3-[4,5-Bis(2-cyano­ethyl­sulfan­yl)-1,3-dithiol-2-yl]-1,3-thia­zolidine-2-thione

The title compound, C₁₂H₁₃N₃S₆, belongs to a group of sulfur-rich compounds. In the crystal structure, the mol­ecules form several short S...S inter­molecular contacts [3.287 (1)–3.497 (1) Å], assembling them into a two-dimensional layer network. One —CH₂—CH₂— group is disordered over two positions in an approximate 4:1 ratio.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.033
• wR factor = 0.081
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.65 mm
PLAT301_ALERT_3_C Main Residue  Disorder .........................       9.00 Perc.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Sulfur-rich compounds, e.g. 4,5-bis(2-cyanoethylsulfanyl)-1,3-dithiol-2-thione or 4,5-bis(2-cyanoethylsulfanyl)-1,3-dithiol-2-one, are well known of being used as precursors for the synthesis of molecular materials of tetrathiafulvalene (TTF) (Bryce, 1991; Williams et al., 1985). Recently TTF analogs with nitrogen containing heterocycles have been reported (Lorcy & Bellec, 2004). As short S···S contacts are efficient organizing forces in the self-assembly of new solid-state materials (Bryce, 1991; Williams et al., 1985), the title compound (I) offers one example of this type of materials.

Compound (I) consists of a thiazolidine ring and a dithiole ring (Fig. 1). Both rings are not planar while the displaced atoms are maximum 0.22 (1) Å (C3) and 0.19 Å (C4) out of the least-squires planes, respectively. The least-squares planes are approximately vertical with a torsion angle of 85.68 (1)°. The C₂S₄ group C5—C6—S3—S4—S5—S6 is nearly planar while the C6 atom is 0.89 (1) Å out of the least-squires plane.

There are four kinds of intramolecular C—H···S and one kind of intermolecular C—H···N hydrogen bonds (Table 2). Besides these interactions, the neighboring molecules are connected by intermolecular S···S contacts (S3···S4ⁱ 3.364 (1) Å; S2···S4ⁱⁱ 3.497 (1) Å; S2···S2ⁱⁱⁱ 3.287 (1) Å [symmetry codes:(i)1/2 - x,1/2 + y,1/2 - z; (ii)1/2 - x,3/2 - y,1 - z; (iii)1/2 - x,5/2 - y,1 - z)] to form a two-dimensional layer network (Fig. 2).

Related literature

For related literature, see: Bryce (1991); Lorcy & Bellec (2004); Williams et al. (1985).

S2. Experimental

A solution of 1,3-thiazolidine-2-thione (0.12 g, 1 mmol) and 4,5-bis(2-cyanoethylsulfanyl)-1,3-dithiol-2-one (0.27 g, 0.9 mmol) in 3 ml of P(OEt)₃ was refluxed for 1 h and cooled to room temperature. Addition of 6 ml of CH₃OH into the solution formed a colorless precipitate. Recrystallization from CH₂Cl₂ afforded colorless cryatals of (I) (yield 0.12 g, 35%). CH&N elemental analysis. Found: C, 36.60; H, 3.39; N, 10.47%. Calculated for C₁₂H₁₃N₃S₆: C, 36.83; H, 3.32; N, 10.74%.

S3. Refinement

One C₂H₄ group is disordered over two sites with occupancy factors of 0.80 (2) and 0.20 (2) for C10/C10 A and C11/C11A. The H atoms are placed in geometrically idealized positions (C—H = 0.99 Å) with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. The disordered atoms C10A and C11A have been omitted.
	Fig. 2. The intermolecular S···S interactions (dashed lines) that link the molecules into a layer. The 2-cyanoethylthio groups and H atoms have been omitted.

