Forced twin-chair conformation in 7-benzoyl- and 7-phenyl­acetyl-r-2,c-4,t-6,t-8-tetra­phenyl-3-thia-7-aza­bicyclo­[3.3.1]nonanes with 1,3-diaxial phenyl groups in the piperidine ring: single- and double-layered supra­molecular sheets built from C—H...O and C—H...π(arene) hydrogen bonds

The crystal structures of 7-benzoyl-r-2,c-4,t-6,t-8-tetra­phenyl-3-thia-7-aza­bicyclo­[3.3.1]nonane, C₃₈H₃₃NOS, (I), and r-2,c-4,t-6,t-8-tetra­phenyl-7-phenyl­acetyl-3-thia-7-aza­bicyclo­[3.3.1]nonane [systematic name: 2-phenyl-1-(r-2,c-4,t-6,t-8-tetra­phenyl-3-thia-7-aza­bicyclo­[3.3.1]nonan-7-yl)ethanone], C₃₉H₃₅NOS, (II), both reveal a forced twin-chair conformation with the 1,3-diaxial phenyl groups in the piperidine ring, and flattening at the N-atom end of the piperidine ring of the bicyclic system. In the crystal structure of (I), mol­ecules are linked into sheets by a combination of two weak C—H...O and one C—H...π(arene) hydrogen bond, while in the crystal structure of (II), the mol­ecules extend into double-layered sheets assisted by three C—H...π(arene) hydrogen bonds.

S1. Comment

The 3,7-diheterabicyclo[3.3.1]nonane ring system offers wide conformational flexibility owing to its possible twin-chair, chair-boat, boat-chair and twin-boat conformations (Jackman et al., 1982; Arjunan et al., 1981; Pantaleo et al., 1981; Jeyaraman & Avila, 1981). Many derivatives of 3,7-diheterabicyclo[3.3.1]nonanes have been found to be good class III antiarrhythmic agents (Cheema et al., 2007; Garrison et al., 1996; Yu et al., 2006). As part of a programme studying the synthesis and stereochemistry of N-acyl azabicyclic systems, we have synthesized a series of N-acyl derivatives of 2,4,6,8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonanes and studied their stereochemistry (Sakthivel & Jeyaraman, 2010). We report here the molecular and crystal structures of phenyl(r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonan-7-yl)methanone, (I), and 2-phenyl-1-(r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonan-7-yl)ethanone, (II).

The asymmetric units of (I) and (II) each contain one molecule. The overall conformations are similar in both compounds. While the precursor of the title compounds, r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-diazabicyclo[3.3.1]nonan-9-one (TABN), is known to exist in a chair-boat conformation, with the piperidine ring of the bicyclic system in a boat form (Pantaleo et al., 1981), the bicyclic compounds (I) and (II) are forced to adopt twin-chair conformations (Figs. 1 and 2) with the 1,3-diaxial phenyl groups in the piperidine ring, because of the stabilizing character of the N—C═O group, to avoid A^1,3-strain (Johnson, 1968).

In both compounds, the thiapyrane ring is slightly distorted from an ideal chair conformation. Within this ring, the displacements of atoms C9 and S3 from the C1/C5/C4/C2 mean plane are 0.768 (2) and -0.864 (2) Å, respectively, in (I), and 0.757 (3) and -0.834 (2) Å, respectively, in (II). The C2—S3—C4 angle in the thiapyrane ring is 98.37 (7)° in (I) and 98.79 (9)° in (II). The two phenyl substitutents in this ring prefer to occupy equatorial positions.

Unlike the thiapyrane ring, the piperidine ring is considerably distorted from an ideal chair conformation in both compounds. Atoms C9 and N7 deviate from the C1/C5/C6/C8 mean plane by -0.699 (2) and 0.462 (2) Å, respectively, in (I), and -0.711 (3) and 0.391 (3) Å, respectively, in (II). These deviations are also reflected in the ranges of the C—C bond lengths and endocyclic C—C—C bond angles observed for both compounds [1.520 (2)–1.539 (2) Å and 108.21 (1)–113.34 (1)° in (I), and 1.519 (3)–1.547 (3) Å and 109.47 (1)–114.13 (2)° in (II)]. The displacement of atom N7 from the C6/C8/C28 plane is -0.077 (2) Å in (I) and -0.074 (2) Å in (II), and the sum of the angles around N7 is 358.15° in (I) and 359.24° in (II) (Tables 1 and 3), showing that this N atom exhibits planar character.

The acyl group prefers a coplanar orientation with respect to atoms C6 and C8, as is evident from the torsion angles C6—N7—C28—O29 and C8—N7—C28—O29 [-6.5 (2) and -175.93 (1)°, respectively, in (I), and 4.5 (3) and -165.67 (2)°, respectively, in (II)]. The angles between the least-squares planes C6/N7/C8 and N7/C28/O29 are 9.39 (3) and 12.65 (3)° in (I) and (II), respectively, showing that the acyl functionality is coplanar with the C6/N7/C8 plane. The N7—C28 bond is 1.36 (2) Å in (I) and 1.37 (2) Å in (II). The contraction of this N—C bond is due to delocalization between the lone pair of electrons of the ring N atom and the hetero π electrons of the carbonyl group. As a result, the N—C bond exhibits partial double-bond character, which leads to restricted rotation about the bond, as also found in solution NMR studies (Rogers & Woodbrey, 1962).

A comparison of the molecular structures of (I) and (II) with that of the precursor, TABN (Pantaleo et al., 1981), reveals that the piperidine ring in (I) and (II) is flipped from a boat conformation to a chair in order to avoid A^1,3-strain (Johnson, 1968) caused by the interaction of the acyl group with the α,α'-diphenyl substituents. This is evidenced by the increased torsion angles about the C1—C8 and C5—C6 bonds in (I) and (II) compared with TABN (Table 5). The ring flipping causes a decrease in the N7···S3 non-bonding distance, to 3.080 (2) Å in (I) and 3.176 (2) Å in (II), compared with 3.841 Å in TABN. As a result, the lone pair–lone pair repulsion of the sp²-hybridized atoms N7 and S3 is increased. However, severe interaction is avoided by ring flattening at the N-atom end of the piperidine ring. The increased lone pair–lone pair repulsion of atoms N7 and S3 in (I) and (II) compared with TABN can be seen from the torsion angles about the C2—S3 and C4—S3 bonds, listed in Table 5. The N7···S3 non-bonding distances and the torsion angles about the C2—S3 and C4—S3 bonds are in agreement with the reported N3···C7 non-bonding distances and the torsion angles about the C6—C7 and C8—C7 bonds of N-acetyl- and N-nitroso-2,4-diphenyl-3-azabicyclo[3.3.1]nonanes (Kumaran et al., 1999; Priya et al., 1993). Due to ring flipping, the phenyl substitutents in the piperidine rings of (I) and (II) are pushed into diaxial positions, with dihedral angles of 37.64 (8) and 66.58 (8)°, respectively. This is in agreement with the ring flipping observed in N-nitroso-2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one (Gdaniec et al., 1997).

The crystal structure of (I) is stabilized by two weak C—H···O hydrogen-bonding interactions and one C—H···π(arene) hydrogen-bonding interaction (Table 2). The molecules of (I) are linked into sheets, the formation of which can be analysed in terms of two substructural motifs formed by the individual hydrogen bonds. In the first of these motifs, the molecules are interlinked via intermolecular bifurcated C25—H25···O29 and C39—H39···O29 bonds, forming a cyclic R₃²(23) motif (Fig. 3) (Bernstein et al.,1995). Aromatic atoms C25 and C39 in the molecule at (x, y, z) act as hydrogen-bond donors to atom O29 in the molecules at (-x + 1, y - 1/2, -z + 3/2) and (x, y - 1, z), respectively. Translation of this motif by the space group then generates a ribbon along the b axis. Neighbouring ribbons run in an anti-parallel fashion, interconnected by the second motif. In the second motif, atom C1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the centroid of the aryl ring C10–C15 of the molecule at (-x + 2, -y, -z + 2), and likewise, the centroid of the aryl ring C10–C15 at (x, y, z) accepts a hydrogen bond from atom C1 in the molecule at (-x + 2, -y, -z + 2) (Fig. 4). The linking of the cyclic R₃²(23) motifs by C—H···π(arene) hydrogen bonds thus generates a sheet in the bc plane (Fig. 5). There are no interactions between adjacent sheets.

