3,4-[2,2-Bis(methoxy­ethoxymethoxy­meth­yl)propyl­enedithio]-3',4'-(ethyl­ene­dithio)tetra­thia­fulvalene: a spiro-substituted BEDT-TTF analogue

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.

S1. Comment

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.

S2. Experimental

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, ν_max, 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).

S3. Refinement

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 U_iso(H) = 1.5 or 1.2U_eq(C).

Computing details

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

	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.
	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

Crystal data

C21H30O6S8	F(000) = 1328
Mr = 634.93	Dx = 1.540 Mg m^−3
Monoclinic, P21/n	Melting point = 356–357 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.8227 (10) Å	Cell parameters from 6442 reflections
b = 19.7775 (4) Å	θ = 2.9–27.5°
c = 20.3661 (4) Å	µ = 0.69 mm^−1
β = 94.905 (1)°	T = 120 K
V = 2738.1 (4) Å^3	Rod, orange
Z = 4	0.24 × 0.10 × 0.07 mm

Data collection

Bruker Nonius KappaCCD diffractometer	6272 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	5278 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −25→25
Tmin = 0.85, Tmax = 0.95	l = −26→26
45147 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.063	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0191P)^2 + 1.4275P] where P = (Fo^2 + 2Fc^2)/3
6272 reflections	(Δ/σ)max = 0.001
439 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