3-[4,5-Bis(2-cyanoethylsulfanyl)-1,3-dithiol-2-yl]-1,3-thiazolidine-2-thione

Crystal data

C12H13N3S6	F(000) = 1616
Mr = 391.61	Dx = 1.568 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5529 reflections
a = 25.252 (5) Å	θ = 3.1–27.5°
b = 8.2516 (17) Å	µ = 0.82 mm^−1
c = 16.017 (3) Å	T = 193 K
β = 96.34 (3)°	Platelet, colorless
V = 3317.0 (12) Å^3	0.65 × 0.60 × 0.20 mm
Z = 8

Data collection

Rigaku Mercury diffractometer	3710 independent reflections
Radiation source: fine-focus sealed tube	3591 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan (Jacobson, 1998)	h = −32→32
Tmin = 0.618, Tmax = 0.853	k = −10→9
12131 measured reflections	l = −17→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 3.7537P] where P = (Fo^2 + 2Fc^2)/3
3710 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.36 e Å^−3
38 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.325225 (16)	0.82215 (5)	0.42436 (3)	0.02940 (11)
S2	0.247064 (18)	1.05371 (5)	0.48278 (2)	0.02610 (11)
S3	0.201298 (15)	0.80445 (5)	0.18681 (2)	0.02303 (10)
S4	0.194822 (17)	0.55846 (5)	0.31728 (3)	0.02608 (11)
S5	0.092782 (16)	0.72706 (5)	0.09868 (3)	0.02730 (11)
S6	0.08521 (2)	0.45029 (6)	0.25284 (3)	0.03507 (13)
N1	0.22439 (5)	0.87341 (17)	0.35390 (8)	0.0224 (3)
N2	−0.03936 (7)	1.0195 (2)	0.13715 (11)	0.0399 (4)
N3	0.03213 (7)	0.6819 (2)	0.53333 (12)	0.0439 (4)
C1	0.26529 (6)	0.90535 (18)	0.41376 (9)	0.0203 (3)
C2	0.18570 (7)	1.0992 (2)	0.41697 (11)	0.0276 (3)
H2A	0.1569	1.1284	0.4515	0.033*
H2B	0.1909	1.1896	0.3781	0.033*
C3	0.17259 (6)	0.9430 (2)	0.36893 (11)	0.0270 (3)
H3A	0.1529	0.8677	0.4024	0.032*
H3B	0.1506	0.9653	0.3151	0.032*
C4	0.22825 (6)	0.7466 (2)	0.29289 (10)	0.0221 (3)
H4	0.2669	0.7215	0.2917	0.027*
C5	0.14035 (6)	0.69990 (18)	0.18623 (10)	0.0194 (3)
C6	0.13725 (6)	0.58876 (19)	0.24673 (10)	0.0209 (3)
C7	0.09026 (7)	0.9462 (2)	0.08893 (11)	0.0280 (3)
H7A	0.1271	0.9875	0.0888	0.034*
H7B	0.0704	0.9743	0.0341	0.034*
C8	0.06425 (7)	1.0329 (2)	0.15818 (11)	0.0297 (4)
H8A	0.0774	0.9842	0.2130	0.036*
H8B	0.0752	1.1482	0.1596	0.036*
C9	0.00602 (8)	1.0239 (2)	0.14670 (11)	0.0295 (4)
C10	0.07459 (10)	0.4652 (3)	0.36427 (16)	0.0303 (6)	0.804 (6)
H10A	0.0514	0.3756	0.3795	0.036*	0.804 (6)
H10B	0.1091	0.4572	0.3999	0.036*	0.804 (6)
