Ethyl 2-(3,3-dibutyl­thio­ureido)-4,5,6,7-tetra­hydro­benzo[b]thio­phene-3-carboxyl­ate

Wang, H.-M.; Xu, J.; Zeng, X.-H.; Tian, J.-H.

doi:10.1107/S1600536809047230

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3094-o3095

doi:10.1107/S1600536809047230

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Ethyl 2-(3,3-dibutylthioureido)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate

Hong-Mei Wang,^a Jing Xu,^a Xiao-Hua Zeng ^a ^* and Jia-Hua Tian ^a

^aInstitute of Medicinal Chemistry, Yunyang Medical College, Shiyan 442000, People's Republic of China
^*Correspondence e-mail: zengken@126.com

(Received 23 October 2009; accepted 9 November 2009; online 14 November 2009)

In the title compound, C₂₀H₃₂N₂O₂S₂, the cyclohexene ring is disordered over two half-boat conformations with occupancy factors of 0.71:0.29. One n-butyl chain is also disordered over two positions with occupancy factors of 0.83:0.17. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond.

Related literature

For the synthesis and biological activity of thienopyrimidin-4(3H)-one derivatives, see: De Laszlo et al. (1992a ,b ); Taguchi et al. (1993a ,b ); Walter (1999a ,b ); Ding et al. (2004 ); Santagati et al. (2003 ); Abbott GmbH Co KG (2004a , 2004b ); Walter & Zeun (2004 ); Ford et al. (2004a ,b ); Duval et al. (2005 ); Waehaelae et al. (2004a ,b ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For related structures, see: Xu et al. (2005 ); Zeng et al. (2005 , 2006 , 2007 , 2008 , 2009 ); Wang et al. (2007 , 2008 ); Zheng et al. (2007 ); Xie et al. (2008 ).

Experimental

Crystal data

C₂₀H₃₂N₂O₂S₂
M_r = 396.60
Monoclinic, P 2₁ /c
a = 10.9311 (11) Å
b = 21.715 (3) Å
c = 9.6841 (3) Å
β = 107.711 (12)°
V = 2189.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 292 K
0.36 × 0.30 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.903, T_max = 0.938
12194 measured reflections
4036 independent reflections
3460 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.153
S = 1.21
4036 reflections
280 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.86 (3)	1.89 (2)	2.643 (4)	145 (3)

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047230/rz2377sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047230/rz2377Isup2.hkl

checkCIF report

Comment top

The derivatives of heterocycles containing the thienopyrimidine system, which are well known bioisosteres of quinazolines, are of great importance because of their remarkable biological properties, including antimicrobial or antifungal activities (De Laszlo et al., 1992a,b; Walter, 1999a,b; Ding et al., 2004; Walter & Zeun, 2004), significant 5-HT_1A and 5-HT_1B receptor activities (Taguchi et al., 1993a,b; Abbott GmbH & Co. KG, 2004a,b), potential selective COX-2 enzyme inhibitor activity (Santagati, et al., 2004), 17beta-hydroxysteroid dehydrogenase inhibitor activity (Waehaelae et al., 2004a,b), potassium channel inhibitor activity (Ford et al., 2004a,b), and tissue transglutaminase inhibitor activity (Duval et al., 2005). Recently, our group has been engaged in the preparation of derivatives of thienopyrimidin-4(3H)-one via aza-Wittig reaction of beta-ethoxycarbonyl iminophosphorane with CS₂. As a continuation of our research for new biologically active heterocycles, the title compound was obtained as an intermediate product from beta-ethoxycarbonyl iminophosphorane in CS₂ and structurally characterized in order to elucidate the cyclization mechanism involved in the reaction.

In the title compound (Fig. 1), bond lengths within the benzothiophene ring system are in good agreement with those observed for closely related structures (Xu et al., 2005; Zeng et al., 2005, 2006, 2007, 2008, 2009; Wang et al., 2007, 2008; Zheng et al., 2007; Xie et al., 2008), and in the ranges of values observed in previously reported structures in the Cambridge Structural Database (Version 5.26; Allen, 2002). The theiophene ring is planar, with a maximum displacement of 0.008 (3)Å for atom C8. The attached cyclohexene ring is disordered over two half-chair conformations with site occupancy factors of 0.71:0.29. A n-butyl chain is also disordered over two positions with site occupancy factors of 0.83:0.17. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bond (Table 1). The crystal packing is enforced only by van der Waals interactions.

