Neutron diffraction analysis of deuterium transfer in chiral β-thiolactam formation in the crystalline state

Since N,N-dibenzyl-1-cyclohexenecarbothioamide is photo-isomerized to the optically active β-thiolactam with the retention of the single-crystal form, the mechanism of chirality induction was identified by X-ray crystal structure analyses during the process of the reaction [Hosoya et al. (2002). Bull. Chem. Soc. Jpn, 75, 2147–2151]. In order to clarify the mechanism of hydrogen transfer in the reaction, the H atoms of the benzyl groups were replaced with deuterium atoms. The crystal structure after photoisomerization was analyzed by neutron diffraction. One of four deuterium atoms of the two benzyl groups is transferred to the C atom of the cyclohexene ring. The absolute configuration of the —C^*HD— group (chiral methylene) in the photoproduct β-thiolactam revealed that the deuterium atom occupies the equatorial position. This suggests that the deuterium atom is not transferred from the benzyl group of a neighbouring molecule, but from one of the benzyl groups within the molecule.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998) for xrayinit, xrayirr; local program for neutronirr. Cell refinement: PROCESS-AUTO (Rigaku, 1998) for xrayinit, xrayirr; HKL (Otwinowski & Minor, 1997) for neutronirr. Data reduction: CrystalStructure 3.6 (Rigaku, 2004) for xrayinit, xrayirr; HKL (Otwinowski & Minor, 1997) for neutronirr. Program(s) used to solve structure: SIR2004 (Burla, 2005) for xrayinit; SHELXS97 (Sheldrick, 1997) for xrayirr; Initial structure determined by X-rays for neutronirr. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

(xrayinit) N,N-di(benzyl-d₇)-1-cyclohexenecarbothioamide

Crystal data

C21H9D14NS	F(000) = 344
Mr = 335.43	Dx = 1.234 Mg m^−3
Monoclinic, P21	Melting point: 346 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.5992 (7) Å	Cell parameters from 7397 reflections
b = 10.1263 (7) Å	θ = 2.1–25.3°
c = 10.0412 (7) Å	µ = 0.19 mm^−1
β = 98.364 (4)°	T = 173 K
V = 865.07 (11) Å^3	Prism, pale yellow
Z = 2	0.30 × 0.10 × 0.10 mm

Data collection

Rigaku RAXIS-RAPID diffractometer	2850 independent reflections
Radiation source: Rigaku rotating anode Ultrax18	2807 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 10 pixels mm^-1	θmax = 25.3°, θmin = 2.1°
ω scan	h = −10→10
Absorption correction: multi-scan ABSCOR, T.Higashi(1995) HIGASHI, T. (1995). ABSCOR - Empirical Absorption Correction based on Fourier Series Approximation. Rigaku Corporation, Tokyo, Japan.	k = −12→11
Tmin = 0.946, Tmax = 0.982	l = −12→12
7397 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0352P)^2 + 0.1521P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.062	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.16 e Å^−3
2850 reflections	Δρmin = −0.17 e Å^−3
301 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.050 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (5)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
S1	0.44364 (4)	0.95991 (4)	0.17728 (3)	0.02203 (11)
N1	0.63270 (14)	1.05319 (13)	0.01080 (12)	0.0187 (3)
C16	0.47237 (17)	1.03036 (17)	−0.21336 (16)	0.0203 (3)
C17	0.49938 (17)	0.89530 (17)	−0.22062 (16)	0.0216 (3)
C20	0.3858 (2)	1.0329 (2)	−0.45272 (17)	0.0295 (4)
C18	0.46862 (18)	0.82915 (19)	−0.34326 (17)	0.0255 (4)
C9	0.89214 (17)	1.16799 (16)	0.06403 (15)	0.0198 (3)
C2	0.76109 (16)	0.93989 (16)	0.21078 (14)	0.0194 (3)
C19	0.41178 (19)	0.8983 (2)	−0.45916 (18)	0.0280 (4)
C15	0.49696 (17)	1.10328 (18)	−0.08056 (15)	0.0217 (3)
C10	1.04763 (17)	1.13195 (16)	0.10623 (15)	0.0210 (3)
C11	1.14360 (17)	1.21243 (18)	0.19497 (15)	0.0232 (3)
C21	0.41627 (19)	1.09881 (19)	−0.33034 (15)	0.0251 (4)
C6	0.96030 (17)	0.9629 (2)	0.41835 (15)	0.0253 (3)
C8	0.78741 (18)	1.08095 (17)	−0.03285 (15)	0.0223 (3)
C4	0.9800 (2)	0.77661 (19)	0.25875 (18)	0.0287 (4)
C7	0.79850 (19)	1.00387 (18)	0.34808 (16)	0.0238 (3)
C12	1.08620 (18)	1.32701 (17)	0.24394 (15)	0.0239 (3)
C13	0.93109 (19)	1.36321 (18)	0.20215 (17)	0.0257 (3)
C1	0.61716 (17)	0.98896 (14)	0.12413 (14)	0.0187 (3)
C3	0.84247 (18)	0.83902 (17)	0.17126 (16)	0.0241 (3)
C14	0.83554 (18)	1.28508 (17)	0.11120 (16)	0.0238 (3)
C5	0.98485 (19)	0.81522 (19)	0.40616 (17)	0.0289 (4)
H17	0.5366 (19)	0.8470 (18)	−0.1403 (17)	0.014 (4)*
H20	0.349 (2)	1.084 (2)	−0.531 (2)	0.026 (5)*
H18	0.486 (2)	0.731 (2)	−0.3470 (18)	0.024 (4)*
H19	0.396 (2)	0.853 (2)	−0.544 (2)	0.029 (5)*
H15A	0.5136 (19)	1.194 (2)	−0.0981 (16)	0.017 (4)*
H15B	0.402 (2)	1.0882 (19)	−0.0323 (17)	0.022 (4)*
H10	1.0903 (18)	1.0490 (18)	0.0756 (16)	0.014 (4)*
H11	1.253 (2)	1.1888 (19)	0.2269 (18)	0.028 (5)*
H21	0.400 (2)	1.193 (2)	−0.3245 (18)	0.028 (5)*
H6B	0.971 (2)	0.988 (2)	0.515 (2)	0.037 (5)*
H6A	1.039 (2)	1.0059 (19)	0.3772 (19)	0.028 (5)*
H8B	0.7643 (19)	1.1245 (19)	−0.1196 (18)	0.017 (4)*
H8A	0.839 (2)	0.9954 (19)	−0.0448 (17)	0.020 (4)*
H4A	1.078 (3)	0.808 (2)	0.226 (2)	0.039 (6)*
H4B	0.975 (2)	0.682 (2)	0.246 (2)	0.029 (5)*
H7A	0.717 (2)	0.9801 (19)	0.4051 (17)	0.025 (4)*
H7B	0.790 (2)	1.101 (2)	0.3378 (19)	0.032 (5)*
H12	1.155 (2)	1.3792 (19)	0.3100 (17)	0.020 (4)*
H13	0.889 (2)	1.438 (2)	0.2380 (17)	0.024 (4)*
H3	0.815 (2)	0.802 (2)	0.077 (2)	0.034 (5)*
H14	0.727 (2)	1.3122 (18)	0.0776 (17)	0.020 (4)*
H5A	0.900 (2)	0.767 (2)	0.447 (2)	0.036 (5)*
H5B	1.094 (2)	0.792 (2)	0.4573 (19)	0.032 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01794 (16)	0.0244 (2)	0.02414 (18)	−0.00081 (15)	0.00429 (12)	0.00096 (17)
N1	0.0169 (6)	0.0216 (7)	0.0170 (6)	−0.0008 (5)	0.0004 (4)	−0.0003 (5)
C16	0.0131 (6)	0.0255 (9)	0.0218 (8)	−0.0029 (6)	0.0004 (5)	0.0030 (7)
C17	0.0159 (7)	0.0273 (9)	0.0204 (7)	−0.0011 (6)	−0.0010 (6)	0.0033 (7)
C20	0.0282 (8)	0.0372 (11)	0.0213 (8)	−0.0036 (7)	−0.0027 (6)	0.0072 (8)
C18	0.0183 (7)	0.0295 (10)	0.0285 (8)	−0.0018 (7)	0.0022 (6)	−0.0038 (7)
C9	0.0182 (7)	0.0230 (8)	0.0184 (7)	−0.0019 (6)	0.0033 (5)	0.0032 (6)
C2	0.0174 (6)	0.0206 (8)	0.0199 (7)	−0.0034 (6)	0.0014 (5)	0.0013 (6)
C19	0.0238 (8)	0.0383 (10)	0.0214 (8)	−0.0054 (7)	0.0012 (6)	−0.0041 (8)
C15	0.0210 (7)	0.0210 (9)	0.0221 (8)	0.0019 (6)	−0.0004 (6)	0.0015 (7)
C10	0.0204 (7)	0.0215 (9)	0.0217 (7)	−0.0003 (6)	0.0049 (6)	0.0024 (6)
C11	0.0182 (7)	0.0284 (9)	0.0225 (7)	−0.0004 (6)	0.0015 (6)	0.0060 (7)
C21	0.0236 (7)	0.0263 (10)	0.0244 (8)	−0.0021 (7)	−0.0002 (6)	0.0044 (7)
C6	0.0245 (7)	0.0281 (8)	0.0214 (7)	−0.0041 (7)	−0.0033 (6)	0.0022 (8)
C8	0.0209 (7)	0.0270 (9)	0.0197 (7)	−0.0023 (6)	0.0054 (6)	−0.0013 (7)
C4	0.0246 (8)	0.0249 (9)	0.0357 (9)	0.0042 (7)	0.0008 (6)	−0.0001 (8)
C7	0.0270 (8)	0.0235 (9)	0.0199 (7)	0.0004 (6)	−0.0003 (6)	−0.0006 (6)
C12	0.0239 (7)	0.0267 (9)	0.0204 (7)	−0.0064 (7)	0.0008 (6)	0.0017 (7)
C13	0.0257 (8)	0.0239 (9)	0.0279 (8)	0.0010 (6)	0.0052 (6)	−0.0026 (7)
C1	0.0212 (7)	0.0164 (9)	0.0183 (7)	−0.0015 (5)	0.0020 (5)	−0.0045 (5)
C3	0.0216 (7)	0.0249 (9)	0.0254 (8)	0.0001 (6)	0.0024 (6)	−0.0023 (7)
C14	0.0190 (7)	0.0264 (9)	0.0262 (8)	0.0004 (6)	0.0033 (6)	0.0003 (7)
C5	0.0236 (8)	0.0303 (9)	0.0305 (8)	0.0003 (7)	−0.0039 (6)	0.0070 (7)

