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The crystal structure of the title compound [systematic name: 2-(1,3-dithiolo[4,5-b][1,4]dithiin-2-yl­idene)-6,6-bis­(methoxy­ethoxy­methoxy­methyl)-1,3-dithiolo[4,5-b][1,4]dithiepine], C21H30O6S8, a spiro-substituted BEDT-TTF analogue [BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene], has a strongly bent heterocyclic framework. The seven-membered ring adopts a pseudo-chair conformation with notably widened ring bond angles, especially at the methyl­ene C atoms [119.49 (11) and 117.60 (11)°]. The axial side chain adopts an extended conformation, but the equatorial side chain curls back on itself and the O atom nearest the ring system is involved in three short contacts to H atoms (2.45-2.53 Å). The mol­ecules pack in centrosymmetrically related pairs, which are isolated from each other by columns of the polyether side chains. This study emphasizes the ease of distortion of the neutral bis(propylenedithio)tetrathiafulvalene ring structure, and how the need to accommodate side chains can easily override the tendency of these donor systems to form stacks in the crystalline state.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108005933/su3017sup1.cif
Contains datablocks 2, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108005933/su30172sup2.hkl
Contains datablock 2

CCDC reference: 690182

Comment top

The radical cation salts of BEDT–TTF, (1), have shown a wide variety of electrical behaviour (Rovira, 2004), including bifunctional materials where conductivity is combined with magnetic properties. Particular highlights are the superconductor (BEDT–TTF)2Cu(NCS)2 (Williams et al., 1991), the paramagnetic superconductor (BEDT–TTF)4·H2O·Fe(C2O4)3·C6H5CN (Kurmoo et al., 1995) and the ferromagnetic conductor (BEDT–TTF)3 (CrMn(oxalate)3) (Coronado et al., 2000). A range of substituted BEDT–TTF derivatives has become available (Wallis & Griffiths, 2005), including some with expanded outer rings (Ozturk et al., 2001). Here, we report the crystal structure of the title donor, (2), which contains one propylenedithio ring with two methoxyethoxymethoxymethyl substituents on the central sp3 C atom. We were interested to see whether the substituents would inhibit the usual packing modes of such donors, in which they pack in one- or two-dimensional stacks. Donors (3) (Karrer et al., 1987), (5) (Yamada et al., 1997) and (6) (Yang et al., 2008) retain the traditional packing modes, despite the increasing bulk of the substituents, while the racemic tetraethyl donor, (4), does not (Kini et al., 1999).

The molecular structure of compound (2), measured at 120 K, is shown in Fig. 1. Selected bond distances, bond angles and torsion angles are given in Table 1. Details of the hydrogen bonding are given in Table 2.

The most notable feature is the very pronounced bend in the structure of the organosulfur core. Thus, although the four central S atoms (S3, S4, S5 and S6) are almost coplanar [to within 0.0132 (2) Å], the outer four S atoms are displaced by ca 1 Å to the same side of that plane (Table 3). Formation of the seven-membered ring has led to expansion of the ring bond angles, most notably at the two methylene atoms, C9 and C11 [119.49 (11) and 117.60 (11)°, respectively], as well as at the two sp2 atoms, C7 and C8 [126.75 (12) and 126.63 (12)°, respectively]. The angles at atoms S7 and S8 are 103.63 (7) and 102.91 (7)°, respectively. The widest angle at the quarternary centre, C10, is also in the ring system [112.07 (13)°]. The bond lengths from S to the methylene C atoms [1.8166 (16)–1.8182 (16) Å] are considerably longer than those to the sp2 C atoms [1.7485 (15)–1.7511 (16) Å] (see Table 1).

The dihydrodithiepine ring adopts a pseudo chair structure, with the two side-chains taking up axial and equatorial positions. The equatorial side-chain makes smaller angles [105.49 (12) and 106.23 (12)°] with the adjacent ring C—C bonds than the axial one [110.75 (13) and 111.79 (13)°]. The first C—O bonds along each chain lie anti to a ring C—C bond [torsion angles C9—C10—C12—O1 = 178.90 (12) and C11—C10—C17—O4 = −170.24 (13)°]. These two substituents adopt quite different conformations (Table 1) and twist for the most part in the opposite sense to each other. The most notable differences are in the conformations about the (ring-C)—C—O—C bond, with only the axial side-chain adopting a fully extended conformation [177.13 (18) cf. −134.64 (14)°], and in the conformations about the (–C)—O—C—(CH2OMe) bond [134.65 (15) cf. 146.78 (14)°] and the only O–C—C–O bond [−75.23 (19) cf. −65.53 (19)°] which, in contrast with the rest of the chain, twist in the same sense. The result is that the axial side-chain is much more extended, while the equatorial one curls back on itself. The first O atom along the equatorial side-chain, O4, is involved in three close intramolecular contacts to H atoms (Table 2), from the ring system (H9B, 2.53 Å), from the axial side-chain (H12A, 2.45 Å) and from within the side-chain (H19A, 2.50 Å). The corresponding contacts to atom O1 of the axial side-chain are ca 0.15 Å longer.

