[(Pyrrolidin-1-yl)carbothio­ylsulfan­yl]methyl pyrrolidine-1-carbodithio­ate

Chou, W.-L.; Yih, K.-H.; Lee, G.-H.; Huang, Y.-H.; Wang, H.-F.

doi:10.1107/S1600536810046027

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3193

https://doi.org/10.1107/S1600536810046027

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[(Pyrrolidin-1-yl)carbothioylsulfanyl]methyl pyrrolidine-1-carbodithioate

Wei-Lung Chou,^a Kuang-Hway Yih,^b ^* Gene-Hsiang Lee,^c ^* Yen-Hsiang Huang ^a and Hsiao-Fen Wang ^b

^aDepartment of Industrial Safety and Health & Institute Occupational Safety and Hazard Prevention, Hungkuang University, Shalu 433, Taichung, Taiwan, ^bDepartment of Applied Cosmetology, Hungkuang University, Shalu 433, Taichung, Taiwan, and ^cInstrumentation Center, College of Science, National Taiwan University, Taipei 106, Taiwan
^*Correspondence e-mail: khyih@sunrise.hk.edu.tw, ghlee@ntu.edu.tw

(Received 10 September 2010; accepted 8 November 2010; online 17 November 2010)

The title compound, C₁₁H₁₈N₂S₄, was unexpectedly obtained during studies on the reactivity of the complex tris(acac-κ²O,O′)gallium(III) (acac is acetylacetonate) with C₄H₈NCS₂H in dichloromethane. The title compound shows disordered two pyrrolidine rings with major and minor occupancies of 0.546 (4) and 0.454 (4). Two (pyrrolidin-1-yl)carbothioylsulfanyl units are linked together through a methylene C atom and weak C—H⋯S interactions are found.

Related literature

For bis(dialkyldithiocarbamates), CH₂(S₂CNR₂)₂, see: R = Me (Thomas, 1945 , 1946 ); R = Et (Heckley et al., 1970 ); R = C₅H₁₀ (Sharma et al., 1991 ). For weak C—H⋯S interactions, see: Kayed et al. (2008 ); Pervez et al. (2010 ); Vangala et al. (2002 ); Yaqub et al. (2010 ). For our previous work on the preparation of In(III) complexes, see: Chou et al. (2007 ). For C=S double-bond lengths, see: Pauling (1960 ).

Experimental

Crystal data

C₁₁H₁₈N₂S₄
M_r = 306.51
Orthorhombic, P c a 2₁
a = 21.9118 (18) Å
b = 4.5705 (4) Å
c = 14.3452 (12) Å
V = 1436.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 150 K
0.25 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.856, T_max = 0.910
17016 measured reflections
3292 independent reflections
2759 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.166
S = 1.07
3292 reflections
180 parameters
17 restraints
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 1579 Friedel pairs
Flack parameter: −0.1 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯S3ⁱ	0.99	2.89	3.811 (9)	155
C10—H10B⋯S4ⁱⁱ	0.99	2.99	3.699 (11)	130
C9—H9A⋯S1ⁱⁱ	0.99	2.87	3.740 (8)	147
C9′—H9′A⋯S1ⁱⁱ	0.99	3.50	4.209 (11)	131
C5′—H5′B⋯S2ⁱ	0.99	2.94	3.704 (14)	137
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046027/bv2162sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046027/bv2162Isup2.hkl

checkCIF report

Comment top

Formation of methylene bis(dialkyldithiocarbamates), CH₂(S₂CNR₂)₂ [R = Me (Thomas, 1946), Et (Heckley et al., 1970), C₅H₁₀ (Sharma et al., 1991)] have been reported in the literature as by-products in the reactions of transition metal halides with anhydrous sodium dialkyldithiocarbamates when methylene chloride was used as solvent or reaction of anhydrous sodium dialkyldithiocarbamates with methylene chloride under refluxing conditions (Sharma et al., 1991).

Our previous report showed complexes [In(S₂CNC₅H₁₀)₃], [In(pyS)₃] and [In(pyS)₂(acac)] (acac: acetylacetonate; pyS: pyridine-2-thionate) are prepared by reacting the complex tris(acac-κ²O,O')indium(III) with HS₂CNC₅H₁₀, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively (Chou et al., 2007). To test the generality of this substitution reaction, we studied the reaction of tris(acac-κ²O,O')gallium(III) complex and C₄H₈NCS₂H. During studies on the reactivity of complex tris(acac-κ²O,O')gallium(III), with C₄H₈NCS₂H in dichloromethane, we unexpectedly obtained the white crystals of title compound (I), identified as methylene bis(pyrrolidinyldithiocarbamate) by X-ray structure, NMR and Mass spectroscopic analyses. It consists of two pyrrolidinyldithiocarbamate units, bridged by a methylene group, i.e. C₄H₈N—CS—S—CH₂—S—CS—NC₄H₈. The ¹H NMR spectrum of (I) in CDCl₃ shows one singlet at 5.33 ppm., assignable to SCH₂S. The IR spectrum shows the following characteristic bands, 1470 cm^-1 (νC=N), 1305 cm^-1 (νC-N), 990 cm^-1 (νC=S), 915 cm^-1 (νC-S). The FAB mass spectrum shows the molecular ions C₁₁H₁₈N₂S₄ with the characteristic isotopic distribution patterns.