Related literature top

For the synthesis and biological activity of thienopyrimidin-4(3H)-one derivatives, see: De Laszlo et al. (1992a,b); Taguchi et al. (1993a,b); Walter (1999a,b); Ding et al. (2004); Santagati et al. (2003); Abbott GmbH Co KG (2004a, 2004b); Walter & Zeun (2004); Ford et al. (2004a,b); Duval et al. (2005); Waehaelae et al. (2004a,b). For a description of the Cambridge Structural Database, see: Allen (2002). For related structures, see: Xu et al. (2005); Zeng et al. (2005, 2006, 2007, 2008, 2009); Wang et al. (2007, 2008); Zheng et al. (2007); Xie et al. (2008).

Experimental top

To a solution of ethyl 2-thiocyanato-4,5,6,7-tetrahydrobenzo[b]thiophene -3-carboxylate (3 mmol) prepared according to Zeng et al. (2005) in CH₃CN (15 ml) was added dibutylamine (3 mmol) at room temperature, and the reaction mixture was stirred for 6 h. The solvent was removed under reduced pressure and the residue was recrystallized from EtOH to give the title compound in yield of 81% (m.p. 442 K). Elemental analysis:calculated for C₂₀H₃₂N₂O₂S₂: C, 60.57; H, 8.13; N, 7.06. Found: C, 59.34; H, 8.55; N, 6.67%. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a hexane/dichloromethane (1:3 v/v) solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are represented by circles of arbitrary size. Only the major components of the disordered groups are shown.

Ethyl 2-(3,3-dibutylthioureido)-4,5,6,7-tetrahydrobenzo[b]thiophene- 3-carboxylate top