The acetal linkages involving the third and fourth bonds along each chain have similar gauche conformations about both C—O bonds. The ethylene bridge at the other end of the donor molecule is disordered between two envelope conformations in which one sp3 C atom is displaced strongly to the same side of the plane of the other four atoms of the dithiin ring [C1 − 0.826 (4) and C2A −0.70 (1) Å], with the other sp3 C atom lying close to this plane [C2 − 0.068 (5) and C1A 0.078 (8) Å]. Only a few structures of this donor system and the closely related TTF fused to two dihydro-1,4-dithiepine rings have been measured, and these carry either two fluoro groups (Dautel & Fourmigue 2000, 2001), two H atoms (Porter et al., 1987), two hydroxymethyl groups (Liu et al., 2004) or a spiro dioxolane ring (Marshallsay et al., 1993) as substituents in place of polyether side-chains. All adopt the pseudo chair conformation in the seven-membered ring, apart from the bis(hydroxymethyl) derivative, (7), for which O—H···O hydrogen bonding plays an important role in determination of the crystal structure. Only two of these structures, the unsubstituted bis(dithiepinyl)TTF and the analogue of (2) bearing a spiro dioxolane group on the seven-membered ring, show a similar bending of the donor skeleton to that observed in (2). In all these structures there is no evidence for conformational disorder in the seven-membered ring, which is in contrast with the six-membered rings in BEDT–TTF and its radical cation salts, and indeed in the structure of (2). Comparison of the two rings of the TTF unit in (2) show that there is little difference in their geometries on fusion to a six- or seven-membered ring; the bonds from S atoms to the seven-ring junction are just slightly shorter [1.7587 (16) and 1.7643 (15) Å] than those to the six-ring junction [1.7699 (17) and 1.7724 (16) Å] (see Table 1).

In the crystal structure of (2), the molecules are packed in centrosymmetrically related pairs, with the best planes containing the four central S atoms lying ca 3.28 Å apart (Fig. 2). However, these pairs do not stack face to face with others, but are isolated from one another. These pairs of molecules lie more or less on edge in the bc plane, with the side-chains extending initially in this plane but penetrating into the a and-a directions as the side-chains twist, with one side-chain much more extended than the other. The side-chains cluster together and form columns of polyether groups stacking in the a direction, at the corners and at the centre of the unit cell, and they are separated by the pairs of organosulfur units. Within these clusters there is a short H···O contact, H18A···O3ii = 2.59 Å (see Table 2 for details). In contrast, the closest related donor is the bis(hydroxymethyl) donor, (7), which forms stacks in the solid state (Liu et al., 2004). However its 2:1 salt with triodide contains orthogonal sets of dimers of the donor. Hydrogen bonding of the hydroxyl groups plays an important role in these particular structures.

Experimental top

Preparative details have been reported previously (Ozturk et al., 2001). Crystals were obtained by recrystallization from which solvent? Or were used directly from the previous work? Analysis, found: C 39.7, H 4.7%; C21H30O6S8 requires: C 39.6, H 4.8%. Spectroscopic analysis: 1H NMR (270 MHz, CDCl3, δ, p.p.m.): 4.70 (4H, s, 2 OCH2O), 3.71 (4H, br s, 6,6-CH2O), 3.64 (4H, m) and 3.57 (4H, m) (2 OCH2CH2O), 3.39 (6H, s, 2 CH3), 3.28 (5'-, 6'-H2), 2.75 (4H, s, 5-, 7-H2); 13C NMR (270 MHz, CDCl3, δ, p.p.m.): 129.6 (br, 3a-, 8a-C), 114.6 and 114.1 (2'-, 3a'-, 7a'-C), 109.8 (2-C), 95.7 (OCH2O), 71.7 and 69.4 (2 OCH2CH2O), 69.4 (br, 6,6-CH2O), 66.9 (2 CH3OCH2), 59.0 (2 OCH3), 44.2 (5-, 7-C), 37.0 (6-C), 30.1 (5'-, 6'-C); IR (KBr, νmax, cm−1): 1300, 1244, 1197, 1172, 1137, 1098, 1040, 1012, 892, 864, 847, 837, 770, 722; m/z: (EI) 634 (M+, 100), 606 ([M - CH2CH2]+, 18).

