5-(4-tert-Butyl­benzyl­sulfan­yl)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

Wang, C.-Y.

doi:10.1107/S160053680706597X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o270

https://doi.org/10.1107/S160053680706597X

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5-(4-tert-Butylbenzylsulfanyl)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

Chen-Yi Wang ^a ^*

^aDepartment of Chemistry, Huzhou University, Huzhou 313000, People's Republic of China
^*Correspondence e-mail: chenyi_wang2006@yahoo.com.cn

(Received 22 November 2007; accepted 6 December 2007; online 12 December 2007)

The title compound, C₂₂H₂₄N₂OS, has been synthesized as a potent fungicidal agent and its crystal structure determined. In the crystal structure, weak intermolecular C—H⋯O interactions are observed. The dihedral angles between the planes of the pyrazole and phenyl rings, and between the benzene and pyrazole rings are 54.2 (2) and 25.0 (3)°, respectively. The methyl groups of the tert-butyl group are disordered over two positions; the site occupancies are ca 0.65 and 0.35.

Related literature

For related literature, see: Becher et al. (1986 ); Bekhit & Abdel-Aziem (2004 ); Comber et al. (1991 ); Dannhardt & Kiefer (2001 ); Gamage et al. (2002 ); Goekan-Kelekci et al. (2007 ); Hashizume et al. (2004 ); Park et al. (2005 ).

Experimental

Crystal data

C₂₂H₂₄N₂OS
M_r = 364.49
Orthorhombic, P b c a
a = 11.129 (3) Å
b = 16.181 (4) Å
c = 22.429 (6) Å
V = 4039.0 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 294 (2) K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.945, T_max = 0.973
19461 measured reflections
3568 independent reflections
1788 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.146
S = 1.01
3568 reflections
271 parameters
57 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2ⁱ	0.97	2.54	3.486 (3)	165
Symmetry code: (i) $[x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680706597X/em2002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706597X/em2002Isup2.hkl

checkCIF report

Comment top

The pyrazole ring is an important structural motif found in many biologically and pharmaceutically active compounds. In the past few years, pyrazoles and their derivatives have attracted much attention because they show several biological activities, such as antimicrobial, anti-inflammatory, antiviral, anticancer, insecticidal, herbicidal and plant growth regulatory (Bekhit et al., 2004; Goekan-Kelekci et al., 2007; Gamage et al., 2002; Hashizume et al., 2004). Many pyrazoles are currently being tested and clinically evaluated as potential new drugs (Dannhardt et al., 2001; Park et al., 2005). For example, the natural pyrazole C-glycoside, pyrazofurin, an antibiotic, was reported to possess a broad spectrum of antimicrobial and antiviral activities in addition to being active against several tumor cell lines (Comber et al., 1991). In the search for more biologically active pyrazole derivatives, the title compound, I, was synthesized and we report here its crystal structure (Fig.1). The title compound contains three planar groups: (a) the phenyl ring composed of atoms C6—C11, (b) the pyrazole ring composed of atoms N, N2, C2, C3 and C4, (c) the C₆H₄ ring composed of atoms C13—C18, The dihedral angles between the planes of (a) and (b), and between (b) and (c) are 54.2 (2) ° and 25.0 (3) ° respectively. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1 & Fig.2).

Related literature top

For related literature, see: Becher et al. (1986); Bekhit & Abdel-Aziem (2004); Comber et al. (1991); Dannhardt & Kiefer (2001); Gamage et al. (2002); Goekan-Kelekci et al. (2007); Hashizume et al. (2004); Park et al. (2005).

Experimental top

To a cooled solution of sodium hydride (0.023 mol) in anhydrous THF (15 ml), was added dropwise (4-tert-butylphenyl)methanethiol (0.022 mol). The reaction mixture was stirred at room temperature for 1 h, and then a solution of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (Becher et al.,1986; 0.020 mol) in anhydrous THF (25 ml) was added dropwise. The mixture was stirred at room temperature for another 2 h, and then poured into water (50 ml) to yield a colourless precipitate (Scheme 1). The resulting precipitate was recrystallized from petroleum ether/ethyl acetate (5:1 v/v) to give colourless crystals (yield 60%).

Structure description top

For related literature, see: Becher et al. (1986); Bekhit & Abdel-Aziem (2004); Comber et al. (1991); Dannhardt & Kiefer (2001); Gamage et al. (2002); Goekan-Kelekci et al. (2007); Hashizume et al. (2004); Park et al. (2005).

