Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106041114/fa3047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106041114/fa3047Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106041114/fa3047IIsup3.hkl |
CCDC references: 632937; 632938
2,3,6,7-Tetrakis(2-cyanoethylsulfanyl)tetrathiafulvalene (1.07 g, 2.0 mmol) was dissolved in anhydrous dimethylformamide (DMF; 20 ml) and degassed thoroughly (Ar, 15 min). CsOH·H2O (0.69 g, 4.1 mmol) dissolved in anhydrous methanol (2 ml) was added dropwise over a period of 30 minutes and the solution was stirred for 1 h. The resulting solution, and a solution of 1,10-dibromodecane (0.30 g, 1.0 mmol) in anhydrous DMF (22 ml), were added simultaneously over 6 h to DMF (100 ml), under pseudo high-dilution conditions using a perfusor pump. After the addition was completed, stirring was continued for a further 10 h. The reaction mixture was then concentrated in vacuo, redissolved in CH2Cl2 (100 ml), washed with water (150 ml) and dried over MgSO4. Removal of the solvent gave a black oil, from which the title compound was isolated by column chromatography (SiO2, CH2Cl2) as an analytically pure yellow solid (0.84 g, 1.5 mmol, yield 75%) that comprised a mixture of the cis and trans isomers (m.p. 378–380 K). Elemental analysis found: C 45.85, H 4.94, N 4.87, S 44.68%; calculated C 45.79, H 4.89, N 4.86, S 44.46%.
The isomers were separated in approximately 90% purity by preparative thin-layer chromatography using CH2Cl2 as eluant. Compound (I): 1H NMR (CDCl3, 300 MHz): δ 1.32–1.42 (m, 12H), 1.66–1.71 (m, 4H), 2.70 (t, J = 7.2 Hz, 4H), 2.79–2.84 (m, 4H), 3.04 (t, J = 7.2 Hz, 4H); 13C NMR (CDCl3): δ 18.7, 27.5, 27.6, 28.2, 30.6, 31.3, 35.7, 112.5, 117.6, 120.9, 134.4. Compound (II): 1H NMR (CDCl3, 300 MHz): 0.89–1.17 (m, 4H), 1.26–1.41 (m, 8H), 1.67–1.70 (m, 4H), 2.68–2.79 (m, 4H), 2.98–3.23 (m, 2H); 13C NMR (CDCl3): 18.8, 26.8, 28.8, 30.7, 31.2, 31.6, 35.7, 114.5, 117.3, 125.1, 132.4. Crystals used for X-ray analysis were in both cases grown from CH2Cl2/n-pentane (1/1).
H atoms were positioned geometrically and allowed to ride during the subsequent refinement, with C—H distances of 0.99 Å and Uiso(H) values of 1.2 Ueq(C). For (II), the largest peak in the difference density is located in the vicinity of one cyanoethylsulfanyl arm, 1.24 Å from C7.
The chemistry of organothio derivatives of tetrathiafulvalene (TTF) has been studied extensively, and there are numerous crystal structures of such molecules in the literature [for example, the polymorphic parent compound, tetra(methylthio)tetrathiafulvalene; Cambridge Structural Database (CSD; Version 5.27 plus January, May and August 2006 updates; Allen, 2002) refcodes DIFVET (Katayama et al., 1985) and (DIFVET01) Endres, 1986]. One reason for this is that TTF derivatives find extensive use in the preparation of various interlocked compounds, including bistable [2]rotaxanes (Tseng et al., 2004) and [2]catenanes (Asakawa et al., 1998), which are prime candidates for future construction of molecular electronics (DeIonno et al., 2006), artificial molecular muscles (Liu et al., 2005) and molecular switches (Kang et al., 2004). Amongst the derivatives that have been characterized crystallographically, there are several in which the two ends of the TTF molecule are tethered via a covalent linker. Various simple chain linkers have been employed for this purpose, including, for example, ether (Le Derf et al., 2001; GUJZAM, GUJZEQ), thioether (Le Derf et al., 1999a; HOJNID) and 2,4-hexadiyne (Simonsen, Thorup & Becher, 1997; PUGGAZ) chains. More complex linkers have also been prepared, incorporating functional groups such as pyromellitic dianhydride (Hansen et al., 2000; WISXOL, WISXUR, WISYAY???), 4,4'-bispyridinium (Simonsen, Zong et al., 1997; RICWEF), 2-thioxo-1,3-dithiole-4,5-dithiolate (John et al., 2000; LOMZOC) and methylenediphenyl (Lau et al., 1997; NIHZEJ, NIHZIN??). One crystal structure has been reported in which a TTF molecule is tethered by saturated thioalkyl chains, namely cis,cis-bis(hexamethylenedithio)TTF (Suresh Kumar et al., 1998; JECXAQ), which includes two hexamethylenedithio chain linkers. We describe here the cis and trans isomers of bis(2-cyanoethylsulfanyl)tetrathiafulvalene (Scheme 1) tethered by a single 1,10-decamethylenedithio chain.
The molecular structures of the cis, (I), and trans, (II), isomers are shown in Figs. 1 and 2, respectively. In (I), the TTF unit is approximately planar, with an r.m.s. deviation of 0.053 Å from the least-squares plane defined by atoms S1–S8 and C1–C6. The 1,10-decamethylenedithio chain in (I) lies approximately in the plane of the TTF group, so that the molecule as a whole resembles a flat disc (Fig. 1), with the 2-cyanoethylsulfanyl groups pointing to either side. The 1,10-decamethylenedithio chain is arranged so that its longest straight section (C14–C19) resembles n-hexane (Fig. 1). By contrast, the TTF unit in (II) deviates considerably from planarity: the least-squares plane through one outer ring of the TTF unit (S1/S2/C3/C4, referred to as plane 1) forms a dihedral angle of 21.7 (1)° with the least-squares plane through the inter-ring region (S1–S4/C1/C2; plane 2), which in turn forms a dihedral angle of 18.6 (1)° with the least-squares plane through the other outer ring [S3/S4/C5/C6; plane 3] (Fig. 2). The constraining influence of the 1,10-decamethylenedithio linker is reflected further by the positions of atoms S5–S8: atoms S6 and S7, part of the 1,10-decamethylenedithio linker, lie 0.087 (3) and 0.126 (3) Å from plane 1 and plane 3, respectively, while atoms S5 and S8, part of the two cyanoethylsulfanyl arms, lie 0.404 (3) and 0.370 (3) Å, respectively, from the same planes. Thus, as well as inducing non-planarity, the linker also twists the molecule about its long axis (i.e. the C1—C2 inter-ring vector of TTF). In the trans isomer, the longest straight section of the 1,10-decamethylenedithio linker (C14–C21) resembles n-octane (Fig. 2).
In both (I) and (II), interactions between molecules are largely segregated so that TTF units are brought into close contact with each other, and the alkyl chains are brought into close contact with each other. In (I), molecules form stacks along a (Fig. 3), in which the TTF groups adopt an interplanar separation of 3.71 (1) Å. For adjacent molecules within a stack [symmetry code: (i) 1 + x, y, z], the straight n-hexyl sections (C14–C19) of the 1,10-decamethylenedithio linker are arranged typically for n-alkyl chains, with a lateral offset of ca 2.5 Å (i.e. 2 × CH2) that allows the CH2 groups of one chain to project into the gaps between CH2 groups in the neighbouring chain (Fig. 4). Between molecules in adjacent stacks [symmetry code: (ii) 1 - x, 1 - y, 1 - z], the n-hexyl sections are arranged with no lateral offset, with a translation of ca 4.7 Å between chains. This arrangement is essentially identical to that in the crystal structure of n-hexane itself [corresponding lattice dimension 4.696 (1) Å; Boese et al., 1999; Cambridge Structural Database refcode HEXANE01)]. Pairs of stacks are aligned in a herringbone manner (Fig. 3), with the C≡N bonds adopting typical antiparallel and `crossed' arrangements. The shortest S···S contacts in (I) [3.4657 (16) Å] occur between atoms S1 and S8iii [symmetry code: (iii) 2 - x, 1/2 + y, 3/2 - z]. The geometry is such that a lone pair of electrons on S1, lying in the plane of the TTF unit, can be envisaged to approach the σ*(S8—C6) orbital in the neighbouring molecule (Rosenfield et al., 1977).