Refinement top

A 0.664 (7):0.336 (7) disorder between two positions for the C1(C1A) and C2(C2A) atoms in the dihydrodithiin ring was refined without applying any constraints. All H atoms were placed in calculated positions and treated as riding atoms, with C—H = 0.98–0.99 Å and with Uiso(H) = 1.5 or 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of compound (2), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probabilty level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal packing of compound (2), viewed along the a axis.
2-(1,3-dithiolo[4,5-b][1,4]dithiin-2-ylidene)-6,6- bis(methoxyethoxymethoxymethyl)-1,3-dithiolo[4,5-b][1,4]dithiepine top
Crystal data top
C21H30O6S8F(000) = 1328
Mr = 634.93Dx = 1.540 Mg m3
Monoclinic, P21/nMelting point = 356–357 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 6.8227 (10) ÅCell parameters from 6442 reflections
b = 19.7775 (4) Åθ = 2.9–27.5°
c = 20.3661 (4) ŵ = 0.69 mm1
β = 94.905 (1)°T = 120 K
V = 2738.1 (4) Å3Rod, orange
Z = 40.24 × 0.10 × 0.07 mm
Data collection top
Bruker Nonius KappaCCD
diffractometer
6272 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode5278 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.2°
ϕ and ω scansh = 88
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 2525
Tmin = 0.85, Tmax = 0.95l = 2626
45147 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0191P)2 + 1.4275P]
where P = (Fo2 + 2Fc2)/3
6272 reflections(Δ/σ)max = 0.001
439 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C21H30O6S8V = 2738.1 (4) Å3
Mr = 634.93Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.8227 (10) ŵ = 0.69 mm1
b = 19.7775 (4) ÅT = 120 K
c = 20.3661 (4) Å0.24 × 0.10 × 0.07 mm
β = 94.905 (1)°
Data collection top
Bruker Nonius KappaCCD
diffractometer
6272 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
5278 reflections with I > 2σ(I)
Tmin = 0.85, Tmax = 0.95Rint = 0.044
45147 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.063H-atom parameters constrained
S = 1.05Δρmax = 0.33 e Å3
6272 reflectionsΔρmin = 0.25 e Å3
439 parameters
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.