The crystal structure of (II) exhibits three types of C—H···π(arene) hydrogen bonds (Table 4). The molecules of (II) are linked into sheets by two C—H···π(arene) hydrogen bonds, and two such sheets are linked by a third C—H···π(arene) hydrogen bond to form a double-layered sheet. The whole structure can be readily analysed in terms of three substructural motifs. In the first motif, aromatic atom C14 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the centroid of the C22–C27 ring in the molecule at (x, -y + 3/2, z - 1/2). Propagation by translation of this C—H···π(arene) hydrogen bond then generates a chain running along the c axis. In the second motif, parallel chains are interlinked by another C—H···π(arene) hydrogen bond formed by aromatic atom C12 in the molecule at (x, y, z) and the centroid of the C37–C42 ring in the molecule at (x, y + 1, z), thus forming a sheet in the bc plane (Fig. 6). The third substructure constitutes a double-layered sheet (Fig. 7), wherein two sheets are interlinked by the third C—H···π(arene) hydrogen bond, formed by aromatic atom C35 in the molecule at (x, y, z) and the centroid of the C37–C42 ring in the molecule at (-x + 1, -y + 2, -z + 1). The double-layered sheets are arranged in the ac plane and there are no interactions between adjacent double-layered sheets.

Related literature

For related literature, see: Arjunan et al. (1981); Bernstein et al. (1995); Cheema et al. (2007); Garrison et al. (1996); Gdaniec et al. (1997); Jackman et al. (1982); Jeyaraman & Avila (1981); Johnson (1968); Kumaran et al. (1999); Pantaleo et al. (1981); Priya et al. (1993); Rogers & Woodbrey (1962); Sakthivel & Jeyaraman (2010); Sheldrick (2008); Yu et al. (2006).

S2. Experimental

Compounds, (I) and (II) were synthesized from 2,4,6,8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonane by benzoylation and phenylacetylation, respectively, in the presence of triethylamine in a dry benzene medium (Sakthivel & Jeyaraman, 2010). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in a benzene–hexane (1:1 v/v) mixture.

S3. Refinement

All H atoms were fixed geometrically and allowed to ride on their parent C atoms, with aromatic C—H = 0.93 Å, tertiary C—H = 0.98 Å and secondary C—H = 0.97 Å, and with U_iso(H) = 1.2U_eq(C). The (100) reflection for (I) was omitted from the refinement as it was completely obscured by the beamstop. The elongated anisotropic displacement ellipsoid of atom S3 in (II) was restrained using SIMU (SHELXL97; Sheldrick, 2008). Both data sets were truncated at ca θ = 26°, as only statistically insignificant data were present above these limits.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. A view of the molecule of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 3. Part of the crystal structure of (I), showing the formation of an R3^2(23) motif that forms the ribbon along the b axis. For the sake of clarity, H atoms not involved in the motif shown have been omitted. [Symmetry codes: (i) -x + 1, y - 1/2, -z + 3/2; (ii) x, y - 1, z.]
	Fig. 4. Part of the crystal structure of (I), showing the C—H···π interaction, which links the ribbons shown in Fig. 2 in the bc plane. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Cg1 is the centroid of the C10–C15 ring. [Please check added text] [Symmetry code: (iii) -x + 2, -y, -z + 2.]
	Fig. 5. Part of the crystal structure of (I), showing the formation of the hydrogen-bonded sheet in the bc plane. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 6. Part of the crystal structure of (II), showing the formation of the sheet in the bc plane. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Cg1 and Cg2 are the centroids of the C22–C27 and C37–C42 rings, respectively. [Please check added text] [Symmetry codes: (i) x, y + 1, z; (ii) x, -y + 3/2, z - 1/2.]
	Fig. 7. Part of the crystal structure of (II), showing the formation of the double-layered sheet in the ac plane. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

(I) phenyl(r-2,c-4,t-6,t-8-tetraphenyl- 3-thia-7-azabicyclo[3.3.1]nonan-7-yl)methanone

Crystal data

C38H33NOS	F(000) = 1168
Mr = 551.72	Dx = 1.283 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7350 reflections
a = 16.139 (5) Å	θ = 1.3–28.7°
b = 10.145 (5) Å	µ = 0.15 mm^−1
c = 17.453 (5) Å	T = 293 K
β = 92.046 (5)°	Prism, colourless
V = 2855.8 (19) Å^3	0.30 × 0.22 × 0.18 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	5605 independent reflections
Radiation source: Fine-focus sealed tube	4267 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω and ϕ scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan [SADABS (Bruker, 2004; Blessing, 1995)]	h = −19→19
Tmin = 0.957, Tmax = 0.974	k = −12→11
27638 measured reflections	l = −21→21

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.6605P] where P = (Fo^2 + 2Fc^2)/3
5605 reflections	(Δ/σ)max = 0.001
370 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those 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
S3	0.82644 (2)	0.33712 (4)	0.98103 (3)	0.0448 (1)
O29	0.70878 (8)	0.34354 (13)	0.78847 (8)	0.0596 (5)
N7	0.74152 (7)	0.16124 (12)	0.85768 (7)	0.0339 (4)
C1	0.82690 (9)	0.06116 (15)	0.96358 (8)	0.0363 (5)
C2	0.88048 (9)	0.17861 (16)	0.99035 (9)	0.0394 (5)
C4	0.73137 (10)	0.29193 (17)	1.02738 (10)	0.0453 (5)
C5	0.69169 (10)	0.16727 (16)	0.99169 (9)	0.0408 (5)
C6	0.66884 (9)	0.18204 (16)	0.90608 (9)	0.0391 (5)
C8	0.80249 (9)	0.05810 (14)	0.87769 (8)	0.0331 (4)
C9	0.74878 (10)	0.05018 (17)	1.00927 (9)	0.0423 (5)
C10	0.96512 (9)	0.19279 (16)	0.95551 (8)	0.0385 (5)
C11	0.99993 (10)	0.09658 (17)	0.91042 (9)	0.0445 (5)
C12	1.07730 (10)	0.11366 (19)	0.88021 (10)	0.0514 (6)
C13	1.12242 (11)	0.2256 (2)	0.89621 (11)	0.0559 (6)
C14	1.09029 (11)	0.32036 (19)	0.94271 (11)	0.0540 (6)
C15	1.01265 (10)	0.30458 (17)	0.97154 (10)	0.0463 (5)
C16	0.67511 (10)	0.41074 (18)	1.03071 (10)	0.0477 (6)
C17	0.66804 (12)	0.5029 (2)	0.97288 (12)	0.0601 (7)
C18	0.61737 (13)	0.6117 (2)	0.97894 (15)	0.0751 (8)
C19	0.57213 (14)	0.6290 (3)	1.04317 (16)	0.0796 (9)
C20	0.57740 (13)	0.5376 (3)	1.10071 (14)	0.0754 (9)
C21	0.62839 (11)	0.4298 (2)	1.09509 (11)	0.0591 (7)
C22	0.59391 (9)	0.10197 (18)	0.87771 (10)	0.0441 (5)
C23	0.56730 (11)	−0.0126 (2)	0.91184 (12)	0.0583 (7)
C24	0.49901 (12)	−0.0802 (2)	0.88170 (14)	0.0724 (8)
C25	0.45601 (12)	−0.0342 (3)	0.81897 (15)	0.0775 (9)
C26	0.48129 (12)	0.0798 (3)	0.78469 (13)	0.0761 (9)
C27	0.54948 (11)	0.1477 (2)	0.81390 (11)	0.0580 (7)
C28	0.75666 (9)	0.25237 (16)	0.80319 (9)	0.0402 (5)
C30	0.83591 (9)	0.24288 (16)	0.76142 (9)	0.0389 (5)
C31	0.85066 (11)	0.14558 (18)	0.70793 (9)	0.0491 (6)
C32	0.92464 (12)	0.1418 (2)	0.67186 (10)	0.0581 (7)
C33	0.98443 (12)	0.2338 (2)	0.68825 (11)	0.0636 (7)
C34	0.97058 (12)	0.3314 (2)	0.74012 (12)	0.0620 (7)
C35	0.89625 (11)	0.33674 (18)	0.77646 (11)	0.0528 (6)
C36	0.77523 (9)	−0.07787 (15)	0.84855 (8)	0.0357 (4)
C37	0.72046 (10)	−0.09110 (17)	0.78593 (9)	0.0436 (5)
C38	0.70216 (11)	−0.21268 (19)	0.75478 (11)	0.0555 (6)
C39	0.73747 (11)	−0.32502 (18)	0.78514 (12)	0.0587 (7)
C40	0.79081 (12)	−0.31406 (17)	0.84747 (12)	0.0568 (7)
C41	0.80947 (10)	−0.19264 (16)	0.87882 (10)	0.0466 (6)
H1	0.85950	−0.01860	0.97440	0.0440*
H2	0.89130	0.16560	1.04540	0.0470*
H4	0.74720	0.26960	1.08050	0.0540*
H5	0.64000	0.15130	1.01800	0.0490*
H6	0.65310	0.27460	0.89890	0.0470*
H8	0.85270	0.08030	0.85050	0.0400*
H9A	0.76350	0.04830	1.06360	0.0510*
H9B	0.72010	−0.03130	0.99620	0.0510*
H11	0.97080	0.01910	0.90030	0.0530*
H12	1.09890	0.04890	0.84890	0.0620*
H13	1.17430	0.23710	0.87570	0.0670*
H14	1.12110	0.39550	0.95480	0.0650*
H15	0.99140	0.37020	1.00250	0.0560*
H17	0.69800	0.49150	0.92880	0.0720*
H18	0.61390	0.67330	0.93950	0.0900*
H19	0.53810	0.70240	1.04760	0.0960*
H20	0.54620	0.54840	1.14400	0.0900*
H21	0.63170	0.36890	1.13490	0.0710*
H23	0.59540	−0.04460	0.95540	0.0700*
H24	0.48240	−0.15810	0.90470	0.0870*
H25	0.40990	−0.07960	0.79940	0.0930*
H26	0.45230	0.11160	0.74150	0.0910*
H27	0.56580	0.22520	0.79040	0.0700*
H31	0.81020	0.08260	0.69650	0.0590*
H32	0.93420	0.07630	0.63600	0.0700*
H33	1.03480	0.22990	0.66400	0.0760*
H34	1.01130	0.39420	0.75090	0.0740*
H35	0.88670	0.40390	0.81130	0.0630*
H37	0.69560	−0.01630	0.76460	0.0520*
H38	0.66540	−0.21880	0.71260	0.0670*
H39	0.72530	−0.40700	0.76370	0.0700*
H40	0.81480	−0.38950	0.86890	0.0680*
H41	0.84590	−0.18760	0.92130	0.0560*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S3	0.0406 (2)	0.0369 (2)	0.0567 (3)	−0.0011 (2)	−0.0019 (2)	−0.0060 (2)
O29	0.0545 (7)	0.0500 (8)	0.0743 (9)	0.0168 (6)	0.0012 (6)	0.0231 (7)
N7	0.0327 (6)	0.0295 (7)	0.0392 (7)	0.0019 (5)	−0.0028 (5)	0.0024 (5)
C1	0.0384 (8)	0.0317 (8)	0.0383 (8)	0.0013 (6)	−0.0042 (6)	0.0037 (6)
C2	0.0387 (8)	0.0400 (9)	0.0389 (8)	−0.0002 (7)	−0.0068 (6)	0.0009 (7)
C4	0.0456 (9)	0.0477 (10)	0.0424 (9)	0.0000 (8)	0.0002 (7)	−0.0065 (8)
C5	0.0377 (8)	0.0424 (10)	0.0426 (8)	−0.0028 (7)	0.0041 (7)	−0.0023 (7)
C6	0.0337 (8)	0.0369 (9)	0.0467 (9)	0.0036 (7)	0.0001 (6)	−0.0021 (7)
C8	0.0309 (7)	0.0304 (8)	0.0377 (8)	0.0019 (6)	−0.0019 (6)	0.0039 (6)
C9	0.0452 (9)	0.0431 (10)	0.0384 (8)	−0.0049 (7)	−0.0002 (7)	0.0020 (7)
C10	0.0372 (8)	0.0401 (9)	0.0376 (8)	0.0015 (7)	−0.0080 (6)	0.0031 (7)
C11	0.0394 (9)	0.0421 (10)	0.0512 (9)	0.0030 (7)	−0.0092 (7)	0.0013 (8)
C12	0.0438 (9)	0.0567 (12)	0.0535 (10)	0.0086 (8)	−0.0019 (8)	−0.0015 (9)
C13	0.0432 (9)	0.0674 (13)	0.0572 (11)	−0.0034 (9)	0.0039 (8)	0.0099 (10)
C14	0.0510 (10)	0.0513 (12)	0.0592 (11)	−0.0117 (9)	−0.0045 (8)	0.0045 (9)
C15	0.0453 (9)	0.0440 (10)	0.0491 (9)	−0.0026 (8)	−0.0042 (7)	−0.0036 (8)
C16	0.0433 (9)	0.0473 (11)	0.0524 (10)	−0.0008 (8)	0.0015 (7)	−0.0126 (9)
C17	0.0586 (11)	0.0558 (12)	0.0668 (12)	0.0106 (9)	0.0135 (9)	−0.0065 (10)
C18	0.0735 (14)	0.0583 (14)	0.0940 (16)	0.0194 (11)	0.0095 (12)	−0.0021 (12)
C19	0.0653 (13)	0.0702 (16)	0.1039 (19)	0.0197 (12)	0.0113 (13)	−0.0245 (14)
C20	0.0626 (13)	0.0830 (17)	0.0818 (15)	0.0048 (12)	0.0193 (11)	−0.0309 (14)
C21	0.0565 (11)	0.0629 (13)	0.0583 (11)	−0.0016 (10)	0.0085 (9)	−0.0157 (10)
C22	0.0310 (8)	0.0492 (10)	0.0521 (9)	0.0045 (7)	0.0022 (7)	−0.0120 (8)
C23	0.0419 (10)	0.0619 (13)	0.0709 (12)	−0.0095 (9)	0.0009 (8)	−0.0029 (10)
C24	0.0449 (11)	0.0728 (15)	0.1000 (17)	−0.0167 (10)	0.0082 (11)	−0.0191 (13)
C25	0.0372 (10)	0.0935 (19)	0.1014 (18)	−0.0088 (11)	−0.0020 (11)	−0.0434 (15)
C26	0.0453 (11)	0.105 (2)	0.0764 (14)	0.0106 (12)	−0.0192 (10)	−0.0245 (14)
C27	0.0436 (10)	0.0682 (13)	0.0616 (11)	0.0065 (9)	−0.0074 (8)	−0.0076 (10)
C28	0.0407 (8)	0.0348 (9)	0.0444 (9)	0.0024 (7)	−0.0069 (7)	0.0032 (7)
C30	0.0431 (8)	0.0360 (9)	0.0372 (8)	0.0015 (7)	−0.0043 (6)	0.0102 (7)
C31	0.0582 (11)	0.0489 (11)	0.0398 (9)	−0.0069 (8)	−0.0038 (8)	0.0043 (8)
C32	0.0714 (13)	0.0615 (13)	0.0419 (9)	0.0071 (10)	0.0100 (9)	0.0034 (9)
C33	0.0544 (11)	0.0815 (16)	0.0555 (11)	0.0038 (11)	0.0120 (9)	0.0167 (11)
C34	0.0542 (11)	0.0673 (14)	0.0642 (12)	−0.0180 (10)	−0.0008 (9)	0.0123 (11)
C35	0.0601 (11)	0.0437 (10)	0.0545 (10)	−0.0063 (9)	0.0009 (8)	0.0030 (8)
C36	0.0326 (7)	0.0324 (8)	0.0423 (8)	−0.0001 (6)	0.0045 (6)	0.0013 (7)
C37	0.0451 (9)	0.0354 (9)	0.0499 (9)	−0.0006 (7)	−0.0056 (7)	0.0003 (8)
C38	0.0552 (11)	0.0470 (11)	0.0636 (11)	−0.0077 (9)	−0.0069 (9)	−0.0110 (9)
C39	0.0579 (11)	0.0369 (11)	0.0817 (14)	−0.0071 (8)	0.0063 (10)	−0.0142 (10)
C40	0.0569 (11)	0.0316 (10)	0.0820 (13)	0.0050 (8)	0.0025 (10)	0.0025 (9)
C41	0.0435 (9)	0.0374 (10)	0.0584 (10)	0.0038 (7)	−0.0033 (8)	0.0031 (8)

Geometric parameters (Å, º)

S3—C2	1.8338 (19)	C34—C35	1.378 (3)
S3—C4	1.8186 (19)	C36—C37	1.387 (2)
O29—C28	1.227 (2)	C36—C41	1.385 (2)
N7—C6	1.485 (2)	C37—C38	1.376 (3)
N7—C8	1.470 (2)	C38—C39	1.372 (3)
N7—C28	1.355 (2)	C39—C40	1.368 (3)
C1—C2	1.535 (2)	C40—C41	1.377 (3)
C1—C8	1.537 (2)	C1—H1	0.9800
C1—C9	1.520 (2)	C2—H2	0.9800
C2—C10	1.522 (2)	C4—H4	0.9800
C4—C5	1.539 (2)	C5—H5	0.9800
C4—C16	1.511 (3)	C6—H6	0.9800
C5—C6	1.534 (2)	C8—H8	0.9800
C5—C9	1.528 (2)	C9—H9A	0.9700
C6—C22	1.525 (2)	C9—H9B	0.9700
C8—C36	1.529 (2)	C11—H11	0.9300
C10—C11	1.385 (2)	C12—H12	0.9300
C10—C15	1.392 (2)	C13—H13	0.9300
C11—C12	1.384 (2)	C14—H14	0.9300
C12—C13	1.372 (3)	C15—H15	0.9300
C13—C14	1.372 (3)	C17—H17	0.9300
C14—C15	1.376 (3)	C18—H18	0.9300
C16—C17	1.378 (3)	C19—H19	0.9300
C16—C21	1.389 (3)	C20—H20	0.9300
C17—C18	1.380 (3)	C21—H21	0.9300
C18—C19	1.371 (4)	C23—H23	0.9300
C19—C20	1.367 (4)	C24—H24	0.9300
C20—C21	1.374 (3)	C25—H25	0.9300
C22—C23	1.382 (3)	C26—H26	0.9300
C22—C27	1.383 (3)	C27—H27	0.9300
C23—C24	1.386 (3)	C31—H31	0.9300
C24—C25	1.358 (3)	C32—H32	0.9300
C25—C26	1.371 (4)	C33—H33	0.9300
C26—C27	1.380 (3)	C34—H34	0.9300
C28—C30	1.498 (2)	C35—H35	0.9300
C30—C31	1.385 (2)	C37—H37	0.9300
C30—C35	1.381 (2)	C38—H38	0.9300
C31—C32	1.370 (3)	C39—H39	0.9300
C32—C33	1.365 (3)	C40—H40	0.9300
C33—C34	1.365 (3)	C41—H41	0.9300
C2—C1—C9	111.47 (12)	C1—C2—H2	106.00
C8—C1—C9	108.77 (12)	C10—C2—H2	106.00
S3—C2—C1	113.12 (10)	S3—C4—H4	106.00
S3—C4—C5	111.87 (12)	C5—C4—H4	106.00
C4—C5—C9	108.56 (13)	C16—C4—H4	107.00
C6—C5—C9	113.20 (13)	C4—C5—H5	107.00
N7—C6—C5	111.90 (12)	C6—C5—H5	107.00
N7—C8—C1	111.32 (12)	C9—C5—H5	107.00
C1—C9—C5	110.08 (13)	N7—C6—H6	106.00
O29—C28—N7	122.25 (14)	C5—C6—H6	106.00
O29—C28—C30	119.28 (15)	C22—C6—H6	106.00
C2—S3—C4	98.37 (7)	N7—C8—H8	106.00
C6—N7—C8	120.12 (12)	C1—C8—H8	106.00
C6—N7—C28	117.93 (12)	C36—C8—H8	106.00
C8—N7—C28	121.10 (12)	C1—C9—H9A	110.00
C2—C1—C8	115.76 (12)	C1—C9—H9B	110.00
S3—C2—C10	108.21 (11)	C5—C9—H9A	110.00
C1—C2—C10	117.11 (13)	C5—C9—H9B	110.00
S3—C4—C16	109.49 (12)	H9A—C9—H9B	108.00
C5—C4—C16	115.40 (14)	C10—C11—H11	119.00
C4—C5—C6	113.34 (13)	C12—C11—H11	119.00
N7—C6—C22	111.90 (13)	C11—C12—H12	120.00
C5—C6—C22	115.13 (13)	C13—C12—H12	120.00
N7—C8—C36	112.39 (12)	C12—C13—H13	120.00
C1—C8—C36	113.79 (12)	C14—C13—H13	120.00
C2—C10—C11	123.26 (14)	C13—C14—H14	120.00
C2—C10—C15	119.53 (14)	C15—C14—H14	120.00
C11—C10—C15	117.16 (14)	C10—C15—H15	119.00
C10—C11—C12	121.20 (16)	C14—C15—H15	119.00
C11—C12—C13	120.37 (17)	C16—C17—H17	119.00
C12—C13—C14	119.42 (17)	C18—C17—H17	119.00
C13—C14—C15	120.21 (17)	C17—C18—H18	120.00
C10—C15—C14	121.58 (16)	C19—C18—H18	120.00
C4—C16—C17	123.18 (16)	C18—C19—H19	120.00
C4—C16—C21	119.10 (16)	C20—C19—H19	120.00
C17—C16—C21	117.72 (17)	C19—C20—H20	120.00
C16—C17—C18	121.4 (2)	C21—C20—H20	120.00
C17—C18—C19	120.0 (2)	C16—C21—H21	120.00
C18—C19—C20	119.5 (2)	C20—C21—H21	120.00
C19—C20—C21	120.6 (2)	C22—C23—H23	120.00
C16—C21—C20	120.82 (19)	C24—C23—H23	120.00
C6—C22—C23	124.29 (15)	C23—C24—H24	120.00
C6—C22—C27	117.72 (16)	C25—C24—H24	120.00
C23—C22—C27	117.98 (16)	C24—C25—H25	120.00
C22—C23—C24	120.53 (19)	C26—C25—H25	120.00
C23—C24—C25	120.8 (2)	C25—C26—H26	120.00
C24—C25—C26	119.4 (2)	C27—C26—H26	120.00
C25—C26—C27	120.4 (2)	C22—C27—H27	119.00
C22—C27—C26	120.90 (19)	C26—C27—H27	120.00
N7—C28—C30	118.45 (13)	C30—C31—H31	120.00
C28—C30—C31	122.97 (14)	C32—C31—H31	120.00
C28—C30—C35	118.16 (15)	C31—C32—H32	120.00
C31—C30—C35	118.86 (15)	C33—C32—H32	120.00
C30—C31—C32	120.21 (16)	C32—C33—H33	120.00
C31—C32—C33	120.37 (18)	C34—C33—H33	120.00
C32—C33—C34	120.23 (18)	C33—C34—H34	120.00
C33—C34—C35	119.97 (18)	C35—C34—H34	120.00
C30—C35—C34	120.34 (17)	C30—C35—H35	120.00
C8—C36—C37	121.12 (14)	C34—C35—H35	120.00
C8—C36—C41	121.68 (13)	C36—C37—H37	119.00
C37—C36—C41	116.96 (15)	C38—C37—H37	119.00
C36—C37—C38	121.32 (16)	C37—C38—H38	120.00
C37—C38—C39	120.78 (17)	C39—C38—H38	120.00
C38—C39—C40	118.73 (17)	C38—C39—H39	121.00
C39—C40—C41	120.76 (17)	C40—C39—H39	121.00
C36—C41—C40	121.45 (16)	C39—C40—H40	120.00
C2—C1—H1	107.00	C41—C40—H40	120.00
C8—C1—H1	107.00	C36—C41—H41	119.00
C9—C1—H1	107.00	C40—C41—H41	119.00
S3—C2—H2	106.00
C4—S3—C2—C1	49.37 (12)	N7—C8—C36—C37	25.00 (19)
C4—S3—C2—C10	−179.17 (11)	N7—C8—C36—C41	−160.87 (14)
C2—S3—C4—C5	−53.26 (13)	C1—C8—C36—C37	152.67 (14)
C2—S3—C4—C16	177.51 (12)	C1—C8—C36—C41	−33.19 (19)
C8—N7—C6—C5	38.98 (18)	C2—C10—C11—C12	−179.73 (15)
C8—N7—C6—C22	−91.94 (16)	C15—C10—C11—C12	−2.5 (2)
C28—N7—C6—C5	−130.54 (14)	C2—C10—C15—C14	178.55 (16)
C28—N7—C6—C22	98.54 (16)	C11—C10—C15—C14	1.2 (2)
C6—N7—C8—C1	−45.97 (17)	C10—C11—C12—C13	1.8 (3)
C6—N7—C8—C36	83.00 (15)	C11—C12—C13—C14	0.3 (3)
C28—N7—C8—C1	123.21 (14)	C12—C13—C14—C15	−1.5 (3)
C28—N7—C8—C36	−107.82 (15)	C13—C14—C15—C10	0.8 (3)
C6—N7—C28—O29	−6.5 (2)	C4—C16—C17—C18	−178.47 (18)
C6—N7—C28—C30	171.66 (13)	C21—C16—C17—C18	1.0 (3)
C8—N7—C28—O29	−175.93 (14)	C4—C16—C21—C20	179.09 (18)
C8—N7—C28—C30	2.3 (2)	C17—C16—C21—C20	−0.4 (3)
C8—C1—C2—S3	65.46 (15)	C16—C17—C18—C19	−0.7 (3)
C8—C1—C2—C10	−61.43 (18)	C17—C18—C19—C20	−0.3 (4)
C9—C1—C2—S3	−59.55 (15)	C18—C19—C20—C21	0.9 (4)
C9—C1—C2—C10	173.56 (13)	C19—C20—C21—C16	−0.5 (3)
C2—C1—C8—N7	−71.00 (16)	C6—C22—C23—C24	−179.22 (17)
C2—C1—C8—C36	160.77 (12)	C27—C22—C23—C24	1.2 (3)
C9—C1—C8—N7	55.39 (16)	C6—C22—C27—C26	179.54 (18)
C9—C1—C8—C36	−72.84 (16)	C23—C22—C27—C26	−0.9 (3)
C2—C1—C9—C5	67.19 (16)	C22—C23—C24—C25	−1.2 (3)
C8—C1—C9—C5	−61.64 (16)	C23—C24—C25—C26	0.8 (4)
S3—C2—C10—C11	−138.76 (14)	C24—C25—C26—C27	−0.4 (4)
S3—C2—C10—C15	44.09 (17)	C25—C26—C27—C22	0.5 (3)
C1—C2—C10—C11	−9.5 (2)	O29—C28—C30—C31	−110.16 (19)
C1—C2—C10—C15	173.34 (14)	O29—C28—C30—C35	68.9 (2)
S3—C4—C5—C6	−59.83 (16)	N7—C28—C30—C31	71.6 (2)
S3—C4—C5—C9	66.87 (15)	N7—C28—C30—C35	−109.29 (18)
C16—C4—C5—C6	66.23 (18)	C28—C30—C31—C32	−179.70 (16)
C16—C4—C5—C9	−167.08 (14)	C35—C30—C31—C32	1.2 (3)
S3—C4—C16—C17	37.0 (2)	C28—C30—C35—C34	179.28 (17)
S3—C4—C16—C21	−142.51 (15)	C31—C30—C35—C34	−1.6 (3)
C5—C4—C16—C17	−90.3 (2)	C30—C31—C32—C33	0.0 (3)
C5—C4—C16—C21	90.2 (2)	C31—C32—C33—C34	−0.8 (3)
C4—C5—C6—N7	81.46 (16)	C32—C33—C34—C35	0.4 (3)
C4—C5—C6—C22	−149.29 (14)	C33—C34—C35—C30	0.8 (3)
C9—C5—C6—N7	−42.75 (18)	C8—C36—C37—C38	173.43 (15)
C9—C5—C6—C22	86.51 (17)	C41—C36—C37—C38	−1.0 (2)
C4—C5—C9—C1	−70.44 (16)	C8—C36—C41—C40	−173.51 (15)
C6—C5—C9—C1	56.34 (17)	C37—C36—C41—C40	0.9 (2)
N7—C6—C22—C23	103.55 (19)	C36—C37—C38—C39	0.3 (3)
N7—C6—C22—C27	−76.87 (19)	C37—C38—C39—C40	0.5 (3)
C5—C6—C22—C23	−25.7 (2)	C38—C39—C40—C41	−0.6 (3)
C5—C6—C22—C27	153.88 (16)	C39—C40—C41—C36	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25···O29^i	0.93	2.53	3.431 (3)	162
C39—H39···O29^ii	0.93	2.58	3.395 (3)	146
C1—H1···Cg1^iii	0.98	2.99	3.903 (3)	155

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) −x+2, −y, −z+2.

(II) 2-phenyl-1-(r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonan-7-yl)ethanone

Crystal data

C39H35NOS	F(000) = 1200
Mr = 565.75	Dx = 1.222 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8894 reflections
a = 16.8724 (7) Å	θ = 2.4–25.2°
b = 9.4863 (3) Å	µ = 0.14 mm^−1
c = 19.2376 (8) Å	T = 293 K
β = 93.245 (1)°	Prism, colourless
V = 3074.2 (2) Å^3	0.24 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	6045 independent reflections
Radiation source: fine-focus sealed tube	4500 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and ϕ scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan [SADABS (Bruker, 2004; Blessing, 1995)]	h = −20→20
Tmin = 0.968, Tmax = 0.976	k = −11→11
29474 measured reflections	l = −23→23

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 1.2416P] where P = (Fo^2 + 2Fc^2)/3
6045 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those 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
S3	0.89583 (3)	0.97493 (6)	0.58434 (3)	0.0545 (2)
O29	0.69118 (9)	0.89333 (17)	0.66310 (7)	0.0624 (5)
N7	0.74493 (9)	0.77418 (16)	0.57538 (7)	0.0406 (4)
C1	0.84872 (11)	0.7641 (2)	0.48802 (9)	0.0456 (6)
C2	0.89182 (12)	0.9070 (2)	0.49573 (10)	0.0486 (6)
C4	0.93113 (12)	0.8170 (2)	0.62982 (10)	0.0484 (6)
C5	0.88196 (11)	0.6841 (2)	0.60947 (10)	0.0461 (6)
C6	0.79485 (11)	0.6926 (2)	0.62746 (9)	0.0441 (6)
C8	0.75942 (11)	0.77090 (19)	0.50032 (9)	0.0418 (6)
C9	0.88949 (12)	0.6505 (2)	0.53268 (10)	0.0501 (6)
C10	0.85747 (12)	1.0171 (2)	0.44534 (10)	0.0496 (6)
C11	0.81835 (15)	1.1365 (2)	0.46602 (12)	0.0670 (8)
C12	0.78521 (17)	1.2308 (3)	0.41785 (13)	0.0791 (10)
C13	0.78934 (16)	1.2065 (3)	0.34857 (13)	0.0749 (9)
C14	0.82864 (16)	1.0897 (3)	0.32687 (12)	0.0722 (9)
C15	0.86323 (14)	0.9959 (3)	0.37470 (11)	0.0616 (8)
C16	0.93808 (11)	0.8452 (2)	0.70715 (10)	0.0466 (6)
C17	0.99827 (13)	0.7783 (3)	0.74648 (12)	0.0626 (8)
C18	1.00846 (16)	0.7999 (3)	0.81707 (13)	0.0752 (9)
C19	0.96014 (15)	0.8903 (3)	0.84986 (11)	0.0679 (9)
C20	0.89922 (15)	0.9556 (3)	0.81242 (12)	0.0655 (8)
C21	0.88784 (13)	0.9327 (2)	0.74139 (11)	0.0569 (7)
C22	0.75756 (12)	0.5501 (2)	0.64317 (9)	0.0495 (6)
C23	0.68564 (14)	0.5494 (3)	0.67535 (12)	0.0659 (8)
C24	0.64934 (17)	0.4228 (3)	0.69187 (13)	0.0801 (10)
C25	0.68465 (19)	0.2964 (3)	0.67800 (13)	0.0812 (10)
C26	0.75507 (18)	0.2954 (3)	0.64661 (12)	0.0736 (9)
C27	0.79070 (15)	0.4207 (2)	0.62895 (11)	0.0608 (8)
C28	0.69321 (11)	0.8694 (2)	0.60090 (9)	0.0459 (6)
C30	0.63500 (12)	0.9420 (2)	0.54938 (10)	0.0525 (7)
C31	0.55902 (11)	0.9811 (2)	0.58182 (10)	0.0470 (6)
C32	0.50801 (15)	0.8789 (2)	0.60316 (14)	0.0722 (9)
C33	0.43786 (16)	0.9134 (3)	0.63196 (16)	0.0860 (10)
C34	0.41812 (16)	1.0507 (3)	0.64054 (14)	0.0793 (10)
C35	0.46691 (15)	1.1533 (3)	0.61936 (13)	0.0719 (9)
C36	0.53730 (13)	1.1190 (2)	0.58962 (11)	0.0570 (7)
C37	0.71118 (11)	0.6604 (2)	0.45813 (9)	0.0448 (6)
C38	0.71698 (12)	0.6558 (2)	0.38627 (10)	0.0529 (7)
C39	0.67066 (14)	0.5661 (3)	0.34477 (11)	0.0633 (8)
C40	0.61678 (16)	0.4796 (2)	0.37417 (13)	0.0694 (9)
C41	0.61004 (15)	0.4825 (2)	0.44497 (13)	0.0688 (9)
C42	0.65671 (13)	0.5725 (2)	0.48663 (11)	0.0561 (7)
H1	0.85290	0.73480	0.43950	0.0550*
H2	0.94680	0.89100	0.48380	0.0580*
H4	0.98510	0.79970	0.61550	0.0580*
H5	0.90580	0.60520	0.63610	0.0550*
H6	0.79450	0.74660	0.67090	0.0530*
H8	0.74130	0.86240	0.48190	0.0500*
H9A	0.94510	0.64530	0.52270	0.0600*
H9B	0.86530	0.55970	0.52180	0.0600*
H11	0.81420	1.15380	0.51330	0.0800*
H12	0.75990	1.31130	0.43300	0.0950*
H13	0.76570	1.26860	0.31620	0.0900*
H14	0.83220	1.07310	0.27950	0.0870*
H15	0.89060	0.91800	0.35920	0.0740*
H17	1.03240	0.71760	0.72470	0.0750*
H18	1.04860	0.75250	0.84260	0.0900*
H19	0.96850	0.90760	0.89730	0.0810*
H20	0.86530	1.01550	0.83480	0.0790*
H21	0.84590	0.97690	0.71660	0.0680*
H23	0.66160	0.63430	0.68590	0.0790*
H24	0.60080	0.42400	0.71250	0.0960*
H25	0.66070	0.21210	0.68990	0.0970*
H26	0.77930	0.21010	0.63700	0.0880*
H27	0.83830	0.41780	0.60690	0.0730*
H30A	0.65940	1.02640	0.53190	0.0630*
H30B	0.62310	0.87960	0.51020	0.0630*
H32	0.52120	0.78440	0.59800	0.0870*
H33	0.40390	0.84270	0.64560	0.1030*
H34	0.37120	1.07410	0.66090	0.0950*
H35	0.45310	1.24740	0.62480	0.0860*
H36	0.57010	1.19040	0.57480	0.0680*
H38	0.75300	0.71470	0.36570	0.0630*
H39	0.67600	0.56430	0.29690	0.0760*
H40	0.58500	0.41950	0.34640	0.0830*
H41	0.57380	0.42350	0.46510	0.0830*
H42	0.65120	0.57360	0.53450	0.0670*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S3	0.0709 (4)	0.0499 (3)	0.0425 (3)	−0.0017 (2)	0.0026 (2)	0.0014 (2)
O29	0.0637 (9)	0.0831 (11)	0.0404 (8)	0.0234 (8)	0.0039 (6)	−0.0136 (7)
N7	0.0429 (8)	0.0446 (8)	0.0347 (7)	0.0054 (7)	0.0062 (6)	−0.0026 (6)
C1	0.0499 (11)	0.0507 (11)	0.0369 (9)	0.0067 (9)	0.0099 (8)	−0.0040 (8)
C2	0.0481 (11)	0.0570 (12)	0.0415 (10)	0.0034 (9)	0.0103 (8)	0.0013 (9)
C4	0.0438 (10)	0.0551 (11)	0.0466 (11)	0.0063 (9)	0.0045 (8)	0.0007 (9)
C5	0.0481 (11)	0.0454 (10)	0.0451 (10)	0.0097 (8)	0.0046 (8)	0.0017 (8)
C6	0.0477 (10)	0.0488 (10)	0.0360 (9)	0.0054 (8)	0.0039 (8)	0.0002 (8)
C8	0.0486 (10)	0.0430 (10)	0.0345 (9)	0.0076 (8)	0.0077 (8)	−0.0003 (7)
C9	0.0508 (11)	0.0532 (11)	0.0470 (11)	0.0112 (9)	0.0094 (9)	−0.0041 (9)
C10	0.0498 (11)	0.0564 (12)	0.0433 (10)	−0.0059 (9)	0.0095 (8)	0.0061 (9)
C11	0.0876 (17)	0.0639 (14)	0.0502 (12)	0.0111 (12)	0.0095 (12)	0.0049 (11)
C12	0.102 (2)	0.0657 (15)	0.0690 (16)	0.0167 (14)	0.0006 (14)	0.0092 (12)
C13	0.0895 (18)	0.0677 (16)	0.0655 (15)	−0.0048 (14)	−0.0129 (13)	0.0186 (12)
C14	0.0917 (18)	0.0816 (17)	0.0431 (12)	−0.0132 (14)	0.0022 (12)	0.0105 (11)
C15	0.0715 (14)	0.0678 (14)	0.0464 (11)	−0.0011 (11)	0.0124 (10)	0.0037 (10)
C16	0.0427 (10)	0.0512 (11)	0.0456 (10)	−0.0042 (8)	0.0011 (8)	0.0038 (8)
C17	0.0515 (12)	0.0699 (14)	0.0653 (14)	0.0045 (11)	−0.0056 (10)	0.0052 (11)
C18	0.0689 (15)	0.0906 (19)	0.0634 (15)	−0.0093 (14)	−0.0191 (12)	0.0180 (14)
C19	0.0782 (16)	0.0833 (17)	0.0415 (11)	−0.0329 (14)	−0.0021 (11)	0.0080 (11)
C20	0.0767 (16)	0.0695 (15)	0.0520 (13)	−0.0127 (12)	0.0180 (12)	−0.0057 (11)
C21	0.0573 (12)	0.0641 (13)	0.0495 (11)	0.0037 (10)	0.0049 (10)	0.0028 (10)
C22	0.0577 (12)	0.0551 (12)	0.0354 (9)	−0.0011 (9)	−0.0008 (9)	0.0044 (8)
C23	0.0678 (15)	0.0738 (15)	0.0568 (13)	−0.0053 (12)	0.0100 (11)	0.0091 (11)
C24	0.0776 (17)	0.100 (2)	0.0630 (15)	−0.0246 (16)	0.0077 (13)	0.0155 (14)
C25	0.111 (2)	0.0713 (17)	0.0594 (15)	−0.0303 (16)	−0.0120 (15)	0.0106 (13)
C26	0.110 (2)	0.0561 (14)	0.0536 (13)	−0.0085 (14)	−0.0062 (14)	0.0008 (11)
C27	0.0810 (16)	0.0535 (12)	0.0476 (12)	0.0012 (11)	0.0020 (11)	0.0019 (9)
C28	0.0464 (10)	0.0516 (11)	0.0401 (10)	0.0049 (9)	0.0063 (8)	−0.0050 (8)
C30	0.0526 (11)	0.0607 (12)	0.0448 (11)	0.0124 (10)	0.0070 (9)	−0.0012 (9)
C31	0.0468 (11)	0.0506 (11)	0.0434 (10)	0.0086 (9)	0.0005 (8)	−0.0041 (8)
C32	0.0730 (16)	0.0497 (12)	0.0963 (19)	0.0069 (11)	0.0260 (14)	0.0024 (12)
C33	0.0677 (16)	0.0802 (18)	0.113 (2)	0.0010 (14)	0.0314 (15)	0.0196 (16)
C34	0.0629 (15)	0.097 (2)	0.0802 (17)	0.0298 (15)	0.0235 (13)	0.0116 (15)
C35	0.0716 (16)	0.0639 (15)	0.0802 (17)	0.0284 (13)	0.0040 (13)	−0.0078 (12)
C36	0.0559 (12)	0.0501 (11)	0.0645 (13)	0.0070 (10)	−0.0020 (10)	−0.0025 (10)
C37	0.0492 (11)	0.0442 (10)	0.0411 (10)	0.0111 (8)	0.0034 (8)	−0.0029 (8)
C38	0.0546 (12)	0.0604 (12)	0.0438 (10)	0.0117 (10)	0.0046 (9)	−0.0058 (9)
C39	0.0730 (15)	0.0699 (15)	0.0463 (11)	0.0203 (12)	−0.0038 (11)	−0.0150 (11)
C40	0.0849 (17)	0.0531 (13)	0.0679 (15)	0.0045 (12)	−0.0160 (13)	−0.0157 (11)
C41	0.0820 (17)	0.0553 (13)	0.0678 (15)	−0.0133 (12)	−0.0061 (12)	0.0007 (11)
C42	0.0693 (14)	0.0532 (12)	0.0454 (11)	−0.0037 (10)	−0.0009 (10)	−0.0004 (9)

Geometric parameters (Å, º)

S3—C2	1.820 (2)	C37—C38	1.392 (3)
S3—C4	1.818 (2)	C37—C42	1.378 (3)
O29—C28	1.220 (2)	C38—C39	1.379 (3)
N7—C6	1.489 (2)	C39—C40	1.370 (3)
N7—C8	1.478 (2)	C40—C41	1.373 (4)
N7—C28	1.366 (2)	C41—C42	1.386 (3)
C1—C2	1.542 (3)	C1—H1	0.9800
C1—C8	1.540 (3)	C2—H2	0.9800
C1—C9	1.519 (3)	C4—H4	0.9800
C2—C10	1.518 (3)	C5—H5	0.9800
C4—C5	1.547 (3)	C6—H6	0.9800
C4—C16	1.510 (3)	C8—H8	0.9800
C5—C6	1.531 (3)	C9—H9A	0.9700
C5—C9	1.524 (3)	C9—H9B	0.9700
C6—C22	1.528 (3)	C11—H11	0.9300
C8—C37	1.531 (3)	C12—H12	0.9300
C10—C11	1.381 (3)	C13—H13	0.9300
C10—C15	1.383 (3)	C14—H14	0.9300
C11—C12	1.383 (3)	C15—H15	0.9300
C12—C13	1.358 (4)	C17—H17	0.9300
C13—C14	1.369 (4)	C18—H18	0.9300
C14—C15	1.385 (4)	C19—H19	0.9300
C16—C17	1.386 (3)	C20—H20	0.9300
C16—C21	1.380 (3)	C21—H21	0.9300
C17—C18	1.375 (3)	C23—H23	0.9300
C18—C19	1.362 (4)	C24—H24	0.9300
C19—C20	1.369 (4)	C25—H25	0.9300
C20—C21	1.386 (3)	C26—H26	0.9300
C22—C23	1.393 (3)	C27—H27	0.9300
C22—C27	1.383 (3)	C30—H30A	0.9700
C23—C24	1.393 (4)	C30—H30B	0.9700
C24—C25	1.372 (4)	C32—H32	0.9300
C25—C26	1.363 (4)	C33—H33	0.9300
C26—C27	1.383 (4)	C34—H34	0.9300
C28—C30	1.520 (3)	C35—H35	0.9300
C30—C31	1.504 (3)	C36—H36	0.9300
C31—C32	1.375 (3)	C38—H38	0.9300
C31—C36	1.369 (3)	C39—H39	0.9300
C32—C33	1.375 (4)	C40—H40	0.9300
C33—C34	1.357 (4)	C41—H41	0.9300
C34—C35	1.352 (4)	C42—H42	0.9300
C35—C36	1.386 (3)
C2—C1—C8	114.13 (15)	S3—C4—H4	107.00
C2—C1—C9	111.93 (15)	C5—C4—H4	107.00
C8—C1—C9	111.02 (15)	C16—C4—H4	107.00
S3—C2—C1	113.19 (13)	C4—C5—H5	107.00
S3—C2—C10	110.32 (13)	C6—C5—H5	107.00
C1—C2—C10	112.50 (16)	C9—C5—H5	107.00
S3—C4—C5	113.16 (13)	N7—C6—H6	106.00
S3—C4—C16	109.47 (13)	C5—C6—H6	106.00
C5—C4—C16	113.85 (16)	C22—C6—H6	106.00
C4—C5—C6	114.06 (16)	N7—C8—H8	106.00
C4—C5—C9	110.05 (15)	C1—C8—H8	106.00
C6—C5—C9	111.35 (15)	C37—C8—H8	106.00
N7—C6—C5	112.89 (15)	C1—C9—H9A	110.00
N7—C6—C22	111.67 (15)	C1—C9—H9B	110.00
C5—C6—C22	114.16 (16)	C5—C9—H9A	110.00
N7—C8—C1	111.61 (14)	C5—C9—H9B	110.00
N7—C8—C37	114.82 (15)	H9A—C9—H9B	108.00
C1—C8—C37	112.66 (15)	C10—C11—H11	119.00
C1—C9—C5	109.89 (15)	C12—C11—H11	119.00
C2—C10—C11	123.51 (18)	C11—C12—H12	120.00
C2—C10—C15	118.83 (19)	C13—C12—H12	120.00
C11—C10—C15	117.6 (2)	C12—C13—H13	120.00
C10—C11—C12	121.3 (2)	C14—C13—H13	120.00
C11—C12—C13	120.4 (3)	C13—C14—H14	120.00
C12—C13—C14	119.3 (2)	C15—C14—H14	120.00
C13—C14—C15	120.7 (2)	C10—C15—H15	120.00
C10—C15—C14	120.6 (2)	C14—C15—H15	120.00
C4—C16—C17	118.08 (18)	C16—C17—H17	119.00
C4—C16—C21	124.15 (18)	C18—C17—H17	119.00
C17—C16—C21	117.77 (19)	C17—C18—H18	120.00
C16—C17—C18	121.2 (2)	C19—C18—H18	120.00
C17—C18—C19	120.4 (2)	C18—C19—H19	120.00
C18—C19—C20	119.5 (2)	C20—C19—H19	120.00
C19—C20—C21	120.4 (2)	C19—C20—H20	120.00
C16—C21—C20	120.7 (2)	C21—C20—H20	120.00
C6—C22—C23	118.08 (19)	C16—C21—H21	120.00
C6—C22—C27	124.79 (18)	C20—C21—H21	120.00
C23—C22—C27	117.1 (2)	C22—C23—H23	120.00
C22—C23—C24	120.7 (2)	C24—C23—H23	120.00
C23—C24—C25	120.5 (3)	C23—C24—H24	120.00
C24—C25—C26	119.4 (3)	C25—C24—H24	120.00
C25—C26—C27	120.3 (3)	C24—C25—H25	120.00
C22—C27—C26	121.9 (2)	C26—C25—H25	120.00
O29—C28—N7	121.95 (17)	C25—C26—H26	120.00
O29—C28—C30	120.14 (17)	C27—C26—H26	120.00
C2—S3—C4	98.79 (9)	C22—C27—H27	119.00
C6—N7—C8	121.86 (14)	C26—C27—H27	119.00
C6—N7—C28	116.77 (14)	C28—C30—H30A	109.00
C8—N7—C28	120.61 (14)	C28—C30—H30B	109.00
N7—C28—C30	117.87 (15)	C31—C30—H30A	109.00
C28—C30—C31	112.07 (16)	C31—C30—H30B	109.00
C30—C31—C32	120.86 (18)	H30A—C30—H30B	108.00
C30—C31—C36	121.40 (18)	C31—C32—H32	119.00
C32—C31—C36	117.72 (19)	C33—C32—H32	119.00
C31—C32—C33	121.4 (2)	C32—C33—H33	120.00
C32—C33—C34	120.0 (2)	C34—C33—H33	120.00
C33—C34—C35	119.8 (3)	C33—C34—H34	120.00
C34—C35—C36	120.4 (2)	C35—C34—H34	120.00
C31—C36—C35	120.7 (2)	C34—C35—H35	120.00
C8—C37—C38	118.86 (16)	C36—C35—H35	120.00
C8—C37—C42	123.36 (16)	C31—C36—H36	120.00
C38—C37—C42	117.53 (18)	C35—C36—H36	120.00
C37—C38—C39	121.66 (19)	C37—C38—H38	119.00
C38—C39—C40	119.9 (2)	C39—C38—H38	119.00
C39—C40—C41	119.4 (2)	C38—C39—H39	120.00
C40—C41—C42	120.6 (2)	C40—C39—H39	120.00
C37—C42—C41	120.9 (2)	C39—C40—H40	120.00
C2—C1—H1	106.00	C41—C40—H40	120.00
C8—C1—H1	106.00	C40—C41—H41	120.00
C9—C1—H1	106.00	C42—C41—H41	120.00
S3—C2—H2	107.00	C37—C42—H42	120.00
C1—C2—H2	107.00	C41—C42—H42	120.00
C10—C2—H2	107.00
C4—S3—C2—C1	48.78 (15)	N7—C8—C37—C38	175.80 (16)
C4—S3—C2—C10	175.84 (14)	N7—C8—C37—C42	1.7 (3)
C2—S3—C4—C5	−50.62 (15)	C1—C8—C37—C38	−54.9 (2)
C2—S3—C4—C16	−178.77 (14)	C1—C8—C37—C42	130.90 (19)
C8—N7—C6—C5	35.0 (2)	C2—C10—C11—C12	−177.3 (2)
C8—N7—C6—C22	−95.26 (19)	C15—C10—C11—C12	0.8 (3)
C28—N7—C6—C5	−135.00 (17)	C2—C10—C15—C14	176.3 (2)
C28—N7—C6—C22	94.77 (19)	C11—C10—C15—C14	−1.9 (3)
C6—N7—C8—C1	−36.6 (2)	C10—C11—C12—C13	1.1 (4)
C6—N7—C8—C37	93.2 (2)	C11—C12—C13—C14	−1.9 (4)
C28—N7—C8—C1	133.01 (17)	C12—C13—C14—C15	0.7 (4)
C28—N7—C8—C37	−97.2 (2)	C13—C14—C15—C10	1.2 (4)
C6—N7—C28—O29	4.5 (3)	C4—C16—C17—C18	179.5 (2)
C6—N7—C28—C30	−173.18 (16)	C21—C16—C17—C18	−1.0 (3)
C8—N7—C28—O29	−165.67 (18)	C4—C16—C21—C20	−178.6 (2)
C8—N7—C28—C30	16.7 (2)	C17—C16—C21—C20	2.0 (3)
C8—C1—C2—S3	66.47 (18)	C16—C17—C18—C19	−1.3 (4)
C8—C1—C2—C10	−59.4 (2)	C17—C18—C19—C20	2.5 (4)
C9—C1—C2—S3	−60.69 (19)	C18—C19—C20—C21	−1.5 (4)
C9—C1—C2—C10	173.41 (16)	C19—C20—C21—C16	−0.7 (4)
C2—C1—C8—N7	−79.14 (19)	C6—C22—C23—C24	−179.1 (2)
C2—C1—C8—C37	149.97 (15)	C27—C22—C23—C24	−0.3 (3)
C9—C1—C8—N7	48.5 (2)	C6—C22—C27—C26	177.8 (2)
C9—C1—C8—C37	−82.40 (18)	C23—C22—C27—C26	−0.9 (3)
C2—C1—C9—C5	67.1 (2)	C22—C23—C24—C25	1.3 (4)
C8—C1—C9—C5	−61.7 (2)	C23—C24—C25—C26	−1.2 (4)
S3—C2—C10—C11	−13.9 (3)	C24—C25—C26—C27	0.1 (4)
S3—C2—C10—C15	168.03 (17)	C25—C26—C27—C22	1.0 (4)
C1—C2—C10—C11	113.5 (2)	O29—C28—C30—C31	−27.1 (3)
C1—C2—C10—C15	−64.5 (2)	N7—C28—C30—C31	150.55 (17)
S3—C4—C5—C6	−62.51 (19)	C28—C30—C31—C32	−66.7 (3)
S3—C4—C5—C9	63.45 (18)	C28—C30—C31—C36	114.9 (2)
C16—C4—C5—C6	63.3 (2)	C30—C31—C32—C33	−179.1 (2)
C16—C4—C5—C9	−170.71 (16)	C36—C31—C32—C33	−0.6 (4)
S3—C4—C16—C17	−146.46 (18)	C30—C31—C36—C35	179.7 (2)
S3—C4—C16—C21	34.1 (2)	C32—C31—C36—C35	1.3 (3)
C5—C4—C16—C17	85.8 (2)	C31—C32—C33—C34	−0.7 (4)
C5—C4—C16—C21	−93.7 (2)	C32—C33—C34—C35	1.4 (4)
C4—C5—C6—N7	80.62 (19)	C33—C34—C35—C36	−0.7 (4)
C4—C5—C6—C22	−150.42 (16)	C34—C35—C36—C31	−0.7 (4)
C9—C5—C6—N7	−44.7 (2)	C8—C37—C38—C39	−175.0 (2)
C9—C5—C6—C22	84.30 (19)	C42—C37—C38—C39	−0.5 (3)
C4—C5—C9—C1	−67.9 (2)	C8—C37—C42—C41	174.65 (19)
C6—C5—C9—C1	59.6 (2)	C38—C37—C42—C41	0.4 (3)
N7—C6—C22—C23	−65.0 (2)	C37—C38—C39—C40	0.6 (4)
N7—C6—C22—C27	116.2 (2)	C38—C39—C40—C41	−0.6 (4)
C5—C6—C22—C23	165.40 (18)	C39—C40—C41—C42	0.4 (3)
C5—C6—C22—C27	−13.3 (3)	C40—C41—C42—C37	−0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1^i	0.93	2.95	3.811 (3)	155
C14—H14···Cg2^ii	0.93	2.88	3.593 (3)	135
C35—H35···Cg1^iii	0.93	2.71	3.473 (3)	140

Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x+1, −y+2, −z+1.