In (II), the intermolecular interactions are segregated clearly into layered regions lying parallel to the ac planes (Fig. 5). In the plane at y = 1/2, the straight n-octyl sections (C14–C21) of the 1,10-decamethylenedithio chains are brought into close contact (Fig. 6). As for (I), pairs of molecules can be envisaged in this region [symmetry code: (iv) 1 - x, 1 - y, 1 - z], with their n-octyl sections lying parallel with no lateral offset, and with an inter-chain translation of ca 4.7 Å. This arrangement again resembles closely that in n-octane itself [corresponding lattice dimension 4.752 (1) Å; Boese et al., 1999; HEXANE01]. In the perpendicular direction, adjacent chains [symmetry code: (v) 2 - x, 1 - y, 1 - z] are arranged with a much greater lateral offset, so that only approximately half of each n-octyl section is in contact with its neighbour (Fig. 6). In the ac planes at y = 1/4 and 3/4 (Fig. 5), the TTF units are brought into contact. Where the molecules meet in a face-to-face manner, one S atom of the 1,10-decamethylenedithio chain lies over the centroid of a neighbouring five-membered ring [S7···Cg(S1/S2/C1/C3/C4)vi = 3.53 Å; symmetry code (vi) -1/2 + x, 3/2 - y, 1/2 + z]. The shortest in-plane S···S contacts in (II) are 3.3399 (9) Å, between S5 and S8vii [symmetry code: (vii) x, y, -1 + z], displaying no clear directional features. The 2-cyanoethylsulfanyl groups adopt antiparallel and crossed arrangements similar to those in (I).
From the CSD, 24 comparable non-tethered structures were identified, for which three-dimensional coordinates are available (Table 1). Of these, the TTF unit deviates significantly from planarity in only three, namely DIFVET (Katayama et al., 1985), FIQBUD (Bond & Jeppesen, 2005) and KUSLEP (Nakano et al., 1992). By contrast, for 26 tethered examples identified (with three-dimensional coordinates available; Table 1), only three contain planar TTF units. Two of these, KAQXAB (Le Derf et al., 1999b) and NIHZIN (Lau et al., 1997), are cis isomers, while the third (WISXUR; Hansen et al., 2000) is a trans isomer. For NIHZIN, the related trans isomer has also been characterized (NIHZEJ; Lau et al., 1997), and it contains a planar TTF unit. For WISXUR, the linker incorporates a pyromellitic dianhydride group, and the planar TTF conformation appears to arise as a consequence of intramolecular and intermolecular π–π stacking interactions.
For both compounds, data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C22H28N2S8 | F(000) = 1208 |
Mr = 576.94 | Dx = 1.446 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1332 reflections |
a = 5.3573 (8) Å | θ = 3.2–17.7° |
b = 18.296 (3) Å | µ = 0.69 mm−1 |
c = 27.041 (5) Å | T = 180 K |
β = 90.753 (8)° | Lath, orange |
V = 2650.3 (8) Å3 | 0.30 × 0.10 × 0.05 mm |
Z = 4 |
Bruker–Nonius X8APEX-II CCD diffractometer | 4935 independent reflections |
Radiation source: fine-focus sealed tube | 2471 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.129 |
thin–slice ω and φ scans | θmax = 25.6°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −6→6 |
Tmin = 0.649, Tmax = 0.966 | k = −22→21 |
28437 measured reflections | l = −32→32 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/3 |
4935 reflections | (Δ/σ)max = 0.001 |
289 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C22H28N2S8 | V = 2650.3 (8) Å3 |
Mr = 576.94 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.3573 (8) Å | µ = 0.69 mm−1 |
b = 18.296 (3) Å | T = 180 K |
c = 27.041 (5) Å | 0.30 × 0.10 × 0.05 mm |
β = 90.753 (8)° |
Bruker–Nonius X8APEX-II CCD diffractometer | 4935 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2471 reflections with I > 2σ(I) |
Tmin = 0.649, Tmax = 0.966 | Rint = 0.129 |
28437 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.38 e Å−3 |
4935 reflections | Δρmin = −0.33 e Å−3 |
289 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) -3.7108(0.0012)x - 0.9278(0.0057)y + 19.6999(0.0063)z = 10.4415(0.0074) * 0.0422 (0.0013) S1 * 0.0664 (0.0013) S2 * -0.0817 (0.0013) S3 * -0.1092 (0.0014) S4 * -0.0395 (0.0014) S5 * 0.0500 (0.0015) S6 * 0.0840 (0.0015) S7 * -0.0064 (0.0015) S8 * 0.0012 (0.0038) C1 * -0.0386 (0.0038) C2 * -0.0058 (0.0034) C3 * -0.0086 (0.0035) C4 * 0.0268 (0.0034) C5 * 0.0194 (0.0035) C6 Rms deviation of fitted atoms = 0.0525 |
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 | ||
S1 | 0.6332 (2) | 0.81323 (6) | 0.68974 (4) | 0.0325 (3) | |
S2 | 0.4186 (2) | 0.68000 (6) | 0.64428 (4) | 0.0348 (3) | |
S3 | 1.0266 (2) | 0.70907 (6) | 0.75264 (5) | 0.0355 (3) | |
S4 | 0.8024 (2) | 0.58023 (6) | 0.70296 (4) | 0.0367 (3) | |
S5 | 0.3128 (2) | 0.91522 (6) | 0.63006 (4) | 0.0333 (3) | |
S6 | 0.0596 (2) | 0.76337 (6) | 0.57975 (4) | 0.0363 (3) | |
S7 | 1.3557 (2) | 0.61713 (7) | 0.81872 (5) | 0.0398 (4) | |
S8 | 1.1156 (2) | 0.47305 (6) | 0.76212 (5) | 0.0336 (3) | |
N1 | 0.2474 (8) | 0.9266 (2) | 0.48602 (16) | 0.0476 (12) | |
N2 | 0.7392 (8) | 0.7028 (3) | 0.95233 (18) | 0.0604 (14) | |
C1 | 0.6429 (8) | 0.7178 (2) | 0.68499 (15) | 0.0272 (11) | |