H atoms were placed geometrically, with ADP's of 1.2U_eq 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.92931 (7)	−0.19257 (2)	0.25645 (2)	0.02846 (11)
S2	0.45510 (7)	−0.17913 (2)	0.30982 (2)	0.03196 (12)
S3	1.03112 (6)	−0.08482 (2)	0.35575 (2)	0.02050 (9)
S4	0.63329 (6)	−0.07817 (2)	0.40302 (2)	0.02265 (10)
S5	1.13098 (6)	0.06391 (2)	0.42054 (2)	0.01774 (9)
S6	0.73644 (6)	0.06801 (2)	0.46921 (2)	0.01871 (9)
S7	1.18311 (6)	0.21397 (2)	0.422145 (19)	0.01801 (9)
S8	0.72935 (6)	0.21764 (2)	0.48358 (2)	0.02019 (9)
O1	0.84546 (16)	0.38924 (6)	0.50937 (6)	0.0228 (3)
O2	0.68666 (16)	0.42442 (6)	0.40843 (6)	0.0252 (3)
O3	0.27596 (17)	0.46986 (6)	0.38853 (6)	0.0298 (3)
O4	1.30031 (17)	0.37757 (6)	0.58138 (6)	0.0266 (3)
O5	1.45554 (17)	0.37805 (6)	0.68887 (6)	0.0252 (3)
O6	1.08803 (18)	0.38947 (7)	0.74213 (6)	0.0332 (3)
C1	0.6943 (4)	−0.20206 (19)	0.20675 (15)	0.0298 (10)	0.664 (7)
H1A	0.6505	−0.1572	0.1897	0.036*	0.664 (7)
H1B	0.7137	−0.2314	0.1684	0.036*	0.664 (7)
C1A	0.7176 (8)	−0.2418 (3)	0.2304 (3)	0.0265 (18)	0.336 (7)
H1A1	0.7315	−0.2594	0.1855	0.032*	0.336 (7)
H1A2	0.7106	−0.2811	0.2603	0.032*	0.336 (7)
C2	0.5350 (6)	−0.2322 (2)	0.24511 (19)	0.0286 (9)	0.664 (7)
H2A	0.5839	−0.2754	0.2649	0.034*	0.664 (7)
H2B	0.4197	−0.2427	0.2139	0.034*	0.664 (7)
C2A	0.5292 (12)	−0.2023 (5)	0.2300 (4)	0.0339 (19)	0.336 (7)
H2A1	0.4225	−0.2293	0.2068	0.041*	0.336 (7)
H2A2	0.5434	−0.1605	0.2041	0.041*	0.336 (7)
C3	0.8482 (2)	−0.13833 (8)	0.31666 (8)	0.0203 (3)
C4	0.6678 (2)	−0.13457 (8)	0.33753 (8)	0.0209 (3)
C5	0.8631 (2)	−0.03875 (8)	0.39894 (8)	0.0177 (3)
C6	0.9044 (2)	0.02230 (8)	0.42543 (8)	0.0169 (3)
C7	1.0350 (2)	0.14433 (8)	0.43727 (7)	0.0163 (3)
C8	0.8554 (2)	0.14588 (8)	0.45992 (8)	0.0173 (3)
C9	1.2289 (2)	0.25336 (8)	0.50266 (7)	0.0175 (3)
H9A	1.2642	0.2170	0.5349	0.021*
H9B	1.3464	0.2825	0.5012	0.021*
C10	1.0672 (2)	0.29610 (8)	0.53019 (7)	0.0162 (3)
C11	0.8948 (2)	0.25256 (8)	0.54961 (8)	0.0189 (3)
H11B	0.8156	0.2803	0.5780	0.023*
H11A	0.9500	0.2145	0.5768	0.023*
C12	0.9982 (2)	0.35204 (8)	0.48176 (8)	0.0184 (3)
H12A	1.1093	0.3824	0.4741	0.022*
H12B	0.9481	0.3321	0.4390	0.022*
C13	0.7777 (3)	0.44444 (9)	0.46958 (9)	0.0262 (4)
H13B	0.6830	0.4710	0.4933	0.031*
H13A	0.8904	0.4742	0.4623	0.031*
C14	0.5131 (2)	0.38467 (9)	0.41340 (9)	0.0268 (4)
H14A	0.4710	0.3881	0.4586	0.032*
H14B	0.5420	0.3366	0.4046	0.032*
C15	0.3515 (3)	0.40890 (9)	0.36497 (9)	0.0264 (4)
H15A	0.4027	0.4165	0.3215	0.032*
H15B	0.2459	0.3745	0.3596	0.032*
C16	0.1237 (3)	0.49680 (11)	0.34444 (11)	0.0403 (5)
H16A	0.1742	0.5051	0.3015	0.060*
H16B	0.0770	0.5394	0.3622	0.060*
H16C	0.0146	0.4645	0.3391	0.060*
C17	1.1590 (2)	0.32701 (8)	0.59490 (8)	0.0207 (3)
H17B	1.0546	0.3475	0.6193	0.025*
H17A	1.2239	0.2911	0.6228	0.025*
C18	1.4790 (3)	0.37387 (10)	0.62124 (9)	0.0293 (4)
H18A	1.5450	0.3307	0.6123	0.035*
H18B	1.5658	0.4111	0.6090	0.035*
C19	1.3782 (3)	0.44117 (9)	0.70945 (9)	0.0289 (4)
H19A	1.2982	0.4626	0.6722	0.035*
H19B	1.4872	0.4722	0.7240	0.035*
C20	1.2534 (3)	0.42821 (10)	0.76520 (9)	0.0322 (4)
