Azin­yl sulfides. LXXXI. 14-Phen­yl-7-thia­pyrano[2,3-c;6,5-c']diquinoline-14-carbonitrile

The mol­ecules of the title compound, C₂₆H₁₅N₃S, have a penta­cyclic ring system which is almost planar, with the central ring in a flattened boat conformation. The folding angle between the two quinoline rings is 6.75 (7)°. The 14-phen­yl substituent is in a quasi-axial conformation, while the 14-cyano substituent is in a quasi-equatorial conformation with respect to the thio­pyran ring. The S...C-C_phen­yl and S...C-C_CN angles are 116.8 (2) and 129.3 (2)°, respectively. The plane of the phen­yl group is nearly coplanar with the plane bis­ecting the dihedral angle of the penta­cyclic ring system.

S1. Comment

The incorporation of polarizable heteroatoms within the donor framework is regarded as an important way of designing new polyheterocyclic donor molecules in the search for organic materials with interesting electronic, optoelectronic and magnetic properties (Marti et al., 1994). Very few papers have appeared in the literature to date on the synthesis and properties of fused pentacyclic heterocycles. Some pentacyclic heterocycles, such as azathiapentaphenes and diazadithiapentacenes, show photoelectric properties (Yoshida et al., 1994), and diazapentacenes show photodynamic therapeutic activity against cancer cell lines, bacteria and viruses (Gloster et al., 1999). Very recent studies demonstrated significant electronic conductivity enhancement of disubstituted homopentacenes (Anthony et al., 2001). On the other hand, quinolines condensed with some heterocycles have become important compounds because of their affinity to the benzodiazepine receptors (Moreau et al., 1988; Anzini et al., 1990) and their cytotoxic activity (Ma et al., 1994, 1999; Tasdemir et al., 2001).

The purpose of this study is to determine the structure of the title diazathiapentaphene, (I), and to compare it with the structures of related multicyclic heterocycles, (II)–(V), also shown in the scheme.

The molecular configuration and atom labelling are shown in Fig. 1. In contrast with the isomeric thiopyranodiquinoline, (II) (Nowak et al., 2002), and the pentaphenes, (III) (Pluta & Suwi\`nska, 2000) and (IV) (Besnard et al., 2004), the overall pentacyclic ring system in (I) is close to planar. It is only slightly folded along the S···C21 axis, as well as along the C3—C4 and C13—C14 axes between the thiopyran and quinoline rings. The butterfly angle between the two quinoline planes is very small in comparison with the pentacyclic heterocycles (II)–(IV): 6.75 (7)° versus 44.73 (3), 150.2 (1) and 20.5 (1)°, respectively.

The central thiopyran ring has a flattened boat conformation, with atoms S and C21 slightly displaced out of the basal plane [C3/C4/C13/C14], by −0.092 (5) and −0.122 (5) Å, respectively, compared with 0.580 (3) and 0.563 (3) Å, respectively, in thiopyranodiquinoline (II). The dihedral angle between the planes determined by the atoms of the two halves of the thiopyran ring (i.e. S/C3/C4/C21 and S/C13/C14/C21) is 9.32 (14)°. It is worth noting that the quinoline ring system is not quite planar, the dihedral angles between the pyridine and benzene rings being 0.91 (11) and 0.41 (11)°, respectively.

Bond lengths and bond angles are given in Table 1. Whereas the S—C, N—C and C—C bond lengths are similar to those found in the isomeric thiopyranodiquinoline, (II), the bond angles differ significantly. The C3—S—C13 and C4—C21—C14 angles are quite large compared with the corresponding angles in isomer (II), at 98.88 (10) and 110.53 (16)°, respectively. Bond angles C4—C3—S, C14—C13—S, C3—C4—C21 and C13—C14—C21 differ strongly from the unstrained sp² and sp³ angles (Table 1). The increase of these bond angles is related to the requirements of the flattened boat conformation of the thiopyran ring.

The most intriguing molecular features of (I) are the location and orientation of the substituents. As also observed for the phenylthiopyranodiarenes, (II) and (V) (Quintela et al., 2000), the phenyl substituent is in a quasi-axial conformation with respect to the thiopyran ring, with torsion angles C22—C21—C4—C3 − 111.66 (19), C22—C21—C4—C5 66.0 (2), C22—C21—C14—C13 108.9 (2) and C22—C21—C14—C15 − 68.1 (2)°.