C2 | 0.8003 (8) | 0.6757 (2) | 0.71065 (15) | 0.0257 (11) | |
C3 | 0.3998 (8) | 0.8252 (2) | 0.64391 (15) | 0.0276 (11) | |
C4 | 0.3048 (8) | 0.7647 (2) | 0.62303 (16) | 0.0284 (11) | |
C5 | 1.1244 (7) | 0.6214 (2) | 0.77246 (15) | 0.0280 (11) | |
C6 | 1.0222 (7) | 0.5635 (2) | 0.75010 (16) | 0.0254 (11) | |
C7 | 0.5866 (8) | 0.9441 (2) | 0.59601 (16) | 0.0341 (12) | |
H7A | 0.5745 | 0.9972 | 0.5893 | 0.041* | |
H7B | 0.7377 | 0.9358 | 0.6167 | 0.041* | |
C8 | 0.6142 (8) | 0.9034 (2) | 0.54727 (17) | 0.0342 (12) | |
H8A | 0.7713 | 0.9191 | 0.5316 | 0.041* | |
H8B | 0.6279 | 0.8505 | 0.5542 | 0.041* | |
C9 | 0.4070 (10) | 0.9153 (2) | 0.51235 (19) | 0.0373 (13) | |
C10 | 1.1998 (8) | 0.6633 (2) | 0.86848 (16) | 0.0378 (12) | |
H10A | 1.3171 | 0.6680 | 0.8969 | 0.045* | |
H10B | 1.1541 | 0.7132 | 0.8575 | 0.045* | |
C11 | 0.9634 (9) | 0.6236 (3) | 0.88558 (18) | 0.0427 (13) | |
H11A | 0.8496 | 0.6156 | 0.8569 | 0.051* | |
H11B | 1.0089 | 0.5753 | 0.8995 | 0.051* | |
C12 | 0.8364 (10) | 0.6673 (3) | 0.9232 (2) | 0.0509 (16) | |
C13 | 0.1812 (8) | 0.7071 (2) | 0.52946 (15) | 0.0359 (12) | |
H13A | 0.1909 | 0.7370 | 0.4990 | 0.043* | |
H13B | 0.3523 | 0.6908 | 0.5382 | 0.043* | |
C14 | 0.0179 (8) | 0.6404 (2) | 0.51930 (16) | 0.0343 (12) | |
H14A | 0.0645 | 0.6195 | 0.4869 | 0.041* | |
H14B | −0.1581 | 0.6566 | 0.5166 | 0.041* | |
C15 | 0.0356 (7) | 0.5800 (2) | 0.55839 (17) | 0.0327 (12) | |
H15A | 0.0246 | 0.6025 | 0.5916 | 0.039* | |
H15B | −0.1091 | 0.5468 | 0.5542 | 0.039* | |
C16 | 0.2738 (8) | 0.5352 (2) | 0.55613 (16) | 0.0319 (12) | |
H16A | 0.4181 | 0.5683 | 0.5610 | 0.038* | |
H16B | 0.2864 | 0.5137 | 0.5227 | 0.038* | |
C17 | 0.2922 (8) | 0.4739 (2) | 0.59402 (16) | 0.0328 (12) | |
H17A | 0.3038 | 0.4955 | 0.6275 | 0.039* | |
H17B | 0.1379 | 0.4442 | 0.5923 | 0.039* | |
C18 | 0.5149 (8) | 0.4247 (2) | 0.58620 (17) | 0.0364 (12) | |
H18A | 0.6682 | 0.4539 | 0.5918 | 0.044* | |
H18B | 0.5137 | 0.4090 | 0.5512 | 0.044* | |
C19 | 0.5313 (9) | 0.3563 (2) | 0.61867 (17) | 0.0398 (13) | |
H19A | 0.3745 | 0.3283 | 0.6143 | 0.048* | |
H19B | 0.6689 | 0.3254 | 0.6064 | 0.048* | |
C20 | 0.5738 (8) | 0.3691 (2) | 0.67353 (17) | 0.0360 (12) | |
H20A | 0.5542 | 0.3219 | 0.6910 | 0.043* | |
H20B | 0.4421 | 0.4024 | 0.6855 | 0.043* | |
C21 | 0.8267 (8) | 0.4012 (2) | 0.68766 (17) | 0.0326 (12) | |
H21A | 0.8560 | 0.4458 | 0.6678 | 0.039* | |
H21B | 0.9591 | 0.3654 | 0.6797 | 0.039* | |
C22 | 0.8437 (8) | 0.4205 (2) | 0.74275 (16) | 0.0313 (12) | |
H22A | 0.8416 | 0.3744 | 0.7620 | 0.038* | |
H22B | 0.6923 | 0.4484 | 0.7515 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0382 (8) | 0.0234 (6) | 0.0354 (8) | 0.0057 (6) | −0.0145 (6) | −0.0024 (6) |
S2 | 0.0384 (8) | 0.0266 (7) | 0.0388 (8) | 0.0021 (6) | −0.0198 (6) | −0.0019 (6) |
S3 | 0.0407 (8) | 0.0269 (7) | 0.0382 (8) | −0.0020 (6) | −0.0193 (6) | 0.0000 (6) |
S4 | 0.0461 (8) | 0.0260 (7) | 0.0374 (8) | 0.0024 (6) | −0.0227 (7) | −0.0009 (6) |
S5 | 0.0367 (8) | 0.0298 (7) | 0.0335 (8) | 0.0089 (6) | −0.0030 (6) | 0.0029 (6) |
S6 | 0.0307 (7) | 0.0383 (7) | 0.0394 (8) | 0.0083 (6) | −0.0155 (6) | −0.0043 (6) |
S7 | 0.0297 (8) | 0.0474 (8) | 0.0419 (9) | 0.0010 (6) | −0.0185 (7) | 0.0011 (7) |
S8 | 0.0284 (7) | 0.0273 (7) | 0.0450 (9) | 0.0015 (6) | −0.0106 (6) | 0.0035 (6) |
N1 | 0.051 (3) | 0.047 (3) | 0.045 (3) | −0.008 (2) | −0.013 (2) | 0.011 (2) |
N2 | 0.052 (3) | 0.067 (3) | 0.062 (4) | 0.008 (3) | −0.002 (3) | 0.011 (3) |
C1 | 0.031 (3) | 0.028 (3) | 0.022 (3) | 0.000 (2) | −0.008 (2) | 0.002 (2) |
C2 | 0.036 (3) | 0.016 (2) | 0.024 (3) | −0.001 (2) | −0.008 (2) | −0.002 (2) |
C3 | 0.029 (3) | 0.033 (3) | 0.021 (3) | 0.001 (2) | −0.004 (2) | 0.003 (2) |
C4 | 0.027 (3) | 0.028 (3) | 0.030 (3) | 0.004 (2) | −0.004 (2) | 0.003 (2) |
C5 | 0.021 (3) | 0.035 (3) | 0.028 (3) | 0.000 (2) | −0.006 (2) | 0.000 (2) |
C6 | 0.020 (3) | 0.024 (2) | 0.032 (3) | 0.004 (2) | −0.008 (2) | 0.002 (2) |
C7 | 0.029 (3) | 0.036 (3) | 0.037 (3) | −0.007 (2) | −0.011 (2) | 0.007 (2) |
C8 | 0.029 (3) | 0.036 (3) | 0.037 (3) | 0.004 (2) | −0.002 (3) | 0.005 (2) |
C9 | 0.052 (4) | 0.026 (3) | 0.034 (3) | −0.003 (3) | −0.003 (3) | −0.002 (2) |
C10 | 0.043 (3) | 0.038 (3) | 0.032 (3) | −0.007 (2) | −0.018 (2) | 0.001 (2) |
C11 | 0.037 (3) | 0.054 (3) | 0.038 (3) | −0.002 (3) | −0.012 (3) | 0.000 (3) |
C12 | 0.044 (4) | 0.058 (4) | 0.050 (4) | −0.002 (3) | −0.013 (3) | 0.021 (3) |
C13 | 0.037 (3) | 0.050 (3) | 0.020 (3) | −0.001 (2) | −0.004 (2) | 0.000 (2) |
C14 | 0.030 (3) | 0.038 (3) | 0.034 (3) | 0.001 (2) | −0.011 (2) | −0.003 (2) |
C15 | 0.023 (3) | 0.033 (3) | 0.042 (3) | −0.005 (2) | −0.006 (2) | −0.005 (2) |
C16 | 0.031 (3) | 0.041 (3) | 0.024 (3) | −0.004 (2) | −0.002 (2) | −0.002 (2) |
C17 | 0.035 (3) | 0.032 (3) | 0.031 (3) | −0.002 (2) | 0.002 (2) | −0.001 (2) |
C18 | 0.031 (3) | 0.040 (3) | 0.037 (3) | 0.000 (2) | −0.002 (3) | −0.002 (2) |
C19 | 0.039 (3) | 0.033 (3) | 0.047 (4) | −0.001 (2) | −0.003 (3) | 0.005 (3) |
C20 | 0.033 (3) | 0.036 (3) | 0.039 (3) | 0.001 (2) | −0.002 (3) | 0.005 (2) |