C10A	0.0490 (3)	0.5679 (11)	0.3294 (6)	0.025 (2)	0.196 (6)
H10C	0.0529	0.6857	0.3199	0.030*	0.196 (6)
H10D	0.0106	0.5409	0.3217	0.030*	0.196 (6)
C11	0.04842 (9)	0.6272 (3)	0.37826 (16)	0.0303 (6)	0.804 (6)
H11A	0.0708	0.7158	0.3595	0.036*	0.804 (6)
H11B	0.0133	0.6322	0.3443	0.036*	0.804 (6)
C11A	0.0726 (3)	0.5240 (12)	0.4167 (6)	0.028 (2)	0.196 (6)
H11C	0.1115	0.5420	0.4249	0.034*	0.196 (6)
H11D	0.0646	0.4104	0.4309	0.034*	0.196 (6)
C12	0.04136 (7)	0.6504 (3)	0.46880 (14)	0.0392 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0214 (2)	0.0305 (2)	0.0344 (2)	0.00107 (15)	−0.00575 (16)	0.00277 (17)
S2	0.0355 (2)	0.0223 (2)	0.0197 (2)	−0.00333 (16)	−0.00102 (16)	−0.00293 (14)
S3	0.02128 (19)	0.0286 (2)	0.01934 (19)	−0.00545 (14)	0.00284 (14)	−0.00153 (14)
S4	0.0316 (2)	0.0218 (2)	0.0242 (2)	0.00501 (15)	−0.00018 (16)	0.00094 (14)
S5	0.0259 (2)	0.0270 (2)	0.0267 (2)	0.00202 (16)	−0.00711 (15)	−0.00758 (16)
S6	0.0436 (3)	0.0310 (2)	0.0334 (2)	−0.01937 (19)	0.0168 (2)	−0.01416 (18)
N1	0.0165 (6)	0.0277 (7)	0.0225 (7)	0.0013 (5)	0.0002 (5)	−0.0074 (5)
N2	0.0379 (9)	0.0416 (10)	0.0405 (10)	0.0022 (7)	0.0066 (7)	−0.0003 (7)
N3	0.0435 (10)	0.0484 (11)	0.0411 (10)	−0.0047 (8)	0.0109 (8)	−0.0173 (8)
C1	0.0232 (7)	0.0189 (7)	0.0183 (7)	−0.0039 (6)	0.0006 (5)	0.0029 (6)
C2	0.0294 (8)	0.0268 (8)	0.0267 (8)	0.0031 (7)	0.0037 (6)	−0.0052 (6)
C3	0.0188 (7)	0.0319 (9)	0.0300 (9)	0.0024 (6)	0.0018 (6)	−0.0098 (7)
C4	0.0169 (7)	0.0266 (8)	0.0225 (7)	0.0025 (6)	0.0007 (5)	−0.0055 (6)
C5	0.0175 (6)	0.0194 (7)	0.0213 (7)	0.0004 (5)	0.0014 (5)	−0.0054 (5)
C6	0.0215 (7)	0.0190 (7)	0.0226 (7)	0.0006 (6)	0.0045 (6)	−0.0063 (6)
C7	0.0305 (8)	0.0304 (9)	0.0224 (8)	0.0047 (7)	0.0001 (6)	0.0037 (6)
C8	0.0338 (9)	0.0264 (8)	0.0273 (9)	0.0043 (7)	−0.0036 (7)	−0.0028 (6)
C9	0.0406 (10)	0.0235 (8)	0.0242 (8)	0.0055 (7)	0.0028 (7)	−0.0002 (6)
C10	0.0401 (12)	0.0207 (10)	0.0329 (14)	−0.0023 (9)	0.0162 (9)	0.0002 (9)
C10A	0.018 (4)	0.027 (4)	0.030 (5)	0.001 (3)	0.002 (3)	−0.002 (4)
C11	0.0290 (11)	0.0281 (12)	0.0345 (15)	0.0031 (9)	0.0068 (9)	−0.0045 (10)
C11A	0.026 (4)	0.036 (5)	0.022 (5)	0.002 (4)	0.005 (3)	0.000 (4)
C12	0.0282 (9)	0.0433 (11)	0.0479 (12)	−0.0104 (8)	0.0119 (8)	−0.0189 (9)