Computing details top

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

Figures top

	Fig. 1. View of the title compound, I, with displacement ellipsoids drawn at the 30% probability level and minor disorder component omitted for clarity.
	Fig. 2. Packing diagram of I. Dashed lines indicate C—H···O hydrogen-bond interactions.
	Fig. 3. The formation of the title compound.

5-(4-tert-Butylbenzylsulfanyl)-3-methyl-1-phenyl-1H-pyrazole-4- carbaldehyde top

Crystal data top

C₂₂H₂₄N₂OS	F(000) = 1552
M_r = 364.49	D_x = 1.199 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2619 reflections
a = 11.129 (3) Å	θ = 2.4–23.4°
b = 16.181 (4) Å	µ = 0.17 mm⁻¹
c = 22.429 (6) Å	T = 294 K
V = 4039.0 (18) Å³	Orthorhombic, colourless
Z = 8	0.24 × 0.20 × 0.16 mm

Data collection top

Bruker SMART 1000 diffractometer	3568 independent reflections
Radiation source: fine-focus sealed tube	1788 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→13
T_min = 0.945, T_max = 0.973	k = −16→19
19461 measured reflections	l = −26→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0543P)² + 1.5678P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
3568 reflections	Δρ_max = 0.19 e Å⁻³
271 parameters	Δρ_min = −0.21 e Å⁻³
57 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0053 (5)

Crystal data top

C₂₂H₂₄N₂OS	V = 4039.0 (18) Å³
M_r = 364.49	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.129 (3) Å	µ = 0.17 mm⁻¹
b = 16.181 (4) Å	T = 294 K
c = 22.429 (6) Å	0.24 × 0.20 × 0.16 mm

Data collection top

Bruker SMART 1000 diffractometer	3568 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1788 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.973	R_int = 0.087
19461 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	57 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.01	Δρ_max = 0.19 e Å⁻³
3568 reflections	Δρ_min = −0.21 e Å⁻³
271 parameters