C21 | 0.032 (3) | 0.028 (3) | 0.038 (3) | 0.003 (2) | 0.001 (3) | 0.002 (2) |
C22 | 0.030 (3) | 0.031 (3) | 0.033 (3) | −0.005 (2) | −0.007 (2) | 0.007 (2) |
S1—C1 | 1.751 (4) | C11—H11A | 0.990 |
S1—C3 | 1.762 (4) | C11—H11B | 0.990 |
S2—C4 | 1.759 (4) | C13—C14 | 1.525 (5) |
S2—C1 | 1.761 (4) | C13—H13A | 0.990 |
S3—C2 | 1.759 (4) | C13—H13B | 0.990 |
S3—C5 | 1.768 (4) | C14—C15 | 1.531 (5) |
S4—C6 | 1.751 (4) | C14—H14A | 0.990 |
S4—C2 | 1.759 (4) | C14—H14B | 0.990 |
S5—C3 | 1.750 (4) | C15—C16 | 1.519 (5) |
S5—C7 | 1.821 (4) | C15—H15A | 0.990 |
S6—C4 | 1.748 (5) | C15—H15B | 0.990 |
S6—C13 | 1.832 (4) | C16—C17 | 1.520 (5) |
S7—C5 | 1.751 (4) | C16—H16A | 0.990 |
S7—C10 | 1.803 (4) | C16—H16B | 0.990 |
S8—C6 | 1.758 (4) | C17—C18 | 1.512 (5) |
S8—C22 | 1.817 (4) | C17—H17A | 0.990 |
N1—C9 | 1.125 (6) | C17—H17B | 0.990 |
N2—C12 | 1.151 (6) | C18—C19 | 1.531 (5) |
C1—C2 | 1.331 (5) | C18—H18A | 0.990 |
C3—C4 | 1.340 (5) | C18—H18B | 0.990 |
C5—C6 | 1.334 (5) | C19—C20 | 1.516 (6) |
C7—C8 | 1.523 (5) | C19—H19A | 0.990 |
C7—H7A | 0.990 | C19—H19B | 0.990 |
C7—H7B | 0.990 | C20—C21 | 1.521 (6) |
C8—C9 | 1.464 (6) | C20—H20A | 0.990 |
C8—H8A | 0.990 | C20—H20B | 0.990 |
C8—H8B | 0.990 | C21—C22 | 1.532 (5) |
C10—C11 | 1.537 (6) | C21—H21A | 0.990 |
C10—H10A | 0.990 | C21—H21B | 0.990 |
C10—H10B | 0.990 | C22—H22A | 0.990 |
C11—C12 | 1.468 (7) | C22—H22B | 0.990 |
C1—S1—C3 | 95.4 (2) | S6—C13—H13B | 109.2 |
C4—S2—C1 | 95.1 (2) | H13A—C13—H13B | 107.9 |
C2—S3—C5 | 94.6 (2) | C13—C14—C15 | 115.0 (4) |
C6—S4—C2 | 95.3 (2) | C13—C14—H14A | 108.5 |
C3—S5—C7 | 99.6 (2) | C15—C14—H14A | 108.5 |
C4—S6—C13 | 103.5 (2) | C13—C14—H14B | 108.5 |
C5—S7—C10 | 100.5 (2) | C15—C14—H14B | 108.5 |
C6—S8—C22 | 102.7 (2) | H14A—C14—H14B | 107.5 |
C2—C1—S1 | 123.9 (3) | C16—C15—C14 | 114.0 (4) |
C2—C1—S2 | 121.4 (3) | C16—C15—H15A | 108.8 |
S1—C1—S2 | 114.6 (2) | C14—C15—H15A | 108.8 |
C1—C2—S4 | 121.2 (3) | C16—C15—H15B | 108.8 |
C1—C2—S3 | 124.2 (3) | C14—C15—H15B | 108.8 |
S4—C2—S3 | 114.6 (2) | H15A—C15—H15B | 107.7 |
C4—C3—S5 | 126.0 (3) | C15—C16—C17 | 114.7 (3) |
C4—C3—S1 | 117.1 (3) | C15—C16—H16A | 108.6 |
S5—C3—S1 | 116.9 (2) | C17—C16—H16A | 108.6 |
C3—C4—S6 | 124.9 (3) | C15—C16—H16B | 108.6 |
C3—C4—S2 | 117.5 (3) | C17—C16—H16B | 108.6 |
S6—C4—S2 | 117.4 (2) | H16A—C16—H16B | 107.6 |
C6—C5—S7 | 124.8 (3) | C18—C17—C16 | 112.9 (3) |
C6—C5—S3 | 117.7 (3) | C18—C17—H17A | 109.0 |
S7—C5—S3 | 117.5 (2) | C16—C17—H17A | 109.0 |
C5—C6—S4 | 117.3 (3) | C18—C17—H17B | 109.0 |
C5—C6—S8 | 123.4 (3) | C16—C17—H17B | 109.0 |
S4—C6—S8 | 119.1 (2) | H17A—C17—H17B | 107.8 |
C8—C7—S5 | 112.5 (3) | C17—C18—C19 | 116.5 (4) |
C8—C7—H7A | 109.1 | C17—C18—H18A | 108.2 |
S5—C7—H7A | 109.1 | C19—C18—H18A | 108.2 |
C8—C7—H7B | 109.1 | C17—C18—H18B | 108.2 |
S5—C7—H7B | 109.1 | C19—C18—H18B | 108.2 |
H7A—C7—H7B | 107.8 | H18A—C18—H18B | 107.3 |
C9—C8—C7 | 113.8 (4) | C20—C19—C18 | 116.2 (4) |
C9—C8—H8A | 108.8 | C20—C19—H19A | 108.2 |
C7—C8—H8A | 108.8 | C18—C19—H19A | 108.2 |
C9—C8—H8B | 108.8 | C20—C19—H19B | 108.2 |
C7—C8—H8B | 108.8 | C18—C19—H19B | 108.2 |
H8A—C8—H8B | 107.7 | H19A—C19—H19B | 107.4 |
N1—C9—C8 | 177.9 (5) | C19—C20—C21 | 115.3 (4) |
C11—C10—S7 | 113.2 (3) | C19—C20—H20A | 108.4 |
C11—C10—H10A | 108.9 | C21—C20—H20A | 108.4 |
S7—C10—H10A | 108.9 | C19—C20—H20B | 108.4 |
C11—C10—H10B | 108.9 | C21—C20—H20B | 108.4 |
S7—C10—H10B | 108.9 | H20A—C20—H20B | 107.5 |
H10A—C10—H10B | 107.7 | C20—C21—C22 | 112.0 (4) |
C12—C11—C10 | 110.0 (4) | C20—C21—H21A | 109.2 |
C12—C11—H11A | 109.7 | C22—C21—H21A | 109.2 |
C10—C11—H11A | 109.7 | C20—C21—H21B | 109.2 |
C12—C11—H11B | 109.7 | C22—C21—H21B | 109.2 |
C10—C11—H11B | 109.7 | H21A—C21—H21B | 107.9 |
H11A—C11—H11B | 108.2 | C21—C22—S8 | 116.1 (3) |
N2—C12—C11 | 178.7 (6) | C21—C22—H22A | 108.3 |
C14—C13—S6 | 112.0 (3) | S8—C22—H22A | 108.3 |
C14—C13—H13A | 109.2 | C21—C22—H22B | 108.3 |
S6—C13—H13A | 109.2 | S8—C22—H22B | 108.3 |
C14—C13—H13B | 109.2 | H22A—C22—H22B | 107.4 |
C3—S1—C1—C2 | 177.1 (4) | C2—S3—C5—C6 | 3.9 (4) |
C3—S1—C1—S2 | −4.6 (3) | C2—S3—C5—S7 | −178.0 (2) |
C4—S2—C1—C2 | −176.6 (4) | S7—C5—C6—S4 | −177.5 (2) |
C4—S2—C1—S1 | 5.1 (3) | S3—C5—C6—S4 | 0.4 (5) |
S1—C1—C2—S4 | −178.8 (2) | S7—C5—C6—S8 | −2.9 (6) |
S2—C1—C2—S4 | 3.1 (5) | S3—C5—C6—S8 | 175.1 (2) |
S1—C1—C2—S3 | −1.0 (6) | C2—S4—C6—C5 | −4.5 (4) |
S2—C1—C2—S3 | −179.1 (2) | C2—S4—C6—S8 | −179.4 (3) |
C6—S4—C2—C1 | −174.9 (4) | C22—S8—C6—C5 | 157.5 (4) |
C6—S4—C2—S3 | 7.0 (3) | C22—S8—C6—S4 | −27.9 (3) |
C5—S3—C2—C1 | 175.2 (4) | C3—S5—C7—C8 | 66.2 (3) |
C5—S3—C2—S4 | −6.8 (3) | S5—C7—C8—C9 | 62.2 (5) |
C7—S5—C3—C4 | −106.9 (4) | C5—S7—C10—C11 | 62.7 (4) |
C7—S5—C3—S1 | 73.3 (3) | S7—C10—C11—C12 | −175.4 (3) |
C1—S1—C3—C4 | 2.2 (4) | C4—S6—C13—C14 | 121.3 (3) |
C1—S1—C3—S5 | −178.1 (2) | S6—C13—C14—C15 | −73.0 (4) |
S5—C3—C4—S6 | −3.9 (6) | C13—C14—C15—C16 | −75.1 (5) |
S1—C3—C4—S6 | 175.9 (2) | C14—C15—C16—C17 | −178.8 (4) |
S5—C3—C4—S2 | −178.6 (2) | C15—C16—C17—C18 | 172.4 (4) |
S1—C3—C4—S2 | 1.1 (5) | C16—C17—C18—C19 | −172.9 (4) |
C13—S6—C4—C3 | 129.4 (4) | C17—C18—C19—C20 | −66.7 (5) |