The solid-state structure has been established by X-ray crystallography. The molecular structure of the title compound is shown in Fig. 1. In (I), the C1—S2 and C6—S4 bond lengths of 1.725 (10) and 1.693 (8) Å, respectively, are slightly longer than a normal C=S double bond (ca 1.61 Å) (Pauling, 1960), while the C1—S1 and C6—S3 distance of 1.743 (10) and 1.827 (8) Å, respectively, are clearly single bonds. The angle of S3—C11—S1 (114.05 (18)°) is larger than the ideal tetrahedral value of 109.47°, probably due to repulsion between the two C=S bonding electron pairs. Two pyrrolidinyl groups are found to be disordered over two positions (C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) and (C1', C2', C3', C4', C5', C6', C7', C8', C9', C10') and refined ratios of the major and minor components being 0.546 (4): 0.454 (4). As a result of two different packings are shown in Fig. 2(a) and (b). The weak interactions of C—H···S (3.683 (6) - 3.823 (11) Å) in (I) are also found in those of (E)-2-[1-(1-benzothiophen-3-yl)ethylidene]hydrazinecarbothioamide (3.613 (3) - 3.762 (4) Å) (Kayed et al., 2008), 4-(5-chloro-2- methylphenyl)-1-[2-oxo-5-(trifluoromethoxy)indolin-3-ylidene]thiosemicarbazide (3.245 (4) Å) (Pervez et al., 2010), bis(4-aminophenyl)disulfide (3.7387 (18) Å) (Vangala et al., 2002) and 1-[1-(4-bromophenyl)ethylidene]-4-(2,4-dimethoxyphenyl)thiosemicarbazide (3.774 (3) Å) (Yaqub et al., 2010), respectively.

Related literature top

For bis(dialkyldithiocarbamates), CH₂(S₂CNR₂)₂, see: R = Me (Thomas, 1945, 1946); R = Et (Heckley et al., 1970); R = C₅H₁₀ (Sharma et al., 1991). For weak C—H···S interactions, see: Kayed et al. (2008); Pervez et al. (2010); Vangala et al. (2002); Yaqub et al. (2010). For our previous work on the preparation of In(III) complexes, see: Chou et al. (2007). For C=S double-bond lengths, see: Pauling (1960).

Experimental top

The synthesis of the title compound (I) was carried out as follows. 10 ml of CH₂Cl₂ was added to a flask of Ga(acac)₃ (0.367 g, 1.0 mmol) and C₄H₈NCS₂H (0.345 g, 3.0 mmol). The solution was stirred for 2 days at room temperature. The solution is concentrated under vacuum and n-hexane (10 ml) was added to initiate precipitation. The pale-white solids were isolated by filtration (G4), washed with n-hexane (2 x 10 ml) and subsequently drying under vacuum yielding [CH₂(S₂CNC₄H₈)₂] (0.459 g, 50%). Further purification was accomplished by recrystallization from 1/10 CH₂Cl₂/n-hexane. The pale-white crystals of (I) for X-ray structure analysis were obtained by slow diffusion of n-hexane into the CH₂Cl₂ solution of the title compound at room temperature for 3 days. Spectroscopic analysis: ¹H NMR (CDCl₃, 298 K, δ, p.p.m.): δ 1.65, 1.74 (m, 4H, NCCH₂), δ 2.98, 3.29 (m, 4H, NCH₂), 5.33 (s, 2H, SCH₂). 13C{¹H} NMR (CDCl₃, 298 K, δ, p.p.m.): δ 24.8 (s, NCH₂CH₂), 49.8 (s, NCH₂), 50.0 (s, SCH₂S), 191.5 (s, CS). MS (m/z): 306.5 (M⁺). Anal. Calcd for C₁₁H₁₈N₂S₄: C, 43.10; H, 5.92; N, 9.14. Found: C, 43.31; H, 5.69; N, 9.02.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing two independent molecules and the 50% probability displacement ellipsoids.
	Fig. 2. The packing diagram of (I), showing two different packing patterns.