H20A	1.3308	0.4036	0.8009	0.039*
H20B	1.2100	0.4717	0.7832	0.039*
C21	0.9587 (3)	0.37781 (14)	0.79190 (11)	0.0553 (6)
H21A	1.0278	0.3524	0.8282	0.083*
H21B	0.8449	0.3517	0.7735	0.083*
H21C	0.9140	0.4212	0.8084	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0332 (2)	0.0290 (2)	0.0234 (2)	−0.00085 (19)	0.00401 (18)	−0.01047 (18)
S2	0.0244 (2)	0.0342 (3)	0.0366 (3)	−0.00546 (19)	−0.00132 (19)	−0.0149 (2)
S3	0.0210 (2)	0.0186 (2)	0.0221 (2)	−0.00051 (16)	0.00307 (16)	−0.00439 (16)
S4	0.0216 (2)	0.0212 (2)	0.0256 (2)	−0.00360 (16)	0.00443 (17)	−0.00670 (17)
S5	0.01738 (19)	0.01618 (19)	0.0199 (2)	0.00078 (15)	0.00308 (15)	−0.00253 (15)
S6	0.01713 (19)	0.0168 (2)	0.0225 (2)	−0.00110 (15)	0.00357 (15)	−0.00277 (16)
S7	0.02007 (19)	0.0172 (2)	0.01720 (19)	−0.00124 (15)	0.00430 (15)	−0.00126 (15)
S8	0.01498 (18)	0.0172 (2)	0.0281 (2)	0.00277 (15)	0.00023 (16)	−0.00370 (16)
O1	0.0247 (6)	0.0205 (6)	0.0233 (6)	0.0089 (5)	0.0027 (5)	−0.0003 (5)
O2	0.0202 (6)	0.0288 (7)	0.0263 (7)	−0.0009 (5)	−0.0001 (5)	0.0077 (5)
O3	0.0258 (6)	0.0225 (6)	0.0402 (8)	0.0052 (5)	−0.0026 (5)	−0.0036 (6)
O4	0.0308 (7)	0.0269 (7)	0.0214 (6)	−0.0108 (5)	−0.0028 (5)	0.0003 (5)
O5	0.0261 (6)	0.0266 (7)	0.0222 (6)	0.0024 (5)	−0.0023 (5)	−0.0037 (5)
O6	0.0333 (7)	0.0441 (8)	0.0229 (7)	−0.0047 (6)	0.0066 (5)	−0.0041 (6)
C1	0.0394 (18)	0.031 (2)	0.0182 (15)	−0.0049 (14)	−0.0029 (12)	−0.0025 (14)
C1A	0.037 (3)	0.020 (4)	0.022 (3)	−0.005 (2)	−0.002 (2)	−0.004 (3)
C2	0.0412 (19)	0.024 (2)	0.0203 (18)	−0.0077 (18)	−0.0011 (14)	−0.0044 (15)
C2A	0.042 (4)	0.028 (5)	0.030 (4)	0.000 (4)	−0.011 (3)	−0.009 (3)
C3	0.0275 (9)	0.0169 (8)	0.0161 (8)	−0.0006 (7)	−0.0005 (7)	−0.0019 (6)
C4	0.0241 (8)	0.0177 (8)	0.0203 (8)	−0.0009 (7)	−0.0020 (7)	−0.0029 (6)
C5	0.0190 (8)	0.0178 (8)	0.0164 (8)	0.0007 (6)	0.0014 (6)	0.0008 (6)
C6	0.0175 (7)	0.0175 (8)	0.0155 (8)	0.0003 (6)	0.0007 (6)	0.0004 (6)
C7	0.0186 (8)	0.0149 (8)	0.0152 (7)	0.0002 (6)	0.0003 (6)	−0.0008 (6)
C8	0.0175 (8)	0.0166 (8)	0.0178 (8)	0.0008 (6)	0.0002 (6)	−0.0017 (6)
C9	0.0177 (7)	0.0171 (8)	0.0173 (8)	0.0003 (6)	−0.0007 (6)	−0.0012 (6)
C10	0.0166 (7)	0.0160 (8)	0.0159 (8)	0.0011 (6)	0.0009 (6)	−0.0010 (6)
C11	0.0210 (8)	0.0178 (8)	0.0183 (8)	0.0010 (6)	0.0043 (6)	−0.0024 (6)
C12	0.0176 (8)	0.0168 (8)	0.0209 (8)	0.0033 (6)	0.0026 (6)	−0.0005 (6)
C13	0.0279 (9)	0.0196 (9)	0.0304 (10)	0.0070 (7)	−0.0014 (7)	0.0015 (7)
C14	0.0231 (9)	0.0234 (9)	0.0340 (10)	−0.0007 (7)	0.0033 (7)	0.0066 (8)
C15	0.0259 (9)	0.0214 (9)	0.0316 (10)	0.0003 (7)	0.0014 (7)	−0.0014 (7)
C16	0.0264 (10)	0.0381 (12)	0.0552 (14)	0.0080 (9)	−0.0043 (9)	0.0062 (10)
C17	0.0232 (8)	0.0202 (8)	0.0185 (8)	−0.0030 (7)	0.0007 (6)	−0.0009 (6)
C18	0.0237 (9)	0.0369 (11)	0.0276 (10)	−0.0048 (8)	0.0043 (7)	−0.0072 (8)
C19	0.0330 (10)	0.0229 (9)	0.0305 (10)	−0.0024 (8)	0.0007 (8)	−0.0072 (8)
C20	0.0352 (10)	0.0355 (11)	0.0255 (10)	0.0003 (8)	−0.0003 (8)	−0.0099 (8)
C21	0.0518 (14)	0.0797 (19)	0.0376 (13)	−0.0077 (13)	0.0231 (11)	0.0007 (12)

