)	S2—C14—C15—C16	−178.3 (2)
O2—S1—N1—C1	51.2 (2)	C7—C8—C9—C10	0.6 (5)
O1—S1—N1—C1	179.49 (16)	C11—C10—C9—C8	−1.6 (4)
C7—S1—N1—C1	−65.69 (18)	C13—C10—C9—C8	178.0 (3)
S1—N1—C1—C2	137.8 (2)	C18—C17—C16—C15	−0.5 (4)
S1—N1—C1—C6	−99.4 (2)	C20—C17—C16—C15	−179.7 (3)
C15—C14—C19—C18	0.7 (4)	C14—C15—C16—C17	0.4 (4)
S2—C14—C19—C18	178.6 (2)	N2—C6—C5—C4	69.8 (3)
C9—C10—C11—C12	1.2 (4)	C1—C6—C5—C4	−53.0 (3)
C13—C10—C11—C12	−178.4 (3)	C6—C5—C4—C3	55.0 (4)
C12—C7—C8—C9	0.8 (4)	C5—C4—C3—C2	−54.5 (4)
S1—C7—C8—C9	−177.7 (2)	C1—C2—C3—C4	54.7 (4)
N1—C1—C2—C3	66.9 (3)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) x−1/2, −y+1/2, −z+1; (iv) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₆N₂O₄S₂
M_r	422.55
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	11.5704 (14), 12.2585 (15), 15.3757 (19)
V (Å³)	2180.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.75 × 0.65 × 0.32

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.822, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	9486, 4196, 3748
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.00
No. of reflections	4196
No. of parameters	256
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.24
Absolute structure	Flack (1983), 1706 Friedel pairs
Absolute structure parameter	0.07 (7)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia,1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) x−1/2, −y+1/2, −z+1; (iv) −x+1, y+1/2, −z+3/2.

Acknowledgements

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

References

Ackermann, L., Bergman, R. G. & Loy, R. N. (2003). J. Am. Chem. Soc. 125, 11956–15963. Web of Science CrossRef PubMed CAS Google Scholar
Bisai, A., Prasad, B. A. B. & Singh, V. K. (2005). Tetrahedron Lett. 46, 7935–7939. CrossRef CAS Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Costa, A. M., Garcia, C., Carroll, P. J. & Walsh, P. J. (2005). Tetrahedron, 61, 6442–6446. CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Guo, C., Qiu, J. & Zhang, X. (1997). Tetrahedron, 53, 4145–4158. CAS Google Scholar
Nieger, M., Josten, W. & Vogtle, F. (2004). Private communication (CCDC deposition No. 235640). CCDC, Union Road, Cambridge, England. Google Scholar
Pritchett, S., Gantzel, P. & Walsh, P. J. (1999). Organometallics, 18, 823–831. CrossRef CAS Google Scholar
Schwarz, A. D., Chu, Z. & Mountford, P. (2010). Organometallics, 29, 1246–1260. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tasker, P., Squires, C., Parsons, S. & Messenger, D. (2005). Private communication (CCDC deposition No. 276825). CCDC, Union Road, Cambridge, England. Google Scholar