Geometric parameters (Å, º)

S1—C1	1.6821 (15)	C10—H10	0.984 (18)
N1—C1	1.3342 (19)	C11—C12	1.379 (3)
N1—C15	1.4662 (19)	C11—H11	0.981 (19)
N1—C8	1.4868 (18)	C21—H21	0.96 (2)
C16—C21	1.389 (2)	C6—C5	1.518 (3)
C16—C17	1.391 (2)	C6—C7	1.523 (2)
C16—C15	1.512 (2)	C6—H6B	0.99 (2)
C17—C18	1.393 (2)	C6—H6A	0.95 (2)
C17—H17	0.958 (17)	C8—H8B	0.970 (18)
C20—C19	1.384 (3)	C8—H8A	0.988 (19)
C20—C21	1.390 (2)	C4—C3	1.506 (2)
C20—H20	0.96 (2)	C4—C5	1.526 (3)
C18—C19	1.385 (3)	C4—H4A	1.00 (2)
C18—H18	1.00 (2)	C4—H4B	0.96 (2)
C9—C14	1.391 (2)	C7—H7A	0.999 (18)
C9—C10	1.391 (2)	C7—H7B	0.99 (2)
C9—C8	1.510 (2)	C12—C13	1.388 (2)
C2—C3	1.331 (2)	C12—H12	0.976 (18)
C2—C1	1.4908 (19)	C13—C14	1.385 (2)
C2—C7	1.515 (2)	C13—H13	0.94 (2)
C19—H19	0.96 (2)	C3—H3	1.02 (2)
C15—H15A	0.953 (19)	C14—H14	0.980 (18)
C15—H15B	1.021 (18)	C5—H5A	1.01 (2)
C10—C11	1.388 (2)	C5—H5B	1.03 (2)
C1—N1—C15	122.20 (13)	C5—C6—H6A	107.6 (12)
C1—N1—C8	123.27 (12)	C7—C6—H6A	109.4 (11)
C15—N1—C8	114.53 (12)	H6B—C6—H6A	109.7 (16)
C21—C16—C17	119.12 (17)	N1—C8—C9	113.32 (12)
C21—C16—C15	119.28 (16)	N1—C8—H8B	106.0 (10)
C17—C16—C15	121.56 (16)	C9—C8—H8B	109.8 (11)
C16—C17—C18	120.49 (17)	N1—C8—H8A	107.8 (10)
C16—C17—H17	119.7 (11)	C9—C8—H8A	110.7 (10)
C18—C17—H17	119.8 (11)	H8B—C8—H8A	109.0 (14)
C19—C20—C21	120.23 (18)	C3—C4—C5	111.51 (14)
C19—C20—H20	121.8 (12)	C3—C4—H4A	107.4 (13)
C21—C20—H20	117.9 (12)	C5—C4—H4A	109.6 (12)
C19—C18—C17	119.86 (19)	C3—C4—H4B	109.1 (12)
C19—C18—H18	120.3 (10)	C5—C4—H4B	112.0 (12)
C17—C18—H18	119.9 (10)	H4A—C4—H4B	107.2 (18)
C14—C9—C10	119.23 (14)	C2—C7—C6	111.34 (13)
C14—C9—C8	120.77 (14)	C2—C7—H7A	110.1 (10)
C10—C9—C8	120.00 (15)	C6—C7—H7A	109.9 (10)
C3—C2—C1	120.64 (13)	C2—C7—H7B	109.1 (11)
C3—C2—C7	123.25 (13)	C6—C7—H7B	111.4 (11)
C1—C2—C7	115.91 (13)	H7A—C7—H7B	104.7 (16)
C20—C19—C18	119.90 (18)	C11—C12—C13	119.50 (15)
C20—C19—H19	120.4 (12)	C11—C12—H12	119.1 (11)
C18—C19—H19	119.6 (12)	C13—C12—H12	121.4 (11)
N1—C15—C16	112.29 (13)	C14—C13—C12	120.03 (17)
N1—C15—H15A	108.9 (10)	C14—C13—H13	119.7 (10)
C16—C15—H15A	108.4 (10)	C12—C13—H13	120.2 (10)
N1—C15—H15B	105.8 (10)	N1—C1—C2	118.85 (12)
C16—C15—H15B	109.1 (10)	N1—C1—S1	124.02 (11)
H15A—C15—H15B	112.6 (15)	C2—C1—S1	117.13 (10)
C11—C10—C9	119.81 (15)	C2—C3—C4	123.41 (14)
C11—C10—H10	119.2 (9)	C2—C3—H3	120.2 (12)
C9—C10—H10	121.0 (9)	C4—C3—H3	116.4 (12)
C12—C11—C10	120.85 (14)	C13—C14—C9	120.55 (15)
C12—C11—H11	117.7 (11)	C13—C14—H14	120.6 (11)
C10—C11—H11	121.4 (11)	C9—C14—H14	118.8 (11)
C16—C21—C20	120.39 (18)	C6—C5—C4	110.26 (14)
C16—C21—H21	118.5 (11)	C6—C5—H5A	108.9 (13)
C20—C21—H21	121.2 (11)	C4—C5—H5A	110.4 (12)
C5—C6—C7	111.06 (14)	C6—C5—H5B	108.0 (12)
C5—C6—H6B	109.4 (13)	C4—C5—H5B	108.7 (11)
C7—C6—H6B	109.6 (12)	H5A—C5—H5B	110.5 (16)
C21—C16—C17—C18	−0.9 (2)	C1—C2—C7—C6	−170.77 (14)
C15—C16—C17—C18	176.87 (14)	C5—C6—C7—C2	−45.25 (18)
C16—C17—C18—C19	0.5 (2)	C10—C11—C12—C13	−1.0 (2)
C21—C20—C19—C18	−0.1 (3)	C11—C12—C13—C14	−0.5 (2)
C17—C18—C19—C20	0.0 (3)	C15—N1—C1—C2	179.33 (14)
C1—N1—C15—C16	−112.01 (15)	C8—N1—C1—C2	−1.2 (2)
C8—N1—C15—C16	68.48 (18)	C15—N1—C1—S1	−1.1 (2)
C21—C16—C15—N1	−145.29 (15)	C8—N1—C1—S1	178.39 (12)
C17—C16—C15—N1	37.0 (2)	C3—C2—C1—N1	−70.75 (19)
C14—C9—C10—C11	0.4 (2)	C7—C2—C1—N1	114.16 (15)
C8—C9—C10—C11	179.81 (14)	C3—C2—C1—S1	109.63 (14)
C9—C10—C11—C12	1.1 (2)	C7—C2—C1—S1	−65.46 (16)
C17—C16—C21—C20	0.8 (2)	C1—C2—C3—C4	−174.28 (15)
C15—C16—C21—C20	−177.01 (15)	C7—C2—C3—C4	0.4 (3)
C19—C20—C21—C16	−0.3 (3)	C5—C4—C3—C2	16.0 (2)
C1—N1—C8—C9	−62.2 (2)	C12—C13—C14—C9	1.9 (2)
C15—N1—C8—C9	117.27 (15)	C10—C9—C14—C13	−1.9 (2)
C14—C9—C8—N1	−49.3 (2)	C8—C9—C14—C13	178.68 (15)
C10—C9—C8—N1	131.23 (15)	C7—C6—C5—C4	62.94 (18)
C3—C2—C7—C6	14.3 (2)	C3—C4—C5—C6	−46.56 (19)

(xrayirr) N,N-di(benzyl-d₇)-1-cyclohexenecarbothioamide & (3S)-2-benzyl-d₇-3-phenyl-d₅-2-azaspiro[3.5]nonane-3,5 − d₂-1-thione

Crystal data

C21H9D14NS	F(000) = 344
Mr = 335.43	Dx = 1.208 Mg m^−3
Monoclinic, P21	Melting point: 346 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.7075 (5) Å	Cell parameters from 8684 reflections
b = 10.2068 (6) Å	θ = 2.1–27.5°
c = 10.0908 (9) Å	µ = 0.18 mm^−1
β = 99.909 (3)°	T = 173 K
V = 883.45 (11) Å^3	Prism, pale yellow
Z = 2	0.20 × 0.20 × 0.10 mm

Data collection

Rigaku RAXIS-RAPID diffractometer	3665 independent reflections
Radiation source: Rigaku rotating anode Ultrax18	3573 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ω scan	h = −11→11
Absorption correction: multi-scan ABSCOR, T.Higashi(1995) HIGASHI, T. (1995). ABSCOR - Empirical Absorption Correction based on Fourier Series Approximation. Rigaku Corporation, Tokyo, Japan.	k = −12→13
Tmin = 0.964, Tmax = 0.982	l = −13→13
8684 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	Constrainedaint
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0758P)^2 + 0.1336P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.116	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.39 e Å^−3
3665 reflections	Δρmin = −0.17 e Å^−3
270 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
8 restraints	Extinction coefficient: 0.032 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (7)

