Chiral and meso-bis([2.2]­para­cyclo­phan-4-yl)­methane and meso-bis­([2.2]­para­cyclo­phan-4-yl) sulfide

The [2.2]­para­cyclo­phane groups of the title compounds, chiral and meso-bis­(tri­cyclo­[8.2.2.2^4,7]­hexa­deca-4,6,10,12,13,15-hexa­en-5-yl)­methane (the former as a racemate), C₃₃H₃₂, and meso-bis­(tri­cyclo­[8.2.2.2^4,7]­hexa­deca-4,6,10,12,13,15-hexa­en-5-yl) sulfide, C₃₂H₃₀S, show the characteristic structural features of the parent compound [2.2]­para­cyclo­phane and the related compound di­methylbis([2.2]­para­cyclo­phan-4-yl)­silane, C₃₄­H₃₆­Si: the aromatic rings are puckered, resulting in a boat conformation. The planes of the four coplanar C atoms are slightly twisted with respect to each other. The Csp³-Csp³ bond lengths of the ethyl­ene bridges are elongated by the electronic and steric effects of the skeleton.

S1. Comment

Because of the (planar) chirality of monosubstituted [2.2]paracyclophanes (Q), compounds ZQ₂ composed of a central atom or group (Z) carrying two Q ligands can occur as meso and chiral diastereomers. Some time ago we reported the X-ray structures of the first pair of such diastereomers, in which Z was Si(CH₃)₂ (Jones et al., 1997), and recently the structure of meso-bis[2.2]paracyclophan-4-yl (Z = nil) has been determined (Jones & Kuś, 1998). The configurations of the title compounds (1 m) and (1c) as determined by NMR data, where the chemical equivalence or non-equivalence of the H atoms of the central methylene group indicate the chiral or meso-configuration, respectively, were confirmed by the X-ray structures; (1c) crystallizes as a racemate with imposed twofold symmetry. The X-ray diffraction study of the sulfide (2 m) was necessary because NMR data gave no indication of its configuration.

The paracyclophanyl groups in the title compounds show the characteristic structural features of substituted [2.2]paracyclophanes, similar to the diastereomeric pair of dimethyl-bis[2.2]paracyclophan-4-yl)silanes C₃₄H₃₆Si, (3) (Jones et al., 1997). The aromatic rings are distorted into boat shapes and the carbon atoms bearing the ethylene bridges are displaced out of the plane of the four other atoms. The mean aromatic planes are slightly inclined with respect to one another; the angles within paracyclophanyl groups vary from 0.3 (2)° in (2 m) to 1.7 (1)° in (1 m), cf. 1.6 (4) to 4.5 (4)° in (3).

The para carbon atoms are displaced out of the planes by amounts similar to those in the parent compound (4), [2.2]paracyclophane, (0.156 Å and 0.157 Å; Stalke, 1996). The values vary from 0.153 (2) to 0.172 (2) Å in (1c), 0.146 (2) to 0.160 (2) Å in (1 m) and 0.140 (3) Å to 0.167 (3) Å in (2 m). In contrast to the diastereomeric pair (3), no differences in the displacements between the substituted and non-substituted rings can be recognized.

The non-bonded distances of the corresponding bridgehead carbon atoms, which eclipse one another transannularly, are less than 2.8 Å [2.780 (2) Å and 2.792 (2) Å in (1c), 2.767 (2) to 2.774 (2) Å in (1 m) and 2.763 (3) Å to 2.777 (3) Å in (2 m)]. The intramolecular separation of the planes results in values of 3.084 (2) to 3.135 (2) Å in (1c), 3.041 (2) Å to 3.128 (2) Å in (1 m) and 3.052 (3) Å to 3.098 (3) Å in (2 m). The deviations from the geometry of the parent compound (4) [2.779 Å and 3.093 Å (Stalke, 1996)] are less pronounced than in the diastereomeric pair of (3) with their bulkier central Si(CH₃)₂ moieties.

The torsion angle C9···C2—C1···C10 indicates a mutual twist of the aromatic rings. Individual values are 4.61 (3)° (C9···C2—C1···C10) in (1c), −1.26 (4)° (C9^···C2—C1^···C10) and 2.00 (4)° (C9'···C2'—C1'^···C10') in (1 m). The sulfur-bridged compound (2 m) displays values of 4.64 (5)° (C9···C2—C1···C10) and −0.90 (5)° (C9'···C2'—C1'···C10').

As usual, the Csp³—Csp³ bonds of the ethylene bridges are characteristically elongated to values of 1.581 (2) and 1.585 (2) Å in (1c), 1.577 (2) to 1.582 (3) Å in (1 m) and 1.572 (3) to 1.580 (3) Å, similar to the parent compound (4) (1.571 Å; Stalke, 1996).

The carbon-carbon bonds in (1c) and (1 m) and the sulfur-carbon bonds in (2 m) between the two halves of the molecules lie in the range of the mean standard bond length of 1.513 Å for a Csp³—C_ar (Allen et al., 1987) and 1.768 Å for a C_ar—S bond length (Allen et al., 1987): 1.518 (2) Å in (1c), 1.513 (2) and 1.521 (2) Å in (1 m) and 1.778 (2) and 1.780 (2) Å in (2 m).

The torsion angles C5—C4—Z—C4' and C4—Z—C4'—C5' indicate the orientation of the paracyclophane groups with respect to each other. The central bond C4—Z in all cases shows torsion angles close to 120° and thus an ac conformation: −113.80 (12)° [C5—C4—C17—C4ⁱ; symmetry code: (i) 1 − x, y, 3/2 − z] in (1c), 106.24 (15)° (C5—C4—C17–C4') in (1 m) and −111.86 (16)° (C5—C4—S—C4') in (2 m). In constrast, the bond Z—C4' has a flattened sc conformation: −30.64 (19)° (C4—C17—C4'—C5') in (1 m) and 33.75 (18)° (C4—S—C4'—C5') in (2 m).

S2. Refinement

All hydrogen atoms were refined using a riding model. For compound (1 m) very few single crystals were available, and these could not be cut because they deformed: the crystal size is therefore greter than would normally be acceptable. For (2 m), which diffracted more weakly, 307 similarity restraints were applied to the U^ij components of carbon atoms.

Computing details

For all compounds, data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: XP5 (Siemens, 1994); software used to prepare material for publication: SHELXL93.

Figures

	Fig. 1. The molecule of compound (1c) in the crystal. Ellipsoids correspond to 50% probability levels. H atom radii are arbitrary. Symmetry code: (i) 1 − x, y, 3/2 − z.
	Fig. 2. The molecule of compound (1 m) in the crystal. Ellipsoids correspond to 50% probability levels. H atom radii are arbitrary.
	Fig. 3. The molecule of compound (2 m) in the crystal. Ellipsoids correspond to 50% probability levels. H atom radii are arbitrary.

