Two 9-alkylthiophenanthrenes at 193 K (alkyl = dodecyl and tetradecyl)

Two isostructural 9-thiophenanthrene derivatives, 9-dodec­ylthiophenanthrene, C₂₆H₃₄S, (I), and 9-tetradecylthiophen­anthrene, C₂₈H₃₈S, (II), are reported. They crystallize in the monoclinic space group P2₁/c with four molecules in a unit cell. The S-C_phenanthrene bonds are 1.767 (2) and 1.772 (4) Å and S-C_alkyl bonds are 1.809 (2) and 1.804 (4) Å for (I) and (II), respectively. The bond angles at S are 104.04 (11) and 104.0 (2)° for (I) and (II), respectively.

S1. Comment

In the connection of our studies concerning 9-thioderivatives of phenanthrene (Kansikas & Sipilä, 1997; Sipilä et al., 1999) two new compounds with a long straight alkyl chain were synthesized and characterized by X-ray analysis. The long, colourless needles of 9-dodecylthiophenanthrene, (I), and 9-tetradecylthiophenathrene, (II), have melting points of 347 (1) K and 350 (1) K, respectively. They are measured in open capillary tubes with an electrothermal apparatus and are uncorrected. The present compounds are isostructural with the earlier reported 9-alkylthiophenanthrenes [alkyl = ethyl, (III), propyl, (IV) and butyl, (V)] (Kansikas & Sipilä, 1997). Among these structures the b axis lengthening, from 20.644 (9) to 38.696 (2) Å, is nearly linear; 1.5 Å increase per one added C atom in the alkyl chain. The molecular packing is presented in Figs. 2 and 4, which show tubular channels through the phenanthrene rings in the c axis direction and a herringbone pattern when viewed along the a axis. However, the phenanthrene planes are tilted so that there is no perpendicular stacking overlap between the successive molecules as seen in Fig. 4. The angles between the phenanthrene group and the ab, ac and bc planes are 119.3 (1), 78.0 (1) and 34.7 (1)° for (I) and 119.1 (1), 78.1 (1) and 34.7 (1)° for (II).

The phenanthrene groups in the adjacent sheets form an interplanar angle of 69.0 (1)° for (I) and 69.3 (1)° for (II). Both molecules are nearly planar. The phenanthrene group comprises three planes formed by rings 1 (C1, C2, C3, C4, C4a, C10a), 2 (C4a, C4b, C8a, C9, C10, C10a), and 3 (C4b, C5, C6, C7, C8, C8a). The planar alkyl chains C12–C23 for (I) and C12–C25 for (II) form a fourth plane. Within the phenanthrene groups the interplanar angles are: 1.36 (12) and 1.53 (22)° for 1,2; 0.76 (12) and 0.91 (23)° for 1,3 and 1.00 (12) and 0.95 (22)° for 2,3. The fourth plane through the alkyl chains form the angles of 3.67 (11) and 3.94 (20)° with the rings 2 for compounds (I) and (II), respectively.

We have earlier studied the structures of 9-phenylthiophenanthrene, (VI), and 9 − t-butylthiophenanthrene, (VII) (Sipilä et al., 1999). In these compounds the substituents deviate from the phenanthrene planes. Various bonding parameters, involving the S atom, of compounds (III)–(VII) are here compared to those obtained for (I) and (II). The bond angles C9–S–C12 are between 104.0 (1) and 104.5 (1)° for the aliphatic substituents and 102.1 (1)° for the phenyl group. The molecular geometry can be described by the values of the torsion angle C10–C9–S–C12, which range from −0.1 (2) to 5.9 (2)° in the straight-chain molecules, but are 92.1 (1) and 91.7 (1)° for (VI) and (VII), respectively. Bond lengths S–C9 are 1.767 (2), 1.772 (4), 1.765 (7), 1.764 (2), 1.766 (3), 1.779 (2) and 1.777 (2) Å for compounds (I)–(VII). They are normal S bond distances to the aromatic C atom, as is also the S–C value of 1.769 (2) Å for the phenyl group in (VI). The S bond distances S–C12 to the straight-chain alkyl groups are longer, ranging from 1.794 (4) to 1.806 (2) Å for the compounds (I)-(V), while in (VII) it is 1.861 (2) Å.

S2. Experimental

The 9-alkylthiophenanthrenes were prepared from 9-bromophenanthrene, KOH and alkylthiol in dimethylformamide according to the previously reported procedure (Sipilä & Hase, 1996). The side product dialkyldisulfide was removed by flash chromatography and the crystals suitable for X-ray analysis were obtained by recrystallization from ethanol.