Geometric parameters (Å, º)

S1—C3	1.7541 (17)	C2A—H2A1	0.9900
S1—C1A	1.785 (5)	C2A—H2A2	0.9900
S1—C1	1.831 (3)	C3—C4	1.338 (2)
S2—C4	1.7496 (17)	C5—C6	1.342 (2)
S2—C2A	1.803 (8)	C7—C8	1.346 (2)
S2—C2	1.806 (4)	C9—C10	1.534 (2)
S3—C5	1.7581 (16)	C9—H9A	0.9900
S3—C3	1.7724 (16)	C9—H9B	0.9900
S4—C5	1.7593 (16)	C10—C12	1.529 (2)
S4—C4	1.7699 (17)	C10—C11	1.537 (2)
S5—C6	1.7617 (16)	C10—C17	1.537 (2)
S5—C7	1.7643 (15)	C11—H11B	0.9900
S6—C8	1.7587 (16)	C11—H11A	0.9900
S6—C6	1.7606 (16)	C12—H12A	0.9900
S7—C7	1.7511 (16)	C12—H12B	0.9900
S7—C9	1.8182 (15)	C13—H13B	0.9900
S8—C8	1.7485 (16)	C13—H13A	0.9900
S8—C11	1.8166 (16)	C14—C15	1.494 (2)
O1—C13	1.414 (2)	C14—H14A	0.9900
O1—C12	1.4297 (18)	C14—H14B	0.9900
O2—C13	1.400 (2)	C15—H15A	0.9900
O2—C14	1.432 (2)	C15—H15B	0.9900
O3—C15	1.411 (2)	C16—H16A	0.9800
O3—C16	1.418 (2)	C16—H16B	0.9800
O4—C18	1.407 (2)	C16—H16C	0.9800
O4—C17	1.4317 (19)	C17—H17B	0.9900
O5—C18	1.403 (2)	C17—H17A	0.9900
O5—C19	1.432 (2)	C18—H18A	0.9900
O6—C20	1.411 (2)	C18—H18B	0.9900
O6—C21	1.419 (2)	C19—C20	1.498 (3)
C1—C2	1.514 (6)	C19—H19A	0.9900
C1—H1A	0.9900	C19—H19B	0.9900
C1—H1B	0.9900	C20—H20A	0.9900
C1A—C2A	1.504 (11)	C20—H20B	0.9900
C1A—H1A1	0.9900	C21—H21A	0.9800
C1A—H1A2	0.9900	C21—H21B	0.9800
C2—H2A	0.9900	C21—H21C	0.9800
C2—H2B	0.9900
C3—S1—C1A	104.23 (19)	C12—C10—C17	110.22 (13)
C3—S1—C1	97.78 (11)	C9—C10—C17	106.23 (12)
C1A—S1—C1	29.7 (2)	C11—C10—C17	105.49 (12)
C4—S2—C2A	97.5 (3)	C10—C11—S8	117.60 (11)
C4—S2—C2	103.58 (14)	C10—C11—H11B	107.9
C2A—S2—C2	21.3 (2)	S8—C11—H11B	107.9
C5—S3—C3	94.01 (8)	C10—C11—H11A	107.9
C5—S4—C4	93.85 (8)	S8—C11—H11A	107.9
C6—S5—C7	93.91 (7)	H11B—C11—H11A	107.2
C8—S6—C6	93.95 (7)	O1—C12—C10	108.24 (12)
C7—S7—C9	103.63 (7)	O1—C12—H12A	110.0
C8—S8—C11	102.91 (7)	C10—C12—H12A	110.0
C13—O1—C12	112.68 (12)	O1—C12—H12B	110.0
C13—O2—C14	113.51 (13)	C10—C12—H12B	110.0
C15—O3—C16	112.01 (14)	H12A—C12—H12B	108.4
C18—O4—C17	114.64 (13)	O2—C13—O1	112.96 (14)
C18—O5—C19	114.50 (14)	O2—C13—H13B	109.0
C20—O6—C21	112.27 (16)	O1—C13—H13B	109.0
C2—C1—S1	112.9 (3)	O2—C13—H13A	109.0