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.45166 (5)	0.95906 (4)	0.17436 (4)	0.03530 (10)	0.8519 (8)
N1	0.63742 (16)	1.04679 (14)	0.01160 (13)	0.0327 (3)	0.8519 (8)
C1	0.62519 (17)	0.98356 (15)	0.12240 (14)	0.0302 (3)	0.8519 (8)
C3	0.84274 (19)	0.83090 (17)	0.16753 (16)	0.0384 (4)	0.8519 (8)
H3	0.8103	0.7996	0.0785	0.046*	0.8519 (8)
C4	0.9803 (2)	0.76316 (19)	0.2543 (2)	0.0453 (4)	0.8519 (8)
H4A	0.9666	0.6671	0.2455	0.054*	0.8519 (8)
H4B	1.0772	0.7867	0.2212	0.054*	0.8519 (8)
C5	0.9965 (2)	0.8001 (2)	0.3998 (2)	0.0472 (5)	0.8519 (8)
H5A	0.9197	0.7506	0.4417	0.057*	0.8519 (8)
H5B	1.1021	0.7764	0.4470	0.057*	0.8519 (8)
C6	0.9709 (2)	0.9437 (2)	0.41482 (19)	0.0539 (6)	0.8519 (8)
H6A	1.0512	0.9923	0.3762	0.065*	0.8519 (8)
H6B	0.9846	0.9653	0.5118	0.065*	0.8519 (8)
C8	0.79008 (18)	1.07354 (17)	−0.03145 (14)	0.0359 (3)	0.8519 (8)
H8A	0.7707	1.1152	−0.1214	0.043*	0.8519 (8)
H8B	0.8442	0.9894	−0.0395	0.043*	0.8519 (8)
C9	0.89486 (16)	1.16145 (16)	0.06513 (14)	0.0327 (3)	0.8519 (8)
C10	1.04987 (18)	1.12689 (16)	0.10940 (15)	0.0337 (3)	0.8519 (8)
H10	1.0904	1.0485	0.0781	0.040*	0.8519 (8)
C11	1.14479 (19)	1.20704 (19)	0.19909 (16)	0.0384 (4)	0.8519 (8)
H11	1.2507	1.1834	0.2287	0.046*	0.8519 (8)
C12	1.0876 (2)	1.32059 (18)	0.24589 (16)	0.0389 (4)	0.8519 (8)
H12	1.1532	1.3746	0.3083	0.047*	0.8519 (8)
C13	0.9336 (2)	1.35564 (18)	0.20132 (17)	0.0390 (4)	0.8519 (8)
H13	0.8932	1.4338	0.2331	0.047*	0.8519 (8)
C14	0.83901 (18)	1.27673 (17)	0.11068 (16)	0.0378 (4)	0.8519 (8)
H14	0.7341	1.3020	0.0792	0.045*	0.8519 (8)
C15	0.50096 (19)	1.09974 (16)	−0.08121 (14)	0.0361 (3)	0.8519 (8)
H15A	0.5180	1.1940	−0.0967	0.043*	0.8519 (8)
H15B	0.4070	1.0916	−0.0388	0.043*	0.8519 (8)
C16	0.47344 (17)	1.02921 (16)	−0.21426 (15)	0.0339 (3)	0.8519 (8)
C17	0.4916 (2)	0.89667 (19)	−0.22260 (17)	0.0401 (4)	0.8519 (8)
H17	0.5268	0.8482	−0.1428	0.048*	0.8519 (8)
C18	0.4599 (2)	0.8309 (2)	−0.34522 (18)	0.0426 (5)	0.8519 (8)
H18	0.4722	0.7386	−0.3492	0.051*	0.8519 (8)
C19	0.4104 (2)	0.9020 (2)	−0.46052 (16)	0.0466 (5)	0.8519 (8)
H19	0.3904	0.8589	−0.5452	0.056*	0.8519 (8)
C20	0.3896 (3)	1.0364 (2)	−0.45360 (17)	0.0525 (5)	0.8519 (8)
H20	0.3528	1.0846	−0.5333	0.063*	0.8519 (8)
C21	0.4224 (2)	1.1009 (2)	−0.33068 (16)	0.0465 (4)	0.8519 (8)
H21	0.4101	1.1932	−0.3262	0.056*	0.8519 (8)
C2	0.76675 (14)	0.92910 (12)	0.20754 (11)	0.0312 (3)
C7	0.80963 (17)	0.99001 (14)	0.34634 (12)	0.0394 (3)
H7A	0.7311	0.9652	0.4020	0.047*
H7B	0.8093	1.0867	0.3382	0.047*
S1'	0.4313 (4)	0.9398 (4)	0.1756 (3)	0.0405 (7)*	0.1481 (8)
N1'	0.6532 (16)	1.0303 (13)	0.0228 (14)	0.044 (4)*	0.1481 (8)
C1'	0.5930 (8)	0.9683 (8)	0.1319 (6)	0.0127 (12)*	0.1481 (8)
C3'	0.7984 (7)	0.7801 (5)	0.1953 (7)	0.0292 (16)*	0.1481 (8)
H3'1	0.7158	0.7294	0.2284	0.035*	0.1481 (8)
H3'2	0.7961	0.7571	0.0996	0.035*	0.1481 (8)
C4'	0.9580 (10)	0.7442 (14)	0.2775 (7)	0.046 (7)*	0.1481 (8)
H4'1	1.0426	0.7796	0.2338	0.055*	0.1481 (8)
H4'2	0.9696	0.6478	0.2839	0.055*	0.1481 (8)
C5'	0.9668 (10)	0.8039 (5)	0.4185 (7)	0.0205 (15)*	0.1481 (8)
H5'1	0.8747	0.7748	0.4562	0.025*	0.1481 (8)
H5'2	1.0608	0.7696	0.4776	0.025*	0.1481 (8)
C6'	0.9728 (5)	0.9541 (5)	0.4206 (5)	0.0262 (11)*	0.1481 (8)
H6'1	0.9911	0.9883	0.5138	0.031*	0.1481 (8)