[(Pyrrolidin-1-yl)carbothioylsulfanyl]methyl pyrrolidine-1-carbodithioate top

Crystal data top

C₁₁H₁₈N₂S₄	F(000) = 648
M_r = 306.51	D_x = 1.417 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2540 reflections
a = 21.9118 (18) Å	θ = 2.3–26.6°
b = 4.5705 (4) Å	µ = 0.64 mm⁻¹
c = 14.3452 (12) Å	T = 150 K
V = 1436.6 (2) Å³	Block, light-brown
Z = 4	0.25 × 0.25 × 0.15 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3292 independent reflections
Radiation source: fine-focus sealed tube	2759 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −28→28
T_min = 0.856, T_max = 0.910	k = −5→5
17016 measured reflections	l = −18→18

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)] = 0.062	H-atom parameters constrained
wR(F²) = 0.166	w = 1/[σ²(F_o²) + (0.1007P)² + 0.6346P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.003
3292 reflections	Δρ_max = 1.05 e Å⁻³
180 parameters	Δρ_min = −0.27 e Å⁻³
17 restraints	Absolute structure: Flack (1983), 1579 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.1 (2)

Crystal data top

C₁₁H₁₈N₂S₄	V = 1436.6 (2) Å³
M_r = 306.51	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 21.9118 (18) Å	µ = 0.64 mm⁻¹
b = 4.5705 (4) Å	T = 150 K
c = 14.3452 (12) Å	0.25 × 0.25 × 0.15 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3292 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2759 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.910	R_int = 0.043
17016 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.166	Δρ_max = 1.05 e Å⁻³
S = 1.07	Δρ_min = −0.27 e Å⁻³
3292 reflections	Absolute structure: Flack (1983), 1579 Friedel pairs
180 parameters	Absolute structure parameter: −0.1 (2)
17 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	Occ. (<1)
S1	0.34241 (4)	0.48896 (18)	0.20742 (6)	0.0247 (3)
S2	0.24742 (5)	0.4861 (2)	0.05150 (8)	0.0332 (3)
S3	0.40977 (4)	0.48200 (19)	0.02225 (7)	0.0292 (3)
S4	0.50250 (6)	0.4996 (2)	0.18040 (8)	0.0333 (3)
N1	0.23596 (13)	0.7324 (7)	0.2179 (2)	0.0280 (7)
N2	0.51532 (12)	0.7401 (7)	0.0131 (2)	0.0292 (7)
C1	0.2724 (4)	0.593 (2)	0.1603 (7)	0.0232 (12)	0.546 (4)
C2	0.1742 (5)	0.840 (3)	0.1934 (7)	0.0354 (9)	0.546 (4)
H2A	0.1450	0.6753	0.1894	0.043*	0.546 (4)
H2B	0.1749	0.9430	0.1327	0.043*	0.546 (4)
C3	0.1558 (4)	1.0519 (19)	0.2724 (6)	0.0388 (19)	0.546 (4)
H3A	0.1691	1.2541	0.2580	0.047*	0.546 (4)
H3B	0.1111	1.0507	0.2820	0.047*	0.546 (4)
C4	0.1889 (4)	0.935 (2)	0.3579 (6)	0.039 (2)	0.546 (4)
H4A	0.1669	0.7670	0.3857	0.047*	0.546 (4)
H4B	0.1943	1.0887	0.4057	0.047*	0.546 (4)
C5	0.2514 (4)	0.838 (2)	0.3155 (7)	0.0288 (11)	0.546 (4)
H5A	0.2803	1.0043	0.3132	0.035*	0.546 (4)
H5B	0.2698	0.6784	0.3528	0.035*	0.546 (4)
C1'	0.2682 (6)	0.549 (3)	0.1543 (10)	0.0232 (12)	0.454 (4)
C2'	0.1763 (6)	0.843 (4)	0.1926 (8)	0.0354 (9)	0.454 (4)
H2'A	0.1520	0.6948	0.1589	0.043*	0.454 (4)
H2'B	0.1794	1.0226	0.1541	0.043*	0.454 (4)
C3'	0.1491 (4)	0.910 (2)	0.2897 (7)	0.0388 (19)	0.454 (4)
H3'A	0.1174	1.0640	0.2862	0.047*	0.454 (4)
H3'B	0.1314	0.7321	0.3184	0.047*	0.454 (4)
C4'	0.2053 (4)	1.016 (2)	0.3437 (9)	0.039 (2)	0.454 (4)
H4'A	0.1985	1.0058	0.4119	0.047*	0.454 (4)
H4'B	0.2164	1.2183	0.3262	0.047*	0.454 (4)
C5'	0.2549 (5)	0.793 (3)	0.3119 (10)	0.0288 (11)	0.454 (4)
H5'A	0.2962	0.8811	0.3136	0.035*	0.454 (4)