Crystal data top

C₂₀H₃₂N₂O₂S₂	F(000) = 856
M_r = 396.60	D_x = 1.203 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9055 reflections
a = 10.9311 (11) Å	θ = 2.2–27.6°
b = 21.715 (3) Å	µ = 0.26 mm⁻¹
c = 9.6841 (3) Å	T = 292 K
β = 107.711 (12)°	Block, colourless
V = 2189.8 (4) Å³	0.36 × 0.30 × 0.25 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4036 independent reflections
Radiation source: fine-focus sealed tube	3460 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.903, T_max = 0.938	k = −21→26
12194 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0275P)² + 2.0031P] where P = (F_o² + 2F_c²)/3
4036 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.30 e Å⁻³
13 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₀H₃₂N₂O₂S₂	V = 2189.8 (4) Å³
M_r = 396.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.9311 (11) Å	µ = 0.26 mm⁻¹
b = 21.715 (3) Å	T = 292 K
c = 9.6841 (3) Å	0.36 × 0.30 × 0.25 mm
β = 107.711 (12)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4036 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3460 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.938	R_int = 0.027
12194 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	13 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.30 e Å⁻³
4036 reflections	Δρ_min = −0.23 e Å⁻³
280 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)
C1	1.0984 (4)	−0.00230 (16)	0.7833 (4)	0.0631 (9)
C2	1.1175 (5)	−0.0488 (2)	0.9023 (5)	0.0856 (12)
H2A	1.0446	−0.0765	0.8804	0.103*	0.71
H2B	1.1237	−0.0280	0.9928	0.103*	0.71
H2C	1.0714	−0.0361	0.9687	0.103*	0.29
H2D	1.0832	−0.0882	0.8616	0.103*	0.29
C3	1.2396 (7)	−0.0852 (4)	0.9174 (11)	0.097 (2)	0.71
H3A	1.2660	−0.1048	1.0119	0.117*	0.71
H3B	1.2207	−0.1175	0.8448	0.117*	0.71
C4	1.3461 (8)	−0.0488 (4)	0.9018 (8)	0.093 (2)	0.71
H4A	1.4202	−0.0754	0.9147	0.112*	0.71
H4B	1.3686	−0.0177	0.9771	0.112*	0.71
C4'	1.315 (2)	−0.0763 (7)	0.8441 (17)	0.077 (5)	0.29
H4'1	1.4018	−0.0918	0.8832	0.092*	0.29
H4'2	1.2627	−0.1081	0.7835	0.092*	0.29
C3'	1.2569 (14)	−0.0586 (11)	0.9758 (17)	0.113 (9)	0.29
H3'1	1.2705	−0.0918	1.0458	0.135*	0.29
H3'2	1.2968	−0.0215	1.0251	0.135*	0.29
C5	1.3142 (4)	−0.01737 (18)	0.7532 (4)	0.0751 (10)
H5A	1.3787	0.0136	0.7554	0.090*	0.71
H5B	1.3163	−0.0476	0.6803	0.090*	0.71
H5C	1.3789	0.0116	0.8067	0.090*	0.29
H5D	1.3339	−0.0286	0.6653	0.090*	0.29
C6	1.1838 (3)	0.01239 (15)	0.7127 (3)	0.0577 (8)
C7	1.1347 (3)	0.05951 (15)	0.6064 (3)	0.0551 (8)
C8	1.0133 (3)	0.07897 (14)	0.6033 (3)	0.0542 (7)
C9	1.1975 (3)	0.08581 (17)	0.5067 (4)	0.0634 (9)
C10	1.3820 (4)	0.0835 (2)	0.4231 (5)	0.0951 (14)
H10A	1.3581	0.1259	0.3967	0.114*
H10B	1.4735	0.0824	0.4730	0.114*
C11	1.3540 (5)	0.0462 (2)	0.2931 (5)	0.1069 (16)
H11A	1.3741	0.0040	0.3193	0.160*
H11B	1.4048	0.0602	0.2340	0.160*
H11C	1.2646	0.0498	0.2398	0.160*
C12	0.8369 (3)	0.15459 (17)	0.5066 (4)	0.0659 (9)
C13	0.6951 (5)	0.2433 (2)	0.4072 (6)	0.1029 (15)
H13A	0.6756	0.2414	0.4983	0.123*
H13B	0.7147	0.2858	0.3911	0.123*
C14	0.5827 (5)	0.2238 (3)	0.2904 (6)	0.1242 (19)
H14A	0.5686	0.1800	0.2980	0.149*	0.83
H14B	0.5957	0.2317	0.1973	0.149*	0.83
H14C	0.5373	0.1905	0.3203	0.149*	0.17
H14D	0.6066	0.2106	0.2064	0.149*	0.17
C15	0.4615 (9)	0.2616 (5)	0.3037 (12)	0.181 (5)	0.83
H15A	0.3847	0.2396	0.2496	0.217*	0.83
H15B	0.4641	0.2612	0.4047	0.217*	0.83
C16	0.4496 (12)	0.3174 (5)	0.2607 (16)	0.232 (7)	0.83