H6'2	1.0548	0.9877	0.3727	0.031*	0.1481 (8)
C8'	0.8238 (10)	1.0011 (9)	0.0878 (9)	0.0351 (17)*	0.1481 (8)
H8'	0.8764	0.9403	0.0320	0.042*	0.1481 (8)
C14'	0.8539 (4)	1.2412 (5)	0.1673 (5)	0.039 (2)*	0.1481 (8)
H14'	0.7442	1.2507	0.1590	0.046*	0.1481 (8)
C9'	0.9162 (5)	1.1269 (5)	0.1236 (6)	0.0322 (17)*	0.1481 (8)
C10'	1.0768 (6)	1.1129 (5)	0.1357 (7)	0.034 (2)*	0.1481 (8)
H10'	1.1194	1.0348	0.1058	0.041*	0.1481 (8)
C11'	1.1751 (5)	1.2131 (6)	0.1916 (6)	0.0144 (14)*	0.1481 (8)
H11'	1.2849	1.2035	0.1999	0.017*	0.1481 (8)
C12'	1.1128 (5)	1.3274 (6)	0.2354 (6)	0.0169 (15)*	0.1481 (8)
H12'	1.1800	1.3959	0.2736	0.020*	0.1481 (8)
C13'	0.9522 (5)	1.3414 (5)	0.2232 (6)	0.040 (3)*	0.1481 (8)
H13'	0.9097	1.4195	0.2532	0.048*	0.1481 (8)
C15'	0.5725 (14)	1.1009 (13)	−0.0730 (11)	0.048 (2)*	0.1481 (8)
H15C	0.6328	1.1802	−0.0881	0.057*	0.1481 (8)
H15D	0.4743	1.1296	−0.0450	0.057*	0.1481 (8)
C16'	0.5327 (6)	1.0182 (5)	−0.2118 (4)	0.0341 (19)*	0.1481 (8)
C17'	0.5117 (7)	0.8833 (5)	−0.2091 (5)	0.0232 (14)*	0.1481 (8)
H17'	0.5238	0.8384	−0.1255	0.028*	0.1481 (8)
C18'	0.4731 (9)	0.8141 (5)	−0.3289 (6)	0.037 (3)*	0.1481 (8)
H18A	0.4588	0.7218	−0.3271	0.044*	0.1481 (8)
C19'	0.4554 (10)	0.8798 (7)	−0.4512 (5)	0.041 (3)*	0.1481 (8)
H19'	0.4290	0.8325	−0.5331	0.061*	0.1481 (8)
C20'	0.4763 (9)	1.0147 (7)	−0.4538 (4)	0.041 (2)*	0.1481 (8)
H20'	0.4643	1.0596	−0.5374	0.049*	0.1481 (8)
C21'	0.5150 (8)	1.0839 (5)	−0.3341 (5)	0.035 (2)*	0.1481 (8)
H21'	0.5293	1.1761	−0.3359	0.042*	0.1481 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.03990 (17)	0.03442 (19)	0.03237 (15)	0.00252 (15)	0.00850 (12)	0.00233 (14)
N1	0.0339 (6)	0.0343 (6)	0.0282 (5)	−0.0080 (5)	0.0007 (4)	−0.0041 (5)
C1	0.0323 (6)	0.0296 (7)	0.0275 (6)	−0.0057 (5)	0.0016 (5)	−0.0074 (5)
C3	0.0382 (7)	0.0384 (8)	0.0364 (7)	0.0012 (7)	0.0002 (6)	−0.0040 (6)
C4	0.0367 (7)	0.0399 (9)	0.0549 (9)	0.0110 (7)	−0.0039 (7)	0.0022 (7)
C5	0.0376 (8)	0.0524 (10)	0.0485 (9)	−0.0017 (7)	−0.0015 (7)	0.0121 (7)
C6	0.0622 (10)	0.0548 (11)	0.0369 (8)	−0.0125 (9)	−0.0130 (7)	0.0067 (8)
C8	0.0386 (7)	0.0432 (8)	0.0255 (6)	−0.0099 (6)	0.0042 (5)	−0.0033 (5)
C9	0.0343 (6)	0.0376 (7)	0.0248 (6)	−0.0059 (6)	0.0006 (5)	0.0022 (5)
C10	0.0349 (6)	0.0341 (7)	0.0321 (7)	−0.0017 (6)	0.0060 (5)	0.0028 (5)
C11	0.0284 (6)	0.0514 (9)	0.0349 (7)	−0.0033 (7)	0.0042 (5)	0.0072 (6)
C12	0.0372 (7)	0.0452 (9)	0.0327 (7)	−0.0133 (7)	0.0017 (6)	−0.0022 (6)
C13	0.0398 (7)	0.0370 (8)	0.0377 (7)	0.0002 (7)	−0.0004 (6)	−0.0038 (6)
C14	0.0337 (6)	0.0412 (8)	0.0361 (7)	−0.0024 (6)	−0.0007 (5)	−0.0025 (6)
C15	0.0412 (7)	0.0342 (7)	0.0301 (6)	0.0000 (7)	−0.0014 (6)	0.0057 (6)
C16	0.0309 (6)	0.0377 (8)	0.0307 (6)	−0.0048 (6)	−0.0013 (5)	0.0077 (5)
C17	0.0373 (7)	0.0463 (9)	0.0330 (7)	−0.0003 (7)	−0.0044 (6)	0.0084 (6)
C18	0.0381 (8)	0.0444 (9)	0.0410 (8)	−0.0033 (7)	−0.0053 (6)	−0.0012 (7)
C19	0.0489 (9)	0.0602 (10)	0.0270 (7)	−0.0111 (9)	−0.0039 (6)	−0.0036 (7)
C20	0.0640 (11)	0.0560 (10)	0.0310 (7)	−0.0118 (9)	−0.0102 (7)	0.0109 (7)
C21	0.0570 (9)	0.0451 (9)	0.0326 (7)	−0.0078 (8)	−0.0061 (7)	0.0113 (6)
C2	0.0340 (5)	0.0311 (6)	0.0260 (5)	−0.0029 (5)	−0.0020 (4)	0.0006 (4)
C7	0.0481 (7)	0.0411 (7)	0.0256 (5)	−0.0012 (6)	−0.0033 (5)	−0.0027 (5)