H5'B	0.2544	0.6145	0.3508	0.035*	0.454 (4)
C6	0.4816 (3)	0.6102 (15)	0.0724 (6)	0.0200 (9)*	0.546 (4)
C7	0.5772 (5)	0.855 (3)	0.0389 (7)	0.0366 (10)	0.546 (4)
H7A	0.6075	0.6954	0.0428	0.044*	0.546 (4)
H7B	0.5760	0.9611	0.0990	0.044*	0.546 (4)
C8	0.5912 (4)	1.0600 (16)	−0.0409 (6)	0.033 (2)	0.546 (4)
H8A	0.5747	1.2579	−0.0287	0.040*	0.546 (4)
H8B	0.6358	1.0747	−0.0513	0.040*	0.546 (4)
C9	0.5603 (4)	0.9224 (18)	−0.1231 (5)	0.0301 (17)	0.546 (4)
H9A	0.5837	0.7523	−0.1464	0.036*	0.546 (4)
H9B	0.5551	1.0652	−0.1743	0.036*	0.546 (4)
C10	0.4984 (4)	0.827 (3)	−0.0837 (8)	0.0322 (10)	0.546 (4)
H10A	0.4687	0.9902	−0.0839	0.039*	0.546 (4)
H10B	0.4813	0.6600	−0.1191	0.039*	0.546 (4)
C6'	0.4807 (5)	0.551 (2)	0.0695 (8)	0.0200 (9)*	0.454 (4)
C7'	0.5740 (6)	0.853 (4)	0.0417 (8)	0.0366 (10)	0.454 (4)
H7'A	0.5983	0.7013	0.0740	0.044*	0.454 (4)
H7'B	0.5693	1.0245	0.0832	0.044*	0.454 (4)
C8'	0.6031 (4)	0.939 (2)	−0.0505 (8)	0.033 (2)	0.454 (4)
H8'A	0.6318	1.1039	−0.0417	0.040*	0.454 (4)
H8'B	0.6256	0.7717	−0.0778	0.040*	0.454 (4)
C9'	0.5511 (5)	1.027 (2)	−0.1120 (8)	0.0301 (17)	0.454 (4)
H9'A	0.5618	1.0074	−0.1788	0.036*	0.454 (4)
H9'B	0.5383	1.2315	−0.0996	0.036*	0.454 (4)
C10'	0.5010 (5)	0.808 (4)	−0.0837 (10)	0.0322 (10)	0.454 (4)
H10C	0.4599	0.8968	−0.0892	0.039*	0.454 (4)
H10D	0.5027	0.6299	−0.1230	0.039*	0.454 (4)
C11	0.37625 (18)	0.2698 (7)	0.1150 (4)	0.0358 (8)
H11A	0.4081	0.1426	0.1423	0.043*
H11B	0.3444	0.1413	0.0882	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0171 (4)	0.0341 (5)	0.0230 (6)	0.0012 (3)	−0.0019 (4)	0.0022 (3)
S2	0.0255 (5)	0.0514 (7)	0.0228 (6)	−0.0023 (4)	0.0000 (4)	−0.0059 (4)
S3	0.0214 (5)	0.0404 (6)	0.0259 (7)	−0.0009 (3)	0.0048 (4)	−0.0009 (4)
S4	0.0291 (5)	0.0535 (8)	0.0174 (6)	0.0030 (4)	0.0006 (4)	0.0072 (4)
N1	0.0272 (14)	0.0342 (15)	0.0226 (15)	0.0002 (12)	0.0001 (12)	0.0005 (12)
N2	0.0245 (13)	0.0388 (17)	0.0244 (15)	0.0028 (12)	0.0007 (12)	0.0005 (13)
C1	0.0175 (18)	0.031 (3)	0.0217 (19)	−0.0108 (19)	0.0036 (15)	0.003 (2)
C2	0.0293 (18)	0.049 (2)	0.0284 (18)	0.0045 (17)	−0.0025 (15)	−0.0022 (18)
C3	0.044 (3)	0.042 (5)	0.030 (4)	0.011 (3)	0.016 (3)	0.014 (3)
C4	0.026 (4)	0.059 (5)	0.033 (4)	−0.008 (3)	0.008 (3)	−0.002 (3)
C5	0.0359 (19)	0.025 (3)	0.0251 (18)	0.0014 (19)	−0.0016 (16)	−0.007 (2)
C1'	0.0175 (18)	0.031 (3)	0.0217 (19)	−0.0108 (19)	0.0036 (15)	0.003 (2)
C2'	0.0293 (18)	0.049 (2)	0.0284 (18)	0.0045 (17)	−0.0025 (15)	−0.0022 (18)
C3'	0.044 (3)	0.042 (5)	0.030 (4)	0.011 (3)	0.016 (3)	0.014 (3)
C4'	0.026 (4)	0.059 (5)	0.033 (4)	−0.008 (3)	0.008 (3)	−0.002 (3)
C5'	0.0359 (19)	0.025 (3)	0.0251 (18)	0.0014 (19)	−0.0016 (16)	−0.007 (2)
C7	0.0239 (18)	0.053 (3)	0.033 (2)	−0.0054 (17)	−0.0006 (16)	0.0003 (19)
C8	0.028 (3)	0.020 (5)	0.052 (5)	0.003 (3)	−0.010 (3)	0.009 (3)
C9	0.039 (3)	0.030 (5)	0.021 (3)	0.005 (3)	0.013 (3)	0.000 (3)
C10	0.037 (2)	0.036 (2)	0.0245 (19)	0.0014 (17)	−0.0037 (15)	−0.0016 (17)
C7'	0.0239 (18)	0.053 (3)	0.033 (2)	−0.0054 (17)	−0.0006 (16)	0.0003 (19)
C8'	0.028 (3)	0.020 (5)	0.052 (5)	0.003 (3)	−0.010 (3)	0.009 (3)
C9'	0.039 (3)	0.030 (5)	0.021 (3)	0.005 (3)	0.013 (3)	0.000 (3)
C10'	0.037 (2)	0.036 (2)	0.0245 (19)	0.0014 (17)	−0.0037 (15)	−0.0016 (17)
C11	0.0294 (15)	0.0314 (17)	0.047 (2)	−0.0009 (17)	0.0098 (14)	0.003 (2)