Geometric parameters (Å, º)

S1—C1	1.6535 (16)	C3—H3A	0.9900
S2—C1	1.7450 (17)	C3—H3B	0.9900
S2—C2	1.8146 (19)	C4—H4	1.0000
C2—C3	1.519 (2)	C7—C8	1.528 (2)
N1—C3	1.472 (2)	C7—H7A	0.9900
N1—C1	1.355 (2)	C7—H7B	0.9900
N1—C4	1.442 (2)	C8—C9	1.463 (3)
S3—C4	1.8227 (17)	C8—H8A	0.9900
S3—C5	1.7635 (15)	C8—H8B	0.9900
C5—C6	1.343 (2)	C10—C11	1.519 (3)
S4—C6	1.7580 (17)	C10—H10A	0.9900
S4—C4	1.8301 (17)	C10—H10B	0.9900
S5—C5	1.7571 (17)	C10A—C11A	1.502 (13)
S6—C6	1.7521 (16)	C10A—H10C	0.9900
S5—C7	1.8155 (18)	C10A—H10D	0.9900
S6—C10	1.838 (2)	C11—C12	1.493 (3)
S6—C10A	1.878 (10)	C11—H11A	0.9900
N2—C9	1.140 (3)	C11—H11B	0.9900
N3—C12	1.115 (3)	C11A—C12	1.598 (10)
C2—H2A	0.9900	C11A—H11C	0.9900
C2—H2B	0.9900	C11A—H11D	0.9900
C1—S2—C2	92.60 (8)	S5—C7—H7A	108.6
C5—S3—C4	96.48 (8)	C8—C7—H7B	108.6
C6—S4—C4	96.34 (7)	S5—C7—H7B	108.6
C6—S6—C10A	97.0 (3)	H7A—C7—H7B	107.6
C1—N1—C4	121.14 (13)	C9—C8—C7	113.04 (15)
C1—N1—C3	115.46 (13)	C9—C8—H8A	109.0
C4—N1—C3	121.42 (13)	C7—C8—H8A	109.0
N1—C1—S1	127.54 (12)	C9—C8—H8B	109.0
N1—C1—S2	110.54 (11)	C7—C8—H8B	109.0
S1—C1—S2	121.92 (9)	H8A—C8—H8B	107.8
C3—C2—S2	104.05 (12)	N2—C9—C8	178.8 (2)
C3—C2—H2A	110.9	C11—C10—S6	108.34 (16)
S2—C2—H2A	110.9	C11—C10—H10A	110.0
C3—C2—H2B	110.9	S6—C10—H10A	110.0
S2—C2—H2B	110.9	C11—C10—H10B	110.0
H2A—C2—H2B	109.0	S6—C10—H10B	110.0
N1—C3—C2	105.42 (13)	H10A—C10—H10B	108.4
N1—C3—H3A	110.7	C11A—C10A—S6	108.1 (6)
C2—C3—H3A	110.7	C11A—C10A—H10C	110.1
N1—C3—H3B	110.7	S6—C10A—H10C	110.1
C2—C3—H3B	110.7	C11A—C10A—H10D	110.1
H3A—C3—H3B	108.8	S6—C10A—H10D	110.1
N1—C4—S3	113.31 (11)	H10C—C10A—H10D	108.4
N1—C4—S4	113.80 (11)	C12—C11—C10	110.9 (2)
S3—C4—S4	106.70 (8)	C12—C11—H11A	109.5
N1—C4—H4	107.6	C10—C11—H11A	109.5
S3—C4—H4	107.6	C12—C11—H11B	109.5
S4—C4—H4	107.6	C10—C11—H11B	109.5
C6—C5—S5	125.02 (12)	H11A—C11—H11B	108.0
C6—C5—S3	116.79 (12)	C10A—C11A—C12	99.3 (6)
S5—C5—S3	117.46 (9)	C10A—C11A—H11C	111.9
C5—C6—S6	126.12 (13)	C12—C11A—H11C	111.9
C5—C6—S4	116.81 (12)	C10A—C11A—H11D	111.9
S6—C6—S4	116.33 (9)	C12—C11A—H11D	111.9
C5—S5—C7	102.13 (8)	H11C—C11A—H11D	109.6
C6—S6—C10	101.62 (9)	N3—C12—C11	171.9 (3)
C8—C7—S5	114.69 (13)	N3—C12—C11A	143.3 (4)
C8—C7—H7A	108.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···S3	0.99	2.86	3.2875 (19)	107
C4—H4···S1	1.00	2.58	3.1113 (18)	113
C7—H7A···S3	0.99	2.76	3.274 (2)	113
C8—H8B···N3^i	0.99	2.60	3.136 (3)	114
C10—H10B···S4	0.99	2.79	3.299 (2)	113

Symmetry code: (i) x, −y+2, z−1/2.