(1c) chiral bis([2.2]paracyclophan-4-yl)methane

Crystal data

C33H32	F(000) = 920
Mr = 428.59	Dx = 1.260 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.928 (3) Å	Cell parameters from 64 reflections
b = 7.8409 (6) Å	θ = 4.8–12.5°
c = 11.5716 (12) Å	µ = 0.07 mm^−1
β = 92.256 (8)°	T = 173 K
V = 2260.0 (4) Å^3	Hexagonal tablet, colourless
Z = 4	0.76 × 0.46 × 0.22 mm

Data collection

Siemens P4 diffractometer	Rint = 0.025
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.2°
Graphite monochromator	h = 0→32
ω–scans	k = −10→2
3066 measured reflections	l = −15→15
2589 independent reflections	3 standard reflections every 247 reflections
1912 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.131	Calculated w = 1/[σ^2(Fo^2) + (0.0763P)^2 + 0.4887P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2587 reflections	Δρmax = 0.27 e Å^−3
151 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL93 (Sheldrick, 1993), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0080 (12)

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.

torsion angles

4.61 (0.03) C9 - C2 - C1 - C10 − 113.80 (0.12) C4 - C17 - C4_$1 - C5_$1

intramolecular distances

2.7919 (0.0018) C3 - C14 2.7795 (0.0018) C6 - C11 3.1350 (0.0018) C4 - C15 3.1009 (0.0018) C5 - C16 3.0931 (0.0019) C7 - C12 3.0839 (0.0019) C8 - C13

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

13.4395 (0.0163) x − 5.5890 (0.0031) y − 5.4327 (0.0087) z = 0.7251 (0.0120)

* 0.0107 (0.0006) C4 * −0.0108 (0.0006) C5 * 0.0108 (0.0006) C7 * −0.0108 (0.0006) C8 − 0.1716 (0.0019) C3 − 0.1552 (0.0019) C6

Rms deviation of fitted atoms = 0.0108

− 13.7193 (0.0176) x + 5.5243 (0.0032) y + 5.4310 (0.0088) z = 2.2540 (0.0126)

Angle to previous plane (with approximate e.s.d.) = 0.80 (0.11)

* 0.0000 (0.0006) C12 * 0.0000 (0.0006) C13 * 0.0000 (0.0006) C15 * 0.0000 (0.0006) C16 − 0.1555 (0.0020) C11 − 0.1531 (0.0020) C14

Rms deviation of fitted atoms = 0.0000

Refinement. Refinement on F² for ALL reflections except for 2 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
C1	0.43287 (6)	0.3431 (2)	1.02048 (13)	0.0327 (4)
H1A	0.42529	0.3286	1.10324	0.039*
H1B	0.45867	0.4384	1.01436	0.039*
C2	0.45959 (5)	0.1738 (2)	0.97480 (11)	0.0260 (3)
H2A	0.49890 (5)	0.1907	0.97259	0.031*
H2B	0.45298 (5)	0.0799	1.02962	0.031*
C3	0.43813 (5)	0.1229 (2)	0.85551 (11)	0.0211 (3)
C4	0.44971 (5)	0.2154 (2)	0.75542 (11)	0.0187 (3)
C5	0.41162 (5)	0.2169 (2)	0.66368 (11)	0.0211 (3)
H5	0.41848 (5)	0.2828	0.59696	0.025*
C6	0.36378 (5)	0.1247 (2)	0.66675 (11)	0.0232 (3)
C7	0.36015 (5)	0.0024 (2)	0.75298 (12)	0.0267 (3)
H7	0.33269 (5)	−0.0816	0.74796	0.032*
C8	0.39680 (5)	0.0034 (2)	0.84660 (12)	0.0259 (3)
H8	0.39360 (5)	−0.0793	0.90592	0.031*
C9	0.31484 (6)	0.1811 (2)	0.59501 (13)	0.0304 (3)
H9A	0.29319	0.0794	0.57320	0.036*
H9B	0.32675	0.2345	0.52287	0.036*
C10	0.27823 (6)	0.3117 (2)	0.65983 (14)	0.0353 (4)
H10A	0.27066	0.4108	0.60874	0.042*
H10B	0.24357	0.2563	0.67529	0.042*
C11	0.30363 (5)	0.3742 (2)	0.77273 (12)	0.0262 (3)
C12	0.29664 (6)	0.2846 (2)	0.87486 (12)	0.0283 (3)
H12	0.26521	0.2179	0.88308	0.034*
C13	0.33508 (6)	0.2916 (2)	0.96484 (12)	0.0274 (3)
H13	0.32978	0.2295	1.03396	0.033*
C14	0.38138 (5)	0.3890 (2)	0.95453 (11)	0.0254 (3)
C15	0.38177 (5)	0.5063 (2)	0.86446 (12)	0.0266 (3)
H15	0.40865 (5)	0.5922	0.86445	0.032*
C16	0.34327 (6)	0.4992 (2)	0.77442 (12)	0.0273 (3)
H16	0.34403	0.5803	0.71352	0.033*
C17	0.5000	0.3238 (2)	0.7500	0.0204 (4)
H17	0.5028	0.3981	0.8192	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0300 (8)	0.0421 (9)	0.0259 (7)	0.0032 (7)	−0.0014 (6)	−0.0096 (6)
C2	0.0239 (7)	0.0328 (8)	0.0214 (6)	0.0032 (6)	0.0020 (5)	0.0043 (6)
C3	0.0185 (6)	0.0215 (6)	0.0235 (7)	0.0039 (5)	0.0035 (5)	0.0000 (5)
C4	0.0171 (6)	0.0178 (6)	0.0214 (6)	0.0028 (5)	0.0032 (5)	−0.0024 (5)
C5	0.0185 (6)	0.0235 (6)	0.0216 (6)	0.0015 (5)	0.0044 (5)	−0.0024 (5)
C6	0.0186 (6)	0.0276 (7)	0.0236 (7)	0.0011 (5)	0.0018 (5)	−0.0082 (5)
C7	0.0208 (6)	0.0239 (7)	0.0357 (8)	−0.0041 (5)	0.0065 (6)	−0.0058 (6)
C8	0.0258 (7)	0.0231 (7)	0.0296 (7)	−0.0002 (5)	0.0084 (6)	0.0021 (6)
C9	0.0193 (6)	0.0425 (9)	0.0291 (7)	0.0008 (6)	−0.0022 (5)	−0.0079 (6)
C10	0.0245 (7)	0.0442 (9)	0.0367 (8)	0.0091 (7)	−0.0047 (6)	−0.0073 (7)
C11	0.0209 (6)	0.0286 (7)	0.0292 (7)	0.0082 (5)	0.0014 (5)	−0.0034 (6)
C12	0.0222 (7)	0.0284 (7)	0.0348 (8)	0.0001 (6)	0.0090 (6)	−0.0037 (6)
C13	0.0296 (7)	0.0281 (7)	0.0251 (7)	0.0028 (6)	0.0090 (6)	−0.0004 (6)
C14	0.0262 (7)	0.0277 (7)	0.0225 (7)	0.0035 (6)	0.0033 (5)	−0.0073 (5)
C15	0.0250 (7)	0.0215 (7)	0.0337 (7)	0.0004 (5)	0.0073 (6)	−0.0055 (6)
C16	0.0287 (7)	0.0241 (7)	0.0295 (7)	0.0075 (5)	0.0065 (6)	0.0025 (6)
C17	0.0178 (8)	0.0208 (9)	0.0226 (9)	0.000	0.0010 (7)	0.000

Geometric parameters (Å, º)