H atoms were placed geometrically, with ADP's of 1.2Ueq of the attached atom. A disorder in the positions of C atoms C1 and C2 was refined to 34:66. No constraints were applied to the positions of the disordered atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.92931 (7)0.19257 (2)0.25645 (2)0.02846 (11)
S20.45510 (7)0.17913 (2)0.30982 (2)0.03196 (12)
S31.03112 (6)0.08482 (2)0.35575 (2)0.02050 (9)
S40.63329 (6)0.07817 (2)0.40302 (2)0.02265 (10)
S51.13098 (6)0.06391 (2)0.42054 (2)0.01774 (9)
S60.73644 (6)0.06801 (2)0.46921 (2)0.01871 (9)
S71.18311 (6)0.21397 (2)0.422145 (19)0.01801 (9)
S80.72935 (6)0.21764 (2)0.48358 (2)0.02019 (9)
O10.84546 (16)0.38924 (6)0.50937 (6)0.0228 (3)
O20.68666 (16)0.42442 (6)0.40843 (6)0.0252 (3)
O30.27596 (17)0.46986 (6)0.38853 (6)0.0298 (3)
O41.30031 (17)0.37757 (6)0.58138 (6)0.0266 (3)
O51.45554 (17)0.37805 (6)0.68887 (6)0.0252 (3)
O61.08803 (18)0.38947 (7)0.74213 (6)0.0332 (3)
C10.6943 (4)0.20206 (19)0.20675 (15)0.0298 (10)0.664 (7)
H1A0.65050.15720.18970.036*0.664 (7)
H1B0.71370.23140.16840.036*0.664 (7)
C1A0.7176 (8)0.2418 (3)0.2304 (3)0.0265 (18)0.336 (7)
H1A10.73150.25940.18550.032*0.336 (7)
H1A20.71060.28110.26030.032*0.336 (7)
C20.5350 (6)0.2322 (2)0.24511 (19)0.0286 (9)0.664 (7)
H2A0.58390.27540.26490.034*0.664 (7)
H2B0.41970.24270.21390.034*0.664 (7)
C2A0.5292 (12)0.2023 (5)0.2300 (4)0.0339 (19)0.336 (7)
H2A10.42250.22930.20680.041*0.336 (7)
H2A20.54340.16050.20410.041*0.336 (7)
C30.8482 (2)0.13833 (8)0.31666 (8)0.0203 (3)
C40.6678 (2)0.13457 (8)0.33753 (8)0.0209 (3)
C50.8631 (2)0.03875 (8)0.39894 (8)0.0177 (3)
C60.9044 (2)0.02230 (8)0.42543 (8)0.0169 (3)
C71.0350 (2)0.14433 (8)0.43727 (7)0.0163 (3)
C80.8554 (2)0.14588 (8)0.45992 (8)0.0173 (3)
C91.2289 (2)0.25336 (8)0.50266 (7)0.0175 (3)
H9A1.26420.21700.53490.021*
H9B1.34640.28250.50120.021*
C101.0672 (2)0.29610 (8)0.53019 (7)0.0162 (3)
C110.8948 (2)0.25256 (8)0.54961 (8)0.0189 (3)
H11B0.81560.28030.57800.023*
H11A0.95000.21450.57680.023*
C120.9982 (2)0.35204 (8)0.48176 (8)0.0184 (3)
H12A1.10930.38240.47410.022*
H12B0.94810.33210.43900.022*
C130.7777 (3)0.44444 (9)0.46958 (9)0.0262 (4)
H13B0.68300.47100.49330.031*
H13A0.89040.47420.46230.031*
C140.5131 (2)0.38467 (9)0.41340 (9)0.0268 (4)
H14A0.47100.38810.45860.032*
H14B0.54200.33660.40460.032*
C150.3515 (3)0.40890 (9)0.36497 (9)0.0264 (4)
H15A0.40270.41650.32150.032*
H15B0.24590.37450.35960.032*
C160.1237 (3)0.49680 (11)0.34444 (11)0.0403 (5)
H16A0.17420.50510.30150.060*
H16B0.07700.53940.36220.060*
H16C0.01460.46450.33910.060*
C171.1590 (2)0.32701 (8)0.59490 (8)0.0207 (3)
H17B1.05460.34750.61930.025*
H17A1.22390.29110.62280.025*
C181.4790 (3)0.37387 (10)0.62124 (9)0.0293 (4)
H18A1.54500.33070.61230.035*
H18B1.56580.41110.60900.035*
C191.3782 (3)0.44117 (9)0.70945 (9)0.0289 (4)
H19A1.29820.46260.67220.035*
H19B1.48720.47220.72400.035*
C201.2534 (3)0.42821 (10)0.76520 (9)0.0322 (4)
H20A1.33080.40360.80090.039*
H20B1.21000.47170.78320.039*