S3. Refinement

The Laue class and extinction rules in compound (II) indicated clearly the space group P2₁/c and it was possible to solve the structure. In this solution, however, the alkyl chains were exactly overlapping, but at the opposite directions. Thus the phenanthrene groups, including the S atoms, had an occupancy factor of 0.5. When the structure was solved in the space group P1 with two molecules in an asymmetric unit, molecular packing was similar to that of compound (I). One of those two molecules was then removed, the monoclinic symmetry operations were added again and the remaining molecule showed to possess a correct location. However, the torsion angles revealed it to be in the inverted position compared to (I).

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: WinGX (Farrugia, 1998); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXL93.

Figures

	Fig. 1. View of C26H34S, (I), showing atom labels. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the molecular packing of compound (I) down the c axis.
	Fig. 3. View of C28H38S, (II), showing atom labels. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. View of the molecular packing of compound (II) along the a axis.

(I) 9-(Dodecylthio)phenanthrene

Crystal data

C26H34S	Dx = 1.156 Mg m^−3
Mr = 378.59	Melting point: 353 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
a = 9.105 (2) Å	Cell parameters from 25 reflections
b = 35.679 (7) Å	θ = 4–10°
c = 6.7840 (14) Å	µ = 1.35 mm^−1
β = 99.28 (3)°	T = 193 K
V = 2175.0 (8) Å^3	Needle, colourless
Z = 4	0.31 × 0.12 × 0.10 mm
F(000) = 824