C13—S6—C4—S2 | −55.8 (3) | C18—C19—C20—C21 | −67.1 (5) |
C1—S2—C4—C3 | −3.8 (4) | C19—C20—C21—C22 | 173.5 (3) |
C1—S2—C4—S6 | −178.9 (2) | C20—C21—C22—S8 | −170.1 (3) |
C10—S7—C5—C6 | −121.0 (4) | C6—S8—C22—C21 | 85.2 (3) |
C10—S7—C5—S3 | 61.1 (3) |
C22H28N2S8 | F(000) = 1208 |
Mr = 576.94 | Dx = 1.452 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7137 reflections |
a = 7.8916 (4) Å | θ = 2.7–25.2° |
b = 26.1798 (16) Å | µ = 0.69 mm−1 |
c = 12.9931 (8) Å | T = 180 K |
β = 100.576 (2)° | Plate, yellow |
V = 2638.8 (3) Å3 | 0.35 × 0.10 × 0.05 mm |
Z = 4 |
Bruker–Nonius X8APEX-II CCD diffractometer | 5891 independent reflections |
Radiation source: fine-focus sealed tube | 3807 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
thin–slice ω and φ scans | θmax = 27.9°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→8 |
Tmin = 0.817, Tmax = 0.966 | k = −34→31 |
63502 measured reflections | l = −16→16 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0336P)2 + 1.4311P] where P = (Fo2 + 2Fc2)/3 |
5891 reflections | (Δ/σ)max = 0.001 |
289 parameters | Δρmax = 1.04 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C22H28N2S8 | V = 2638.8 (3) Å3 |
Mr = 576.94 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.8916 (4) Å | µ = 0.69 mm−1 |
b = 26.1798 (16) Å | T = 180 K |
c = 12.9931 (8) Å | 0.35 × 0.10 × 0.05 mm |
β = 100.576 (2)° |
Bruker–Nonius X8APEX-II CCD diffractometer | 5891 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3807 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.966 | Rint = 0.060 |
63502 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.04 e Å−3 |
5891 reflections | Δρmin = −0.43 e Å−3 |
289 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) Plane 1: ——– 1.3180(0.0048)x + 24.6318(0.0094)y - 4.1627(0.0125)z = 16.5074(0.0106) * -0.0109 (0.0006) S1 * 0.0108 (0.0006) S2 * 0.0237 (0.0013) C3 * -0.0237 (0.0013) C4 0.4043 (0.0033) S5 0.0874 (0.0032) S6 Rms deviation of fitted atoms = 0.0184 Plane 2: ——– -0.1560(0.0017)x + 26.1650(0.0016)y + 0.3940(0.0031)z = 18.7398(0.0022) * 0.0402 (0.0007) S1 * 0.0004 (0.0007) S2 * 0.0013 (0.0007) S3 * 0.0409 (0.0007) S4 * -0.0398 (0.0018) C1 * -0.0429 (0.0018) C2 Rms deviation of fitted atoms = 0.0334 A ngle to plane 1 (with approximate e.s.d.) = 21.72 (0.04) Plane 3: ——– -1.4062(0.0047)x + 24.5171(0.0095)y + 4.2830(0.0122)z = 19.6195(0.0037) * 0.0088 (0.0006) S3 * -0.0089 (0.0006) S4 * -0.0193 (0.0013) C5 * 0.0194 (0.0013) C6 0.1261 (0.0032) S7 0.3700 (0.0032) S8 Rms deviation of fitted atoms = 0.0150 A ngle to plane 1 (with approximate e.s.d.) = 18.62 (0.04) |
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 | ||
S1 | 0.54871 (8) | 0.71442 (2) | 0.43823 (4) | 0.02250 (15) | |
S2 | 0.91156 (8) | 0.71349 (2) | 0.54241 (4) | 0.02222 (15) | |
S3 | 0.42909 (8) | 0.70878 (2) | 0.66647 (4) | 0.02325 (15) | |
S4 | 0.79250 (7) | 0.71091 (2) | 0.76946 (4) | 0.02163 (15) | |
S5 | 0.63998 (9) | 0.69065 (3) | 0.22673 (5) | 0.03493 (18) | |
S6 | 1.04179 (8) | 0.67736 (2) | 0.35142 (5) | 0.02763 (16) | |
S7 | 0.30244 (8) | 0.67274 (2) | 0.85860 (5) | 0.02597 (16) | |
S8 | 0.70891 (8) | 0.68462 (3) | 0.98097 (5) | 0.02824 (17) | |
N1 | 0.1906 (4) | 0.54786 (11) | 0.1443 (2) | 0.0578 (8) | |
N2 | 0.6905 (5) | 0.54588 (11) | 1.0771 (3) | 0.0860 (11) | |
C1 | 0.6955 (3) | 0.71045 (8) | 0.55729 (17) | 0.0195 (5) | |
C2 | 0.6448 (3) | 0.70862 (8) | 0.65055 (17) | 0.0193 (5) | |
C3 | 0.7009 (3) | 0.69485 (9) | 0.36232 (17) | 0.0216 (5) | |
C4 | 0.8667 (3) | 0.69231 (9) | 0.41115 (17) | 0.0210 (5) | |
C5 | 0.4767 (3) | 0.68745 (8) | 0.79765 (17) | 0.0201 (5) | |
C6 | 0.6426 (3) | 0.69014 (9) | 0.84573 (16) | 0.0196 (5) | |
C7 | 0.4410 (4) | 0.65599 (12) | 0.2017 (2) | 0.0470 (8) | |
H7A | 0.3591 | 0.6716 | 0.2418 | 0.056* | |
H7B | 0.3900 | 0.6584 | 0.1263 | 0.056* | |
C8 | 0.4658 (4) | 0.60191 (13) | 0.2311 (3) | 0.0530 (9) | |
H8A | 0.4818 | 0.5983 | 0.3081 | 0.064* | |
H8B | 0.5701 | 0.5886 | 0.2080 | 0.064* | |
C9 | 0.3073 (4) | 0.57155 (13) | 0.1790 (3) | 0.0534 (9) | |
C10 | 0.9058 (3) | 0.64738 (11) | 0.9949 (2) | 0.0333 (6) | |
H10A | 0.9829 | 0.6633 | 0.9520 | 0.040* | |
H10B | 0.9650 | 0.6488 | 1.0690 | 0.040* | |
C11 | 0.8784 (3) | 0.59158 (11) | 0.9626 (2) | 0.0381 (7) | |
H11A | 0.8218 | 0.5898 | 0.8881 | 0.046* | |
H11B | 0.9917 | 0.5744 | 0.9698 | 0.046* | |
C12 | 0.7732 (4) | 0.56499 (12) | 1.0261 (3) | 0.0526 (9) | |
C13 | 1.1468 (3) | 0.62642 (9) | 0.4354 (2) | 0.0287 (6) | |
H13A | 1.2710 | 0.6264 | 0.4318 | 0.034* | |
H13B | 1.1367 | 0.6342 | 0.5086 | 0.034* | |
C14 | 1.0760 (3) | 0.57330 (9) | 0.4088 (2) | 0.0324 (6) | |
H14A | 1.1509 | 0.5484 | 0.4531 | 0.039* | |
H14B | 1.0829 | 0.5659 | 0.3350 | 0.039* | |
C15 | 0.8911 (3) | 0.56494 (10) | 0.42337 (19) | 0.0295 (6) | |
H15A | 0.8165 | 0.5904 | 0.3805 | 0.035* | |
H15B | 0.8534 | 0.5306 | 0.3963 | 0.035* | |
C16 | 0.8636 (3) | 0.56897 (9) | 0.5358 (2) | 0.0277 (6) | |
H16A | 0.9332 | 0.5423 | 0.5780 | 0.033* | |
H16B | 0.9065 | 0.6026 | 0.5643 | 0.033* | |
C17 | 0.6770 (3) | 0.56319 (10) | 0.5481 (2) | 0.0294 (6) | |