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	Occ. (<1)
S1	0.56005 (9)	0.18185 (6)	0.52594 (4)	0.0692 (3)
O1	0.7233 (2)	−0.07664 (16)	0.52505 (12)	0.0888 (9)
N1	0.4568 (2)	0.09456 (16)	0.61696 (12)	0.0539 (7)
N2	0.4616 (3)	0.02084 (17)	0.64732 (13)	0.0622 (8)
C1	0.5704 (4)	−0.1109 (2)	0.63859 (17)	0.0809 (12)
H1A	0.5296	−0.1218	0.6755	0.121*
H1B	0.6556	−0.1146	0.6447	0.121*
H1C	0.5461	−0.1507	0.6093	0.121*
C2	0.5388 (3)	−0.0253 (2)	0.61720 (16)	0.0589 (9)
C3	0.5853 (3)	0.0175 (2)	0.56780 (14)	0.0520 (8)
C4	0.5313 (3)	0.09467 (19)	0.56915 (13)	0.0503 (8)
C5	0.6746 (3)	−0.0098 (2)	0.52514 (16)	0.0676 (10)
H5	0.6964	0.0273	0.4953	0.081*
C6	0.3817 (3)	0.1594 (2)	0.63937 (14)	0.0535 (9)
C7	0.3931 (3)	0.1839 (2)	0.69794 (15)	0.0651 (10)
H7	0.4507	0.1598	0.7224	0.078*
C8	0.3183 (4)	0.2443 (3)	0.71983 (18)	0.0787 (12)
H8	0.3249	0.2607	0.7594	0.094*
C9	0.2340 (4)	0.2806 (3)	0.6837 (2)	0.0861 (13)
H9	0.1839	0.3216	0.6987	0.103*
C10	0.2239 (4)	0.2559 (3)	0.6255 (2)	0.0875 (13)
H10	0.1668	0.2806	0.6010	0.105*
C11	0.2967 (3)	0.1955 (2)	0.60299 (16)	0.0704 (10)
H11	0.2890	0.1789	0.5635	0.084*
C12	0.6681 (3)	0.2339 (2)	0.57569 (17)	0.0752 (11)
H12A	0.7027	0.2808	0.5550	0.090*
H12B	0.6257	0.2546	0.6104	0.090*
C13	0.7670 (3)	0.17787 (19)	0.59573 (16)	0.0594 (9)
C14	0.7591 (3)	0.1360 (2)	0.64906 (15)	0.0621 (10)
H14	0.6952	0.1469	0.6746	0.075*
C15	0.8436 (3)	0.0784 (2)	0.66528 (15)	0.0655 (10)
H15	0.8356	0.0516	0.7018	0.079*
C16	0.9402 (3)	0.0589 (2)	0.62918 (15)	0.0588 (9)
C17	0.9495 (3)	0.1031 (2)	0.57631 (17)	0.0720 (11)
H17	1.0145	0.0932	0.5512	0.086*
C18	0.8651 (4)	0.1614 (2)	0.55988 (17)	0.0709 (11)
H18	0.8745	0.1900	0.5242	0.085*
C19	1.0287 (3)	−0.0081 (2)	0.64643 (16)	0.0720 (11)
C20	0.9655 (8)	−0.0873 (4)	0.6579 (6)	0.115 (3)	0.655 (12)
H20A	1.0227	−0.1284	0.6699	0.172*	0.655 (12)
H20B	0.9256	−0.1051	0.6222	0.172*	0.655 (12)
H20C	0.9073	−0.0796	0.6890	0.172*	0.655 (12)
C21	1.1021 (7)	0.0212 (5)	0.7014 (3)	0.073 (2)	0.655 (12)
H21A	1.0489	0.0298	0.7345	0.110*	0.655 (12)
H21B	1.1424	0.0720	0.6921	0.110*	0.655 (12)
H21C	1.1605	−0.0201	0.7117	0.110*	0.655 (12)
C22	1.1279 (8)	−0.0210 (6)	0.5970 (3)	0.094 (3)	0.655 (12)
H22A	1.1839	−0.0624	0.6100	0.141*	0.655 (12)
H22B	1.1697	0.0300	0.5904	0.141*	0.655 (12)
H22C	1.0905	−0.0386	0.5606	0.141*	0.655 (12)
C20'	0.9620 (13)	−0.0696 (9)	0.6921 (7)	0.087 (5)	0.345 (12)
H20D	0.8867	−0.0868	0.6753	0.130*	0.345 (12)
H20E	0.9480	−0.0415	0.7291	0.130*	0.345 (12)
H20F	1.0116	−0.1172	0.6990	0.130*	0.345 (12)
C21'	1.1392 (14)	0.0222 (13)	0.6765 (9)	0.132 (9)	0.345 (12)
H21D	1.1231	0.0745	0.6952	0.197*	0.345 (12)
H21E	1.2022	0.0288	0.6477	0.197*	0.345 (12)
H21F	1.1638	−0.0170	0.7063	0.197*	0.345 (12)
C22'	1.0496 (18)	−0.0659 (9)	0.5928 (5)	0.101 (6)	0.345 (12)
H22D	1.1070	−0.1076	0.6035	0.151*	0.345 (12)
H22E	1.0797	−0.0344	0.5598	0.151*	0.345 (12)
H22F	0.9751	−0.0916	0.5818	0.151*	0.345 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0791 (7)	0.0673 (6)	0.0612 (6)	0.0141 (5)	0.0036 (5)	0.0218 (5)
O1	0.100 (2)	0.0657 (18)	0.101 (2)	0.0241 (16)	−0.0006 (17)	−0.0163 (16)
N1	0.0617 (18)	0.0461 (16)	0.0538 (16)	0.0022 (14)	−0.0019 (15)	0.0038 (13)
N2	0.069 (2)	0.0478 (17)	0.0697 (19)	−0.0030 (15)	−0.0048 (16)	0.0110 (15)
C1	0.091 (3)	0.050 (2)	0.102 (3)	0.000 (2)	−0.007 (3)	0.014 (2)
C2	0.061 (2)	0.046 (2)	0.070 (2)	−0.0044 (19)	−0.008 (2)	0.0021 (18)
C3	0.053 (2)	0.049 (2)	0.054 (2)	0.0004 (17)	−0.0086 (18)	−0.0034 (16)
C4	0.056 (2)	0.051 (2)	0.0435 (18)	0.0005 (16)	−0.0050 (17)	0.0027 (15)
C5	0.072 (3)	0.063 (2)	0.067 (2)	0.004 (2)	−0.009 (2)	−0.008 (2)
C6	0.057 (2)	0.048 (2)	0.055 (2)	0.0002 (17)	0.0020 (18)	0.0028 (16)
C7	0.074 (2)	0.066 (2)	0.055 (2)	−0.004 (2)	−0.0009 (19)	0.0041 (19)
C8	0.103 (3)	0.072 (3)	0.061 (2)	−0.005 (3)	0.014 (3)	−0.009 (2)
C9	0.097 (3)	0.073 (3)	0.088 (3)	0.015 (2)	0.022 (3)	−0.007 (2)
C10	0.089 (3)	0.090 (3)	0.083 (3)	0.030 (3)	0.000 (2)	−0.009 (3)
C11	0.079 (3)	0.072 (3)	0.061 (2)	0.014 (2)	−0.006 (2)	−0.003 (2)
C12	0.089 (3)	0.043 (2)	0.094 (3)	−0.002 (2)	0.009 (2)	0.008 (2)
C13	0.065 (2)	0.0383 (19)	0.075 (2)	−0.0072 (18)	0.003 (2)	0.0000 (18)
C14	0.068 (2)	0.067 (2)	0.051 (2)	−0.003 (2)	0.0059 (19)	−0.0109 (19)
C15	0.081 (3)	0.066 (2)	0.050 (2)	−0.001 (2)	−0.002 (2)	0.0011 (18)
C16	0.065 (2)	0.056 (2)	0.055 (2)	−0.0014 (19)	−0.003 (2)	−0.0115 (17)
C17	0.065 (3)	0.076 (3)	0.075 (3)	0.000 (2)	0.018 (2)	0.001 (2)
C18	0.074 (3)	0.066 (3)	0.073 (3)	−0.011 (2)	0.015 (2)	0.014 (2)
C19	0.082 (3)	0.067 (3)	0.068 (3)	0.013 (2)	−0.005 (2)	−0.011 (2)
C20	0.110 (6)	0.058 (4)	0.175 (8)	−0.011 (4)	−0.029 (6)	−0.012 (5)
C21	0.053 (4)	0.095 (5)	0.072 (4)	0.011 (3)	−0.006 (4)	0.001 (4)
C22	0.101 (6)	0.100 (6)	0.082 (4)	0.033 (5)	−0.001 (4)	−0.015 (4)
C20'	0.101 (9)	0.059 (7)	0.100 (9)	0.018 (6)	−0.013 (7)	−0.001 (6)
C21'	0.113 (11)	0.123 (11)	0.158 (13)	−0.008 (9)	0.001 (9)	−0.008 (9)
C22'	0.120 (10)	0.085 (8)	0.098 (8)	0.017 (7)	0.014 (7)	−0.001 (7)