H16A	0.5305	0.3381	0.2977	0.348*	0.83
H16B	0.3864	0.3376	0.2953	0.348*	0.83
H16C	0.4228	0.3184	0.1567	0.348*	0.83
C15'	0.4923 (18)	0.2749 (12)	0.213 (3)	0.090 (8)	0.17
H15C	0.5365	0.3140	0.2372	0.108*	0.17
H15D	0.4727	0.2690	0.1094	0.108*	0.17
C16'	0.372 (2)	0.2782 (14)	0.248 (5)	0.125 (13)	0.17
H16D	0.3180	0.3090	0.1892	0.188*	0.17
H16E	0.3897	0.2888	0.3487	0.188*	0.17
H16F	0.3298	0.2390	0.2303	0.188*	0.17
C17	0.9008 (4)	0.23002 (19)	0.3483 (5)	0.0814 (11)
H17A	0.8536	0.2535	0.2637	0.098*
H17B	0.9449	0.1968	0.3162	0.098*
C18	0.9998 (4)	0.2719 (2)	0.4523 (5)	0.0897 (13)
H18A	0.9553	0.3058	0.4813	0.108*
H18B	1.0437	0.2487	0.5388	0.108*
C19	1.0961 (5)	0.2970 (2)	0.3882 (5)	0.1017 (15)
H19A	1.0523	0.3158	0.2955	0.122*
H19B	1.1485	0.2635	0.3709	0.122*
C20	1.1828 (5)	0.3447 (2)	0.4862 (6)	0.126 (2)
H20A	1.1321	0.3792	0.4981	0.190*
H20B	1.2465	0.3582	0.4432	0.190*
H20C	1.2244	0.3266	0.5791	0.190*
N1	0.9493 (3)	0.12572 (14)	0.5138 (3)	0.0637 (7)
H1A	0.997 (3)	0.1387 (16)	0.464 (3)	0.076*
N2	0.8108 (3)	0.20414 (16)	0.4177 (4)	0.0801 (9)
O1	1.3122 (2)	0.06116 (13)	0.5196 (3)	0.0769 (7)
O2	1.1519 (3)	0.12628 (13)	0.4189 (3)	0.0869 (8)
S1	0.95706 (9)	0.03954 (4)	0.72506 (10)	0.0662 (3)
S2	0.74212 (10)	0.13005 (5)	0.60210 (13)	0.0823 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.080 (2)	0.060 (2)	0.0549 (19)	−0.0045 (17)	0.0284 (17)	−0.0010 (16)
C2	0.106 (3)	0.085 (3)	0.075 (3)	0.006 (2)	0.041 (2)	0.018 (2)
C3	0.109 (6)	0.097 (6)	0.093 (6)	0.026 (4)	0.040 (5)	0.035 (5)
C4	0.094 (5)	0.099 (6)	0.083 (6)	0.014 (5)	0.021 (5)	0.019 (4)
C4'	0.083 (12)	0.078 (11)	0.068 (10)	0.020 (9)	0.021 (9)	−0.004 (8)
C3'	0.18 (2)	0.106 (17)	0.053 (10)	0.055 (16)	0.040 (12)	0.009 (9)
C5	0.079 (2)	0.074 (2)	0.077 (3)	0.010 (2)	0.030 (2)	0.006 (2)
C6	0.0649 (19)	0.0570 (19)	0.0541 (18)	−0.0018 (16)	0.0225 (15)	−0.0035 (15)
C7	0.0634 (19)	0.0523 (17)	0.0542 (18)	−0.0054 (15)	0.0248 (15)	−0.0023 (14)
C8	0.0610 (18)	0.0520 (18)	0.0511 (17)	−0.0049 (15)	0.0194 (15)	−0.0051 (14)
C9	0.068 (2)	0.062 (2)	0.067 (2)	−0.0079 (17)	0.0303 (18)	0.0015 (18)
C10	0.081 (3)	0.113 (4)	0.108 (4)	−0.012 (3)	0.053 (3)	0.013 (3)
C11	0.111 (4)	0.130 (4)	0.102 (4)	−0.005 (3)	0.065 (3)	0.004 (3)
C12	0.062 (2)	0.065 (2)	0.068 (2)	0.0013 (17)	0.0149 (17)	−0.0078 (18)
C13	0.098 (3)	0.094 (3)	0.116 (4)	0.013 (3)	0.031 (3)	0.008 (3)
C14	0.090 (4)	0.154 (5)	0.118 (4)	0.010 (4)	0.015 (3)	0.014 (4)
C15	0.111 (7)	0.256 (15)	0.161 (9)	0.068 (8)	0.021 (6)	0.083 (9)
C16	0.180 (11)	0.235 (14)	0.296 (17)	0.081 (11)	0.096 (11)	0.137 (14)
C15'	0.09 (2)	0.087 (19)	0.09 (2)	0.015 (16)	0.029 (17)	0.017 (16)
C16'	0.10 (3)	0.10 (2)	0.18 (4)	−0.02 (2)	0.05 (3)	0.03 (2)
C17	0.084 (3)	0.076 (3)	0.079 (3)	0.008 (2)	0.017 (2)	0.016 (2)
C18	0.092 (3)	0.086 (3)	0.087 (3)	−0.001 (2)	0.020 (2)	0.009 (2)
C19	0.109 (4)	0.089 (3)	0.104 (4)	−0.005 (3)	0.027 (3)	0.015 (3)
C20	0.119 (4)	0.102 (4)	0.137 (5)	−0.025 (3)	0.007 (4)	0.003 (4)
N1	0.0641 (17)	0.0633 (18)	0.0680 (19)	0.0034 (14)	0.0262 (14)	0.0037 (15)
N2	0.073 (2)	0.076 (2)	0.090 (2)	0.0137 (17)	0.0216 (18)	0.0066 (19)
O1	0.0683 (15)	0.0907 (19)	0.0836 (18)	−0.0001 (14)	0.0410 (14)	0.0126 (14)
O2	0.094 (2)	0.0862 (19)	0.095 (2)	0.0115 (16)	0.0501 (17)	0.0313 (16)
S1	0.0714 (6)	0.0700 (6)	0.0664 (6)	−0.0047 (4)	0.0345 (4)	0.0008 (4)
S2	0.0682 (6)	0.0924 (8)	0.0923 (8)	−0.0011 (5)	0.0333 (5)	−0.0054 (6)