C210.9587 (3)0.37781 (14)0.79190 (11)0.0553 (6)
H21A1.02780.35240.82820.083*
H21B0.84490.35170.77350.083*
H21C0.91400.42120.80840.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0332 (2)0.0290 (2)0.0234 (2)0.00085 (19)0.00401 (18)0.01047 (18)
S20.0244 (2)0.0342 (3)0.0366 (3)0.00546 (19)0.00132 (19)0.0149 (2)
S30.0210 (2)0.0186 (2)0.0221 (2)0.00051 (16)0.00307 (16)0.00439 (16)
S40.0216 (2)0.0212 (2)0.0256 (2)0.00360 (16)0.00443 (17)0.00670 (17)
S50.01738 (19)0.01618 (19)0.0199 (2)0.00078 (15)0.00308 (15)0.00253 (15)
S60.01713 (19)0.0168 (2)0.0225 (2)0.00110 (15)0.00357 (15)0.00277 (16)
S70.02007 (19)0.0172 (2)0.01720 (19)0.00124 (15)0.00430 (15)0.00126 (15)
S80.01498 (18)0.0172 (2)0.0281 (2)0.00277 (15)0.00023 (16)0.00370 (16)
O10.0247 (6)0.0205 (6)0.0233 (6)0.0089 (5)0.0027 (5)0.0003 (5)
O20.0202 (6)0.0288 (7)0.0263 (7)0.0009 (5)0.0001 (5)0.0077 (5)
O30.0258 (6)0.0225 (6)0.0402 (8)0.0052 (5)0.0026 (5)0.0036 (6)
O40.0308 (7)0.0269 (7)0.0214 (6)0.0108 (5)0.0028 (5)0.0003 (5)
O50.0261 (6)0.0266 (7)0.0222 (6)0.0024 (5)0.0023 (5)0.0037 (5)
O60.0333 (7)0.0441 (8)0.0229 (7)0.0047 (6)0.0066 (5)0.0041 (6)
C10.0394 (18)0.031 (2)0.0182 (15)0.0049 (14)0.0029 (12)0.0025 (14)
C1A0.037 (3)0.020 (4)0.022 (3)0.005 (2)0.002 (2)0.004 (3)
C20.0412 (19)0.024 (2)0.0203 (18)0.0077 (18)0.0011 (14)0.0044 (15)
C2A0.042 (4)0.028 (5)0.030 (4)0.000 (4)0.011 (3)0.009 (3)
C30.0275 (9)0.0169 (8)0.0161 (8)0.0006 (7)0.0005 (7)0.0019 (6)
C40.0241 (8)0.0177 (8)0.0203 (8)0.0009 (7)0.0020 (7)0.0029 (6)
C50.0190 (8)0.0178 (8)0.0164 (8)0.0007 (6)0.0014 (6)0.0008 (6)
C60.0175 (7)0.0175 (8)0.0155 (8)0.0003 (6)0.0007 (6)0.0004 (6)
C70.0186 (8)0.0149 (8)0.0152 (7)0.0002 (6)0.0003 (6)0.0008 (6)
C80.0175 (8)0.0166 (8)0.0178 (8)0.0008 (6)0.0002 (6)0.0017 (6)
C90.0177 (7)0.0171 (8)0.0173 (8)0.0003 (6)0.0007 (6)0.0012 (6)
C100.0166 (7)0.0160 (8)0.0159 (8)0.0011 (6)0.0009 (6)0.0010 (6)
C110.0210 (8)0.0178 (8)0.0183 (8)0.0010 (6)0.0043 (6)0.0024 (6)
C120.0176 (8)0.0168 (8)0.0209 (8)0.0033 (6)0.0026 (6)0.0005 (6)
C130.0279 (9)0.0196 (9)0.0304 (10)0.0070 (7)0.0014 (7)0.0015 (7)
C140.0231 (9)0.0234 (9)0.0340 (10)0.0007 (7)0.0033 (7)0.0066 (8)
C150.0259 (9)0.0214 (9)0.0316 (10)0.0003 (7)0.0014 (7)0.0014 (7)
C160.0264 (10)0.0381 (12)0.0552 (14)0.0080 (9)0.0043 (9)0.0062 (10)
C170.0232 (8)0.0202 (8)0.0185 (8)0.0030 (7)0.0007 (6)0.0009 (6)
C180.0237 (9)0.0369 (11)0.0276 (10)0.0048 (8)0.0043 (7)0.0072 (8)
C190.0330 (10)0.0229 (9)0.0305 (10)0.0024 (8)0.0007 (8)0.0072 (8)
C200.0352 (10)0.0355 (11)0.0255 (10)0.0003 (8)0.0003 (8)0.0099 (8)
C210.0518 (14)0.0797 (19)0.0376 (13)0.0077 (13)0.0231 (11)0.0007 (12)
Geometric parameters (Å, º) top
S1—C31.7541 (17)C2A—H2A10.9900
S1—C1A1.785 (5)C2A—H2A20.9900
S1—C11.831 (3)C3—C41.338 (2)
S2—C41.7496 (17)C5—C61.342 (2)
S2—C2A1.803 (8)C7—C81.346 (2)
S2—C21.806 (4)C9—C101.534 (2)
S3—C51.7581 (16)C9—H9A0.9900
S3—C31.7724 (16)C9—H9B0.9900
S4—C51.7593 (16)C10—C121.529 (2)
S4—C41.7699 (17)C10—C111.537 (2)
S5—C61.7617 (16)C10—C171.537 (2)