The S···C21—C22 angle is 116.8 (2)°, which is larger than in compounds (II) and (V). Whereas the plane of the phenyl group in isomer (II) is nearly perpendicular to the plane bisecting the dihedral angle of the thiopyranodiarene ring system, the phenyl group plane in (I) is nearly coplanar with the bisecting plane. The torsion angles C23—C22—C21—C4 and C27—C22—C21—C4 are 58.8 (2) and −120.2 (2)°, respectively, and the dihedral angle between the phenyl group plane and the C3/C4/C13/C14 plane is 88.91 (17)°.

The cyano group is in a quasi-equatorial position with respect to the central thiopyran ring, with torsion angles C28—C21—C4—C3 126.56 (19), C28—C21—C4—C5 − 55.8 (2), C28—C21—C14—C13 − 128.71 (19) and C28—C21—C14—C15 54.3 (2)°, and an S···C21—C28 angle of 129.30 (2)°.

There are very close contacts between quinoline atoms H6 and H16 and the substituent C atoms. The non-bonded distances H6···C27 2.663 (6), H16···C27 2.671 (6), H6···C28 2.444 (6) and H16···C28 2.403 (6) Å are each shorter than the sum of the van der Waals radii (2.90 Å; Bondi, 1964). These steric interactions cause deshielding of the H6/H16 and H23/H27 atoms in the ¹H NMR spectrum and were confirmed using the nuclear Overhauser enhancement effect (Pluta, 1994).

In each unit cell, there are two molecules related by inversion symmetry. The main pentacyclic rings of the molecules are parallel to each other, as shown in Fig. 2a. This parallel alignment does not, however, produce significant overlap between the pentacyclic ring systems. since they are shifted from each other in order to accomodate the bulky subtituents. The small overlap occurring between the C5–C10 ring of one molecule and the C15–C20 ring of another is shown in Fig. 2b. The distance between the two planes that partly overlap is 3.36 (1) Å. Despite the π–π interactions, linear hydrogen bonding involving atoms C2, H2 and N1 can occur, as indicated by the distance between H2 and N1, which is is 2.53 (1) Å, and the H2···C2—N1 angle, which is 151.7 (1)°.

S2. Experimental

The title compound was synthesized and purified as previously reported by Pluta (1994). Small needles were obtained on slow evaporation from a monomethyl ether of diethylene glycol solution. As a result of their limited size, the crystals diffracted too weakly to be studied with conventional X-ray diffraction techniques. Synchrotron radiation was therefore used.

S3. Refinement

Due to the limited range of motion of the diffractometer available, the completness of the data was low. The H atoms could be located in difference Fourier maps but, due to the low number of reflections, they were fixed at their ideal positions, with C—H distances of 0.93 Å and with U_iso(H) = 1.2U_eq(C). Please check added text.

Computing details

Data collection: Please provide missing information and reference; cell refinement: Please provide missing information and reference; data reduction: TWINSOLVE (Rigaku/MSC & Prekat, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999) in WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999); molecular graphics: Please provide missing information and reference; software used to prepare material for publication: Please provide missing information and reference.

Figures

	Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing of the molecules of (I) in the crystal. (a) A view showing the parallel arrangement of the main ring systems. (b) The overlap between molecules 1 and 2, indicated by arrows in (a).

14-Phenyl-7-thiapyrano[2,3 − c;6,5 − c']diquinoline-14-carbonitrile

Crystal data

C26H15N3S	Z = 2
Mr = 401.47	F(000) = 416
Triclinic, P1	Dx = 1.404 Mg m^−3
Hall symbol: -P 1	Synchrotron radiation, λ = 0.996 Å
a = 7.9135 (1) Å	Cell parameters from 300 reflections
b = 9.3622 (4) Å	θ = 5–45°
c = 13.3280 (5) Å	µ = 0.42 mm^−1
α = 75.724 (2)°	T = 293 K
β = 84.369 (1)°	Needle, white
γ = 84.415 (2)°	0.80 × 0.01 × 0.01 mm
V = 949.59 (6) Å^3

Data collection

MARCCD 165 detector diffractometer	Rint = 0.048
ϕ scans	θmax = 32.9°, θmin = 3.4°
4040 measured reflections	h = −8→8
2099 independent reflections	k = −10→10
1983 reflections with I > 2σ(I)	l = −14→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.092P)^2 + 0.2098P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.137	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.17 e Å^−3
2099 reflections	Δρmin = −0.20 e Å^−3
271 parameters

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.