Geometric parameters (Å, º) top

C1—C6	1.352 (4)	C12—N2	1.353 (5)
C1—C2	1.498 (5)	C12—N1	1.362 (4)
C1—S1	1.732 (4)	C12—S2	1.672 (4)
C2—C3'	1.488 (15)	C13—C14	1.457 (6)
C2—C3	1.520 (8)	C13—N2	1.502 (5)
C2—H2A	0.9700	C13—H13A	0.9700
C2—H2B	0.9700	C13—H13B	0.9700
C2—H2C	0.9700	C14—C15'	1.522 (16)
C2—H2D	0.9700	C14—C15	1.597 (9)
C3—C4	1.452 (11)	C14—H14A	0.9700
C3—H3A	0.9700	C14—H14B	0.9700
C3—H3B	0.9700	C14—H14C	0.9700
C4—C5	1.534 (7)	C14—H14D	0.9700
C4—H4A	0.9700	C15—C16	1.274 (11)
C4—H4B	0.9700	C15—H15A	0.9700
C4'—C5	1.552 (14)	C15—H15B	0.9700
C4'—C3'	1.63 (2)	C16—H16A	0.9600
C4'—H4'1	0.9700	C16—H16B	0.9600
C4'—H4'2	0.9700	C16—H16C	0.9600
C3'—H3'1	0.9700	C15'—C16'	1.454 (19)
C3'—H3'2	0.9700	C15'—H15C	0.9700
C5—C6	1.505 (5)	C15'—H15D	0.9700
C5—H5A	0.9700	C16'—H16D	0.9600
C5—H5B	0.9700	C16'—H16E	0.9600
C5—H5C	0.9700	C16'—H16F	0.9600
C5—H5D	0.9700	C17—N2	1.461 (5)
C6—C7	1.435 (4)	C17—C18	1.532 (6)
C7—C8	1.385 (4)	C17—H17A	0.9700
C7—C9	1.460 (4)	C17—H17B	0.9700
C8—N1	1.380 (4)	C18—C19	1.480 (6)
C8—S1	1.715 (3)	C18—H18A	0.9700
C9—O2	1.219 (4)	C18—H18B	0.9700
C9—O1	1.333 (4)	C19—C20	1.524 (6)
C10—C11	1.449 (6)	C19—H19A	0.9700
C10—O1	1.458 (4)	C19—H19B	0.9700
C10—H10A	0.9700	C20—H20A	0.9600
C10—H10B	0.9700	C20—H20B	0.9600
C11—H11A	0.9600	C20—H20C	0.9600
C11—H11B	0.9600	N1—H1A	0.86 (3)
C11—H11C	0.9600