H17A | 0.6090 | 0.5915 | 0.5106 | 0.035* | |
H17B | 0.6312 | 0.5308 | 0.5147 | 0.035* | |
C18 | 0.6518 (3) | 0.56315 (9) | 0.6605 (2) | 0.0293 (6) | |
H18A | 0.7048 | 0.5944 | 0.6952 | 0.035* | |
H18B | 0.7137 | 0.5335 | 0.6967 | 0.035* | |
C19 | 0.4649 (3) | 0.56084 (10) | 0.6739 (2) | 0.0328 (6) | |
H19A | 0.4107 | 0.5301 | 0.6376 | 0.039* | |
H19B | 0.4036 | 0.5911 | 0.6396 | 0.039* | |
C20 | 0.4414 (3) | 0.55928 (10) | 0.7877 (2) | 0.0308 (6) | |
H20A | 0.4793 | 0.5254 | 0.8172 | 0.037* | |
H20B | 0.5177 | 0.5853 | 0.8275 | 0.037* | |
C21 | 0.2578 (3) | 0.56871 (9) | 0.8040 (2) | 0.0321 (6) | |
H21A | 0.1804 | 0.5439 | 0.7612 | 0.038* | |
H21B | 0.2525 | 0.5622 | 0.8784 | 0.038* | |
C22 | 0.1912 (3) | 0.62219 (9) | 0.7759 (2) | 0.0276 (6) | |
H22A | 0.0673 | 0.6234 | 0.7801 | 0.033* | |
H22B | 0.2012 | 0.6292 | 0.7024 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0215 (3) | 0.0317 (4) | 0.0144 (3) | 0.0013 (3) | 0.0035 (2) | 0.0025 (2) |
S2 | 0.0215 (3) | 0.0284 (3) | 0.0171 (3) | −0.0013 (3) | 0.0045 (2) | −0.0009 (2) |
S3 | 0.0211 (3) | 0.0317 (4) | 0.0173 (3) | 0.0018 (3) | 0.0044 (2) | 0.0028 (3) |
S4 | 0.0214 (3) | 0.0298 (3) | 0.0142 (3) | −0.0019 (2) | 0.0045 (2) | −0.0008 (2) |
S5 | 0.0345 (4) | 0.0556 (5) | 0.0147 (3) | −0.0066 (3) | 0.0047 (3) | −0.0047 (3) |
S6 | 0.0296 (4) | 0.0300 (4) | 0.0275 (4) | 0.0008 (3) | 0.0162 (3) | 0.0032 (3) |
S7 | 0.0267 (4) | 0.0300 (4) | 0.0247 (3) | −0.0006 (3) | 0.0138 (3) | −0.0026 (3) |
S8 | 0.0315 (4) | 0.0401 (4) | 0.0139 (3) | 0.0034 (3) | 0.0063 (3) | 0.0027 (3) |
N1 | 0.0485 (18) | 0.065 (2) | 0.0547 (18) | −0.0070 (15) | −0.0038 (14) | 0.0031 (15) |
N2 | 0.118 (3) | 0.0473 (19) | 0.111 (3) | −0.0008 (18) | 0.070 (2) | 0.0178 (18) |
C1 | 0.0217 (13) | 0.0199 (12) | 0.0170 (12) | 0.0008 (10) | 0.0036 (10) | 0.0019 (10) |
C2 | 0.0218 (13) | 0.0197 (12) | 0.0155 (12) | 0.0004 (10) | 0.0011 (10) | 0.0007 (9) |
C3 | 0.0297 (15) | 0.0224 (12) | 0.0140 (12) | −0.0036 (10) | 0.0070 (10) | 0.0011 (10) |
C4 | 0.0283 (15) | 0.0195 (12) | 0.0174 (13) | −0.0029 (10) | 0.0100 (11) | 0.0008 (10) |
C5 | 0.0256 (14) | 0.0208 (12) | 0.0155 (12) | 0.0020 (10) | 0.0081 (10) | 0.0004 (10) |
C6 | 0.0254 (14) | 0.0215 (12) | 0.0126 (12) | 0.0016 (10) | 0.0053 (10) | −0.0001 (9) |
C7 | 0.0443 (19) | 0.058 (2) | 0.0394 (18) | −0.0043 (15) | 0.0089 (14) | −0.0070 (15) |
C8 | 0.0381 (19) | 0.072 (2) | 0.048 (2) | 0.0126 (16) | 0.0056 (15) | 0.0001 (17) |
C9 | 0.045 (2) | 0.049 (2) | 0.072 (2) | −0.0044 (16) | 0.0233 (18) | −0.0114 (18) |
C10 | 0.0247 (15) | 0.0543 (18) | 0.0206 (14) | 0.0032 (13) | 0.0037 (11) | 0.0118 (13) |
C11 | 0.0327 (17) | 0.0505 (19) | 0.0324 (16) | 0.0096 (13) | 0.0095 (13) | 0.0104 (13) |
C12 | 0.064 (2) | 0.0389 (18) | 0.060 (2) | 0.0091 (16) | 0.0243 (18) | 0.0105 (16) |
C13 | 0.0220 (14) | 0.0321 (15) | 0.0335 (15) | 0.0011 (11) | 0.0091 (11) | 0.0025 (12) |
C14 | 0.0339 (16) | 0.0264 (14) | 0.0404 (16) | 0.0020 (11) | 0.0161 (13) | −0.0012 (12) |
C15 | 0.0312 (15) | 0.0247 (14) | 0.0349 (15) | −0.0019 (11) | 0.0120 (12) | −0.0029 (11) |
C16 | 0.0263 (15) | 0.0216 (13) | 0.0366 (15) | −0.0003 (10) | 0.0094 (12) | 0.0020 (11) |
C17 | 0.0260 (15) | 0.0278 (14) | 0.0358 (16) | −0.0029 (11) | 0.0095 (11) | −0.0033 (12) |
C18 | 0.0298 (15) | 0.0244 (14) | 0.0354 (16) | 0.0014 (11) | 0.0108 (12) | 0.0020 (11) |
C19 | 0.0310 (16) | 0.0343 (15) | 0.0355 (16) | −0.0035 (12) | 0.0123 (12) | −0.0088 (12) |
C20 | 0.0327 (16) | 0.0249 (14) | 0.0373 (16) | 0.0025 (11) | 0.0132 (12) | 0.0037 (12) |
C21 | 0.0346 (16) | 0.0266 (14) | 0.0388 (16) | −0.0036 (12) | 0.0166 (12) | −0.0004 (12) |
C22 | 0.0213 (14) | 0.0343 (15) | 0.0296 (14) | −0.0003 (11) | 0.0107 (11) | −0.0032 (11) |
S1—C1 | 1.757 (2) | C11—H11A | 0.990 |
S1—C3 | 1.764 (2) | C11—H11B | 0.990 |
S2—C1 | 1.753 (2) | C13—C14 | 1.515 (3) |
S2—C4 | 1.766 (2) | C13—H13A | 0.990 |
S3—C2 | 1.752 (2) | C13—H13B | 0.990 |
S3—C5 | 1.767 (2) | C14—C15 | 1.521 (3) |
S4—C2 | 1.757 (2) | C14—H14A | 0.990 |
S4—C6 | 1.763 (2) | C14—H14B | 0.990 |
S5—C3 | 1.742 (2) | C15—C16 | 1.519 (3) |
S5—C7 | 1.791 (3) | C15—H15A | 0.990 |
S6—C4 | 1.749 (2) | C15—H15B | 0.990 |
S6—C13 | 1.823 (2) | C16—C17 | 1.518 (3) |
S7—C5 | 1.751 (2) | C16—H16A | 0.990 |
S7—C22 | 1.825 (2) | C16—H16B | 0.990 |
S8—C6 | 1.745 (2) | C17—C18 | 1.509 (4) |
S8—C10 | 1.815 (3) | C17—H17A | 0.990 |
N1—C9 | 1.133 (4) | C17—H17B | 0.990 |
N2—C12 | 1.130 (4) | C18—C19 | 1.517 (3) |
C1—C2 | 1.345 (3) | C18—H18A | 0.990 |
C3—C4 | 1.346 (3) | C18—H18B | 0.990 |
C5—C6 | 1.345 (3) | C19—C20 | 1.524 (3) |
C7—C8 | 1.470 (4) | C19—H19A | 0.990 |
C7—H7A | 0.990 | C19—H19B | 0.990 |
C7—H7B | 0.990 | C20—C21 | 1.522 (3) |
C8—C9 | 1.531 (5) | C20—H20A | 0.990 |
C8—H8A | 0.990 | C20—H20B | 0.990 |
C8—H8B | 0.990 | C21—C22 | 1.516 (3) |
C10—C11 | 1.524 (4) | C21—H21A | 0.990 |
C10—H10A | 0.990 | C21—H21B | 0.990 |
C10—H10B | 0.990 | C22—H22A | 0.990 |
C11—C12 | 1.450 (4) | C22—H22B | 0.990 |
C1—S1—C3 | 93.92 (11) | S6—C13—H13B | 108.5 |
C1—S2—C4 | 93.75 (11) | H13A—C13—H13B | 107.5 |
C2—S3—C5 | 94.25 (11) | C13—C14—C15 | 115.2 (2) |