Geometric parameters (Å, º) top

S1—C1	1.743 (10)	C2'—H2'A	0.9900
S1—C1'	1.816 (14)	C2'—H2'B	0.9900
S1—C11	1.820 (5)	C3'—C4'	1.533 (12)
S2—C1'	1.571 (14)	C3'—H3'A	0.9900
S2—C1	1.725 (10)	C3'—H3'B	0.9900
S3—C6'	1.724 (11)	C4'—C5'	1.556 (12)
S3—C11	1.802 (5)	C4'—H4'A	0.9900
S3—C6	1.827 (8)	C4'—H4'B	0.9900
S4—C6'	1.678 (12)	C5'—H5'A	0.9900
S4—C6	1.693 (8)	C5'—H5'B	0.9900
N1—C1	1.313 (10)	C7—C8	1.511 (11)
N1—C1'	1.426 (13)	C7—H7A	0.9900
N1—C5'	1.438 (13)	C7—H7B	0.9900
N1—C2'	1.448 (14)	C8—C9	1.498 (10)
N1—C2	1.483 (11)	C8—H8A	0.9900
N1—C5	1.520 (10)	C8—H8B	0.9900
N2—C6	1.273 (8)	C9—C10	1.531 (10)
N2—C6'	1.406 (11)	C9—H9A	0.9900
N2—C7'	1.445 (13)	C9—H9B	0.9900
N2—C10'	1.457 (14)	C10—H10A	0.9900
N2—C10	1.491 (11)	C10—H10B	0.9900
N2—C7	1.500 (11)	C7'—C8'	1.520 (12)
C2—C3	1.543 (11)	C7'—H7'A	0.9900
C2—H2A	0.9900	C7'—H7'B	0.9900
C2—H2B	0.9900	C8'—C9'	1.498 (11)
C3—C4	1.522 (10)	C8'—H8'A	0.9900
C3—H3A	0.9900	C8'—H8'B	0.9900
C3—H3B	0.9900	C9'—C10'	1.541 (12)
C4—C5	1.563 (10)	C9'—H9'A	0.9900
C4—H4A	0.9900	C9'—H9'B	0.9900
C4—H4B	0.9900	C10'—H10C	0.9900
C5—H5A	0.9900	C10'—H10D	0.9900
C5—H5B	0.9900	C11—H11A	0.9900
C2'—C3'	1.546 (12)	C11—H11B	0.9900