C2—C1—H1A	109.0	O1—C13—H13A	109.0
S1—C1—H1A	109.0	H13B—C13—H13A	107.8
C2—C1—H1B	109.0	O2—C14—C15	110.19 (14)
S1—C1—H1B	109.0	O2—C14—H14A	109.6
H1A—C1—H1B	107.8	C15—C14—H14A	109.6
C2A—C1A—S1	112.8 (5)	O2—C14—H14B	109.6
C2A—C1A—H1A1	109.0	C15—C14—H14B	109.6
S1—C1A—H1A1	109.0	H14A—C14—H14B	108.1
C2A—C1A—H1A2	109.0	O3—C15—C14	108.66 (14)
S1—C1A—H1A2	109.0	O3—C15—H15A	110.0
H1A1—C1A—H1A2	107.8	C14—C15—H15A	110.0
C1—C2—S2	115.0 (3)	O3—C15—H15B	110.0
C1—C2—H2A	108.5	C14—C15—H15B	110.0
S2—C2—H2A	108.5	H15A—C15—H15B	108.3
C1—C2—H2B	108.5	O3—C16—H16A	109.5
S2—C2—H2B	108.5	O3—C16—H16B	109.5
H2A—C2—H2B	107.5	H16A—C16—H16B	109.5
C1A—C2A—S2	115.6 (6)	O3—C16—H16C	109.5
C1A—C2A—H2A1	108.4	H16A—C16—H16C	109.5
S2—C2A—H2A1	108.4	H16B—C16—H16C	109.5
C1A—C2A—H2A2	108.4	O4—C17—C10	110.17 (13)
S2—C2A—H2A2	108.4	O4—C17—H17B	109.6
H2A1—C2A—H2A2	107.4	C10—C17—H17B	109.6
C4—C3—S1	127.58 (13)	O4—C17—H17A	109.6
C4—C3—S3	117.11 (12)	C10—C17—H17A	109.6
S1—C3—S3	115.28 (9)	H17B—C17—H17A	108.1
C3—C4—S2	129.03 (13)	O5—C18—O4	113.41 (14)
C3—C4—S4	117.37 (12)	O5—C18—H18A	108.9
S2—C4—S4	113.60 (9)	O4—C18—H18A	108.9
C6—C5—S3	122.95 (12)	O5—C18—H18B	108.9
C6—C5—S4	122.47 (12)	O4—C18—H18B	108.9
S3—C5—S4	114.57 (9)	H18A—C18—H18B	107.7
C5—C6—S6	122.82 (12)	O5—C19—C20	108.67 (15)
C5—C6—S5	123.53 (12)	O5—C19—H19A	110.0
S6—C6—S5	113.64 (9)	C20—C19—H19A	110.0
C8—C7—S7	126.75 (12)	O5—C19—H19B	110.0
C8—C7—S5	116.78 (12)	C20—C19—H19B	110.0
S7—C7—S5	116.47 (9)	H19A—C19—H19B	108.3
C7—C8—S8	126.63 (12)	O6—C20—C19	109.30 (14)
C7—C8—S6	117.32 (12)	O6—C20—H20A	109.8
S8—C8—S6	116.02 (9)	C19—C20—H20A	109.8
C10—C9—S7	119.49 (11)	O6—C20—H20B	109.8
C10—C9—H9A	107.4	C19—C20—H20B	109.8
S7—C9—H9A	107.4	H20A—C20—H20B	108.3
C10—C9—H9B	107.4	O6—C21—H21A	109.5
S7—C9—H9B	107.4	O6—C21—H21B	109.5
H9A—C9—H9B	107.0	H21A—C21—H21B	109.5
C12—C10—C9	110.75 (13)	O6—C21—H21C	109.5
C12—C10—C11	111.79 (13)	H21A—C21—H21C	109.5
C9—C10—C11	112.07 (13)	H21B—C21—H21C	109.5
C3—S1—C1—C2	−60.1 (3)	C9—S7—C7—C8	61.76 (16)
C1A—S1—C1—C2	45.0 (4)	C9—S7—C7—S5	−118.67 (9)
C3—S1—C1A—C2A	35.3 (6)	C6—S5—C7—C8	12.83 (14)
