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

Wei-Lung Chou; Kuang-Hway Yih; Gene-Hsiang Lee; Yen-Hsiang Huang; Hsiao-Fen Wang

doi:10.1107/S1600536810046027

. 2010 Nov 17;66(Pt 12):o3193. doi: 10.1107/S1600536810046027

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

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

PMCID: PMC3011744 PMID: 21589487

Abstract

The title compound, C₁₁H₁₈N₂S₄, was unexpectedly obtained during studies on the reactivity of the complex tris(acac-κ² O,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(S₂CNR ₂)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,
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[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 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)

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.

Supplementary Material

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

e-66-o3193-sup1.cif^{(27KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046027/bv2162Isup2.hkl

e-66-o3193-Isup2.hkl^{(161.5KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.