Geometric parameters (Å, º)

S1—C1	1.7010 (16)	C2—C8'	1.566 (9)
N1—C1	1.311 (2)	C2—C1'	1.623 (7)
N1—C15	1.483 (2)	C7—C6'	1.532 (4)
N1—C8	1.493 (2)	C7—H7A	0.9900
C1—C2	1.4839 (18)	C7—H7B	0.9900
C3—C2	1.303 (2)	S1'—C1'	1.573 (8)
C3—C4	1.523 (2)	N1'—C15'	1.309 (16)
C3—H3	0.9500	N1'—C1'	1.444 (16)
C4—C5	1.498 (3)	N1'—C8'	1.546 (15)
C4—H4A	0.9900	C3'—C4'	1.535 (7)
C4—H4B	0.9900	C3'—H3'1	0.9900
C5—C6	1.495 (3)	C3'—H3'2	0.9900
C5—H5A	0.9900	C4'—C5'	1.537 (7)
C5—H5B	0.9900	C4'—H4'1	0.9900
C6—C7	1.529 (2)	C4'—H4'2	0.9900
C6—H6A	0.9900	C5'—C6'	1.535 (6)
C6—H6B	0.9900	C5'—H5'1	0.9900
C8—C9	1.510 (2)	C5'—H5'2	0.9900
C8—H8A	0.9900	C6'—H6'1	0.9900
C8—H8B	0.9900	C6'—H6'2	0.9900
C9—C14	1.382 (2)	C8'—C9'	1.526 (10)
C9—C10	1.392 (2)	C8'—H8'	1.0000
C10—C11	1.384 (2)	C14'—C9'	1.3900
C10—H10	0.9500	C14'—C13'	1.3900
C11—C12	1.377 (3)	C14'—H14'	0.9500
C11—H11	0.9500	C9'—C10'	1.3900
C12—C13	1.386 (2)	C10'—C11'	1.3900
C12—H12	0.9500	C10'—H10'	0.9500
C13—C14	1.380 (2)	C11'—C12'	1.3900
C13—H13	0.9500	C11'—H11'	0.9500
C14—H14	0.9500	C12'—C13'	1.3900
C15—C16	1.506 (2)	C12'—H12'	0.9500
C15—H15A	0.9900	C13'—H13'	0.9500
C15—H15B	0.9900	C15'—C16'	1.621 (12)
C16—C17	1.366 (2)	C15'—H15C	0.9900
C16—C21	1.390 (2)	C15'—H15D	0.9900
C17—C18	1.393 (2)	C16'—C17'	1.3900
C17—H17	0.9500	C16'—C21'	1.3900
C18—C19	1.376 (3)	C17'—C18'	1.3900
C18—H18	0.9500	C17'—H17'	0.9500
C19—C20	1.387 (3)	C18'—C19'	1.3900
C19—H19	0.9500	C18'—H18A	0.9500
C20—C21	1.390 (3)	C19'—C20'	1.3900
C20—H20	0.9500	C19'—H19'	0.9500
C21—H21	0.9500	C20'—C21'	1.3900
C2—C7	1.5190 (16)	C20'—H20'	0.9500
C2—C3'	1.555 (5)	C21'—H21'	0.9500
C1—N1—C15	122.98 (14)	C2—C7—C6'	114.4 (2)
C1—N1—C8	123.04 (13)	C2—C7—H7A	109.5
C15—N1—C8	113.98 (13)	C6—C7—H7A	109.5
N1—C1—C2	119.80 (13)	C2—C7—H7B	109.5
N1—C1—S1	122.82 (11)	C6—C7—H7B	109.5
C2—C1—S1	117.38 (10)	H7A—C7—H7B	108.1
C2—C3—C4	124.20 (14)	C15'—N1'—C1'	125.8 (12)
C2—C3—H3	117.9	C15'—N1'—C8'	140.7 (13)
C4—C3—H3	117.9	C1'—N1'—C8'	92.3 (8)
C5—C4—C3	112.45 (16)	N1'—C1'—S1'	139.0 (7)
C5—C4—H4A	109.1	N1'—C1'—C2	92.0 (6)
C3—C4—H4A	109.1	S1'—C1'—C2	129.0 (5)
C5—C4—H4B	109.1	C4'—C3'—C2	110.3 (6)
C3—C4—H4B	109.1	C4'—C3'—H3'1	109.6
H4A—C4—H4B	107.8	C2—C3'—H3'1	109.6
C6—C5—C4	110.82 (16)	C4'—C3'—H3'2	109.6
C6—C5—H5A	109.5	C2—C3'—H3'2	109.6
C4—C5—H5A	109.5	H3'1—C3'—H3'2	108.1
C6—C5—H5B	109.5	C3'—C4'—C5'	107.6 (7)
C4—C5—H5B	109.5	C3'—C4'—H4'1	110.2
H5A—C5—H5B	108.1	C5'—C4'—H4'1	110.2
C5—C6—C7	113.51 (16)	C3'—C4'—H4'2	110.2
C5—C6—H6A	108.9	C5'—C4'—H4'2	110.2
C7—C6—H6A	108.9	H4'1—C4'—H4'2	108.5
C5—C6—H6B	108.9	C6'—C5'—C4'	113.9 (7)
C7—C6—H6B	108.9	C6'—C5'—H5'1	108.8
H6A—C6—H6B	107.7	C4'—C5'—H5'1	108.8
N1—C8—C9	112.96 (12)	C6'—C5'—H5'2	108.8
N1—C8—H8A	109.0	C4'—C5'—H5'2	108.8
C9—C8—H8A	109.0	H5'1—C5'—H5'2	107.7
N1—C8—H8B	109.0	C7—C6'—C5'	101.9 (4)
C9—C8—H8B	109.0	C7—C6'—H6'1	111.4
H8A—C8—H8B	107.8	C5'—C6'—H6'1	111.4
C14—C9—C10	119.10 (13)	C7—C6'—H6'2	111.4
C14—C9—C8	120.82 (13)	C5'—C6'—H6'2	111.4
C10—C9—C8	120.08 (14)	H6'1—C6'—H6'2	109.3
C11—C10—C9	119.81 (15)	C9'—C8'—N1'	111.5 (8)
C11—C10—H10	120.1	C9'—C8'—C2	115.9 (6)
C9—C10—H10	120.1	N1'—C8'—C2	90.5 (7)
C12—C11—C10	120.77 (15)	C9'—C8'—H8'	112.4
C12—C11—H11	119.6	N1'—C8'—H8'	112.4
C10—C11—H11	119.6	C2—C8'—H8'	112.4
C11—C12—C13	119.53 (15)	C9'—C14'—C13'	120.0
C11—C12—H12	120.2	C9'—C14'—H14'	120.0
C13—C12—H12	120.2	C13'—C14'—H14'	120.0
C14—C13—C12	119.87 (16)	C14'—C9'—C10'	120.0
C14—C13—H13	120.1	C14'—C9'—C8'	124.2 (4)
C12—C13—H13	120.1	C10'—C9'—C8'	114.6 (4)
C13—C14—C9	120.90 (15)	C11'—C10'—C9'	120.0
C13—C14—H14	119.6	C11'—C10'—H10'	120.0
C9—C14—H14	119.6	C9'—C10'—H10'	120.0
N1—C15—C16	112.11 (14)	C12'—C11'—C10'	120.0
N1—C15—H15A	109.2	C12'—C11'—H11'	120.0
C16—C15—H15A	109.2	C10'—C11'—H11'	120.0
N1—C15—H15B	109.2	C11'—C12'—C13'	120.0
C16—C15—H15B	109.2	C11'—C12'—H12'	120.0
H15A—C15—H15B	107.9	C13'—C12'—H12'	120.0
C17—C16—C21	119.51 (16)	C12'—C13'—C14'	120.0
C17—C16—C15	121.73 (14)	C12'—C13'—H13'	120.0
C21—C16—C15	118.72 (15)	C14'—C13'—H13'	120.0