Geometric parameters (Å, º) top

S1—C4	1.741 (3)	C14—H14	0.9300
S1—C12	1.844 (4)	C15—C16	1.382 (5)
O1—C5	1.210 (4)	C15—H15	0.9300
N1—C4	1.355 (4)	C16—C17	1.389 (5)
N1—N2	1.375 (3)	C16—C19	1.515 (5)
N1—C6	1.432 (4)	C17—C18	1.381 (5)
N2—C2	1.324 (4)	C17—H17	0.9300
C1—C2	1.507 (4)	C18—H18	0.9300
C1—H1A	0.9600	C19—C20	1.485 (6)
C1—H1B	0.9600	C19—C21'	1.487 (9)
C1—H1C	0.9600	C19—C22'	1.541 (8)
C2—C3	1.406 (4)	C19—C21	1.554 (6)
C3—C4	1.386 (4)	C19—C22	1.578 (6)
C3—C5	1.448 (4)	C19—C20'	1.609 (8)
C5—H5	0.9300	C20—H20A	0.9600
C6—C7	1.378 (4)	C20—H20B	0.9600
C6—C11	1.380 (4)	C20—H20C	0.9600
C7—C8	1.375 (5)	C21—H21A	0.9600
C7—H7	0.9300	C21—H21B	0.9600
C8—C9	1.371 (5)	C21—H21C	0.9600
C8—H8	0.9300	C22—H22A	0.9600
C9—C10	1.371 (5)	C22—H22B	0.9600
C9—H9	0.9300	C22—H22C	0.9600
C10—C11	1.366 (5)	C20'—H20D	0.9600
C10—H10	0.9300	C20'—H20E	0.9600
C11—H11	0.9300	C20'—H20F	0.9600
C12—C13	1.495 (5)	C21'—H21D	0.9600
C12—H12A	0.9700	C21'—H21E	0.9600
C12—H12B	0.9700	C21'—H21F	0.9600
C13—C14	1.378 (4)	C22'—H22D	0.9600
C13—C18	1.382 (5)	C22'—H22E	0.9600
C14—C15	1.372 (5)	C22'—H22F	0.9600