C1—S1—C1'	7.3 (7)	C2'—C3'—H3'A	111.4
C1—S1—C11	103.1 (4)	C4'—C3'—H3'B	111.4
C1'—S1—C11	98.2 (5)	C2'—C3'—H3'B	111.4
C1'—S2—C1	6.3 (9)	H3'A—C3'—H3'B	109.2
C6'—S3—C11	100.1 (4)	C3'—C4'—C5'	101.9 (9)
C6'—S3—C6	8.2 (4)	C3'—C4'—H4'A	111.4
C11—S3—C6	103.5 (3)	C5'—C4'—H4'A	111.4
C6'—S4—C6	9.3 (5)	C3'—C4'—H4'B	111.4
C1—N1—C1'	8.8 (10)	C5'—C4'—H4'B	111.4
C1—N1—C5'	120.5 (7)	H4'A—C4'—H4'B	109.2
C1'—N1—C5'	124.8 (7)	N1—C5'—C4'	101.6 (8)
C1—N1—C2'	124.2 (7)	N1—C5'—H5'A	111.5
C1'—N1—C2'	119.6 (7)	C4'—C5'—H5'A	111.5
C5'—N1—C2'	115.3 (6)	N1—C5'—H5'B	111.5
C1—N1—C2	124.6 (6)	C4'—C5'—H5'B	111.5
C1'—N1—C2	119.8 (7)	H5'A—C5'—H5'B	109.3
C5'—N1—C2	114.9 (6)	N2—C6—S4	126.4 (5)
C2'—N1—C2	1.5 (13)	N2—C6—S3	112.7 (5)
C1—N1—C5	126.7 (6)	S4—C6—S3	119.8 (4)
C1'—N1—C5	131.7 (7)	N2—C7—C8	102.4 (7)
C5'—N1—C5	8.1 (8)	N2—C7—H7A	111.3
C2'—N1—C5	108.7 (6)	C8—C7—H7A	111.3
C2—N1—C5	108.4 (5)	N2—C7—H7B	111.3
C6—N2—C6'	10.3 (7)	C8—C7—H7B	111.3
C6—N2—C7'	119.5 (6)	H7A—C7—H7B	109.2
C6'—N2—C7'	122.4 (7)	C9—C8—C7	104.1 (7)
C6—N2—C10'	127.7 (6)	C9—C8—H8A	110.9
C6'—N2—C10'	124.3 (7)	C7—C8—H8A	110.9
C7'—N2—C10'	112.7 (6)	C9—C8—H8B	110.9
C6—N2—C10	127.1 (5)	C7—C8—H8B	110.9
C6'—N2—C10	124.5 (6)	H8A—C8—H8B	109.0
C7'—N2—C10	113.0 (6)	C8—C9—C10	103.3 (7)
C10'—N2—C10	3.8 (12)	C8—C9—H9A	111.1
C6—N2—C7	121.5 (5)	C10—C9—H9A	111.1
C6'—N2—C7	124.1 (6)	C8—C9—H9B	111.1
C7'—N2—C7	2.3 (9)	C10—C9—H9B	111.1
C10'—N2—C7	110.8 (6)	H9A—C9—H9B	109.1
C10—N2—C7	111.1 (5)	N2—C10—C9	101.5 (6)
N1—C1—S2	120.9 (7)	N2—C10—H10A	111.5
N1—C1—S1	115.1 (7)	C9—C10—H10A	111.5
S2—C1—S1	123.6 (6)	N2—C10—H10B	111.5
N1—C2—C3	105.8 (7)	C9—C10—H10B	111.5
N1—C2—H2A	110.6	H10A—C10—H10B	109.3
C3—C2—H2A	110.6	N2—C6'—S4	118.6 (7)
N1—C2—H2B	110.6	N2—C6'—S3	111.9 (7)
C3—C2—H2B	110.6	S4—C6'—S3	127.1 (6)
H2A—C2—H2B	108.7	N2—C7'—C8'	102.7 (8)
C4—C3—C2	104.3 (7)	N2—C7'—H7'A	111.2
C4—C3—H3A	110.9	C8'—C7'—H7'A	111.2
C2—C3—H3A	110.9	N2—C7'—H7'B	111.2
C4—C3—H3B	110.9	C8'—C7'—H7'B	111.2
C2—C3—H3B	110.9	H7'A—C7'—H7'B	109.1
H3A—C3—H3B	108.9	C9'—C8'—C7'	105.2 (9)
C3—C4—C5	101.8 (7)	C9'—C8'—H8'A	110.7
C3—C4—H4A	111.4	C7'—C8'—H8'A	110.7
C5—C4—H4A	111.4	C9'—C8'—H8'B	110.7
C3—C4—H4B	111.4	C7'—C8'—H8'B	110.7
C5—C4—H4B	111.4	H8'A—C8'—H8'B	108.8
H4A—C4—H4B	109.3	C8'—C9'—C10'	102.2 (9)
N1—C5—C4	104.6 (6)	C8'—C9'—H9'A	111.3
N1—C5—H5A	110.8	C10'—C9'—H9'A	111.3
C4—C5—H5A	110.8	C8'—C9'—H9'B	111.3
N1—C5—H5B	110.8	C10'—C9'—H9'B	111.3
C4—C5—H5B	110.8	H9'A—C9'—H9'B	109.2
H5A—C5—H5B	108.9	N2—C10'—C9'	103.7 (9)
N1—C1'—S2	124.3 (9)	N2—C10'—H10C	111.0
N1—C1'—S1	105.3 (8)	C9'—C10'—H10C	111.0
S2—C1'—S1	128.8 (8)	N2—C10'—H10D	111.0
N1—C2'—C3'	101.0 (8)	C9'—C10'—H10D	111.0
N1—C2'—H2'A	111.6	H10C—C10'—H10D	109.0
C3'—C2'—H2'A	111.6	S3—C11—S1	114.05 (18)
N1—C2'—H2'B	111.6	S3—C11—H11A	108.7
C3'—C2'—H2'B	111.6	S1—C11—H11A	108.7
H2'A—C2'—H2'B	109.4	S3—C11—H11B	108.7
C4'—C3'—C2'	102.0 (9)	S1—C11—H11B	108.7
C4'—C3'—H3'A	111.4	H11A—C11—H11B	107.6