Data collection

Enraf-Nonius CAD4 diffractometer	Rint = 0.017
Radiation source: fine-focus sealed tube	θmax = 65.0°, θmin = 2.5°
Graphite monochromator	h = −10→1
ω/2θ scans	k = −29→41
3928 measured reflections	l = −7→7
3688 independent reflections	3 standard reflections every 200 reflections
3198 reflections with I > 2σ(I)	intensity decay: 0.8%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.10	Calculated w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 1.4963P] where P = (Fo^2 + 2Fc^2)/3
3664 reflections	(Δ/σ)max = −0.001
244 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.35 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 on F² for ALL reflections except for 5 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S	0.78808 (6)	0.13583 (2)	0.33972 (8)	0.0380 (2)
C1	1.3331 (2)	0.18312 (6)	0.3556 (3)	0.0347 (5)
H1A	1.3585	0.17032	0.4792	0.042*
C2	1.4417 (2)	0.20153 (6)	0.2758 (3)	0.0365 (5)
H2A	1.5420	0.20093	0.3418	0.044*
C3	1.4040 (2)	0.22116 (6)	0.0967 (3)	0.0358 (5)
H3A	1.4786	0.23451	0.0427	0.043*
C4b	0.9935 (2)	0.20064 (5)	−0.0272 (3)	0.0288 (4)
C4a	1.1466 (2)	0.20193 (5)	0.0741 (3)	0.0278 (4)
C4	1.2611 (2)	0.22132 (6)	−0.0012 (3)	0.0331 (5)
H4A	1.2378	0.23480	−0.1230	0.040*
C5	0.9467 (2)	0.21934 (6)	−0.2092 (3)	0.0345 (5)
H5A	1.0177	0.23298	−0.2688	0.041*
C6	0.8024 (3)	0.21844 (6)	−0.3023 (3)	0.0398 (5)
H6A	0.7742	0.23135	−0.4250	0.048*
C7	0.6961 (3)	0.19855 (7)	−0.2175 (3)	0.0390 (5)
H7A	0.5954	0.19803	−0.2819	0.047*
C8a	0.8853 (2)	0.18045 (6)	0.0590 (3)	0.0285 (4)
C8	0.7376 (2)	0.17981 (6)	−0.0412 (3)	0.0350 (5)
H8A	0.6650	0.16606	0.0147	0.042*
C9	0.9297 (2)	0.16113 (6)	0.2480 (3)	0.0313 (5)
C10a	1.1852 (2)	0.18284 (6)	0.2584 (3)	0.0312 (5)
C10	1.0721 (2)	0.16298 (6)	0.3418 (3)	0.0328 (5)
H10A	1.0984	0.15076	0.4670	0.039*
C12	0.8815 (2)	0.11545 (6)	0.5705 (3)	0.0362 (5)
H12A	0.9660	0.09979	0.5444	0.043*
H12B	0.9206	0.13550	0.6655	0.043*
C13	0.7692 (3)	0.09148 (6)	0.6587 (3)	0.0380 (5)
H13A	0.6866	0.10753	0.6878	0.046*
H13B	0.7269	0.07236	0.5598	0.046*
C14	0.8417 (3)	0.07208 (6)	0.8499 (3)	0.0387 (5)
H14A	0.8858	0.09136	0.9467	0.046*
H14B	0.9237	0.05599	0.8193	0.046*
C15	0.7343 (3)	0.04812 (7)	0.9468 (4)	0.0411 (5)
H15A	0.6539	0.06427	0.9818	0.049*
H15B	0.6881	0.02920	0.8493	0.049*
C16	0.8106 (3)	0.02825 (7)	1.1337 (3)	0.0401 (5)
H16A	0.8904	0.01204	1.0974	0.048*
H16B	0.8582	0.04728	1.2294	0.048*
C17	0.7073 (3)	0.00437 (7)	1.2368 (4)	0.0417 (5)
H17A	0.6274	0.02050	1.2732	0.050*
H17B	0.6600	−0.01479	1.1416	0.050*
C18	0.7858 (3)	−0.01514 (7)	1.4235 (4)	0.0411 (5)
H18A	0.8659	−0.03113	1.3866	0.049*
H18B	0.8331	0.00411	1.5181	0.049*
C19	0.6850 (3)	−0.03922 (7)	1.5292 (4)	0.0438 (6)