S5—C71.7643 (15)C11—H11B0.9900
S6—C81.7587 (16)C11—H11A0.9900
S6—C61.7606 (16)C12—H12A0.9900
S7—C71.7511 (16)C12—H12B0.9900
S7—C91.8182 (15)C13—H13B0.9900
S8—C81.7485 (16)C13—H13A0.9900
S8—C111.8166 (16)C14—C151.494 (2)
O1—C131.414 (2)C14—H14A0.9900
O1—C121.4297 (18)C14—H14B0.9900
O2—C131.400 (2)C15—H15A0.9900
O2—C141.432 (2)C15—H15B0.9900
O3—C151.411 (2)C16—H16A0.9800
O3—C161.418 (2)C16—H16B0.9800
O4—C181.407 (2)C16—H16C0.9800
O4—C171.4317 (19)C17—H17B0.9900
O5—C181.403 (2)C17—H17A0.9900
O5—C191.432 (2)C18—H18A0.9900
O6—C201.411 (2)C18—H18B0.9900
O6—C211.419 (2)C19—C201.498 (3)
C1—C21.514 (6)C19—H19A0.9900
C1—H1A0.9900C19—H19B0.9900
C1—H1B0.9900C20—H20A0.9900
C1A—C2A1.504 (11)C20—H20B0.9900
C1A—H1A10.9900C21—H21A0.9800
C1A—H1A20.9900C21—H21B0.9800
C2—H2A0.9900C21—H21C0.9800
C2—H2B0.9900
C3—S1—C1A104.23 (19)C12—C10—C17110.22 (13)
C3—S1—C197.78 (11)C9—C10—C17106.23 (12)
C1A—S1—C129.7 (2)C11—C10—C17105.49 (12)
C4—S2—C2A97.5 (3)C10—C11—S8117.60 (11)
C4—S2—C2103.58 (14)C10—C11—H11B107.9
C2A—S2—C221.3 (2)S8—C11—H11B107.9
C5—S3—C394.01 (8)C10—C11—H11A107.9
C5—S4—C493.85 (8)S8—C11—H11A107.9
C6—S5—C793.91 (7)H11B—C11—H11A107.2
C8—S6—C693.95 (7)O1—C12—C10108.24 (12)
C7—S7—C9103.63 (7)O1—C12—H12A110.0
C8—S8—C11102.91 (7)C10—C12—H12A110.0
C13—O1—C12112.68 (12)O1—C12—H12B110.0
C13—O2—C14113.51 (13)C10—C12—H12B110.0
C15—O3—C16112.01 (14)H12A—C12—H12B108.4
C18—O4—C17114.64 (13)O2—C13—O1112.96 (14)
C18—O5—C19114.50 (14)O2—C13—H13B109.0
C20—O6—C21112.27 (16)O1—C13—H13B109.0
C2—C1—S1112.9 (3)O2—C13—H13A109.0
C2—C1—H1A109.0O1—C13—H13A109.0
S1—C1—H1A109.0H13B—C13—H13A107.8
C2—C1—H1B109.0O2—C14—C15110.19 (14)
S1—C1—H1B109.0O2—C14—H14A109.6
H1A—C1—H1B107.8C15—C14—H14A109.6
C2A—C1A—S1112.8 (5)O2—C14—H14B109.6
C2A—C1A—H1A1109.0C15—C14—H14B109.6
S1—C1A—H1A1109.0H14A—C14—H14B108.1
C2A—C1A—H1A2109.0O3—C15—C14108.66 (14)
S1—C1A—H1A2109.0O3—C15—H15A110.0
H1A1—C1A—H1A2107.8C14—C15—H15A110.0
C1—C2—S2115.0 (3)O3—C15—H15B110.0
C1—C2—H2A108.5C14—C15—H15B110.0
S2—C2—H2A108.5H15A—C15—H15B108.3
C1—C2—H2B108.5O3—C16—H16A109.5
S2—C2—H2B108.5O3—C16—H16B109.5
H2A—C2—H2B107.5H16A—C16—H16B109.5
C1A—C2A—S2115.6 (6)O3—C16—H16C109.5
C1A—C2A—H2A1108.4H16A—C16—H16C109.5
S2—C2A—H2A1108.4H16B—C16—H16C109.5
C1A—C2A—H2A2108.4O4—C17—C10110.17 (13)
S2—C2A—H2A2108.4O4—C17—H17B109.6
H2A1—C2A—H2A2107.4C10—C17—H17B109.6
C4—C3—S1127.58 (13)O4—C17—H17A109.6
C4—C3—S3117.11 (12)C10—C17—H17A109.6
S1—C3—S3115.28 (9)H17B—C17—H17A108.1
C3—C4—S2129.03 (13)O5—C18—O4113.41 (14)
C3—C4—S4117.37 (12)O5—C18—H18A108.9
S2—C4—S4113.60 (9)O4—C18—H18A108.9
C6—C5—S3122.95 (12)O5—C18—H18B108.9
C6—C5—S4122.47 (12)O4—C18—H18B108.9
S3—C5—S4114.57 (9)H18A—C18—H18B107.7
C5—C6—S6122.82 (12)O5—C19—C20108.67 (15)
C5—C6—S5123.53 (12)O5—C19—H19A110.0
S6—C6—S5113.64 (9)C20—C19—H19A110.0
C8—C7—S7126.75 (12)O5—C19—H19B110.0
C8—C7—S5116.78 (12)C20—C19—H19B110.0
S7—C7—S5116.47 (9)H19A—C19—H19B108.3
C7—C8—S8126.63 (12)O6—C20—C19109.30 (14)
C7—C8—S6117.32 (12)O6—C20—H20A109.8