C2—S4—C6 | 94.49 (11) | C13—C14—H14A | 108.5 |
C3—S5—C7 | 106.61 (13) | C15—C14—H14A | 108.5 |
C4—S6—C13 | 101.98 (11) | C13—C14—H14B | 108.5 |
C5—S7—C22 | 103.07 (11) | C15—C14—H14B | 108.5 |
C6—S8—C10 | 103.77 (11) | H14A—C14—H14B | 107.5 |
C2—C1—S2 | 123.89 (18) | C16—C15—C14 | 114.8 (2) |
C2—C1—S1 | 122.54 (18) | C16—C15—H15A | 108.6 |
S2—C1—S1 | 113.43 (12) | C14—C15—H15A | 108.6 |
C1—C2—S3 | 124.25 (18) | C16—C15—H15B | 108.6 |
C1—C2—S4 | 122.11 (18) | C14—C15—H15B | 108.6 |
S3—C2—S4 | 113.47 (13) | H15A—C15—H15B | 107.5 |
C4—C3—S5 | 122.50 (18) | C17—C16—C15 | 114.0 (2) |
C4—C3—S1 | 116.94 (18) | C17—C16—H16A | 108.7 |
S5—C3—S1 | 119.57 (14) | C15—C16—H16A | 108.7 |
C3—C4—S6 | 125.47 (18) | C17—C16—H16B | 108.7 |
C3—C4—S2 | 116.41 (18) | C15—C16—H16B | 108.7 |
S6—C4—S2 | 117.64 (13) | H16A—C16—H16B | 107.6 |
C6—C5—S7 | 125.44 (17) | C18—C17—C16 | 113.9 (2) |
C6—C5—S3 | 116.59 (17) | C18—C17—H17A | 108.8 |
S7—C5—S3 | 117.40 (13) | C16—C17—H17A | 108.8 |
C5—C6—S8 | 123.34 (17) | C18—C17—H17B | 108.8 |
C5—C6—S4 | 116.85 (17) | C16—C17—H17B | 108.8 |
S8—C6—S4 | 118.92 (13) | H17A—C17—H17B | 107.7 |
C8—C7—S5 | 111.7 (2) | C17—C18—C19 | 114.5 (2) |
C8—C7—H7A | 109.3 | C17—C18—H18A | 108.6 |
S5—C7—H7A | 109.3 | C19—C18—H18A | 108.6 |
C8—C7—H7B | 109.3 | C17—C18—H18B | 108.6 |
S5—C7—H7B | 109.3 | C19—C18—H18B | 108.6 |
H7A—C7—H7B | 107.9 | H18A—C18—H18B | 107.6 |
C7—C8—C9 | 109.0 (3) | C18—C19—C20 | 114.0 (2) |
C7—C8—H8A | 109.9 | C18—C19—H19A | 108.8 |
C9—C8—H8A | 109.9 | C20—C19—H19A | 108.8 |
C7—C8—H8B | 109.9 | C18—C19—H19B | 108.8 |
C9—C8—H8B | 109.9 | C20—C19—H19B | 108.8 |
H8A—C8—H8B | 108.3 | H19A—C19—H19B | 107.7 |
N1—C9—C8 | 177.0 (4) | C21—C20—C19 | 114.8 (2) |
C11—C10—S8 | 114.33 (18) | C21—C20—H20A | 108.6 |
C11—C10—H10A | 108.7 | C19—C20—H20A | 108.6 |
S8—C10—H10A | 108.7 | C21—C20—H20B | 108.6 |
C11—C10—H10B | 108.7 | C19—C20—H20B | 108.6 |
S8—C10—H10B | 108.7 | H20A—C20—H20B | 107.5 |
H10A—C10—H10B | 107.6 | C22—C21—C20 | 114.4 (2) |
C12—C11—C10 | 111.7 (2) | C22—C21—H21A | 108.7 |
C12—C11—H11A | 109.3 | C20—C21—H21A | 108.7 |
C10—C11—H11A | 109.3 | C22—C21—H21B | 108.7 |
C12—C11—H11B | 109.3 | C20—C21—H21B | 108.7 |
C10—C11—H11B | 109.3 | H21A—C21—H21B | 107.6 |
H11A—C11—H11B | 107.9 | C21—C22—S7 | 114.83 (18) |
N2—C12—C11 | 177.6 (4) | C21—C22—H22A | 108.6 |
C14—C13—S6 | 115.29 (19) | S7—C22—H22A | 108.6 |
C14—C13—H13A | 108.5 | C21—C22—H22B | 108.6 |
S6—C13—H13A | 108.5 | S7—C22—H22B | 108.6 |
C14—C13—H13B | 108.5 | H22A—C22—H22B | 107.5 |
C4—S2—C1—C2 | 160.8 (2) | C2—S3—C5—C6 | 14.8 (2) |
C4—S2—C1—S1 | −23.38 (14) | C2—S3—C5—S7 | −173.36 (14) |
C3—S1—C1—C2 | −162.6 (2) | S7—C5—C6—S8 | −5.8 (3) |
C3—S1—C1—S2 | 21.52 (14) | S3—C5—C6—S8 | 165.34 (13) |
S2—C1—C2—S3 | 176.67 (13) | S7—C5—C6—S4 | −174.83 (13) |
S1—C1—C2—S3 | 1.2 (3) | S3—C5—C6—S4 | −3.7 (3) |
S2—C1—C2—S4 | 1.8 (3) | C10—S8—C6—C5 | 140.9 (2) |
S1—C1—C2—S4 | −173.68 (12) | C10—S8—C6—S4 | −50.24 (17) |
C5—S3—C2—C1 | 164.1 (2) | C2—S4—C6—C5 | −9.4 (2) |
C5—S3—C2—S4 | −20.68 (14) | C2—S4—C6—S8 | −178.95 (14) |
C6—S4—C2—C1 | −165.4 (2) | C3—S5—C7—C8 | −69.9 (2) |
C6—S4—C2—S3 | 19.20 (14) | S5—C7—C8—C9 | −163.2 (2) |
C7—S5—C3—C4 | 143.6 (2) | C6—S8—C10—C11 | −70.4 (2) |
C7—S5—C3—S1 | −48.09 (19) | S8—C10—C11—C12 | −61.3 (3) |
C1—S1—C3—C4 | −10.3 (2) | C4—S6—C13—C14 | 85.4 (2) |
C1—S1—C3—S5 | −179.22 (15) | S6—C13—C14—C15 | −65.2 (3) |
S5—C3—C4—S6 | −7.8 (3) | C13—C14—C15—C16 | −64.8 (3) |
S1—C3—C4—S6 | −176.37 (13) | C14—C15—C16—C17 | 177.1 (2) |
S5—C3—C4—S2 | 164.05 (13) | C15—C16—C17—C18 | 175.5 (2) |
S1—C3—C4—S2 | −4.5 (3) | C16—C17—C18—C19 | 176.2 (2) |
C13—S6—C4—C3 | −128.2 (2) | C17—C18—C19—C20 | 178.3 (2) |
C13—S6—C4—S2 | 60.02 (16) | C18—C19—C20—C21 | 167.2 (2) |
C1—S2—C4—C3 | 16.8 (2) | C19—C20—C21—C22 | −66.3 (3) |
C1—S2—C4—S6 | −170.66 (14) | C20—C21—C22—S7 | −65.7 (3) |
C22—S7—C5—C6 | −129.3 (2) | C5—S7—C22—C21 | 86.8 (2) |
C22—S7—C5—S3 | 59.67 (16) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C22H28N2S8 | C22H28N2S8 |
Mr | 576.94 | 576.94 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 180 | 180 |
a, b, c (Å) | 5.3573 (8), 18.296 (3), 27.041 (5) | 7.8916 (4), 26.1798 (16), 12.9931 (8) |
β (°) | 90.753 (8) | 100.576 (2) |
V (Å3) | 2650.3 (8) | 2638.8 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.69 | 0.69 |
Crystal size (mm) | 0.30 × 0.10 × 0.05 | 0.35 × 0.10 × 0.05 |
Data collection | ||
Diffractometer | Bruker–Nonius X8APEX-II CCD | Bruker–Nonius X8APEX-II CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.649, 0.966 | 0.817, 0.966 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28437, 4935, 2471 | 63502, 5891, 3807 |
Rint | 0.129 | 0.060 |
(sin θ/λ)max (Å−1) | 0.607 | 0.659 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.115, 0.98 | 0.039, 0.099, 1.07 |
No. of reflections | 4935 | 5891 |
No. of parameters | 289 | 289 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.33 | 1.04, −0.43 |
Computer programs: APEX2 (Bruker–Nonius, 2004), SAINT (Bruker, 2003), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL.