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

	x	y	z	Uiso*/Ueq
S	0.17109 (7)	0.09451 (7)	0.02566 (4)	0.0540 (3)
N1	0.1020 (2)	0.4516 (2)	0.12709 (15)	0.0521 (6)
N2	0.4089 (3)	−0.2903 (3)	0.03093 (15)	0.0554 (6)
N3	0.6848 (2)	0.0723 (2)	0.25702 (14)	0.0515 (6)
C2	0.1095 (3)	0.3491 (3)	0.07657 (18)	0.0496 (7)
C3	0.1942 (2)	0.2065 (3)	0.10839 (16)	0.0418 (6)
C4	0.2786 (2)	0.1698 (2)	0.19758 (14)	0.0350 (6)
C5	0.2717 (2)	0.2799 (2)	0.25620 (15)	0.0363 (6)
C6	0.3461 (2)	0.2622 (3)	0.35166 (16)	0.0411 (6)
C7	0.3326 (3)	0.3721 (3)	0.40339 (17)	0.0465 (6)
C8	0.2433 (3)	0.5075 (3)	0.3643 (2)	0.0540 (7)
C9	0.1694 (3)	0.5289 (3)	0.27344 (19)	0.0513 (7)
C10	0.1807 (2)	0.4186 (3)	0.21786 (17)	0.0434 (6)
C12	0.3155 (3)	−0.1663 (3)	0.01273 (17)	0.0513 (7)
C13	0.3027 (2)	−0.0621 (3)	0.07486 (15)	0.0430 (6)
C14	0.3902 (2)	−0.0895 (2)	0.16263 (14)	0.0357 (6)
C15	0.4954 (2)	−0.2263 (3)	0.18527 (15)	0.0405 (6)
C16	0.5958 (3)	−0.2757 (3)	0.27198 (17)	0.0464 (6)
C17	0.6915 (3)	−0.4072 (3)	0.2883 (2)	0.0566 (7)
C18	0.6924 (3)	−0.5007 (3)	0.2208 (2)	0.0602 (7)
C19	0.5986 (3)	−0.4588 (3)	0.1371 (2)	0.0576 (7)
C20	0.4999 (3)	−0.3225 (3)	0.11785 (17)	0.0470 (6)
C21	0.3724 (2)	0.0153 (3)	0.23726 (14)	0.0340 (5)
C22	0.2731 (2)	−0.0632 (2)	0.33866 (14)	0.0330 (5)
C23	0.1035 (2)	−0.0844 (2)	0.33240 (16)	0.0387 (6)
C24	0.0069 (2)	−0.1530 (3)	0.41923 (17)	0.0460 (6)
C25	0.0769 (3)	−0.2016 (3)	0.51382 (16)	0.0473 (6)
C26	0.2439 (3)	−0.1804 (3)	0.52083 (16)	0.0451 (6)
C27	0.3421 (2)	−0.1109 (3)	0.43413 (15)	0.0391 (6)
C28	0.5488 (2)	0.0458 (2)	0.25191 (14)	0.0364 (6)
H2	0.0555	0.3704	0.0151	0.06*
H6	0.4059	0.173	0.3797	0.049*
H7	0.3836	0.3567	0.4656	0.056*
H8	0.2345	0.582	0.4	0.065*
H9	0.1098	0.619	0.2474	0.062*
H12	0.2524	−0.1441	−0.0452	0.062*
H16	0.596	−0.2166	0.3188	0.056*
H17	0.7572	−0.4353	0.3451	0.068*
H18	0.7569	−0.5909	0.2333	0.072*
H19	0.5994	−0.5205	0.092	0.069*
H23	0.0551	−0.052	0.2691	0.046*
H24	−0.1065	−0.1669	0.4142	0.055*
H25	0.0112	−0.2482	0.5723	0.057*
H26	0.2916	−0.2131	0.5843	0.054*
H27	0.4549	−0.0961	0.4399	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0649 (4)	0.0559 (6)	0.0450 (4)	−0.0034 (3)	−0.0228 (3)	−0.0126 (3)
N1	0.0529 (11)	0.0431 (17)	0.0558 (12)	0.0025 (9)	−0.0129 (9)	−0.0025 (10)