C1'—N1—C1—S2	52 (6)	C10'—N2—C6—S4	172.3 (10)
C5'—N1—C1—S2	173.4 (8)	C10—N2—C6—S4	177.1 (8)
C2'—N1—C1—S2	−8.8 (15)	C7—N2—C6—S4	−9.9 (11)
C2—N1—C1—S2	−7.1 (13)	C6'—N2—C6—S3	−70 (4)
C5—N1—C1—S2	179.6 (7)	C7'—N2—C6—S3	−179.6 (10)
C1'—N1—C1—S1	−120 (7)	C10'—N2—C6—S3	4.0 (12)
C5'—N1—C1—S1	0.9 (12)	C10—N2—C6—S3	8.7 (10)
C2'—N1—C1—S1	178.7 (10)	C7—N2—C6—S3	−178.2 (7)
C2—N1—C1—S1	−179.6 (8)	C6'—S4—C6—N2	−114 (4)
C5—N1—C1—S1	7.1 (12)	C6'—S4—C6—S3	54 (3)
C1'—S2—C1—N1	−95 (7)	C6'—S3—C6—N2	106 (4)
C1'—S2—C1—S1	77 (7)	C11—S3—C6—N2	172.9 (4)
C1'—S1—C1—N1	126 (6)	C6'—S3—C6—S4	−63 (4)
C11—S1—C1—N1	173.6 (7)	C11—S3—C6—S4	3.7 (5)
C1'—S1—C1—S2	−47 (6)	C6—N2—C7—C8	−164.2 (6)
C11—S1—C1—S2	1.4 (8)	C6'—N2—C7—C8	−176.1 (7)
C1—N1—C2—C3	−166.2 (8)	C7'—N2—C7—C8	−133 (32)
C1'—N1—C2—C3	−174.8 (9)	C10'—N2—C7—C8	13.9 (13)
C5'—N1—C2—C3	13.3 (13)	C10—N2—C7—C8	9.8 (12)
C2'—N1—C2—C3	−93 (32)	N2—C7—C8—C9	−32.0 (10)
C5—N1—C2—C3	8.1 (11)	C7—C8—C9—C10	42.8 (10)
N1—C2—C3—C4	−29.8 (11)	C6—N2—C10—C9	−170.8 (6)
C2—C3—C4—C5	38.6 (10)	C6'—N2—C10—C9	−158.5 (7)
C1—N1—C5—C4	−169.9 (8)	C7'—N2—C10—C9	17.1 (13)
C1'—N1—C5—C4	−160.6 (9)	C10'—N2—C10—C9	−70 (11)
C5'—N1—C5—C4	−128 (7)	C7—N2—C10—C9	15.6 (11)
C2'—N1—C5—C4	17.5 (11)	C8—C9—C10—N2	−35.2 (10)
C2—N1—C5—C4	15.9 (10)	C6—N2—C6'—S4	−66 (4)
C3—C4—C5—N1	−33.6 (9)	C7'—N2—C6'—S4	10.4 (13)
C1—N1—C1'—S2	−116 (7)	C10'—N2—C6'—S4	−179.0 (9)
C5'—N1—C1'—S2	−179.4 (10)	C10—N2—C6'—S4	−174.4 (8)
C2'—N1—C1'—S2	7.9 (17)	C7—N2—C6'—S4	12.3 (12)
C2—N1—C1'—S2	9.6 (16)	C6—N2—C6'—S3	97 (4)
C5—N1—C1'—S2	−174.2 (8)	C7'—N2—C6'—S3	174.0 (10)
C1—N1—C1'—S1	51 (6)	C10'—N2—C6'—S3	−15.4 (12)
C5'—N1—C1'—S1	−12.6 (13)	C10—N2—C6'—S3	−10.8 (11)
C2'—N1—C1'—S1	174.7 (10)	C7—N2—C6'—S3	175.9 (8)
C2—N1—C1'—S1	176.4 (8)	C6—S4—C6'—N2	49 (3)
C5—N1—C1'—S1	−7.3 (14)	C6—S4—C6'—S3	−111 (4)
C1—S2—C1'—N1	73 (7)	C11—S3—C6'—N2	−174.7 (6)
C1—S2—C1'—S1	−91 (7)	C6—S3—C6'—N2	−60 (4)
C1—S1—C1'—N1	−45 (5)	C11—S3—C6'—S4	−12.9 (7)
C11—S1—C1'—N1	−177.6 (7)	C6—S3—C6'—S4	102 (4)
C1—S1—C1'—S2	121 (7)	C6—N2—C7'—C8'	170.5 (8)
C11—S1—C1'—S2	−11.6 (12)	C6'—N2—C7'—C8'	159.0 (8)
C1—N1—C2'—C3'	166.3 (8)	C10'—N2—C7'—C8'	−12.6 (16)