S8—C8—S6116.02 (9)C19—C20—H20A109.8
C10—C9—S7119.49 (11)O6—C20—H20B109.8
C10—C9—H9A107.4C19—C20—H20B109.8
S7—C9—H9A107.4H20A—C20—H20B108.3
C10—C9—H9B107.4O6—C21—H21A109.5
S7—C9—H9B107.4O6—C21—H21B109.5
H9A—C9—H9B107.0H21A—C21—H21B109.5
C12—C10—C9110.75 (13)O6—C21—H21C109.5
C12—C10—C11111.79 (13)H21A—C21—H21C109.5
C9—C10—C11112.07 (13)H21B—C21—H21C109.5
C3—S1—C1—C260.1 (3)C9—S7—C7—C861.76 (16)
C1A—S1—C1—C245.0 (4)C9—S7—C7—S5118.67 (9)
C3—S1—C1A—C2A35.3 (6)C6—S5—C7—C812.83 (14)
C1—S1—C1A—C2A45.4 (6)C6—S5—C7—S7166.78 (9)
S1—C1—C2—S267.3 (4)S7—C7—C8—S83.2 (2)
C4—S2—C2—C132.5 (4)S5—C7—C8—S8177.25 (9)
C2A—S2—C2—C143.0 (9)S7—C7—C8—S6178.80 (9)
S1—C1A—C2A—S269.4 (8)S5—C7—C8—S60.76 (17)
C4—S2—C2A—C1A57.4 (7)C11—S8—C8—C759.49 (16)
C2—S2—C2A—C1A50.9 (8)C11—S8—C8—S6118.55 (9)
C1A—S1—C3—C40.6 (3)C6—S6—C8—C711.75 (14)
C1—S1—C3—C429.0 (2)C6—S6—C8—S8170.03 (9)
C1A—S1—C3—S3177.0 (3)C7—S7—C9—C1076.96 (13)
C1—S1—C3—S3153.43 (15)S7—C9—C10—C1255.09 (16)
C5—S3—C3—C49.24 (14)S7—C9—C10—C1170.50 (16)
C5—S3—C3—S1172.90 (9)S7—C9—C10—C17174.78 (11)
S1—C3—C4—S22.9 (3)C12—C10—C11—S851.53 (16)
S3—C3—C4—S2179.53 (10)C9—C10—C11—S873.50 (15)
S1—C3—C4—S4176.11 (10)C17—C10—C11—S8171.33 (11)
S3—C3—C4—S41.44 (18)C8—S8—C11—C1081.68 (13)
C2A—S2—C4—C321.0 (4)C11—C10—C12—O153.14 (16)
C2—S2—C4—C30.2 (2)C17—C10—C12—O163.84 (16)
C2A—S2—C4—S4159.9 (3)C9—C10—C12—O1178.90 (12)
C2—S2—C4—S4179.28 (17)C13—O1—C12—C10177.18 (13)
C5—S4—C4—C311.30 (14)C12—O1—C13—O264.71 (18)
C5—S4—C4—S2169.53 (9)C14—O2—C13—O162.64 (18)
C3—S3—C5—C6161.75 (14)C13—O2—C14—C15134.65 (15)
C3—S3—C5—S416.77 (10)O2—C14—C15—O375.19 (18)
C4—S4—C5—C6161.19 (14)C16—O3—C15—C14178.92 (15)
C4—S4—C5—S317.34 (10)C12—C10—C17—O449.40 (17)
S3—C5—C6—S6179.49 (8)C9—C10—C17—O470.63 (16)
S4—C5—C6—S62.1 (2)C11—C10—C17—O4170.24 (13)
S3—C5—C6—S50.1 (2)C18—O4—C17—C10134.64 (14)
S4—C5—C6—S5178.50 (9)C17—O4—C18—O557.5 (2)
C8—S6—C6—C5160.43 (14)C19—O5—C18—O464.15 (19)
C8—S6—C6—S520.11 (9)C18—O5—C19—C20146.78 (14)
C7—S5—C6—C5160.12 (14)O5—C19—C20—O665.38 (19)
C7—S5—C6—S620.43 (10)C21—O6—C20—C19177.42 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O5i0.992.263.181 (4)154
C9—H9B···O40.992.532.951 (2)106
C12—H12A···O40.992.452.812 (2)101
C12—H12B···S70.992.873.2839 (17)106
C18—H18B···O3ii0.992.593.528 (2)158
C19—H19A···O40.992.502.904 (2)104
Symmetry codes: (i) x+2, y, z+1; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC21H30O6S8
Mr634.93
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)6.8227 (10), 19.7775 (4), 20.3661 (4)
β (°) 94.905 (1)
V3)2738.1 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.69
Crystal size (mm)0.24 × 0.10 × 0.07
Data collection
DiffractometerBruker Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.85, 0.95
No. of measured, independent and
observed [I > 2σ(I)] reflections
45147, 6272, 5278
Rint0.044
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.063, 1.05
No. of reflections6272
No. of parameters439
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.25