H19A	0.6043	−0.02334	1.5653	0.053*
H19B	0.6385	−0.05870	1.4354	0.053*
C20	0.7645 (3)	−0.05813 (7)	1.7158 (4)	0.0426 (6)
H20A	0.8127	−0.03864	1.8082	0.051*
H20B	0.8441	−0.07434	1.6789	0.051*
C21	0.6642 (3)	−0.08182 (7)	1.8254 (4)	0.0418 (5)
H21A	0.5817	−0.06601	1.8568	0.050*
H21B	0.6202	−0.10224	1.7361	0.050*
C22	0.7453 (3)	−0.09881 (7)	2.0174 (3)	0.0415 (5)
H22A	0.7884	−0.07842	2.1075	0.050*
H22B	0.8285	−0.11447	1.9864	0.050*
C23	0.6446 (3)	−0.12269 (8)	2.1243 (4)	0.0532 (7)
H23A	0.7021	−0.13294	2.2470	0.080*
H23B	0.6034	−0.14329	2.0370	0.080*
H23C	0.5632	−0.10722	2.1579	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0391 (3)	0.0412 (3)	0.0351 (3)	−0.0050 (2)	0.0110 (2)	0.0077 (2)
C1	0.0371 (12)	0.0363 (12)	0.0301 (11)	0.0033 (9)	0.0039 (9)	0.0043 (9)
C2	0.0324 (11)	0.0381 (12)	0.0389 (12)	0.0009 (9)	0.0054 (9)	−0.0012 (10)
C3	0.0364 (12)	0.0351 (12)	0.0378 (12)	−0.0016 (9)	0.0120 (9)	0.0015 (9)
C4b	0.0373 (11)	0.0238 (10)	0.0265 (10)	0.0004 (8)	0.0088 (8)	−0.0016 (8)
C4a	0.0328 (11)	0.0242 (10)	0.0273 (10)	0.0019 (8)	0.0074 (8)	0.0000 (8)
C4	0.0386 (12)	0.0294 (11)	0.0328 (11)	−0.0004 (9)	0.0102 (9)	0.0029 (9)
C5	0.0408 (12)	0.0331 (11)	0.0296 (11)	−0.0039 (9)	0.0061 (9)	0.0044 (9)
C6	0.0471 (13)	0.0399 (13)	0.0312 (12)	−0.0014 (10)	0.0025 (10)	0.0058 (9)
C7	0.0354 (12)	0.0456 (13)	0.0344 (12)	−0.0013 (10)	0.0007 (9)	−0.0001 (10)
C8a	0.0334 (11)	0.0266 (10)	0.0263 (10)	0.0010 (8)	0.0075 (8)	−0.0015 (8)
C8	0.0375 (12)	0.0355 (12)	0.0334 (11)	−0.0037 (9)	0.0097 (9)	−0.0017 (9)
C9	0.0404 (12)	0.0276 (10)	0.0287 (11)	−0.0005 (9)	0.0141 (9)	−0.0004 (8)
C10a	0.0392 (12)	0.0260 (10)	0.0301 (11)	0.0027 (9)	0.0108 (9)	0.0005 (8)
C10	0.0373 (12)	0.0336 (11)	0.0287 (11)	0.0014 (9)	0.0087 (9)	0.0051 (9)
C12	0.0414 (12)	0.0360 (12)	0.0338 (12)	0.0009 (10)	0.0140 (9)	0.0073 (9)
C13	0.0416 (12)	0.0370 (12)	0.0385 (12)	−0.0008 (10)	0.0158 (10)	0.0050 (10)
C14	0.0456 (13)	0.0351 (12)	0.0387 (12)	−0.0006 (10)	0.0165 (10)	0.0058 (10)
C15	0.0438 (13)	0.0385 (12)	0.0448 (13)	0.0003 (10)	0.0184 (10)	0.0080 (10)
C16	0.0441 (13)	0.0377 (12)	0.0417 (13)	0.0015 (10)	0.0168 (10)	0.0066 (10)
C17	0.0458 (13)	0.0384 (12)	0.0441 (13)	0.0010 (10)	0.0168 (11)	0.0088 (10)
C18	0.0483 (14)	0.0356 (12)	0.0428 (13)	0.0023 (10)	0.0179 (11)	0.0062 (10)
C19	0.0481 (14)	0.0409 (13)	0.0450 (14)	−0.0006 (11)	0.0152 (11)	0.0094 (11)
C20	0.0494 (14)	0.0367 (12)	0.0445 (13)	0.0020 (10)	0.0163 (11)	0.0059 (10)
C21	0.0456 (13)	0.0379 (12)	0.0435 (13)	0.0004 (10)	0.0122 (10)	0.0081 (10)
C22	0.0479 (13)	0.0375 (12)	0.0401 (13)	−0.0002 (10)	0.0098 (10)	0.0037 (10)
C23	0.063 (2)	0.052 (2)	0.0465 (15)	−0.0001 (13)	0.0146 (13)	0.0168 (12)

Geometric parameters (Å, º)

S—C9	1.767 (2)	C8a—C9	1.455 (3)
S—C12	1.809 (2)	C9—C10	1.350 (3)
C1—C2	1.370 (3)	C10—C10a	1.439 (3)
C1—C10a	1.401 (3)	C12—C13	1.527 (3)
C2—C3	1.396 (3)	C13—C14	1.524 (3)
C3—C4	1.362 (3)	C14—C15	1.526 (3)
C4—C4a	1.413 (3)	C15—C16	1.520 (3)
C4a—C4b	1.453 (3)	C16—C17	1.520 (3)
C4a—C10a	1.418 (3)	C17—C18	1.519 (3)
C4b—C5	1.407 (3)	C18—C19	1.518 (3)
C4b—C8a	1.420 (3)	C19—C20	1.512 (4)
C5—C6	1.363 (3)	C20—C21	1.523 (3)
C6—C7	1.397 (3)	C21—C22	1.516 (3)
C7—C8	1.369 (3)	C22—C23	1.519 (3)
C8—C8a	1.406 (3)
C9—S—C12	104.01 (10)	C8a—C9—C10	120.1 (2)
C2—C1—C10a	121.2 (2)	C8a—C9—S	116.0 (2)
C1—C2—C3	119.5 (2)	C10—C9—S	123.9 (2)
C4—C3—C2	120.5 (2)	C1—C10a—C4a	119.6 (2)
C4—C4a—C4b	123.5 (2)	C1—C10a—C10	120.9 (2)
C4b—C4a—C10a	119.0 (2)	C9—C10—C10a	122.1 (2)
C4a—C4b—C5	122.1 (2)	C4a—C10a—C10	119.5 (2)
C4a—C4b—C8a	119.9 (2)	C13—C12—S	108.2 (2)
C5—C4b—C8a	118.0 (2)	C12—C13—C14	111.2 (2)
C4—C4a—C10a	117.5 (2)	C13—C14—C15	113.7 (2)
C3—C4—C4a	121.6 (2)	C16—C15—C14	112.5 (2)
C6—C5—C4b	121.9 (2)	C15—C16—C17	114.3 (2)
C5—C6—C7	120.1 (2)	C16—C17—C18	113.5 (2)
C8—C7—C6	119.7 (2)	C19—C18—C17	114.5 (2)
C8—C8a—C4b	118.8 (2)	C20—C19—C18	113.8 (2)
C8—C8a—C9	121.8 (2)	C19—C20—C21	114.4 (2)
C4b—C8a—C9	119.4 (2)	C22—C21—C20	113.2 (2)
C7—C8—C8a	121.5 (2)	C21—C22—C23	112.7 (2)
C10a—C1—C2—C3	1.6 (3)	C12—S—C9—C10	−0.1 (2)
C1—C2—C3—C4	−1.7 (3)	C12—S—C9—C8a	179.4 (2)
C5—C4b—C4a—C4	−0.9 (3)	C2—C1—C10a—C4a	0.0 (3)
C8a—C4b—C4a—C4	180.0 (2)	C2—C1—C10a—C10	179.1 (2)
C5—C4b—C4a—C10a	179.1 (2)	C4—C4a—C10a—C1	−1.4 (3)
C8a—C4b—C4a—C10a	0.0 (3)	C4b—C4a—C10a—C1	178.6 (2)
C2—C3—C4—C4a	0.2 (3)	C4—C4a—C10a—C10	179.5 (2)
C10a—C4a—C4—C3	1.4 (3)	C4b—C4a—C10a—C10	−0.6 (3)
C4b—C4a—C4—C3	−178.6 (2)	C8a—C9—C10—C10a	−1.7 (3)
C8a—C4b—C5—C6	0.0 (3)	S—C9—C10—C10a	177.8 (2)
C4a—C4b—C5—C6	−179.1 (2)	C1—C10a—C10—C9	−177.6 (2)
C4b—C5—C6—C7	0.0 (3)	C4a—C10a—C10—C9	1.5 (3)
C5—C6—C7—C8	−0.4 (3)	C9—S—C12—C13	−177.79 (15)
C5—C4b—C8a—C8	0.4 (3)	S—C12—C13—C14	177.7 (2)
C4a—C4b—C8a—C8	179.6 (2)	C12—C13—C14—C15	179.2 (2)
C5—C4b—C8a—C9	−179.4 (2)	C13—C14—C15—C16	178.3 (2)
C4a—C4b—C8a—C9	−0.2 (3)	C14—C15—C16—C17	179.3 (2)
C6—C7—C8—C8a	0.8 (3)	C15—C16—C17—C18	−179.8 (2)
C4b—C8a—C8—C7	−0.9 (3)	C16—C17—C18—C19	−179.9 (2)
C9—C8a—C8—C7	178.9 (2)	C17—C18—C19—C20	−179.4 (2)
C8—C8a—C9—C10	−178.7 (2)	C18—C19—C20—C21	178.9 (2)
C4b—C8a—C9—C10	1.1 (3)	C19—C20—C21—C22	−177.1 (2)
C8—C8a—C9—S	1.8 (3)	C20—C21—C22—C23	−179.4 (2)
C4b—C8a—C9—S	−178.44 (15)

(II)

Crystal data

C28H38S	Dx = 1.144 Mg m^−3
Mr = 406.64	Melting point: 351 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
a = 9.1000 (14) Å	Cell parameters from 25 reflections
b = 38.696 (2) Å	θ = 4–10°
c = 6.804 (8) Å	µ = 1.27 mm^−1
β = 99.67 (3)°	T = 193 K
V = 2362 (3) Å^3	Needle, colourless
Z = 4	0.30 × 0.09 × 0.08 mm
F(000) = 888

Data collection

Enraf-Nonius CAD4 diffractometer	Rint = 0.092
Radiation source: fine-focus sealed tube	θmax = 65.0°, θmin = 2.3°
Graphite monochromator	h = −10→10
ω/2θ scans	k = −45→18
8468 measured reflections	l = −6→7
4007 independent reflections	3 standard reflections every 200 reflections
2146 reflections with I > 2σ(I)	intensity decay: 0.9%

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.04	Calculated w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 2.3038P] where P = (Fo^2 + 2Fc^2)/3
3997 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.33 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 on F² for ALL reflections except for 10 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S	0.29406 (11)	0.35533 (3)	0.6938 (2)	0.0386 (3)
C1	0.8397 (4)	0.31152 (10)	0.7117 (7)	0.0335 (10)
H1A	0.8660	0.32342	0.8347	0.040*
C2	0.9475 (4)	0.29447 (10)	0.6323 (6)	0.0348 (11)
H2A	1.0480	0.29480	0.6986	0.042*
C3	0.9088 (4)	0.27658 (11)	0.4535 (7)	0.0348 (10)
H3A	0.9832	0.26427	0.3997	0.042*
C4	0.7653 (4)	0.27652 (10)	0.3546 (6)	0.0308 (10)
H4A	0.7417	0.26437	0.2320	0.037*
C4a	0.6509 (4)	0.29418 (9)	0.4310 (6)	0.0253 (9)
C4b	0.4985 (4)	0.29535 (9)	0.3290 (6)	0.0276 (10)
C5	0.4505 (4)	0.27838 (10)	0.1479 (6)	0.0327 (10)
H5A	0.5216	0.26588	0.0886	0.039*
C6	0.3060 (5)	0.27902 (11)	0.0528 (7)	0.0391 (11)
H6A	0.2772	0.26708	−0.0696	0.047*
C7	0.2008 (5)	0.29758 (11)	0.1389 (7)	0.0390 (11)
H7A	0.0998	0.29825	0.0745	0.047*
C8	0.2425 (4)	0.31464 (10)	0.3143 (6)	0.0343 (10)
H8A	0.1698	0.32719	0.3701	0.041*
C8a	0.3900 (4)	0.31416 (10)	0.4144 (6)	0.0275 (9)
C9	0.4358 (4)	0.33191 (9)	0.6026 (6)	0.0288 (10)
C10	0.5775 (4)	0.33026 (10)	0.6979 (6)	0.0317 (10)
H10A	0.6043	0.34147	0.8230	0.038*
C10a	0.6893 (4)	0.31178 (9)	0.6135 (6)	0.0286 (9)
C12	0.3880 (4)	0.37394 (11)	0.9242 (6)	0.0355 (10)
H12A	0.4266	0.35539	1.0193	0.043*
H12B	0.4733	0.38819	0.8990	0.043*
C13	0.2764 (4)	0.39635 (11)	1.0116 (7)	0.0391 (11)
H13A	0.2348	0.41401	0.9124	0.047*
H13B	0.1931	0.38170	1.0395	0.047*
C14	0.3487 (4)	0.41428 (10)	1.2036 (7)	0.0363 (11)
H14A	0.3918	0.39645	1.3009	0.044*
H14B	0.4317	0.42888	1.1743	0.044*
C15	0.2432 (5)	0.43659 (11)	1.2985 (7)	0.0395 (11)
H15A	0.1980	0.45410	1.2006	0.047*
H15B	0.1618	0.42194	1.3322	0.047*
C16	0.3186 (5)	0.45473 (11)	1.4844 (7)	0.0392 (11)
H16A	0.3992	0.46945	1.4492	0.047*
H16B	0.3656	0.43708	1.5801	0.047*
C17	0.2182 (5)	0.47696 (11)	1.5876 (7)	0.0386 (11)
H17A	0.1713	0.49469	1.4923	0.046*
H17B	0.1375	0.46229	1.6231	0.046*
C18	0.2948 (5)	0.49484 (11)	1.7727 (7)	0.0395 (11)
H18A	0.3745	0.50977	1.7365	0.047*
H18B	0.3432	0.47710	1.8668	0.047*
C19	0.1945 (5)	0.51679 (11)	1.8793 (7)	0.0416 (11)
H19A	0.1463	0.53459	1.7855	0.050*
H19B	0.1147	0.50190	1.9156	0.050*
C20	0.2724 (5)	0.53448 (11)	2.0644 (7)	0.0397 (11)
H20A	0.3528	0.54914	2.0279	0.048*
H20B	0.3200	0.51662	2.1582	0.048*
C21	0.1748 (5)	0.55663 (11)	2.1712 (7)	0.0452 (12)
H21A	0.0931	0.54210	2.2054	0.054*
H21B	0.1288	0.57483	2.0785	0.054*
C22	0.2533 (5)	0.57371 (11)	2.3589 (7)	0.0430 (12)
H22A	0.3005	0.55553	2.4508	0.052*
H22B	0.3340	0.58849	2.3243	0.052*
C23	0.1554 (5)	0.59547 (11)	2.4674 (7)	0.0432 (12)
H23A	0.0721	0.58105	2.4974	0.052*
H23B	0.1121	0.61443	2.3783	0.052*
C24	0.2366 (5)	0.61097 (11)	2.6603 (7)	0.0431 (12)
H24A	0.2793	0.59202	2.7497	0.052*
H24B	0.3203	0.62528	2.6304	0.052*
C25	0.1383 (5)	0.63299 (12)	2.7681 (8)	0.0551 (14)
H25A	0.1973	0.64216	2.8908	0.083*
H25B	0.0564	0.61890	2.8014	0.083*
H25C	0.0974	0.65220	2.6820	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0360 (6)	0.0428 (6)	0.0368 (6)	0.0057 (5)	0.0058 (5)	−0.0078 (6)
C1	0.030 (2)	0.034 (2)	0.034 (3)	−0.003 (2)	−0.002 (2)	−0.002 (2)
C2	0.024 (2)	0.039 (3)	0.039 (3)	−0.004 (2)	−0.001 (2)	0.000 (2)
C3	0.027 (2)	0.037 (2)	0.042 (3)	0.000 (2)	0.008 (2)	0.001 (2)
C4	0.035 (2)	0.029 (2)	0.029 (2)	−0.001 (2)	0.006 (2)	−0.003 (2)
C4a	0.028 (2)	0.023 (2)	0.024 (2)	−0.003 (2)	0.002 (2)	0.001 (2)
C4b	0.034 (2)	0.022 (2)	0.026 (2)	−0.002 (2)	0.003 (2)	0.002 (2)
C5	0.031 (2)	0.032 (2)	0.032 (3)	0.003 (2)	−0.002 (2)	−0.004 (2)
C6	0.042 (3)	0.043 (3)	0.030 (3)	0.000 (2)	−0.001 (2)	−0.007 (2)
C7	0.030 (2)	0.049 (3)	0.034 (3)	0.002 (2)	−0.006 (2)	0.004 (2)
C8	0.032 (2)	0.039 (3)	0.031 (3)	0.005 (2)	0.002 (2)	0.000 (2)
C8a	0.029 (2)	0.025 (2)	0.028 (2)	0.001 (2)	0.004 (2)	0.005 (2)
C9	0.035 (2)	0.024 (2)	0.028 (2)	0.001 (2)	0.008 (2)	−0.001 (2)
C10	0.034 (2)	0.034 (2)	0.026 (2)	−0.005 (2)	0.001 (2)	−0.006 (2)
C10a	0.034 (2)	0.022 (2)	0.030 (2)	0.000 (2)	0.007 (2)	−0.001 (2)
C12	0.037 (2)	0.039 (3)	0.032 (3)	−0.001 (2)	0.011 (2)	−0.010 (2)
C13	0.038 (2)	0.035 (3)	0.045 (3)	0.002 (2)	0.009 (2)	−0.004 (2)
C14	0.038 (2)	0.034 (2)	0.038 (3)	0.000 (2)	0.011 (2)	−0.004 (2)
C15	0.041 (3)	0.036 (2)	0.044 (3)	0.002 (2)	0.013 (2)	−0.004 (2)
C16	0.041 (3)	0.036 (3)	0.044 (3)	0.002 (2)	0.017 (2)	−0.001 (2)
C17	0.039 (2)	0.034 (2)	0.046 (3)	−0.003 (2)	0.014 (2)	−0.006 (2)
C18	0.043 (3)	0.033 (2)	0.045 (3)	0.001 (2)	0.013 (2)	−0.002 (2)
C19	0.042 (3)	0.039 (3)	0.045 (3)	−0.003 (2)	0.011 (2)	−0.005 (2)
C20	0.038 (2)	0.036 (3)	0.048 (3)	−0.001 (2)	0.014 (2)	−0.002 (2)
C21	0.045 (3)	0.038 (3)	0.053 (3)	−0.004 (2)	0.009 (2)	−0.008 (2)
C22	0.045 (3)	0.037 (3)	0.049 (3)	−0.006 (2)	0.014 (2)	−0.001 (2)
C23	0.047 (3)	0.038 (3)	0.045 (3)	−0.002 (2)	0.009 (2)	−0.004 (2)
C24	0.051 (3)	0.036 (3)	0.041 (3)	0.002 (2)	0.004 (2)	0.000 (2)
C25	0.059 (3)	0.053 (3)	0.053 (3)	0.001 (2)	0.011 (3)	−0.015 (3)

Geometric parameters (Å, º)

S—C9	1.772 (4)	C9—C10	1.344 (5)
S—C12	1.804 (4)	C10—C10a	1.440 (5)
C1—C2	1.366 (6)	C12—C13	1.530 (5)
C1—C10a	1.418 (5)	C13—C14	1.527 (6)
C2—C3	1.392 (6)	C14—C15	1.514 (5)
C3—C4	1.365 (5)	C15—C16	1.507 (6)
C4—C4a	1.415 (5)	C16—C17	1.510 (5)
C4a—C4b	1.443 (5)	C17—C18	1.502 (6)
C4a—C10a	1.408 (6)	C18—C19	1.518 (6)
C4b—C5	1.400 (6)	C19—C20	1.502 (6)
C4b—C8a	1.427 (5)	C20—C21	1.506 (6)
C5—C6	1.365 (5)	C21—C22	1.508 (6)
C6—C7	1.401 (6)	C22—C23	1.506 (6)
C7—C8	1.361 (6)	C23—C24	1.517 (6)
C8—C8a	1.399 (5)	C24—C25	1.512 (6)
C8a—C9	1.451 (6)
C9—S—C12	104.0 (2)	C8a—C9—S	115.7 (3)
C2—C1—C10a	121.1 (4)	C10—C9—S	123.4 (3)
C1—C2—C3	119.5 (4)	C9—C10—C10a	121.1 (4)
C4—C3—C2	120.8 (4)	C4a—C10a—C1	119.3 (4)
C3—C4—C4a	121.4 (4)	C4a—C10a—C10	120.3 (3)
C4—C4a—C4b	123.1 (4)	C1—C10a—C10	120.4 (4)
C10a—C4a—C4	117.9 (3)	C13—C12—S	108.4 (3)
C4b—C4a—C10a	119.0 (4)	C12—C13—C14	111.8 (3)
C4a—C4b—C5	122.7 (4)	C13—C14—C15	114.3 (3)
C5—C4b—C8a	117.6 (4)	C16—C15—C14	113.1 (4)
C4a—C4b—C8a	119.7 (4)	C15—C16—C17	115.5 (4)
C6—C5—C4b	122.8 (4)	C18—C17—C16	114.9 (4)
C5—C6—C7	118.9 (4)	C17—C18—C19	115.3 (4)
C8—C7—C6	120.4 (4)	C20—C19—C18	114.8 (4)
C7—C8—C8a	121.6 (4)	C19—C20—C21	115.5 (4)
C8—C8a—C4b	118.8 (4)	C20—C21—C22	115.1 (4)
C8—C8a—C9	122.2 (4)	C23—C22—C21	115.1 (4)
C4b—C8a—C9	119.0 (3)	C22—C23—C24	113.8 (4)
C8a—C9—C10	120.9 (4)	C25—C24—C23	113.6 (4)
C10a—C1—C2—C3	−1.0 (6)	C12—S—C9—C8a	−179.7 (3)
C1—C2—C3—C4	1.4 (6)	C8a—C9—C10—C10a	2.0 (6)
C2—C3—C4—C4a	−0.8 (6)	S—C9—C10—C10a	−177.9 (3)
C3—C4—C4a—C10a	−0.3 (6)	C4—C4a—C10a—C1	0.8 (5)
C3—C4—C4a—C4b	178.7 (4)	C4b—C4a—C10a—C1	−178.3 (4)
C10a—C4a—C4b—C5	−179.5 (4)	C4—C4a—C10a—C10	179.8 (4)
C4—C4a—C4b—C5	1.5 (6)	C4b—C4a—C10a—C10	0.8 (5)
C10a—C4a—C4b—C8a	−0.1 (5)	C2—C1—C10a—C4a	−0.1 (6)
C4—C4a—C4b—C8a	−179.1 (4)	C2—C1—C10a—C10	−179.2 (4)
C8a—C4b—C5—C6	−0.5 (6)	C9—C10—C10a—C4a	−1.8 (6)
C4a—C4b—C5—C6	178.9 (4)	C9—C10—C10a—C1	177.2 (4)
C4b—C5—C6—C7	0.4 (7)	C9—S—C12—C13	177.3 (3)
C5—C6—C7—C8	0.0 (7)	S—C12—C13—C14	−177.8 (3)
C6—C7—C8—C8a	−0.3 (7)	C12—C13—C14—C15	−179.4 (4)
C7—C8—C8a—C4b	0.2 (6)	C13—C14—C15—C16	−178.4 (4)
C7—C8—C8a—C9	−179.3 (4)	C14—C15—C16—C17	−179.1 (4)
C5—C4b—C8a—C8	0.1 (5)	C15—C16—C17—C18	179.9 (4)
C4a—C4b—C8a—C8	−179.3 (4)	C16—C17—C18—C19	−179.1 (4)
C5—C4b—C8a—C9	179.7 (3)	C17—C18—C19—C20	179.9 (4)
C4a—C4b—C8a—C9	0.3 (5)	C18—C19—C20—C21	179.5 (4)
C8—C8a—C9—C10	178.3 (4)	C19—C20—C21—C22	178.8 (4)
C4b—C8a—C9—C10	−1.2 (6)	C20—C21—C22—C23	−179.2 (4)
C8—C8a—C9—S	−1.8 (5)	C21—C22—C23—C24	177.4 (4)
C4b—C8a—C9—S	178.6 (3)	C22—C23—C24—C25	179.6 (4)
C12—S—C9—C10	0.2 (4)