C6—C1—C2	126.3 (4)	C10—C11—H11B	109.5
C6—C1—S1	113.3 (3)	H11A—C11—H11B	109.5
C2—C1—S1	120.4 (3)	C10—C11—H11C	109.5
C3'—C2—C1	110.3 (8)	H11A—C11—H11C	109.5
C1—C2—C3	109.7 (4)	H11B—C11—H11C	109.5
C3'—C2—H2A	132.0	N2—C12—N1	114.3 (3)
C1—C2—H2A	109.7	N2—C12—S2	124.0 (3)
C3—C2—H2A	109.7	N1—C12—S2	121.7 (3)
C3'—C2—H2B	81.6	C14—C13—N2	112.5 (4)
C1—C2—H2B	109.7	C14—C13—H13A	109.1
C3—C2—H2B	109.7	N2—C13—H13A	109.1
H2A—C2—H2B	108.2	C14—C13—H13B	109.1
C3'—C2—H2C	112.7	N2—C13—H13B	109.1
C1—C2—H2C	109.8	H13A—C13—H13B	107.8
C3—C2—H2C	134.6	C13—C14—C15'	116.0 (11)
H2A—C2—H2C	76.3	C13—C14—C15	108.2 (6)
C3'—C2—H2D	106.3	C13—C14—H14A	110.1
C1—C2—H2D	109.6	C15'—C14—H14A	131.1
C3—C2—H2D	78.4	C15—C14—H14A	110.1
H2B—C2—H2D	133.7	C13—C14—H14B	110.1
H2C—C2—H2D	107.8	C15—C14—H14B	110.1
C4—C3—C2	114.6 (6)	H14A—C14—H14B	108.4
C4—C3—H3A	108.6	C13—C14—H14C	111.9
C2—C3—H3A	108.6	C15'—C14—H14C	112.0
C4—C3—H3B	108.6	H14B—C14—H14C	130.0
C2—C3—H3B	108.6	C13—C14—H14D	111.0
H3A—C3—H3B	107.6	C15'—C14—H14D	95.9
C3—C4—C5	112.3 (7)	C15—C14—H14D	131.3
C3—C4—H4A	109.2	H14C—C14—H14D	108.9
C5—C4—H4A	109.2	C16—C15—C14	117.9 (11)
C3—C4—H4B	109.2	C16—C15—H15A	107.8
C5—C4—H4B	109.2	C14—C15—H15A	107.8
H4A—C4—H4B	107.9	C16—C15—H15B	107.8
C5—C4'—C3'	108.2 (12)	C14—C15—H15B	107.8
C5—C4'—H4'1	110.1	H15A—C15—H15B	107.2
C3'—C4'—H4'1	110.1	C16'—C15'—C14	114.7 (19)
C5—C4'—H4'2	110.1	C16'—C15'—H15C	108.6
C3'—C4'—H4'2	110.1	C14—C15'—H15C	108.6
H4'1—C4'—H4'2	108.4	C16'—C15'—H15D	108.6
C2—C3'—C4'	104.1 (12)	C14—C15'—H15D	108.6
C2—C3'—H3'1	110.9	H15C—C15'—H15D	107.6
C4'—C3'—H3'1	110.9	C15'—C16'—H16D	109.5
C2—C3'—H3'2	110.9	C15'—C16'—H16E	109.5
C4'—C3'—H3'2	110.9	H16D—C16'—H16E	109.5
H3'1—C3'—H3'2	109.0	C15'—C16'—H16F	109.5
C6—C5—C4	111.3 (4)	H16D—C16'—H16F	109.5
C6—C5—C4'	110.0 (8)	H16E—C16'—H16F	109.5
C6—C5—H5A	109.4	N2—C17—C18	111.4 (4)
C4—C5—H5A	109.4	N2—C17—H17A	109.3
C4'—C5—H5A	133.0	C18—C17—H17A	109.3
C6—C5—H5B	109.4	N2—C17—H17B	109.3
C4—C5—H5B	109.4	C18—C17—H17B	109.3
H5A—C5—H5B	108.0	H17A—C17—H17B	108.0
C6—C5—H5C	109.9	C19—C18—C17	113.1 (4)
C4'—C5—H5C	110.8	C19—C18—H18A	108.9
H5B—C5—H5C	130.8	C17—C18—H18A	108.9
C6—C5—H5D	108.9	C19—C18—H18B	108.9
C4—C5—H5D	131.5	C17—C18—H18B	109.0
C4'—C5—H5D	109.0	H18A—C18—H18B	107.8
H5C—C5—H5D	108.1	C18—C19—C20	112.1 (4)
C1—C6—C7	111.5 (3)	C18—C19—H19A	109.2
C1—C6—C5	120.8 (3)	C20—C19—H19A	109.2
C7—C6—C5	127.6 (3)	C18—C19—H19B	109.2
C8—C7—C6	112.3 (3)	C20—C19—H19B	109.2
C8—C7—C9	120.4 (3)	H19A—C19—H19B	107.9
C6—C7—C9	127.2 (3)	C19—C20—H20A	109.5
N1—C8—C7	122.5 (3)	C19—C20—H20B	109.5
N1—C8—S1	125.5 (2)	H20A—C20—H20B	109.5
C7—C8—S1	112.0 (2)	C19—C20—H20C	109.5
O2—C9—O1	121.9 (3)	H20A—C20—H20C	109.5
O2—C9—C7	124.6 (3)	H20B—C20—H20C	109.5
O1—C9—C7	113.5 (3)	C12—N1—C8	130.4 (3)
C11—C10—O1	111.0 (4)	C12—N1—H1A	121 (3)
C11—C10—H10A	109.4	C8—N1—H1A	109 (3)
O1—C10—H10A	109.4	C12—N2—C17	123.9 (3)
C11—C10—H10B	109.4	C12—N2—C13	120.2 (4)
O1—C10—H10B	109.4	C17—N2—C13	114.9 (3)
H10A—C10—H10B	108.0	C9—O1—C10	117.8 (3)
C10—C11—H11A	109.5	C8—S1—C1	90.86 (16)