C4—S1—C12	98.81 (15)	C15—C14—H14	119.3
C4—N1—N2	111.6 (3)	C13—C14—H14	119.3
C4—N1—C6	129.3 (3)	C14—C15—C16	122.2 (3)
N2—N1—C6	119.0 (3)	C14—C15—H15	118.9
C2—N2—N1	105.2 (3)	C16—C15—H15	118.9
C2—C1—H1A	109.5	C15—C16—C17	116.1 (3)
C2—C1—H1B	109.5	C15—C16—C19	121.3 (3)
H1A—C1—H1B	109.5	C17—C16—C19	122.6 (3)
C2—C1—H1C	109.5	C18—C17—C16	121.9 (3)
H1A—C1—H1C	109.5	C18—C17—H17	119.0
H1B—C1—H1C	109.5	C16—C17—H17	119.0
N2—C2—C3	111.3 (3)	C17—C18—C13	120.9 (3)
N2—C2—C1	120.5 (3)	C17—C18—H18	119.6
C3—C2—C1	128.2 (3)	C13—C18—H18	119.6
C4—C3—C2	105.5 (3)	C20—C19—C16	110.7 (5)
C4—C3—C5	125.9 (3)	C21'—C19—C16	114.7 (9)
C2—C3—C5	128.6 (3)	C16—C19—C22'	109.5 (6)
N1—C4—C3	106.4 (3)	C20—C19—C21	112.0 (5)
N1—C4—S1	123.6 (2)	C16—C19—C21	109.0 (4)
C3—C4—S1	129.6 (3)	C20—C19—C22	109.8 (5)
O1—C5—C3	125.5 (4)	C16—C19—C22	111.8 (4)
O1—C5—H5	117.3	C21—C19—C22	103.3 (4)
C3—C5—H5	117.3	C16—C19—C20'	107.8 (6)
C7—C6—C11	120.3 (3)	C19—C20—H20A	109.5
C7—C6—N1	119.5 (3)	C19—C20—H20B	109.5
C11—C6—N1	120.2 (3)	C19—C20—H20C	109.5
C8—C7—C6	119.3 (4)	C19—C21—H21A	109.5
C8—C7—H7	120.3	C19—C21—H21B	109.5
C6—C7—H7	120.3	C19—C21—H21C	109.5
C9—C8—C7	120.5 (4)	C19—C22—H22A	109.5
C9—C8—H8	119.7	C19—C22—H22B	109.5
C7—C8—H8	119.7	C19—C22—H22C	109.5
C8—C9—C10	119.7 (4)	C19—C20'—H20D	109.5
C8—C9—H9	120.2	C19—C20'—H20E	109.5
C10—C9—H9	120.2	H20D—C20'—H20E	109.5
C11—C10—C9	120.7 (4)	C19—C20'—H20F	109.5
C11—C10—H10	119.6	H20D—C20'—H20F	109.5
C9—C10—H10	119.6	H20E—C20'—H20F	109.5
C10—C11—C6	119.5 (3)	C19—C21'—H21D	109.5
C10—C11—H11	120.3	C19—C21'—H21E	109.5
C6—C11—H11	120.3	H21D—C21'—H21E	109.5
C13—C12—S1	112.7 (2)	C19—C21'—H21F	109.5
C13—C12—H12A	109.1	H21D—C21'—H21F	109.5
S1—C12—H12A	109.1	H21E—C21'—H21F	109.5
C13—C12—H12B	109.1	C19—C22'—H22D	109.5
S1—C12—H12B	109.1	C19—C22'—H22E	109.5
H12A—C12—H12B	107.8	H22D—C22'—H22E	109.5
C14—C13—C18	117.4 (3)	C19—C22'—H22F	109.5
C14—C13—C12	120.8 (3)	H22D—C22'—H22F	109.5
C18—C13—C12	121.6 (3)	H22E—C22'—H22F	109.5
C15—C14—C13	121.4 (3)