C1'—N1—C2'—C3'	157.5 (10)	C10—N2—C7'—C8'	−16.7 (15)
C5'—N1—C2'—C3'	−15.8 (15)	C7—N2—C7'—C8'	21 (30)
C2—N1—C2'—C3'	59 (31)	N2—C7'—C8'—C9'	31.1 (14)
C5—N1—C2'—C3'	−20.9 (13)	C7'—C8'—C9'—C10'	−37.1 (14)
N1—C2'—C3'—C4'	35.6 (13)	C6—N2—C10'—C9'	166.5 (7)
C2'—C3'—C4'—C5'	−42.5 (12)	C6'—N2—C10'—C9'	178.5 (7)
C1—N1—C5'—C4'	167.5 (8)	C7'—N2—C10'—C9'	−10.1 (15)
C1'—N1—C5'—C4'	176.6 (9)	C10—N2—C10'—C9'	84 (11)
C2'—N1—C5'—C4'	−10.5 (14)	C7—N2—C10'—C9'	−11.4 (14)
C2—N1—C5'—C4'	−12.0 (12)	C8'—C9'—C10'—N2	28.7 (13)
C5—N1—C5'—C4'	26 (6)	C6'—S3—C11—S1	84.1 (4)
C3'—C4'—C5'—N1	32.6 (11)	C6—S3—C11—S1	76.5 (3)
C6'—N2—C6—S4	98 (4)	C1—S1—C11—S3	79.2 (4)
C7'—N2—C6—S4	−11.3 (12)	C1'—S1—C11—S3	84.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···S3ⁱ	0.99	2.89	3.811 (9)	155
C10—H10B···S4ⁱⁱ	0.99	2.99	3.699 (11)	130
C9—H9A···S1ⁱⁱ	0.99	2.87	3.740 (8)	147
C9′—H9′A···S1ⁱⁱ	0.99	3.50	4.209 (11)	131
C5′—H5′B···S2ⁱ	0.99	2.94	3.704 (14)	137

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₈N₂S₄
M_r	306.51
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	150
a, b, c (Å)	21.9118 (18), 4.5705 (4), 14.3452 (12)
V (Å³)	1436.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.25 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.856, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	17016, 3292, 2759
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.166, 1.07
No. of reflections	3292
No. of parameters	180
No. of restraints	17
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.27
Absolute structure	Flack (1983), 1579 Friedel pairs
Absolute structure parameter	−0.1 (2)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···S3ⁱ	0.99	2.89	3.811 (9)	155
C10—H10B···S4ⁱⁱ	0.99	2.99	3.699 (11)	130
C9—H9A···S1ⁱⁱ	0.99	2.87	3.740 (8)	147
C9'—H9'A···S1ⁱⁱ	0.99	3.50	4.209 (11)	131
C5'—H5'B···S2ⁱ	0.99	2.94	3.704 (14)	137

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

Acknowledgements

We thank the National Science Council of the Republic of China for financial support (NSC98–2113-M-241–011-MY2).

References

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