C1—C14	1.511 (2)	C7—C8	1.389 (2)
C1—C2	1.585 (2)	C9—C10	1.581 (2)
C2—C3	1.514 (2)	C10—C11	1.511 (2)
C3—C8	1.393 (2)	C11—C16	1.391 (2)
C3—C4	1.406 (2)	C11—C12	1.392 (2)
C4—C5	1.396 (2)	C12—C13	1.388 (2)
C4—C17	1.518 (2)	C13—C14	1.393 (2)
C5—C6	1.396 (2)	C14—C15	1.390 (2)
C6—C7	1.389 (2)	C15—C16	1.390 (2)
C6—C9	1.514 (2)	C17—C4^i	1.518 (2)
C14—C1—C2	113.02 (11)	C6—C9—C10	113.38 (11)
C3—C2—C1	112.75 (11)	C11—C10—C9	112.98 (11)
C8—C3—C4	117.46 (12)	C16—C11—C12	117.15 (13)
C8—C3—C2	118.59 (12)	C16—C11—C10	120.92 (13)
C4—C3—C2	122.56 (12)	C12—C11—C10	120.55 (14)
C5—C4—C3	118.36 (11)	C13—C12—C11	120.75 (13)
C5—C4—C17	120.14 (10)	C12—C13—C14	120.47 (13)
C3—C4—C17	121.30 (10)	C15—C14—C13	117.20 (13)
C4—C5—C6	122.17 (12)	C15—C14—C1	120.37 (13)
C7—C6—C5	117.09 (12)	C13—C14—C1	121.08 (13)
C7—C6—C9	121.42 (12)	C14—C15—C16	120.71 (13)
C5—C6—C9	120.35 (13)	C15—C16—C11	120.53 (13)
C6—C7—C8	119.78 (12)	C4—C17—C4^i	111.91 (15)
C7—C8—C3	121.54 (13)
C14—C1—C2—C3	17.0 (2)	C6—C9—C10—C11	8.7 (2)
C1—C2—C3—C8	−95.9 (2)	C9—C10—C11—C16	78.3 (2)
C1—C2—C3—C4	70.2 (2)	C9—C10—C11—C12	−87.9 (2)
C8—C3—C4—C5	16.5 (2)	C16—C11—C12—C13	−14.5 (2)
C2—C3—C4—C5	−149.75 (12)	C10—C11—C12—C13	152.25 (13)
C8—C3—C4—C17	−168.63 (12)	C11—C12—C13—C14	0.2 (2)
C2—C3—C4—C17	25.1 (2)	C12—C13—C14—C15	14.2 (2)
C3—C4—C5—C6	−2.5 (2)	C12—C13—C14—C1	−152.61 (13)
C17—C4—C5—C6	−177.38 (12)	C2—C1—C14—C15	−96.5 (2)
C4—C5—C6—C7	−13.5 (2)	C2—C1—C14—C13	69.8 (2)
C4—C5—C6—C9	154.48 (12)	C13—C14—C15—C16	−14.2 (2)
C5—C6—C7—C8	15.3 (2)	C1—C14—C15—C16	152.66 (13)
C9—C6—C7—C8	−152.61 (13)	C14—C15—C16—C11	−0.1 (2)
C6—C7—C8—C3	−1.2 (2)	C12—C11—C16—C15	14.4 (2)
C4—C3—C8—C7	−15.0 (2)	C10—C11—C16—C15	−152.24 (13)
C2—C3—C8—C7	151.85 (13)	C5—C4—C17—C4^i	−113.80 (12)
C7—C6—C9—C10	78.5 (2)	C3—C4—C17—C4^i	71.47 (11)
C5—C6—C9—C10	−89.0 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

(1m) meso-bis([2.2]paracyclophan-4-yl)methane

Crystal data

C33H32	F(000) = 1840
Mr = 428.59	Dx = 1.220 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.969 (3) Å	Cell parameters from 64 reflections
b = 7.720 (1) Å	θ = 5.3–12.5°
c = 23.329 (3) Å	µ = 0.07 mm^−1
β = 94.044 (6)°	T = 173 K
V = 4665.3 (10) Å^3	Tablet, colourless
Z = 8	1.20 × 0.64 × 0.34 mm

Data collection

Siemens P4 diffractometer	Rint = 0.011
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 3.2°
Graphite monochromator	h = −30→30
ω–scans	k = −9→1
4268 measured reflections	l = −27→0
4095 independent reflections	3 standard reflections every 247 reflections
3240 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H-atom parameters constrained
S = 1.04	Calculated w = 1/[σ^2(Fo^2) + (0.0671P)^2 + 1.794P] where P = (Fo^2 + 2Fc^2)/3
4094 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.23 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.

torsion angles

−1.26 (0.04) C9 - C2 - C1 - C10 2.00 (0.04) C9' - C2' - C1' - C10'

intramolecular distances

2.7672 (0.0021) C3 - C14 2.7707 (0.0022) C6 - C11 3.0627 (0.0020) C4 - C15 3.0581 (0.0022) C5 - C16 3.0767 (0.0022) C7 - C12 3.0817 (0.0021) C8 - C13 2.7744 (0.0020) C3' - C14' 2.7726 (0.0020) C6' - C11' 3.1280 (0.0020) C4' - C15' 3.0994 (0.0020) C5' - C16' 3.0515 (0.0020) C7' - C12' 3.0412 (0.0021) C8' - C13'

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 1.4006 (0.0233) x + 3.3012 (0.0057) y + 21.0869 (0.0086) z = 11.4080 (0.0087)

* −0.0023 (0.0007) C4 * 0.0023 (0.0007) C5 * −0.0023 (0.0007) C7 * 0.0023 (0.0007) C8 − 0.1503 (0.0021) C3 − 0.1460 (0.0023) C6

Rms deviation of fitted atoms = 0.0023

− 1.5982 (0.0246) x + 3.3280 (0.0060) y + 21.0497 (0.0091) z = 8.2787 (0.0092)

Angle to previous plane (with approximate e.s.d.) = 0.49 (0.09)

* −0.0020 (0.0008) C12 * 0.0021 (0.0008) C13 * −0.0021 (0.0008) C15 * 0.0021 (0.0008) C16 0.1485 (0.0023) C11 0.1564 (0.0023) C14

Rms deviation of fitted atoms = 0.0021

24.7457 (0.0057) x − 1.6588 (0.0068) y + 3.4134 (0.0158) z = 9.8645 (0.0116)

Angle to previous plane (with approximate e.s.d.) = 87.63 (0.07)

* −0.0061 (0.0007) C4' * 0.0061 (0.0007) C5' * −0.0061 (0.0007) C7' * 0.0061 (0.0007) C8' 0.1598 (0.0021) C3' 0.1481 (0.0021) C6'

Rms deviation of fitted atoms = 0.0061

24.5234 (0.0062) x − 1.7290 (0.0072) y + 4.0538 (0.0175) z = 13.2107 (0.0127)

Angle to previous plane (with approximate e.s.d.) = 1.70 (0.06)

* 0.0040 (0.0007) C12' * −0.0040 (0.0007) C13' * 0.0040 (0.0007) C15' * −0.0039 (0.0007) C16' −0.1500 (0.0022) C11' −0.1575 (0.0022) C14'