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
S1—C31.7541 (17)S4—C41.7699 (17)
S1—C1A1.785 (5)S5—C61.7617 (16)
S1—C11.831 (3)S5—C71.7643 (15)
S2—C41.7496 (17)S6—C81.7587 (16)
S2—C2A1.803 (8)S6—C61.7606 (16)
S2—C21.806 (4)S7—C71.7511 (16)
S3—C51.7581 (16)S7—C91.8182 (15)
S3—C31.7724 (16)S8—C81.7485 (16)
S4—C51.7593 (16)S8—C111.8166 (16)
C7—S7—C9103.63 (7)C10—C9—S7119.49 (11)
C8—S8—C11102.91 (7)C12—C10—C9110.75 (13)
C8—C7—S7126.75 (12)C12—C10—C11111.79 (13)
C8—C7—S5116.78 (12)C9—C10—C11112.07 (13)
S7—C7—S5116.47 (9)C12—C10—C17110.22 (13)
C7—C8—S8126.63 (12)C9—C10—C17106.23 (12)
C7—C8—S6117.32 (12)C11—C10—C17105.49 (12)
S8—C8—S6116.02 (9)C10—C11—S8117.60 (11)
C9—C10—C12—O1178.90 (12)C11—C10—C17—O4170.24 (13)
C13—O1—C12—C10177.18 (13)C18—O4—C17—C10134.64 (14)
C12—O1—C13—O264.71 (18)C17—O4—C18—O557.5 (2)
C14—O2—C13—O162.64 (18)C19—O5—C18—O464.15 (19)
C13—O2—C14—C15134.65 (15)C18—O5—C19—C20146.78 (14)
O2—C14—C15—O375.19 (18)O5—C19—C20—O665.38 (19)
C16—O3—C15—C14178.92 (15)C21—O6—C20—C19177.42 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O5i0.992.263.181 (4)154
C9—H9B···O40.992.532.951 (2)106
C12—H12A···O40.992.452.812 (2)101
C12—H12B···S70.992.873.2839 (17)106
C18—H18B···O3ii0.992.593.528 (2)158
C19—H19A···O40.992.502.904 (2)104
Symmetry codes: (i) x+2, y, z+1; (ii) x+2, y+1, z+1.
Displacements (Å) of the outer S atoms from the mean plane of the inner TTF S atoms (S3, S4, S5 and S6) top
S1-0.9035 (8)S7-1.2026 (7)
S2-1.0328 (8)S8-1.0717 (8)
 

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