C4—N1—N2—C2	−0.9 (3)	C9—C10—C11—C6	−0.4 (6)
C6—N1—N2—C2	−178.7 (3)	C7—C6—C11—C10	0.1 (5)
N1—N2—C2—C3	0.5 (4)	N1—C6—C11—C10	178.4 (3)
N1—N2—C2—C1	178.1 (3)	C4—S1—C12—C13	50.4 (3)
N2—C2—C3—C4	0.1 (4)	S1—C12—C13—C14	−94.5 (4)
C1—C2—C3—C4	−177.3 (3)	S1—C12—C13—C18	80.7 (4)
N2—C2—C3—C5	177.6 (3)	C18—C13—C14—C15	−1.8 (5)
C1—C2—C3—C5	0.2 (6)	C12—C13—C14—C15	173.6 (3)
N2—N1—C4—C3	1.0 (3)	C13—C14—C15—C16	−0.4 (5)
C6—N1—C4—C3	178.5 (3)	C14—C15—C16—C17	2.2 (5)
N2—N1—C4—S1	−172.5 (2)	C14—C15—C16—C19	−176.7 (3)
C6—N1—C4—S1	5.0 (5)	C15—C16—C17—C18	−1.9 (5)
C2—C3—C4—N1	−0.6 (3)	C19—C16—C17—C18	177.0 (3)
C5—C3—C4—N1	−178.2 (3)	C16—C17—C18—C13	−0.3 (6)
C2—C3—C4—S1	172.3 (3)	C14—C13—C18—C17	2.1 (5)
C5—C3—C4—S1	−5.3 (5)	C12—C13—C18—C17	−173.3 (3)
C12—S1—C4—N1	78.5 (3)	C15—C16—C19—C20	55.1 (7)
C12—S1—C4—C3	−93.3 (3)	C17—C16—C19—C20	−123.7 (6)
C4—C3—C5—O1	178.3 (3)	C15—C16—C19—C21'	−96.3 (11)
C2—C3—C5—O1	1.2 (6)	C17—C16—C19—C21'	84.9 (11)
C4—N1—C6—C7	−125.0 (4)	C15—C16—C19—C22'	132.1 (9)
N2—N1—C6—C7	52.4 (4)	C17—C16—C19—C22'	−46.8 (9)
C4—N1—C6—C11	56.7 (5)	C15—C16—C19—C21	−68.6 (5)
N2—N1—C6—C11	−126.0 (3)	C17—C16—C19—C21	112.6 (5)
C11—C6—C7—C8	0.4 (5)	C15—C16—C19—C22	177.9 (5)
N1—C6—C7—C8	−177.9 (3)	C17—C16—C19—C22	−1.0 (6)
C6—C7—C8—C9	−0.6 (6)	C15—C16—C19—C20'	23.1 (8)
C7—C8—C9—C10	0.4 (6)	C17—C16—C19—C20'	−155.8 (7)
C8—C9—C10—C11	0.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.97	2.54	3.486 (3)	165

Symmetry code: (i) x+3/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₄N₂OS
M_r	364.49
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	11.129 (3), 16.181 (4), 22.429 (6)
V (Å³)	4039.0 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.24 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART 1000
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.945, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	19461, 3568, 1788
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.146, 1.01
No. of reflections	3568
No. of parameters	271
No. of restraints	57
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.97	2.54	3.486 (3)	165

Symmetry code: (i) x+3/2, −y+1/2, −z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NNSFC) (grant No. 30771696) and the Science and Technology Plan of Huzhou (grant No. 2007YS18).

References

Becher, J., Olesen, P. H., Knudsen, N. A. & Toftlund, H. (1986). Sulfur Lett. 4, 175–183. CAS Google Scholar
Bekhit, A. A. & Abdel-Aziem, T. (2004). Bioorg. Med. Chem. 12, 1935–1945. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Comber, R. N., Gray, R. J. & Secrist, J. A. (1991). Carbohydr. Res. 216, 441–452. CrossRef PubMed CAS Google Scholar
Dannhardt, G. & Kiefer, W. (2001). Eur. J. Med. Chem. 36, 109–126. Web of Science CrossRef PubMed CAS Google Scholar
Gamage, S. A., Spicer, J. A., Rewcastle, G. W., Milton, J., Sohal, S., Dangerfield, W., Mistry, P., Vicker, N., Charlton, P. A. & Denny, W. A. (2002). J. Med. Chem. 45, 740–743. Web of Science CrossRef PubMed CAS Google Scholar
Goekan-Kelekci, N., Yabanolu, S., Kuepeli, E., Salgin, U., Ozen, O., Ucar, G., Yesilada, E., Kendi, E., Yesilada, A. & Bilgin, A. A. (2007). Bioorg. Med. Chem. 15, 5775–5786. Web of Science PubMed Google Scholar
Hashizume, M., Sakamoto, N. & Takyo, H. (2004). WO Patent 2004085405. Google Scholar
Park, H. J., Lee, K., Park, S. J., Ahn, B., Lee, J. C., Cho, H. Y. & Lee, K. I. (2005). Bioorg. Med. Chem. Lett. 15, 3307–3312. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2001). SADABS. Version 2.03. University of Göttingen, Germany. Google Scholar