C6—C1—C2—C3'	23.4 (10)	C6—C7—C9—O2	−179.4 (4)
S1—C1—C2—C3'	−155.7 (8)	C8—C7—C9—O1	−178.1 (3)
C6—C1—C2—C3	−9.1 (7)	C6—C7—C9—O1	0.8 (5)
S1—C1—C2—C3	171.9 (5)	N2—C13—C14—C15'	−145.7 (11)
C3'—C2—C3—C4	−57.1 (15)	N2—C13—C14—C15	171.8 (5)
C1—C2—C3—C4	39.8 (10)	C13—C14—C15—C16	76.9 (14)
C2—C3—C4—C5	−59.9 (11)	C15'—C14—C15—C16	−32.1 (19)
C1—C2—C3'—C4'	−54.3 (15)	C13—C14—C15'—C16'	−106 (3)
C3—C2—C3'—C4'	40.2 (10)	C15—C14—C15'—C16'	−19 (2)
C5—C4'—C3'—C2	71.5 (17)	N2—C17—C18—C19	177.6 (4)
C3—C4—C5—C6	45.6 (9)	C17—C18—C19—C20	172.7 (4)
C3—C4—C5—C4'	−48.1 (16)	N2—C12—N1—C8	171.8 (3)
C3'—C4'—C5—C6	−50.6 (14)	S2—C12—N1—C8	−7.6 (5)
C3'—C4'—C5—C4	47.6 (13)	C7—C8—N1—C12	−172.7 (3)
C2—C1—C6—C7	−179.1 (4)	S1—C8—N1—C12	5.7 (5)
S1—C1—C6—C7	0.0 (4)	N1—C12—N2—C17	−7.3 (5)
C2—C1—C6—C5	−1.7 (6)	S2—C12—N2—C17	172.2 (3)
S1—C1—C6—C5	177.4 (3)	N1—C12—N2—C13	−175.5 (3)
C4—C5—C6—C1	−15.9 (6)	S2—C12—N2—C13	3.9 (5)
C4'—C5—C6—C1	17.0 (8)	C18—C17—N2—C12	−81.1 (5)
C4—C5—C6—C7	161.0 (5)	C18—C17—N2—C13	87.7 (4)
C4'—C5—C6—C7	−166.1 (7)	C14—C13—N2—C12	−92.5 (5)
C1—C6—C7—C8	0.8 (4)	C14—C13—N2—C17	98.3 (5)
C5—C6—C7—C8	−176.3 (3)	O2—C9—O1—C10	−0.9 (6)
C1—C6—C7—C9	−178.1 (3)	C7—C9—O1—C10	178.9 (3)
C5—C6—C7—C9	4.8 (6)	C11—C10—O1—C9	−92.2 (5)
C6—C7—C8—N1	177.3 (3)	N1—C8—S1—C1	−177.4 (3)
C9—C7—C8—N1	−3.7 (5)	C7—C8—S1—C1	1.1 (3)
C6—C7—C8—S1	−1.3 (4)	C6—C1—S1—C8	−0.7 (3)
C9—C7—C8—S1	177.7 (3)	C2—C1—S1—C8	178.5 (3)
C8—C7—C9—O2	1.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86 (3)	1.89 (2)	2.643 (4)	145 (3)

Experimental details

Crystal data
Chemical formula	C₂₀H₃₂N₂O₂S₂
M_r	396.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	10.9311 (11), 21.715 (3), 9.6841 (3)
β (°)	107.711 (12)
V (Å³)	2189.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.36 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.903, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	12194, 4036, 3460
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.153, 1.21
No. of reflections	4036
No. of parameters	280
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.23

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86 (3)	1.89 (2)	2.643 (4)	145 (3)

Acknowledgements

We gratefully acknowledge financial support of this work by the National Basic Research Program of China (2003CB114400), the National Natural Science Foundation of China (20372023, 20102001), the Educational Commission of Hubei Province of China (grant No. D20092406, B20092412), the Shiyan Municipal Science and Technology Bureau (grant No. 20061835), and Yunyang Medical College (grant Nos. 2007QDJ14, 2007QDJ15, 2007ZQB19).

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Volume 65| Part 12| December 2009| Pages o3094-o3095

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 2-(3,3-di­butyl­thio­ureido)-4,5,6,7-tetra­hydro­benzo[b]thio­phene-3-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl 2-(3,3-dibutylthioureido)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate