Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019034/gk2065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019034/gk2065Isup2.hkl |
CCDC reference: 647609
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (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
For related literature, see: Bryce (1991); Lorcy & Bellec (2004); Williams et al. (1985).
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%.
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 Uiso(H) = 1.2Ueq(C).
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).
For related literature, see: Bryce (1991); Lorcy & Bellec (2004); Williams et al. (1985).
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.
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) Å3 | 0.65 × 0.60 × 0.20 mm |
Z = 8 |
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 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0329P)2 + 3.7537P] where P = (Fo2 + 2Fc2)/3 |
3710 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.36 e Å−3 |
38 restraints | Δρmin = −0.31 e Å−3 |
C12H13N3S6 | V = 3317.0 (12) Å3 |
Mr = 391.61 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.252 (5) Å | µ = 0.82 mm−1 |
b = 8.2516 (17) Å | T = 193 K |
c = 16.017 (3) Å | 0.65 × 0.60 × 0.20 mm |
β = 96.34 (3)° |
Rigaku Mercury diffractometer | 3710 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 3591 reflections with I > 2σ(I) |
Tmin = 0.618, Tmax = 0.853 | Rint = 0.042 |
12131 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 38 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.36 e Å−3 |
3710 reflections | Δρmin = −0.31 e Å−3 |
209 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
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···N3i | 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. |
Experimental details
Crystal data | |
Chemical formula | C12H13N3S6 |
Mr | 391.61 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 193 |
a, b, c (Å) | 25.252 (5), 8.2516 (17), 16.017 (3) |
β (°) | 96.34 (3) |
V (Å3) | 3317.0 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.65 × 0.60 × 0.20 |
Data collection | |
Diffractometer | Rigaku Mercury |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.618, 0.853 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12131, 3710, 3591 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.081, 1.13 |
No. of reflections | 3710 |
No. of parameters | 209 |
No. of restraints | 38 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.31 |
Computer programs: CrystalClear (Rigaku, 2001), CrystalClear, CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
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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).