C16—C17—C18	121.64 (16)	N1'—C15'—C16'	111.1 (11)
C16—C17—H17	119.2	N1'—C15'—H15C	109.4
C18—C17—H17	119.2	C16'—C15'—H15C	109.4
C19—C18—C17	118.83 (19)	N1'—C15'—H15D	109.4
C19—C18—H18	120.6	C16'—C15'—H15D	109.4
C17—C18—H18	120.6	H15C—C15'—H15D	108.0
C18—C19—C20	120.25 (17)	C17'—C16'—C21'	120.0
C18—C19—H19	119.9	C17'—C16'—C15'	120.6 (5)
C20—C19—H19	119.9	C21'—C16'—C15'	119.4 (5)
C19—C20—C21	120.32 (17)	C18'—C17'—C16'	120.0
C19—C20—H20	119.8	C18'—C17'—H17'	120.0
C21—C20—H20	119.8	C16'—C17'—H17'	120.0
C20—C21—C16	119.45 (19)	C17'—C18'—C19'	120.0
C20—C21—H21	120.3	C17'—C18'—H18A	120.0
C16—C21—H21	120.3	C19'—C18'—H18A	120.0
C3—C2—C1	121.62 (12)	C18'—C19'—C20'	120.0
C3—C2—C7	122.90 (12)	C18'—C19'—H19'	120.0
C1—C2—C7	115.37 (11)	C20'—C19'—H19'	120.0
C7—C2—C3'	117.1 (3)	C21'—C20'—C19'	120.0
C7—C2—C8'	117.3 (3)	C21'—C20'—H20'	120.0
C3'—C2—C8'	108.3 (5)	C19'—C20'—H20'	120.0
C7—C2—C1'	113.2 (3)	C20'—C21'—C16'	120.0
C3'—C2—C1'	111.6 (4)	C20'—C21'—H21'	120.0
C8'—C2—C1'	85.2 (4)	C16'—C21'—H21'	120.0
C2—C7—C6	110.55 (13)
C15—N1—C1—C2	177.69 (13)	C15'—N1'—C1'—C2	−171.1 (13)
C8—N1—C1—C2	−3.2 (2)	C8'—N1'—C1'—C2	−1.3 (7)
C15—N1—C1—S1	−1.8 (2)	C3—C2—C1'—N1'	−77.2 (7)
C8—N1—C1—S1	177.30 (12)	C1—C2—C1'—N1'	15.9 (12)
C2—C3—C4—C5	13.2 (3)	C7—C2—C1'—N1'	119.0 (6)
C3—C4—C5—C6	−42.3 (2)	C3'—C2—C1'—N1'	−106.4 (7)
C4—C5—C6—C7	59.8 (2)	C8'—C2—C1'—N1'	1.3 (7)
C1—N1—C8—C9	−63.7 (2)	C3—C2—C1'—S1'	102.2 (6)
C15—N1—C8—C9	115.49 (14)	C1—C2—C1'—S1'	−164.7 (19)
N1—C8—C9—C14	−48.6 (2)	C7—C2—C1'—S1'	−61.5 (7)
N1—C8—C9—C10	131.44 (15)	C3'—C2—C1'—S1'	73.1 (7)
C14—C9—C10—C11	0.8 (2)	C8'—C2—C1'—S1'	−179.2 (7)
C8—C9—C10—C11	−179.24 (14)	C3—C2—C3'—C4'	67.2 (6)
C9—C10—C11—C12	0.3 (3)	C1—C2—C3'—C4'	173.5 (5)
C10—C11—C12—C13	−0.7 (3)	C7—C2—C3'—C4'	−42.6 (7)
C11—C12—C13—C14	0.0 (3)	C8'—C2—C3'—C4'	92.8 (7)
C12—C13—C14—C9	1.2 (3)	C1'—C2—C3'—C4'	−175.3 (6)
C10—C9—C14—C13	−1.6 (2)	C2—C3'—C4'—C5'	49.1 (10)
C8—C9—C14—C13	178.49 (15)	C3'—C4'—C5'—C6'	−67.9 (10)
C1—N1—C15—C16	−112.42 (17)	C2—C7—C6'—C5'	−55.2 (4)
C8—N1—C15—C16	68.38 (17)	C6—C7—C6'—C5'	−23 (3)
N1—C15—C16—C17	39.4 (2)	C4'—C5'—C6'—C7	68.0 (7)
N1—C15—C16—C21	−143.08 (16)	C15'—N1'—C8'—C9'	50 (2)
C21—C16—C17—C18	−0.2 (3)	C1'—N1'—C8'—C9'	−116.8 (8)
C15—C16—C17—C18	177.30 (15)	C15'—N1'—C8'—C2	168.2 (19)
C16—C17—C18—C19	0.6 (3)	C1'—N1'—C8'—C2	1.4 (7)
C17—C18—C19—C20	−1.3 (3)	C3—C2—C8'—C9'	−124.0 (6)
C18—C19—C20—C21	1.7 (3)	C1—C2—C8'—C9'	110.0 (6)
C19—C20—C21—C16	−1.2 (3)	C7—C2—C8'—C9'	−0.6 (7)
C17—C16—C21—C20	0.5 (3)	C3'—C2—C8'—C9'	−135.8 (6)
C15—C16—C21—C20	−177.07 (18)	C1'—C2—C8'—C9'	113.1 (6)
C4—C3—C2—C1	−174.62 (16)	C3—C2—C8'—N1'	121.6 (6)
C4—C3—C2—C7	1.4 (3)	C1—C2—C8'—N1'	−4.3 (6)
C4—C3—C2—C3'	−84.9 (5)	C7—C2—C8'—N1'	−114.9 (6)
C4—C3—C2—C8'	119.5 (4)	C3'—C2—C8'—N1'	109.9 (7)
C4—C3—C2—C1'	−160.7 (3)	C1'—C2—C8'—N1'	−1.2 (7)
N1—C1—C2—C3	−68.9 (2)	C13'—C14'—C9'—C10'	0.0
S1—C1—C2—C3	110.66 (15)	C13'—C14'—C9'—C8'	166.9 (6)
N1—C1—C2—C7	114.79 (15)	N1'—C8'—C9'—C14'	34.6 (10)
S1—C1—C2—C7	−65.66 (15)	C2—C8'—C9'—C14'	−67.0 (8)
N1—C1—C2—C3'	−100.7 (3)	N1'—C8'—C9'—C10'	−157.8 (7)
S1—C1—C2—C3'	78.9 (3)	C2—C8'—C9'—C10'	100.6 (6)
N1—C1—C2—C8'	1.8 (4)	C14'—C9'—C10'—C11'	0.0
S1—C1—C2—C8'	−178.7 (4)	C8'—C9'—C10'—C11'	−168.1 (6)
N1—C1—C2—C1'	−163.1 (14)	C9'—C10'—C11'—C12'	0.0
S1—C1—C2—C1'	16.4 (13)	C10'—C11'—C12'—C13'	0.0
C3—C2—C7—C6	13.6 (2)	C11'—C12'—C13'—C14'	0.0
C1—C2—C7—C6	−170.16 (14)	C9'—C14'—C13'—C12'	0.0
C3'—C2—C7—C6	45.2 (3)	C1'—N1'—C15'—C16'	−102.8 (14)
C8'—C2—C7—C6	−86.1 (4)	C8'—N1'—C15'—C16'	93.4 (19)
C1'—C2—C7—C6	177.1 (3)	N1'—C15'—C16'—C17'	31.2 (13)
C3—C2—C7—C6'	16.1 (3)	N1'—C15'—C16'—C21'	−150.6 (9)
C1—C2—C7—C6'	−167.6 (2)	C21'—C16'—C17'—C18'	0.0
C3'—C2—C7—C6'	47.7 (4)	C15'—C16'—C17'—C18'	178.1 (6)
C8'—C2—C7—C6'	−83.6 (5)	C16'—C17'—C18'—C19'	0.0
C1'—C2—C7—C6'	179.7 (4)	C17'—C18'—C19'—C20'	0.0
C5—C6—C7—C2	−44.0 (2)	C18'—C19'—C20'—C21'	0.0
C5—C6—C7—C6'	167 (3)	C19'—C20'—C21'—C16'	0.0
C15'—N1'—C1'—S1'	10 (2)	C17'—C16'—C21'—C20'	0.0
C8'—N1'—C1'—S1'	179.3 (9)	C15'—C16'—C21'—C20'	−178.1 (6)

(neutronirr) N,N-di(benzyl-d₇)-1-cyclohexenecarbothioamide & (3R,5R)-2-benzyl-d₇-3-phenyl-d₅-2-azaspiro[3.5]nonane-3,5 − d₂-1-thione

Crystal data

C21H9D14NS	F(000) = 42
Mr = 335.43	Dx = 1.173 Mg m^−3
Monoclinic, P21	Melting point: 346 K
Hall symbol: P 2yb	Neutron radiation, λ = 1.51000 Å
a = 8.9117 (11) Å	Cell parameters from 1880 reflections
b = 10.5512 (17) Å	θ = 5.8–49.1°
c = 10.3463 (13) Å	µ = 0.21 mm^−1
β = 102.589 (8)°	T = 293 K
V = 949.5 (2) Å^3	Prism, pale yellow
Z = 2	4.50 × 1.50 × 1.40 mm

Data collection

BIX-III diffractometer	1301 independent reflections
Radiation source: JAERI JRR-3M reactor	1300 reflections with I > 2σ(I)
Perfect silicon crystal monochromator	Rint = 0.044
ω scan	θmax = 49.1°, θmin = 5.8°
Absorption correction: gaussian ABSG in PLATON, Crystallographic Computing (1970) originally coded by P. Coppens	h = −8→8
Tmin = 0.591, Tmax = 0.784	k = −10→10
1880 measured reflections	l = −10→10

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)] = 0.079	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.197	w = 1/[σ^2(Fo^2) + (0.1086P)^2 + 0.1004P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1301 reflections	Δρmax = 0.04 e Å^−3
297 parameters	Δρmin = −0.04 e Å^−3
25 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (10)