N2	0.0633 (12)	0.0605 (18)	0.0518 (12)	−0.0127 (11)	0.0053 (9)	−0.0318 (10)
N3	0.0435 (11)	0.0613 (17)	0.0542 (12)	−0.0066 (9)	−0.0081 (8)	−0.0198 (9)
C2	0.0549 (13)	0.046 (2)	0.0452 (13)	0.0004 (10)	−0.0161 (10)	−0.0025 (12)
C3	0.0406 (11)	0.0435 (17)	0.0386 (11)	−0.0069 (9)	−0.0066 (8)	−0.0017 (10)
C4	0.0344 (10)	0.0339 (17)	0.0364 (11)	−0.0056 (8)	−0.0018 (8)	−0.0068 (9)
C5	0.0349 (10)	0.0320 (17)	0.0410 (11)	−0.0042 (8)	−0.0017 (8)	−0.0069 (9)
C6	0.0420 (11)	0.0379 (17)	0.0434 (12)	−0.0025 (9)	−0.0043 (8)	−0.0096 (10)
C7	0.0505 (12)	0.045 (2)	0.0486 (12)	−0.0049 (10)	−0.0038 (9)	−0.0189 (11)
C8	0.0579 (14)	0.0417 (19)	0.0663 (15)	−0.0021 (11)	0.0005 (11)	−0.0233 (12)
C9	0.0535 (13)	0.0318 (18)	0.0666 (16)	0.0015 (10)	−0.0019 (11)	−0.0108 (12)
C10	0.0411 (11)	0.0353 (18)	0.0510 (13)	−0.0031 (9)	−0.0014 (9)	−0.0058 (11)
C12	0.0576 (14)	0.061 (2)	0.0430 (12)	−0.0117 (12)	−0.0017 (10)	−0.0242 (12)
C13	0.0451 (11)	0.0487 (18)	0.0374 (11)	−0.0110 (10)	−0.0019 (9)	−0.0122 (10)
C14	0.0381 (10)	0.0368 (17)	0.0351 (11)	−0.0083 (9)	0.0011 (8)	−0.0134 (9)
C15	0.0420 (11)	0.0396 (17)	0.0420 (11)	−0.0064 (9)	0.0051 (9)	−0.0153 (10)
C16	0.0486 (12)	0.0434 (18)	0.0487 (13)	0.0026 (10)	−0.0029 (9)	−0.0168 (10)
C17	0.0538 (13)	0.050 (2)	0.0627 (15)	0.0060 (11)	−0.0016 (10)	−0.0128 (12)
C18	0.0602 (14)	0.043 (2)	0.0765 (18)	0.0049 (11)	0.0087 (12)	−0.0215 (13)
C19	0.0639 (15)	0.046 (2)	0.0677 (16)	−0.0077 (12)	0.0147 (12)	−0.0295 (12)
C20	0.0500 (12)	0.0474 (19)	0.0483 (13)	−0.0105 (10)	0.0096 (10)	−0.0229 (11)
C21	0.0348 (10)	0.0346 (15)	0.0341 (10)	−0.0028 (8)	−0.0067 (7)	−0.0097 (9)
C22	0.0399 (10)	0.0266 (14)	0.0344 (10)	0.0011 (8)	−0.0037 (8)	−0.0118 (8)
C23	0.0419 (11)	0.0343 (16)	0.0412 (11)	−0.0010 (9)	−0.0070 (8)	−0.0104 (9)
C24	0.0386 (11)	0.0444 (18)	0.0550 (14)	−0.0044 (9)	−0.0002 (9)	−0.0127 (11)
C25	0.0551 (13)	0.0410 (17)	0.0438 (12)	−0.0040 (10)	0.0082 (9)	−0.0108 (10)
C26	0.0585 (13)	0.0429 (17)	0.0337 (11)	−0.0012 (10)	−0.0049 (9)	−0.0096 (9)
C27	0.0427 (11)	0.0389 (16)	0.0377 (11)	−0.0020 (9)	−0.0053 (8)	−0.0126 (9)
C28	0.0418 (12)	0.0356 (16)	0.0328 (11)	−0.0006 (9)	−0.0039 (8)	−0.0106 (9)

Geometric parameters (Å, º)

S—C3	1.731 (2)	C7—H7	0.93
S—C13	1.740 (2)	C6—C5	1.421 (3)
N1—C2	1.296 (3)	C6—H6	0.93
N1—C10	1.369 (3)	C13—C12	1.417 (3)
N2—C12	1.298 (3)	C14—C15	1.440 (3)
N2—C20	1.379 (3)	C15—C20	1.417 (3)
N3—C28	1.140 (3)	C15—C16	1.423 (3)
C3—C4	1.374 (3)	C20—C19	1.410 (4)
C4—C21	1.553 (3)	C12—H12	0.93
C13—C14	1.375 (3)	C19—C18	1.356 (4)
C14—C21	1.549 (3)	C19—H19	0.93
C21—C22	1.549 (3)	C18—C17	1.400 (4)
C21—C28	1.492 (3)	C18—H18	0.93
C22—C23	1.389 (3)	C17—C16	1.362 (4)
C22—C27	1.388 (3)	C17—H17	0.93
C4—C5	1.433 (3)	C16—H16	0.93
C3—C2	1.419 (3)	C27—C26	1.383 (3)
C2—H2	0.93	C27—H27	0.93
C10—C9	1.403 (4)	C26—C25	1.371 (3)
C10—C5	1.425 (3)	C26—H26	0.93
C9—C8	1.358 (4)	C25—C24	1.381 (3)
C9—H9	0.93	C25—H25	0.93
C8—C7	1.397 (4)	C24—C23	1.376 (3)
C8—H8	0.93	C24—H24	0.93
C7—C6	1.363 (3)	C23—H23	0.93
C28—C21—C22	113.87 (15)	C15—C14—C21	120.77 (17)
C28—C21—C14	106.51 (16)	C20—C15—C16	116.0 (2)
C22—C21—C14	107.44 (16)	C20—C15—C14	118.68 (19)
C28—C21—C4	105.14 (17)	C16—C15—C14	125.3 (2)
C22—C21—C4	107.73 (15)	N2—C20—C19	116.1 (2)
C3—S—C13	102.44 (11)	N2—C20—C15	122.8 (2)
C3—C4—C21	122.8 (2)	C19—C20—C15	121.1 (2)
C4—C3—S	127.34 (19)	C12—N2—C20	117.0 (2)
C4—C21—C14	116.39 (16)	N2—C12—C13	124.7 (2)
C13—C14—C21	122.84 (19)	N2—C12—H12	117.7
C14—C13—S	126.99 (19)	C13—C12—H12	117.7
N3—C28—C21	176.01 (19)	C18—C19—C20	120.6 (3)
C3—C4—C5	116.8 (2)	C18—C19—H19	119.7
C5—C4—C21	120.39 (17)	C20—C19—H19	119.7
C4—C3—C2	120.2 (2)	C19—C18—C17	119.6 (2)
C2—C3—S	112.44 (16)	C19—C18—H18	120.2
N1—C2—C3	124.6 (2)	C17—C18—H18	120.2
N1—C2—H2	117.7	C16—C17—C18	121.0 (2)
C3—C2—H2	117.7	C16—C17—H17	119.5
C2—N1—C10	117.2 (2)	C18—C17—H17	119.5
N1—C10—C9	117.0 (2)	C17—C16—C15	121.7 (2)
N1—C10—C5	122.9 (2)	C17—C16—H16	119.1
C9—C10—C5	120.1 (2)	C15—C16—H16	119.1
C8—C9—C10	121.7 (2)	C27—C22—C23	118.77 (17)
C8—C9—H9	119.1	C27—C22—C21	124.22 (16)
C10—C9—H9	119.1	C23—C22—C21	117.00 (16)
C9—C8—C7	119.1 (3)	C26—C27—C22	120.34 (19)
C9—C8—H8	120.4	C26—C27—H27	119.8
C7—C8—H8	120.4	C22—C27—H27	119.8
C6—C7—C8	120.9 (2)	C25—C26—C27	120.49 (19)
C6—C7—H7	119.6	C25—C26—H26	119.8
C8—C7—H7	119.6	C27—C26—H26	119.8
C7—C6—C5	122.0 (2)	C26—C25—C24	119.47 (19)
C7—C6—H6	119	C26—C25—H25	120.3
C5—C6—H6	119	C24—C25—H25	120.3
C6—C5—C10	116.2 (2)	C23—C24—C25	120.53 (19)
C6—C5—C4	125.47 (19)	C23—C24—H24	119.7
C10—C5—C4	118.30 (19)	C25—C24—H24	119.7
C14—C13—C12	120.5 (2)	C24—C23—C22	120.39 (18)
C12—C13—S	112.47 (17)	C24—C23—H23	119.8
C13—C14—C15	116.3 (2)	C22—C23—H23	119.8
C4—C21—C22—C27	−120.2 (2)	C2—C3—S—C13	174.22 (14)
C22—C21—C4—C5	66.0 (2)	C3—S—C13—C14	4.4 (2)
C22—C21—C4—C3	−111.66 (19)	C3—S—C13—C12	−174.89 (14)
C28—C21—C4—C5	−55.8 (2)	C12—C13—C14—C15	1.1 (3)
C28—C21—C4—C3	126.56 (19)	S—C13—C14—C15	−178.16 (14)
C4—C21—C22—C23	58.8 (2)	C12—C13—C14—C21	−176.02 (17)
C22—C21—C14—C15	−68.1 (2)	S—C13—C14—C21	4.7 (3)
C22—C21—C14—C13	108.9 (2)	C13—C14—C15—C20	−0.8 (3)
C28—C21—C14—C15	54.3 (2)	C21—C14—C15—C20	176.38 (16)
C28—C21—C14—C13	−128.71 (19)	C13—C14—C15—C16	−179.92 (18)
C14—C21—C4—C3	9.0 (3)	C21—C14—C15—C16	−2.7 (3)
C14—C21—C4—C5	−173.36 (15)	C16—C15—C20—N2	179.72 (19)
C4—C21—C14—C13	−11.9 (3)	C14—C15—C20—N2	0.5 (3)
C4—C21—C14—C15	171.09 (16)	C16—C15—C20—C19	0.1 (3)
C5—C4—C3—C2	1.7 (3)	C14—C15—C20—C19	−179.08 (18)
C21—C4—C3—C2	179.40 (17)	C19—C20—N2—C12	179.12 (19)
C5—C4—C3—S	−176.55 (14)	C15—C20—N2—C12	−0.5 (3)
C21—C4—C3—S	1.2 (3)	C20—N2—C12—C13	0.8 (3)
C4—C3—C2—N1	−1.1 (3)	C14—C13—C12—N2	−1.2 (3)
S—C3—C2—N1	177.35 (18)	S—C13—C12—N2	178.17 (19)
C3—C2—N1—C10	−0.5 (3)	N2—C20—C19—C18	−179.9 (2)
C2—N1—C10—C9	−178.75 (19)	C15—C20—C19—C18	−0.2 (3)
C2—N1—C10—C5	1.5 (3)	C20—C19—C18—C17	−0.3 (4)
N1—C10—C9—C8	−179.9 (2)	C19—C18—C17—C16	1.0 (4)
C5—C10—C9—C8	−0.1 (3)	C18—C17—C16—C15	−1.1 (3)
C10—C9—C8—C7	−0.1 (3)	C20—C15—C16—C17	0.6 (3)
C9—C8—C7—C6	0.0 (3)	C14—C15—C16—C17	179.70 (19)
C8—C7—C6—C5	0.3 (3)	C28—C21—C22—C27	−4.0 (3)
C7—C6—C5—C10	−0.5 (3)	C14—C21—C22—C27	113.7 (2)
C7—C6—C5—C4	−179.39 (18)	C28—C21—C22—C23	174.98 (19)
N1—C10—C5—C6	−179.88 (17)	C14—C21—C22—C23	−67.3 (2)
C9—C10—C5—C6	0.4 (3)	C23—C22—C27—C26	1.1 (3)
N1—C10—C5—C4	−0.9 (3)	C21—C22—C27—C26	−179.9 (2)
C9—C10—C5—C4	179.38 (17)	C22—C27—C26—C25	−0.8 (3)
C3—C4—C5—C6	178.14 (17)	C27—C26—C25—C24	0.1 (4)
C21—C4—C5—C6	0.4 (3)	C26—C25—C24—C23	0.2 (4)
C3—C4—C5—C10	−0.7 (3)	C25—C24—C23—C22	0.1 (4)
C21—C4—C5—C10	−178.51 (15)	C27—C22—C23—C24	−0.8 (3)
C4—C3—S—C13	−7.4 (2)	C21—C22—C23—C24	−179.8 (2)