Rms deviation of fitted atoms = 0.0040

Refinement. Refinement on F² for ALL reflections except for 1 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
C1	0.25939 (7)	0.5062 (2)	0.36923 (8)	0.0481 (5)
H1A	0.26576 (7)	0.3806 (2)	0.37444 (8)	0.058*
H1B	0.22473 (7)	0.5204 (2)	0.34925 (8)	0.058*
C2	0.25972 (6)	0.5949 (2)	0.43025 (8)	0.0413 (4)
H2A	0.22594 (6)	0.6515 (2)	0.43416 (8)	0.050*
H2B	0.26416 (6)	0.5045 (2)	0.46029 (8)	0.050*
C3	0.30194 (6)	0.7277 (2)	0.44000 (6)	0.0289 (3)
C4	0.35295 (6)	0.6819 (2)	0.45757 (6)	0.0265 (3)
C5	0.39265 (6)	0.7900 (2)	0.44350 (6)	0.0302 (3)
H5	0.42716 (6)	0.7597 (2)	0.45565 (6)	0.036*
C6	0.38366 (6)	0.9420 (2)	0.41208 (7)	0.0332 (4)
C7	0.33305 (6)	1.0014 (2)	0.40624 (7)	0.0339 (4)
H7	0.32603 (6)	1.1153 (2)	0.39247 (7)	0.041*
C8	0.29286 (6)	0.8959 (2)	0.42031 (6)	0.0318 (4)
H8	0.25850 (6)	0.9388 (2)	0.41648 (6)	0.038*
C9	0.42438 (7)	1.0126 (2)	0.37517 (9)	0.0491 (5)
H9A	0.45895 (7)	0.9868 (2)	0.39385 (9)	0.059*
H9B	0.42077 (7)	1.1401 (2)	0.37261 (9)	0.059*
C10	0.42059 (7)	0.9340 (3)	0.31237 (8)	0.0567 (6)
H10A	0.41258 (7)	1.0285 (3)	0.28445 (8)	0.068*
H10B	0.45459 (7)	0.8852 (3)	0.30433 (8)	0.068*
C11	0.38035 (6)	0.7951 (3)	0.30351 (6)	0.0392 (4)
C12	0.32927 (6)	0.8363 (2)	0.28597 (6)	0.0375 (4)
H12	0.32201 (6)	0.9385 (2)	0.26420 (6)	0.045*
C13	0.28921 (6)	0.7302 (2)	0.29990 (7)	0.0366 (4)
H13	0.25466 (6)	0.7599 (2)	0.28770 (7)	0.044*
C14	0.29923 (6)	0.5797 (2)	0.33179 (7)	0.0369 (4)
C15	0.34991 (7)	0.5219 (2)	0.33725 (7)	0.0376 (4)
H15	0.35710 (7)	0.4075 (2)	0.35052 (7)	0.045*
C16	0.38997 (7)	0.6279 (3)	0.32373 (6)	0.0404 (4)
H16	0.42446 (7)	0.5864 (3)	0.32825 (6)	0.049*
C17	0.36547 (6)	0.5087 (2)	0.48558 (6)	0.0304 (4)
H17A	0.40214 (6)	0.4811 (2)	0.48080 (6)	0.037*
H17B	0.34419 (6)	0.4183 (2)	0.46527 (6)	0.037*
C1'	0.42562 (7)	0.1488 (2)	0.55630 (7)	0.0395 (4)
H1'1	0.43425 (7)	0.0305 (2)	0.57025 (7)	0.047*
H1'2	0.43797 (7)	0.1605 (2)	0.51730 (7)	0.047*
C2'	0.36508 (6)	0.1727 (2)	0.55273 (7)	0.0345 (4)
H2'1	0.35165 (6)	0.1644 (2)	0.51204 (7)	0.041*
H2'2	0.34958 (6)	0.0772 (2)	0.57403 (7)	0.041*
C3'	0.34851 (5)	0.3432 (2)	0.57694 (6)	0.0265 (3)
C4'	0.35626 (5)	0.5017 (2)	0.54920 (6)	0.0239 (3)
C5'	0.36212 (5)	0.6504 (2)	0.58257 (6)	0.0246 (3)
H5'	0.36813 (5)	0.7576 (2)	0.56420 (6)	0.029*
C6'	0.35949 (5)	0.6480 (2)	0.64205 (6)	0.0251 (3)
C7'	0.33998 (5)	0.4994 (2)	0.66614 (6)	0.0281 (3)
H7'	0.33019 (5)	0.5008 (2)	0.70462 (6)	0.034*
C8'	0.33489 (5)	0.3495 (2)	0.63377 (6)	0.0295 (3)
H8'	0.32177 (5)	0.2481 (2)	0.65064 (6)	0.035*
C9'	0.38728 (6)	0.7831 (2)	0.67935 (7)	0.0340 (4)
H9'1	0.37168 (6)	0.7876 (2)	0.71684 (7)	0.041*
H9'2	0.38231 (6)	0.8978 (2)	0.66084 (7)	0.041*
C10'	0.44693 (7)	0.7468 (2)	0.69008 (9)	0.0495 (5)
H10C	0.46624 (7)	0.8455 (2)	0.67507 (9)	0.059*
H10D	0.45577 (7)	0.7397 (2)	0.73199 (9)	0.059*
C11'	0.46415 (6)	0.5821 (2)	0.66221 (7)	0.0328 (4)
C12'	0.45500 (6)	0.4229 (2)	0.68766 (7)	0.0323 (4)
H12'	0.45243 (6)	0.4165 (2)	0.72803 (7)	0.039*
C13'	0.44961 (6)	0.2743 (2)	0.65493 (7)	0.0316 (4)
H13'	0.44317 (6)	0.1671 (2)	0.67304 (7)	0.038*
C14'	0.45348 (5)	0.2794 (2)	0.59582 (6)	0.0295 (3)
C15'	0.47424 (6)	0.4289 (2)	0.57379 (7)	0.0319 (4)
H15'	0.48528 (6)	0.4283 (2)	0.53583 (7)	0.038*
C16'	0.47912 (6)	0.5789 (2)	0.60628 (7)	0.0349 (4)
H16'	0.49284 (6)	0.6804 (2)	0.59014 (7)	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0393 (10)	0.0420 (10)	0.0622 (12)	−0.0127 (8)	−0.0024 (8)	0.0024 (9)
C2	0.0272 (8)	0.0495 (11)	0.0482 (10)	0.0007 (7)	0.0093 (7)	0.0145 (8)
C3	0.0284 (8)	0.0388 (9)	0.0202 (7)	0.0052 (7)	0.0066 (6)	0.0034 (6)
C4	0.0310 (8)	0.0324 (8)	0.0162 (6)	0.0060 (6)	0.0012 (6)	−0.0015 (6)
C5	0.0277 (8)	0.0344 (8)	0.0272 (7)	0.0029 (7)	−0.0061 (6)	−0.0045 (7)
C6	0.0363 (9)	0.0278 (8)	0.0347 (8)	−0.0042 (7)	−0.0036 (7)	−0.0038 (7)
C7	0.0437 (9)	0.0262 (8)	0.0311 (8)	0.0058 (7)	−0.0032 (7)	−0.0022 (7)
C8	0.0310 (8)	0.0401 (9)	0.0243 (7)	0.0115 (7)	0.0030 (6)	−0.0007 (7)
C9	0.0391 (10)	0.0364 (10)	0.0715 (13)	−0.0105 (8)	0.0012 (9)	0.0109 (9)
C10	0.0392 (10)	0.084 (2)	0.0471 (11)	−0.0105 (10)	0.0044 (8)	0.0317 (11)
C11	0.0337 (9)	0.0649 (12)	0.0197 (7)	0.0016 (8)	0.0071 (6)	0.0065 (8)
C12	0.0403 (9)	0.0507 (11)	0.0213 (7)	0.0057 (8)	0.0000 (6)	0.0033 (7)
C13	0.0306 (8)	0.0483 (10)	0.0299 (8)	0.0028 (7)	−0.0054 (6)	−0.0080 (7)
C14	0.0399 (9)	0.0384 (9)	0.0314 (8)	−0.0035 (7)	−0.0039 (7)	−0.0114 (7)
C15	0.0485 (10)	0.0387 (9)	0.0255 (8)	0.0095 (8)	0.0016 (7)	−0.0081 (7)
C16	0.0372 (9)	0.0641 (12)	0.0206 (7)	0.0157 (8)	0.0062 (6)	0.0018 (8)
C17	0.0367 (8)	0.0323 (8)	0.0221 (7)	0.0078 (7)	0.0012 (6)	0.0007 (6)
C1'	0.0465 (10)	0.0322 (9)	0.0397 (9)	0.0051 (8)	0.0029 (7)	−0.0069 (8)
C2'	0.0447 (9)	0.0257 (8)	0.0319 (8)	−0.0036 (7)	−0.0063 (7)	−0.0021 (7)
C3'	0.0238 (7)	0.0277 (8)	0.0272 (7)	−0.0031 (6)	−0.0055 (6)	0.0006 (6)
C4'	0.0205 (7)	0.0286 (8)	0.0222 (7)	0.0029 (6)	−0.0019 (5)	0.0009 (6)
C5'	0.0224 (7)	0.0245 (7)	0.0264 (7)	0.0035 (6)	−0.0007 (6)	0.0032 (6)
C6'	0.0218 (7)	0.0286 (8)	0.0243 (7)	0.0058 (6)	−0.0011 (5)	−0.0018 (6)
C7'	0.0223 (7)	0.0411 (9)	0.0208 (7)	0.0016 (6)	0.0013 (5)	0.0016 (6)
C8'	0.0259 (8)	0.0337 (9)	0.0285 (8)	−0.0074 (6)	−0.0007 (6)	0.0064 (7)
C9'	0.0383 (9)	0.0328 (9)	0.0301 (8)	0.0039 (7)	−0.0024 (7)	−0.0076 (7)
C10'	0.0391 (10)	0.0426 (10)	0.0644 (12)	0.0021 (8)	−0.0138 (8)	−0.0231 (9)
C11'	0.0208 (7)	0.0344 (9)	0.0418 (9)	−0.0014 (6)	−0.0072 (6)	−0.0060 (7)
C12'	0.0251 (8)	0.0448 (10)	0.0264 (7)	0.0025 (7)	−0.0026 (6)	0.0003 (7)
C13'	0.0302 (8)	0.0300 (8)	0.0345 (8)	0.0029 (6)	0.0011 (6)	0.0077 (7)
C14'	0.0254 (8)	0.0297 (8)	0.0334 (8)	0.0070 (6)	0.0020 (6)	−0.0002 (7)
C15'	0.0234 (7)	0.0407 (9)	0.0322 (8)	0.0032 (7)	0.0061 (6)	0.0040 (7)
C16'	0.0223 (7)	0.0342 (9)	0.0479 (10)	−0.0054 (7)	0.0004 (7)	0.0088 (8)

Geometric parameters (Å, º)

C1—C14	1.511 (2)	C17—C4'	1.521 (2)
C1—C2	1.579 (3)	C1'—C14'	1.515 (2)
C2—C3	1.507 (2)	C1'—C2'	1.579 (2)
C3—C8	1.392 (2)	C2'—C3'	1.507 (2)
C3—C4	1.404 (2)	C3'—C8'	1.397 (2)
C4—C5	1.384 (2)	C3'—C4'	1.405 (2)
C4—C17	1.513 (2)	C4'—C5'	1.389 (2)
C5—C6	1.394 (2)	C5'—C6'	1.394 (2)
C6—C7	1.390 (2)	C6'—C7'	1.388 (2)
C6—C9	1.512 (2)	C6'—C9'	1.509 (2)
C7—C8	1.382 (2)	C7'—C8'	1.383 (2)
C9—C10	1.582 (3)	C9'—C10'	1.577 (2)
C10—C11	1.501 (3)	C10'—C11'	1.510 (2)
C11—C16	1.391 (3)	C11'—C16'	1.388 (2)
C11—C12	1.397 (2)	C11'—C12'	1.393 (2)
C12—C13	1.381 (2)	C12'—C13'	1.379 (2)
C13—C14	1.394 (2)	C13'—C14'	1.390 (2)
C14—C15	1.387 (2)	C14'—C15'	1.388 (2)
C15—C16	1.377 (3)	C15'—C16'	1.385 (2)
C14—C1—C2	113.45 (14)	C14'—C1'—C2'	112.65 (13)
C3—C2—C1	112.88 (13)	C3'—C2'—C1'	113.07 (12)
C8—C3—C4	117.75 (14)	C8'—C3'—C4'	117.43 (13)
C8—C3—C2	118.72 (14)	C8'—C3'—C2'	118.97 (13)
C4—C3—C2	122.29 (14)	C4'—C3'—C2'	122.28 (13)
C5—C4—C3	118.83 (14)	C5'—C4'—C3'	118.36 (12)
C5—C4—C17	119.63 (13)	C5'—C4'—C17	119.93 (13)
C3—C4—C17	121.20 (14)	C3'—C4'—C17	121.19 (13)
C4—C5—C6	122.16 (14)	C4'—C5'—C6'	122.39 (13)
C7—C6—C5	116.82 (15)	C7'—C6'—C5'	117.31 (13)
C7—C6—C9	121.33 (15)	C7'—C6'—C9'	120.71 (13)
C5—C6—C9	120.33 (15)	C5'—C6'—C9'	120.64 (13)
C8—C7—C6	120.49 (15)	C8'—C7'—C6'	119.58 (13)
C7—C8—C3	121.00 (14)	C7'—C8'—C3'	121.77 (14)
C6—C9—C10	112.88 (14)	C6'—C9'—C10'	113.15 (12)
C11—C10—C9	113.49 (14)	C11'—C10'—C9'	113.51 (13)
C16—C11—C12	117.0 (2)	C16'—C11'—C12'	116.90 (15)
C16—C11—C10	120.6 (2)	C16'—C11'—C10'	122.1 (2)
C12—C11—C10	121.0 (2)	C12'—C11'—C10'	119.7 (2)
C13—C12—C11	120.8 (2)	C13'—C12'—C11'	120.76 (14)
C12—C13—C14	120.29 (15)	C12'—C13'—C14'	120.95 (14)
C15—C14—C13	117.2 (2)	C15'—C14'—C13'	116.58 (14)
C15—C14—C1	120.7 (2)	C15'—C14'—C1'	120.63 (14)
C13—C14—C1	120.8 (2)	C13'—C14'—C1'	121.35 (14)
C16—C15—C14	121.0 (2)	C16'—C15'—C14'	121.04 (14)
C15—C16—C11	120.6 (2)	C15'—C16'—C11'	120.58 (15)
C4—C17—C4'	114.14 (12)
C14—C1—C2—C3	−3.4 (2)	C14'—C1'—C2'—C3'	14.1 (2)
C1—C2—C3—C8	85.0 (2)	C1'—C2'—C3'—C8'	−95.9 (2)
C1—C2—C3—C4	−82.0 (2)	C1'—C2'—C3'—C4'	70.7 (2)
C8—C3—C4—C5	−13.5 (2)	C8'—C3'—C4'—C5'	15.0 (2)
C2—C3—C4—C5	153.61 (14)	C2'—C3'—C4'—C5'	−151.71 (13)
C8—C3—C4—C17	173.23 (13)	C8'—C3'—C4'—C17	−173.33 (13)
C2—C3—C4—C17	−19.6 (2)	C2'—C3'—C4'—C17	20.0 (2)
C3—C4—C5—C6	−0.5 (2)	C4—C17—C4'—C5'	−30.6 (2)
C17—C4—C5—C6	172.82 (13)	C4—C17—C4'—C3'	157.82 (13)
C4—C5—C6—C7	13.9 (2)	C3'—C4'—C5'—C6'	−1.4 (2)
C4—C5—C6—C9	−152.2 (2)	C17—C4'—C5'—C6'	−173.15 (13)
C5—C6—C7—C8	−13.2 (2)	C4'—C5'—C6'—C7'	−13.4 (2)
C9—C6—C7—C8	152.8 (2)	C4'—C5'—C6'—C9'	153.50 (14)
C6—C7—C8—C3	−0.7 (2)	C5'—C6'—C7'—C8'	14.2 (2)
C4—C3—C8—C7	14.3 (2)	C9'—C6'—C7'—C8'	−152.70 (14)
C2—C3—C8—C7	−153.33 (15)	C6'—C7'—C8'—C3'	−0.5 (2)
C7—C6—C9—C10	−78.0 (2)	C4'—C3'—C8'—C7'	−14.3 (2)
C5—C6—C9—C10	87.5 (2)	C2'—C3'—C8'—C7'	152.81 (14)
C6—C9—C10—C11	−4.7 (2)	C7'—C6'—C9'—C10'	87.9 (2)
C9—C10—C11—C16	−78.4 (2)	C5'—C6'—C9'—C10'	−78.6 (2)
C9—C10—C11—C12	88.1 (2)	C6'—C9'—C10'—C11'	−1.4 (2)
C16—C11—C12—C13	13.9 (2)	C9'—C10'—C11'—C16'	88.5 (2)
C10—C11—C12—C13	−153.0 (2)	C9'—C10'—C11'—C12'	−77.8 (2)
C11—C12—C13—C14	0.0 (2)	C16'—C11'—C12'—C13'	−14.3 (2)
C12—C13—C14—C15	−14.3 (2)	C10'—C11'—C12'—C13'	152.72 (15)
C12—C13—C14—C1	152.6 (2)	C11'—C12'—C13'—C14'	0.4 (2)
C2—C1—C14—C15	83.4 (2)	C12'—C13'—C14'—C15'	14.2 (2)
C2—C1—C14—C13	−83.1 (2)	C12'—C13'—C14'—C1'	−152.20 (15)
C13—C14—C15—C16	14.8 (2)	C2'—C1'—C14'—C15'	−97.1 (2)
C1—C14—C15—C16	−152.1 (2)	C2'—C1'—C14'—C13'	68.7 (2)
C14—C15—C16—C11	−0.8 (2)	C13'—C14'—C15'—C16'	−15.0 (2)
C12—C11—C16—C15	−13.5 (2)	C1'—C14'—C15'—C16'	151.52 (15)
C10—C11—C16—C15	153.5 (2)	C14'—C15'—C16'—C11'	1.2 (2)
C5—C4—C17—C4'	106.2 (2)	C12'—C11'—C16'—C15'	13.5 (2)
C3—C4—C17—C4'	−80.6 (2)	C10'—C11'—C16'—C15'	−153.18 (15)