Tethered | BIGBAU, EBAYOV, EBAYUB, GUJZAM, GUJZEQ, HOJNID, HUHHEX, JAZFOF, JECXAQ, KAQXAB, LOMZOC, NEJQIC,i NIHZEJ, NIHZIN, NOCHAO, OKINAX, PAMJAO, PEHMIY, PUGGAZ, RICWEF, RIYBOQ, RIYBUW, RIYCIL, WISXOL, WISXUR, WISYAY, ZECNAW |
Non-tethered | COMQIE, DATNIV,i DIFVET, DOLMIA, DUXKOW, DUXKUC, EVAQAT, FIJYAY,i FIJYEC,i FIQBUD, FOJFUF,i FOJGAM,i FOJGEQ,i FOMREF, GEDPUB, GIRGOD,i JOBSOI, JOBSUO, JOFSUS, KUSLEP, KUSLUF, KUSMUG, MAYMIJ, MAYMOP, MUFNUW, NAWSUA, NOGKUP, SAJFOY,i SAJGAL,i SOVWIJ, WUMPEZ, YUZLIO, YUZLOU |
(i) Three-dimensional coordinates not available. |
The chemistry of organothio derivatives of tetrathiafulvalene (TTF) has been studied extensively, and there are numerous crystal structures of such molecules in the literature [for example, the polymorphic parent compound, tetra(methylthio)tetrathiafulvalene; Cambridge Structural Database (CSD; Version 5.27 plus January, May and August 2006 updates; Allen, 2002) refcodes DIFVET (Katayama et al., 1985) and (DIFVET01) Endres, 1986]. One reason for this is that TTF derivatives find extensive use in the preparation of various interlocked compounds, including bistable [2]rotaxanes (Tseng et al., 2004) and [2]catenanes (Asakawa et al., 1998), which are prime candidates for future construction of molecular electronics (DeIonno et al., 2006), artificial molecular muscles (Liu et al., 2005) and molecular switches (Kang et al., 2004). Amongst the derivatives that have been characterized crystallographically, there are several in which the two ends of the TTF molecule are tethered via a covalent linker. Various simple chain linkers have been employed for this purpose, including, for example, ether (Le Derf et al., 2001; GUJZAM, GUJZEQ), thioether (Le Derf et al., 1999a; HOJNID) and 2,4-hexadiyne (Simonsen, Thorup & Becher, 1997; PUGGAZ) chains. More complex linkers have also been prepared, incorporating functional groups such as pyromellitic dianhydride (Hansen et al., 2000; WISXOL, WISXUR, WISYAY???), 4,4'-bispyridinium (Simonsen, Zong et al., 1997; RICWEF), 2-thioxo-1,3-dithiole-4,5-dithiolate (John et al., 2000; LOMZOC) and methylenediphenyl (Lau et al., 1997; NIHZEJ, NIHZIN??). One crystal structure has been reported in which a TTF molecule is tethered by saturated thioalkyl chains, namely cis,cis-bis(hexamethylenedithio)TTF (Suresh Kumar et al., 1998; JECXAQ), which includes two hexamethylenedithio chain linkers. We describe here the cis and trans isomers of bis(2-cyanoethylsulfanyl)tetrathiafulvalene (Scheme 1) tethered by a single 1,10-decamethylenedithio chain.
The molecular structures of the cis, (I), and trans, (II), isomers are shown in Figs. 1 and 2, respectively. In (I), the TTF unit is approximately planar, with an r.m.s. deviation of 0.053 Å from the least-squares plane defined by atoms S1–S8 and C1–C6. The 1,10-decamethylenedithio chain in (I) lies approximately in the plane of the TTF group, so that the molecule as a whole resembles a flat disc (Fig. 1), with the 2-cyanoethylsulfanyl groups pointing to either side. The 1,10-decamethylenedithio chain is arranged so that its longest straight section (C14–C19) resembles n-hexane (Fig. 1). By contrast, the TTF unit in (II) deviates considerably from planarity: the least-squares plane through one outer ring of the TTF unit (S1/S2/C3/C4, referred to as plane 1) forms a dihedral angle of 21.7 (1)° with the least-squares plane through the inter-ring region (S1–S4/C1/C2; plane 2), which in turn forms a dihedral angle of 18.6 (1)° with the least-squares plane through the other outer ring [S3/S4/C5/C6; plane 3] (Fig. 2). The constraining influence of the 1,10-decamethylenedithio linker is reflected further by the positions of atoms S5–S8: atoms S6 and S7, part of the 1,10-decamethylenedithio linker, lie 0.087 (3) and 0.126 (3) Å from plane 1 and plane 3, respectively, while atoms S5 and S8, part of the two cyanoethylsulfanyl arms, lie 0.404 (3) and 0.370 (3) Å, respectively, from the same planes. Thus, as well as inducing non-planarity, the linker also twists the molecule about its long axis (i.e. the C1—C2 inter-ring vector of TTF). In the trans isomer, the longest straight section of the 1,10-decamethylenedithio linker (C14–C21) resembles n-octane (Fig. 2).
In both (I) and (II), interactions between molecules are largely segregated so that TTF units are brought into close contact with each other, and the alkyl chains are brought into close contact with each other. In (I), molecules form stacks along a (Fig. 3), in which the TTF groups adopt an interplanar separation of 3.71 (1) Å. For adjacent molecules within a stack [symmetry code: (i) 1 + x, y, z], the straight n-hexyl sections (C14–C19) of the 1,10-decamethylenedithio linker are arranged typically for n-alkyl chains, with a lateral offset of ca 2.5 Å (i.e. 2 × CH2) that allows the CH2 groups of one chain to project into the gaps between CH2 groups in the neighbouring chain (Fig. 4). Between molecules in adjacent stacks [symmetry code: (ii) 1 - x, 1 - y, 1 - z], the n-hexyl sections are arranged with no lateral offset, with a translation of ca 4.7 Å between chains. This arrangement is essentially identical to that in the crystal structure of n-hexane itself [corresponding lattice dimension 4.696 (1) Å; Boese et al., 1999; Cambridge Structural Database refcode HEXANE01)]. Pairs of stacks are aligned in a herringbone manner (Fig. 3), with the C≡N bonds adopting typical antiparallel and `crossed' arrangements. The shortest S···S contacts in (I) [3.4657 (16) Å] occur between atoms S1 and S8iii [symmetry code: (iii) 2 - x, 1/2 + y, 3/2 - z]. The geometry is such that a lone pair of electrons on S1, lying in the plane of the TTF unit, can be envisaged to approach the σ*(S8—C6) orbital in the neighbouring molecule (Rosenfield et al., 1977).
In (II), the intermolecular interactions are segregated clearly into layered regions lying parallel to the ac planes (Fig. 5). In the plane at y = 1/2, the straight n-octyl sections (C14–C21) of the 1,10-decamethylenedithio chains are brought into close contact (Fig. 6). As for (I), pairs of molecules can be envisaged in this region [symmetry code: (iv) 1 - x, 1 - y, 1 - z], with their n-octyl sections lying parallel with no lateral offset, and with an inter-chain translation of ca 4.7 Å. This arrangement again resembles closely that in n-octane itself [corresponding lattice dimension 4.752 (1) Å; Boese et al., 1999; HEXANE01]. In the perpendicular direction, adjacent chains [symmetry code: (v) 2 - x, 1 - y, 1 - z] are arranged with a much greater lateral offset, so that only approximately half of each n-octyl section is in contact with its neighbour (Fig. 6). In the ac planes at y = 1/4 and 3/4 (Fig. 5), the TTF units are brought into contact. Where the molecules meet in a face-to-face manner, one S atom of the 1,10-decamethylenedithio chain lies over the centroid of a neighbouring five-membered ring [S7···Cg(S1/S2/C1/C3/C4)vi = 3.53 Å; symmetry code (vi) -1/2 + x, 3/2 - y, 1/2 + z]. The shortest in-plane S···S contacts in (II) are 3.3399 (9) Å, between S5 and S8vii [symmetry code: (vii) x, y, -1 + z], displaying no clear directional features. The 2-cyanoethylsulfanyl groups adopt antiparallel and crossed arrangements similar to those in (I).
From the CSD, 24 comparable non-tethered structures were identified, for which three-dimensional coordinates are available (Table 1). Of these, the TTF unit deviates significantly from planarity in only three, namely DIFVET (Katayama et al., 1985), FIQBUD (Bond & Jeppesen, 2005) and KUSLEP (Nakano et al., 1992). By contrast, for 26 tethered examples identified (with three-dimensional coordinates available; Table 1), only three contain planar TTF units. Two of these, KAQXAB (Le Derf et al., 1999b) and NIHZIN (Lau et al., 1997), are cis isomers, while the third (WISXUR; Hansen et al., 2000) is a trans isomer. For NIHZIN, the related trans isomer has also been characterized (NIHZEJ; Lau et al., 1997), and it contains a planar TTF unit. For WISXUR, the linker incorporates a pyromellitic dianhydride group, and the planar TTF conformation appears to arise as a consequence of intramolecular and intermolecular π–π stacking interactions.