C1—S1—C1A—C2A	−45.4 (6)	C6—S5—C7—S7	−166.78 (9)
S1—C1—C2—S2	67.3 (4)	S7—C7—C8—S8	−3.2 (2)
C4—S2—C2—C1	−32.5 (4)	S5—C7—C8—S8	177.25 (9)
C2A—S2—C2—C1	43.0 (9)	S7—C7—C8—S6	178.80 (9)
S1—C1A—C2A—S2	−69.4 (8)	S5—C7—C8—S6	−0.76 (17)
C4—S2—C2A—C1A	57.4 (7)	C11—S8—C8—C7	−59.49 (16)
C2—S2—C2A—C1A	−50.9 (8)	C11—S8—C8—S6	118.55 (9)
C1A—S1—C3—C4	−0.6 (3)	C6—S6—C8—C7	−11.75 (14)
C1—S1—C3—C4	29.0 (2)	C6—S6—C8—S8	170.03 (9)
C1A—S1—C3—S3	177.0 (3)	C7—S7—C9—C10	−76.96 (13)
C1—S1—C3—S3	−153.43 (15)	S7—C9—C10—C12	−55.09 (16)
C5—S3—C3—C4	−9.24 (14)	S7—C9—C10—C11	70.50 (16)
C5—S3—C3—S1	172.90 (9)	S7—C9—C10—C17	−174.78 (11)
S1—C3—C4—S2	−2.9 (3)	C12—C10—C11—S8	51.53 (16)
S3—C3—C4—S2	179.53 (10)	C9—C10—C11—S8	−73.50 (15)
S1—C3—C4—S4	176.11 (10)	C17—C10—C11—S8	171.33 (11)
S3—C3—C4—S4	−1.44 (18)	C8—S8—C11—C10	81.68 (13)
C2A—S2—C4—C3	−21.0 (4)	C11—C10—C12—O1	53.14 (16)
C2—S2—C4—C3	−0.2 (2)	C17—C10—C12—O1	−63.84 (16)
C2A—S2—C4—S4	159.9 (3)	C9—C10—C12—O1	178.90 (12)
C2—S2—C4—S4	−179.28 (17)	C13—O1—C12—C10	177.18 (13)
C5—S4—C4—C3	11.30 (14)	C12—O1—C13—O2	64.71 (18)
C5—S4—C4—S2	−169.53 (9)	C14—O2—C13—O1	62.64 (18)
C3—S3—C5—C6	−161.75 (14)	C13—O2—C14—C15	134.65 (15)
C3—S3—C5—S4	16.77 (10)	O2—C14—C15—O3	−75.19 (18)
C4—S4—C5—C6	161.19 (14)	C16—O3—C15—C14	178.92 (15)
C4—S4—C5—S3	−17.34 (10)	C12—C10—C17—O4	−49.40 (17)
S3—C5—C6—S6	−179.49 (8)	C9—C10—C17—O4	70.63 (16)
S4—C5—C6—S6	2.1 (2)	C11—C10—C17—O4	−170.24 (13)
S3—C5—C6—S5	−0.1 (2)	C18—O4—C17—C10	−134.64 (14)
S4—C5—C6—S5	−178.50 (9)	C17—O4—C18—O5	−57.5 (2)
C8—S6—C6—C5	−160.43 (14)	C19—O5—C18—O4	−64.15 (19)
C8—S6—C6—S5	20.11 (9)	C18—O5—C19—C20	146.78 (14)
C7—S5—C6—C5	160.12 (14)	O5—C19—C20—O6	−65.38 (19)
C7—S5—C6—S6	−20.43 (10)	C21—O6—C20—C19	−177.42 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O5^i	0.99	2.26	3.181 (4)	154
C9—H9B···O4	0.99	2.53	2.951 (2)	106
C12—H12A···O4	0.99	2.45	2.812 (2)	101
C12—H12B···S7	0.99	2.87	3.2839 (17)	106
C18—H18B···O3^ii	0.99	2.59	3.528 (2)	158
C19—H19A···O4	0.99	2.50	2.904 (2)	104

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1.