(2m) meso-bis([2.2]paracyclophan-4-yl)sulfide

Crystal data

C32H30S	Z = 2
Mr = 446.62	F(000) = 476
Triclinic, P1	Dx = 1.264 Mg m^−3
a = 8.1084 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.334 (2) Å	Cell parameters from 55 reflections
c = 12.826 (2) Å	θ = 5.5–12.5°
α = 94.525 (12)°	µ = 0.16 mm^−1
β = 105.516 (12)°	T = 173 K
γ = 105.779 (8)°	Tablet, colourless
V = 1173.3 (3) Å^3	0.60 × 0.30 × 0.08 mm

Data collection

Siemens P4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 3.3°
Graphite monochromator	h = −9→5
ω–scans	k = −14→14
5091 measured reflections	l = −14→15
4117 independent reflections	3 standard reflections every 247 reflections
2443 reflections with I > 2σ(I)	intensity decay: 3%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 0.82	Calculated w = 1/[σ^2(Fo^2) + (0.0439P)^2] where P = (Fo^2 + 2Fc^2)/3
4115 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 0.27 e Å^−3
307 restraints	Δρmin = −0.18 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.

torsion angles

4.64 (0.05) C9 - C2 - C1 - C10 − 0.90 (0.05) C9' - C2' - C1' - C10'

intramolecular distances

2.7733 (0.0028) C3 - C14 2.7767 (0.0030) C6 - C11 3.0722 (0.0027) C4 - C15 3.0742 (0.0028) C5 - C16 3.0820 (0.0029) C7 - C12 3.0902 (0.0028) C8 - C13 2.7627 (0.0028) C3' - C14' 2.7715 (0.0027) C6' - C11' 3.0984 (0.0027) C4' - C15' 3.0699 (0.0027) C5' - C16' 3.0599 (0.0028) C7' - C12' 3.0524 (0.0028) C8' - C13'

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

5.5191 (0.0081) x + 5.5733 (0.0147) y − 7.5008 (0.0084) z = 2.0450 (0.0100)

* −0.0012 (0.0010) C4 * 0.0012 (0.0010) C5 * −0.0012 (0.0010) C7 * 0.0012 (0.0010) C8 0.1606 (0.0028) C3 0.1519 (0.0030) C6

Rms deviation of fitted atoms = 0.0012

5.5002 (0.0086) x + 5.5823 (0.0161) y − 7.5515 (0.0088) z = 5.0673 (0.0108)

Angle to previous plane (with approximate e.s.d.) = 0.31 (0.22)

* −0.0037 (0.0010) C12 * 0.0037 (0.0010) C13 * −0.0037 (0.0010) C15 * 0.0037 (0.0010) C16 − 0.1479 (0.0032) C11 − 0.1493 (0.0030) C14

Rms deviation of fitted atoms = 0.0037

4.9226 (0.0085) x − 1.7289 (0.0099) y + 7.5476 (0.0136) z = 8.3222 (0.0059)

Angle to previous plane (with approximate e.s.d.) = 79.88 (0.08)

* 0.0094 (0.0009) C4' * −0.0094 (0.0010) C5' * 0.0094 (0.0010) C7' * −0.0094 (0.0010) C8' −0.1670 (0.0028) C3' −0.1399 (0.0028) C6'

Rms deviation of fitted atoms = 0.0094

4.9622 (0.0091) x − 1.5981 (0.0105) y + 7.4538 (0.0147) z = 5.2436 (0.0062)

Angle to previous plane (with approximate e.s.d.) = 0.80 (0.23)

* 0.0005 (0.0010) C12' * −0.0005 (0.0010) C13' * 0.0005 (0.0010) C15' * −0.0005 (0.0010) C16' 0.1487 (0.0030) C11' 0.1524 (0.0030) C14'

Rms deviation of fitted atoms = 0.0005

Refinement. Refinement on F² for ALL reflections except for 2 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	0.81745 (8)	0.47511 (5)	0.67668 (4)	0.0437 (2)
C1	1.2905 (3)	0.6149 (2)	0.8248 (2)	0.0554 (7)
H1A	1.4171 (3)	0.6276 (2)	0.8681 (2)	0.066*
H1B	1.2688 (3)	0.5689 (2)	0.7529 (2)	0.066*
C2	1.1631 (3)	0.5454 (2)	0.8867 (2)	0.0464 (6)
H2A	1.1148 (3)	0.4644 (2)	0.8508 (2)	0.056*
H2B	1.2342 (3)	0.5483 (2)	0.9633 (2)	0.056*
C3	1.0086 (3)	0.5910 (2)	0.8872 (2)	0.0320 (5)
C4	0.8639 (3)	0.5791 (2)	0.7934 (2)	0.0322 (5)
C5	0.7714 (3)	0.6586 (2)	0.7841 (2)	0.0364 (5)
H5	0.6743 (3)	0.6497 (2)	0.7199 (2)	0.044*
C6	0.8173 (3)	0.7513 (2)	0.8667 (2)	0.0388 (5)
C7	0.9311 (3)	0.7467 (2)	0.9675 (2)	0.0389 (5)
H7	0.9449 (3)	0.7984 (2)	1.0304 (2)	0.047*
C8	1.0246 (3)	0.6679 (2)	0.9774 (2)	0.0373 (5)
H8	1.1014 (3)	0.6662 (2)	1.0472 (2)	0.045*
C9	0.7798 (3)	0.8605 (2)	0.8389 (2)	0.0560 (7)
H9A	0.7547 (3)	0.8981 (2)	0.9014 (2)	0.067*
H9B	0.6710 (3)	0.8418 (2)	0.7747 (2)	0.067*
C10	0.9407 (4)	0.9462 (2)	0.8122 (2)	0.0671 (8)
H10A	0.8932 (4)	0.9733 (2)	0.7431 (2)	0.081*
H10B	0.9949 (4)	1.0133 (2)	0.8714 (2)	0.081*
C11	1.0852 (3)	0.8951 (2)	0.8006 (2)	0.0445 (6)
C12	1.2301 (3)	0.9002 (2)	0.8909 (2)	0.0457 (6)
H12	1.2689 (3)	0.9605 (2)	0.9513 (2)	0.055*
C13	1.3175 (3)	0.8183 (2)	0.8930 (2)	0.0422 (6)
H13	1.4171 (3)	0.8235 (2)	0.9546 (2)	0.051*
C14	1.2624 (3)	0.7286 (2)	0.8068 (2)	0.0400 (5)
C15	1.1449 (3)	0.7391 (2)	0.7098 (2)	0.0419 (6)
H15	1.1239 (3)	0.6887 (2)	0.6444 (2)	0.050*
C16	1.0586 (3)	0.8212 (2)	0.7066 (2)	0.0446 (6)
H16	0.9799 (3)	0.8272 (2)	0.6390 (2)	0.054*
C1'	0.5861 (3)	0.2264 (2)	0.4611 (2)	0.0564 (7)
H1'1	0.6171 (3)	0.2955 (2)	0.4271 (2)	0.068*
H1'2	0.5622 (3)	0.1591 (2)	0.4055 (2)	0.068*
C2'	0.7516 (3)	0.2308 (2)	0.5616 (2)	0.0407 (6)
H2'1	0.7847 (3)	0.1599 (2)	0.5518 (2)	0.049*
H2'2	0.8555 (3)	0.2959 (2)	0.5625 (2)	0.049*
C3'	0.7142 (3)	0.2433 (2)	0.6705 (2)	0.0324 (5)
C4'	0.7110 (3)	0.3479 (2)	0.71985 (15)	0.0307 (5)
C5'	0.6036 (3)	0.3494 (2)	0.78776 (15)	0.0310 (5)
H5'	0.5976 (3)	0.4204 (2)	0.81821 (15)	0.037*
C6'	0.5046 (3)	0.2488 (2)	0.81202 (15)	0.0316 (5)
C7'	0.5428 (3)	0.1497 (2)	0.7841 (2)	0.0361 (5)
H7'	0.4984 (3)	0.0831 (2)	0.8131 (2)	0.043*
C8'	0.6456 (3)	0.1476 (2)	0.7141 (2)	0.0370 (5)
H8'	0.6700 (3)	0.0788 (2)	0.6953 (2)	0.044*
C9'	0.3370 (3)	0.2458 (2)	0.8434 (2)	0.0423 (6)
H9'1	0.3609 (3)	0.3168 (2)	0.8943 (2)	0.051*
H9'2	0.3087 (3)	0.1808 (2)	0.8830 (2)	0.051*
C10'	0.1690 (3)	0.2339 (2)	0.7424 (2)	0.0516 (6)
H10C	0.0706 (3)	0.1656 (2)	0.7424 (2)	0.062*
H10D	0.1272 (3)	0.3015 (2)	0.7507 (2)	0.062*
C11'	0.2071 (3)	0.2234 (2)	0.6335 (2)	0.0354 (5)
C12'	0.2148 (3)	0.1206 (2)	0.5864 (2)	0.0408 (6)
H12'	0.1483 (3)	0.0509 (2)	0.6021 (2)	0.049*
C13'	0.3185 (3)	0.1186 (2)	0.5168 (2)	0.0415 (6)
H13'	0.3220 (3)	0.0475 (2)	0.4849 (2)	0.050*
C14'	0.4178 (3)	0.2196 (2)	0.4929 (2)	0.0386 (5)
C15'	0.3769 (3)	0.3181 (2)	0.5208 (2)	0.0367 (5)
H15'	0.4207 (3)	0.3850 (2)	0.4920 (2)	0.044*
C16'	0.2729 (3)	0.3196 (2)	0.5903 (2)	0.0378 (5)
H16'	0.2461 (3)	0.3877 (2)	0.6086 (2)	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0491 (4)	0.0388 (3)	0.0325 (3)	−0.0064 (3)	0.0173 (3)	−0.0012 (2)
C1	0.046 (2)	0.063 (2)	0.067 (2)	0.0242 (13)	0.0248 (14)	0.0098 (14)
C2	0.050 (2)	0.0414 (13)	0.0481 (14)	0.0172 (12)	0.0116 (12)	0.0100 (11)
C3	0.0333 (12)	0.0290 (11)	0.0326 (11)	0.0026 (10)	0.0134 (10)	0.0102 (9)
C4	0.0300 (12)	0.0319 (11)	0.0285 (11)	−0.0030 (10)	0.0117 (10)	0.0040 (9)
C5	0.0238 (12)	0.0482 (13)	0.0326 (12)	0.0033 (11)	0.0092 (10)	0.0060 (10)
C6	0.0293 (13)	0.0458 (13)	0.0431 (13)	0.0098 (11)	0.0158 (11)	0.0057 (11)
C7	0.0406 (14)	0.0421 (13)	0.0326 (12)	0.0059 (11)	0.0180 (11)	−0.0017 (10)
C8	0.0364 (13)	0.0415 (13)	0.0276 (11)	0.0019 (11)	0.0090 (10)	0.0082 (10)
C9	0.050 (2)	0.059 (2)	0.062 (2)	0.0264 (14)	0.0143 (14)	0.0037 (13)
C10	0.063 (2)	0.0394 (15)	0.094 (2)	0.0190 (14)	0.012 (2)	0.0104 (14)
C11	0.0401 (14)	0.0314 (12)	0.0555 (15)	0.0016 (11)	0.0106 (12)	0.0178 (11)
C12	0.0436 (15)	0.0365 (13)	0.0447 (13)	−0.0040 (12)	0.0100 (12)	0.0046 (10)
C13	0.0262 (13)	0.0547 (15)	0.0377 (13)	0.0014 (12)	0.0066 (11)	0.0117 (11)
C14	0.0305 (13)	0.0504 (14)	0.0434 (13)	0.0088 (11)	0.0205 (11)	0.0120 (11)
C15	0.0363 (14)	0.0513 (14)	0.0345 (12)	−0.0018 (12)	0.0198 (11)	0.0084 (11)
C16	0.0366 (14)	0.0471 (14)	0.0404 (13)	−0.0018 (12)	0.0068 (11)	0.0206 (11)
C1'	0.0419 (15)	0.097 (2)	0.0335 (13)	0.0242 (14)	0.0143 (12)	0.0046 (13)
C2'	0.0305 (13)	0.0498 (14)	0.0422 (13)	0.0129 (11)	0.0138 (11)	−0.0020 (11)
C3'	0.0186 (11)	0.0420 (13)	0.0349 (11)	0.0114 (10)	0.0041 (10)	0.0027 (10)
C4'	0.0227 (11)	0.0365 (12)	0.0256 (11)	0.0020 (9)	0.0033 (9)	0.0021 (9)
C5'	0.0285 (12)	0.0355 (12)	0.0242 (10)	0.0060 (10)	0.0053 (9)	0.0006 (9)
C6'	0.0257 (12)	0.0413 (13)	0.0246 (10)	0.0064 (10)	0.0056 (9)	0.0077 (9)
C7'	0.0311 (13)	0.0369 (12)	0.0362 (12)	0.0074 (10)	0.0043 (10)	0.0135 (10)
C8'	0.0282 (12)	0.0380 (13)	0.0435 (13)	0.0163 (10)	0.0023 (11)	0.0065 (10)
C9'	0.0363 (13)	0.0544 (15)	0.0362 (12)	0.0088 (11)	0.0158 (11)	0.0086 (11)
C10'	0.0336 (14)	0.078 (2)	0.0482 (14)	0.0213 (13)	0.0166 (12)	0.0109 (13)
C11'	0.0202 (11)	0.0481 (13)	0.0362 (12)	0.0108 (10)	0.0053 (10)	0.0057 (10)
C12'	0.0278 (12)	0.0433 (13)	0.0395 (13)	0.0003 (11)	0.0020 (11)	0.0061 (10)
C13'	0.0386 (14)	0.0399 (13)	0.0372 (12)	0.0139 (11)	−0.0013 (11)	−0.0071 (10)
C14'	0.0292 (13)	0.0567 (15)	0.0250 (11)	0.0119 (11)	0.0035 (10)	−0.0005 (10)
C15'	0.0307 (12)	0.0415 (13)	0.0293 (11)	0.0055 (11)	0.0000 (10)	0.0087 (10)
C16'	0.0319 (13)	0.0400 (13)	0.0414 (13)	0.0194 (11)	0.0028 (11)	0.0043 (10)

Geometric parameters (Å, º)

S—C4	1.778 (2)	C15—C16	1.376 (3)
S—C4'	1.780 (2)	C1'—C14'	1.509 (3)
C1—C14	1.507 (3)	C1'—C2'	1.577 (3)
C1—C2	1.580 (3)	C2'—C3'	1.512 (3)
C2—C3	1.507 (3)	C3'—C8'	1.389 (3)
C3—C8	1.391 (3)	C3'—C4'	1.402 (3)
C3—C4	1.403 (3)	C4'—C5'	1.389 (3)
C4—C5	1.382 (3)	C5'—C6'	1.391 (3)
C5—C6	1.391 (3)	C6'—C7'	1.384 (3)
C6—C7	1.389 (3)	C6'—C9'	1.509 (3)
C6—C9	1.508 (3)	C7'—C8'	1.382 (3)
C7—C8	1.379 (3)	C9'—C10'	1.572 (3)
C9—C10	1.576 (3)	C10'—C11'	1.513 (3)
C10—C11	1.507 (3)	C11'—C16'	1.384 (3)
C11—C16	1.383 (3)	C11'—C12'	1.385 (3)
C11—C12	1.394 (3)	C12'—C13'	1.383 (3)
C12—C13	1.382 (3)	C13'—C14'	1.393 (3)
C13—C14	1.386 (3)	C14'—C15'	1.389 (3)
C14—C15	1.389 (3)	C15'—C16'	1.383 (3)
C4—S—C4'	101.41 (9)	C14'—C1'—C2'	113.0 (2)
C14—C1—C2	112.9 (2)	C3'—C2'—C1'	113.0 (2)
C3—C2—C1	112.6 (2)	C8'—C3'—C4'	116.4 (2)
C8—C3—C4	116.4 (2)	C8'—C3'—C2'	120.7 (2)
C8—C3—C2	119.1 (2)	C4'—C3'—C2'	121.6 (2)
C4—C3—C2	123.3 (2)	C5'—C4'—C3'	119.8 (2)
C5—C4—C3	120.2 (2)	C5'—C4'—S	121.1 (2)
C5—C4—S	118.3 (2)	C3'—C4'—S	118.4 (2)
C3—C4—S	120.8 (2)	C4'—C5'—C6'	121.3 (2)
C4—C5—C6	121.5 (2)	C7'—C6'—C5'	117.4 (2)
C7—C6—C5	116.6 (2)	C7'—C6'—C9'	121.6 (2)
C7—C6—C9	121.9 (2)	C5'—C6'—C9'	119.5 (2)
C5—C6—C9	120.0 (2)	C8'—C7'—C6'	120.1 (2)
C8—C7—C6	120.8 (2)	C7'—C8'—C3'	121.8 (2)
C7—C8—C3	121.4 (2)	C6'—C9'—C10'	113.5 (2)
C6—C9—C10	112.8 (2)	C11'—C10'—C9'	113.3 (2)
C11—C10—C9	113.7 (2)	C16'—C11'—C12'	117.2 (2)
C16—C11—C12	117.1 (2)	C16'—C11'—C10'	120.9 (2)
C16—C11—C10	120.3 (2)	C12'—C11'—C10'	120.4 (2)
C12—C11—C10	121.2 (2)	C13'—C12'—C11'	120.5 (2)
C13—C12—C11	120.4 (2)	C12'—C13'—C14'	120.9 (2)
C12—C13—C14	121.1 (2)	C15'—C14'—C13'	116.8 (2)
C13—C14—C15	116.5 (2)	C15'—C14'—C1'	120.8 (2)
C13—C14—C1	121.3 (2)	C13'—C14'—C1'	121.2 (2)
C15—C14—C1	120.5 (2)	C16'—C15'—C14'	120.5 (2)
C16—C15—C14	121.3 (2)	C15'—C16'—C11'	121.0 (2)
C15—C16—C11	120.7 (2)
C14—C1—C2—C3	15.6 (3)	C14'—C1'—C2'—C3'	−7.7 (3)
C1—C2—C3—C8	−95.4 (2)	C1'—C2'—C3'—C8'	90.7 (2)
C1—C2—C3—C4	71.1 (3)	C1'—C2'—C3'—C4'	−75.9 (3)
C8—C3—C4—C5	14.7 (3)	C8'—C3'—C4'—C5'	−16.1 (3)
C2—C3—C4—C5	−152.1 (2)	C2'—C3'—C4'—C5'	151.1 (2)
C8—C3—C4—S	−174.76 (14)	C8'—C3'—C4'—S	173.75 (14)
C2—C3—C4—S	18.4 (3)	C2'—C3'—C4'—S	−19.1 (3)
C4'—S—C4—C5	−111.9 (2)	C4—S—C4'—C5'	33.8 (2)
C4'—S—C4—C3	77.5 (2)	C4—S—C4'—C3'	−156.2 (2)
C3—C4—C5—C6	−0.5 (3)	C3'—C4'—C5'—C6'	3.0 (3)
S—C4—C5—C6	−171.2 (2)	S—C4'—C5'—C6'	172.89 (14)
C4—C5—C6—C7	−14.0 (3)	C4'—C5'—C6'—C7'	12.2 (3)
C4—C5—C6—C9	152.3 (2)	C4'—C5'—C6'—C9'	−154.5 (2)
C5—C6—C7—C8	14.1 (3)	C5'—C6'—C7'—C8'	−13.9 (3)
C9—C6—C7—C8	−151.8 (2)	C9'—C6'—C7'—C8'	152.5 (2)
C6—C7—C8—C3	0.2 (3)	C6'—C7'—C8'—C3'	0.4 (3)
C4—C3—C8—C7	−14.7 (3)	C4'—C3'—C8'—C7'	14.6 (3)
C2—C3—C8—C7	152.8 (2)	C2'—C3'—C8'—C7'	−152.7 (2)
C7—C6—C9—C10	75.4 (3)	C7'—C6'—C9'—C10'	−87.2 (2)
C5—C6—C9—C10	−90.1 (3)	C5'—C6'—C9'—C10'	78.9 (2)
C6—C9—C10—C11	9.9 (3)	C6'—C9'—C10'—C11'	2.1 (3)
C9—C10—C11—C16	76.2 (3)	C9'—C10'—C11'—C16'	−87.8 (3)
C9—C10—C11—C12	−89.9 (3)	C9'—C10'—C11'—C12'	78.1 (3)
C16—C11—C12—C13	−13.3 (3)	C16'—C11'—C12'—C13'	13.8 (3)
C10—C11—C12—C13	153.1 (2)	C10'—C11'—C12'—C13'	−152.6 (2)
C11—C12—C13—C14	−0.9 (3)	C11'—C12'—C13'—C14'	0.3 (3)
C12—C13—C14—C15	14.2 (3)	C12'—C13'—C14'—C15'	−14.2 (3)
C12—C13—C14—C1	−151.3 (2)	C12'—C13'—C14'—C1'	153.1 (2)
C2—C1—C14—C13	71.7 (3)	C2'—C1'—C14'—C15'	91.9 (3)
C2—C1—C14—C15	−93.3 (2)	C2'—C1'—C14'—C13'	−74.9 (3)
C13—C14—C15—C16	−13.5 (3)	C13'—C14'—C15'—C16'	14.0 (3)
C1—C14—C15—C16	152.2 (2)	C1'—C14'—C15'—C16'	−153.4 (2)
C14—C15—C16—C11	−0.7 (3)	C14'—C15'—C16'—C11'	0.0 (3)
C12—C11—C16—C15	14.1 (3)	C12'—C11'—C16'—C15'	−14.0 (3)
C10—C11—C16—C15	−152.5 (2)	C10'—C11'—C16'—C15'	152.3 (2)