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1'	0.9320 (10)	0.7798 (14)	0.1582 (12)	0.6 (5)*	0.240 (6)
N1'	1.1626 (9)	0.8489 (11)	0.0426 (9)	0.034 (5)*	0.240 (6)
C1'	1.1062 (10)	0.7892 (12)	0.1353 (10)	0.093 (15)*	0.240 (6)
C2'	1.2640 (10)	0.7438 (12)	0.1973 (10)	0.11 (3)*	0.240 (6)
C3'	1.2824 (13)	0.5977 (12)	0.1905 (13)	0.085 (13)*	0.240 (6)
C4'	1.4454 (15)	0.5575 (13)	0.2512 (15)	0.16 (3)*	0.240 (6)
H4A'	1.5236	0.5997	0.1955	0.198*	0.240 (6)
H4B'	1.4546	0.4546	0.2449	0.198*	0.240 (6)
C5'	1.4929 (15)	0.5987 (16)	0.3970 (14)	0.13 (3)*	0.240 (6)
H5A'	1.4219	0.5494	0.4547	0.08 (3)*	0.240 (6)
H5B'	1.6126	0.5725	0.4365	0.14 (6)*	0.240 (6)
C6'	1.4747 (13)	0.7378 (16)	0.4103 (11)	0.11 (2)*	0.240 (6)
H6A'	1.5651	0.7848	0.3718	0.11 (4)*	0.240 (6)
H6B'	1.4938	0.7604	0.5156	0.14 (5)*	0.240 (6)
C7'	1.3181 (12)	0.7953 (14)	0.3399 (9)	0.08 (2)*	0.240 (6)
H7A'	1.2318	0.7729	0.3969	0.08 (2)*	0.240 (6)
H7B'	1.3285	0.8983	0.3365	0.043 (13)*	0.240 (6)
C8'	1.3241 (9)	0.8203 (11)	0.0932 (9)	0.093 (12)*	0.240 (6)
C9'	1.4255 (9)	0.9345 (12)	0.1329 (10)	0.059 (8)*	0.240 (6)
C10'	1.5831 (9)	0.9214 (14)	0.1442 (11)	0.087 (13)*	0.240 (6)
C11'	1.6809 (11)	1.0226 (16)	0.1909 (13)	0.11 (2)*	0.240 (6)
C12'	1.6212 (14)	1.1368 (15)	0.2262 (14)	0.12 (2)*	0.240 (6)
C13'	1.4636 (15)	1.1499 (13)	0.2149 (13)	0.8 (4)*	0.240 (6)
C14'	1.3658 (12)	1.0488 (12)	0.1682 (10)	0.096 (14)*	0.240 (6)
C15'	1.0791 (10)	0.9305 (12)	−0.0666 (9)	0.085 (14)*	0.240 (6)
C16'	1.0465 (11)	0.8587 (13)	−0.1987 (9)	0.058 (9)*	0.240 (6)
C17'	0.9882 (11)	0.7353 (14)	−0.2035 (11)	0.083 (14)*	0.240 (6)
C18'	0.9483 (14)	0.6715 (16)	−0.3240 (12)	0.16 (3)*	0.240 (6)
C19'	0.9667 (16)	0.7312 (19)	−0.4397 (11)	0.21 (4)*	0.240 (6)
C20'	1.0251 (15)	0.8547 (19)	−0.4349 (9)	0.097 (13)*	0.240 (6)
C21'	1.0651 (13)	0.9184 (16)	−0.3143 (9)	0.085 (11)*	0.240 (6)
D10'	1.6296 (9)	0.8324 (15)	0.1167 (12)	0.075 (11)*	0.240 (6)
D11'	1.8036 (11)	1.0124 (19)	0.1997 (15)	0.111 (17)*	0.240 (6)
D12'	1.6974 (17)	1.2156 (17)	0.2626 (16)	0.067 (10)*	0.240 (6)
D13'	1.4171 (18)	1.2389 (13)	0.2425 (15)	0.12 (2)*	0.240 (6)
D14'	1.2431 (12)	1.0590 (11)	0.1594 (10)	0.102 (14)*	0.240 (6)
D17'	0.9738 (11)	0.6888 (13)	−0.1134 (12)	0.063 (9)*	0.240 (6)
D18'	0.9029 (16)	0.5753 (17)	−0.3278 (14)	0.17 (3)*	0.240 (6)
D19'	0.9356 (19)	0.682 (2)	−0.5336 (12)	0.30 (8)*	0.240 (6)
D20'	1.0394 (18)	0.901 (2)	−0.5250 (9)	0.15 (2)*	0.240 (6)
D21'	1.1107 (14)	1.0145 (16)	−0.3105 (10)	0.14 (2)*	0.240 (6)
D8'	1.3646 (9)	0.7643 (12)	0.0329 (10)	0.081 (12)*	0.240 (6)
D15C	0.9707 (10)	0.9617 (12)	−0.0440 (10)	0.030 (7)*	0.240 (6)
D15D	1.1477 (11)	1.0153 (11)	−0.0749 (10)	0.084 (10)*	0.240 (6)
D3'	1.267 (4)	0.573 (4)	0.095 (3)	0.065 (9)*	0.240 (6)
H3'	1.232 (5)	0.521 (4)	0.229 (4)	0.047 (11)*	0.240 (6)
S1	0.9566 (4)	0.7722 (6)	0.1700 (6)	0.045 (4)*	0.760 (6)
N1	1.1479 (5)	0.8519 (5)	0.0095 (4)	0.068 (3)	0.760 (6)
C1	1.1286 (4)	0.7942 (4)	0.1208 (4)	0.054 (3)	0.760 (6)
C2	1.2750 (4)	0.7385 (5)	0.2045 (4)	0.048 (4)	0.760 (6)
C3	1.3288 (6)	0.6299 (5)	0.1689 (5)	0.097 (5)	0.760 (6)
C4	1.4729 (7)	0.5666 (6)	0.2530 (6)	0.119 (8)	0.760 (6)
H4A	1.5721	0.5906	0.2118	0.121 (9)*	0.760 (6)
H4B	1.4584	0.4638	0.2473	0.23 (2)*	0.760 (6)
C5	1.5055 (7)	0.6081 (8)	0.4012 (5)	0.105 (8)	0.760 (6)
H5A	1.4250	0.5605	0.4510	0.20 (3)*	0.760 (6)
H5B	1.6218	0.5798	0.4502	0.21 (3)*	0.760 (6)
C6	1.4889 (6)	0.7508 (7)	0.4128 (4)	0.093 (7)	0.760 (6)
H6A	1.5688	0.7995	0.3633	0.15 (2)*	0.760 (6)
H6B	1.5147	0.7790	0.5169	0.150 (17)*	0.760 (6)
C7	1.3211 (6)	0.7866 (6)	0.3468 (4)	0.087 (8)	0.760 (6)
H7A	1.2437	0.7464	0.4045	0.18 (2)*	0.760 (6)
H7B	1.3088	0.8895	0.3473	0.159 (18)*	0.760 (6)
C8	1.2896 (6)	0.8769 (6)	−0.0201 (5)	0.080 (4)	0.760 (6)
C14	1.3472 (5)	1.0824 (4)	0.1122 (5)	0.096 (4)	0.760 (6)
C9	1.4036 (6)	0.9705 (5)	0.0702 (5)	0.072 (3)	0.760 (6)
C10	1.5580 (6)	0.9393 (6)	0.1137 (8)	0.073 (3)*	0.760 (6)
C11	1.6558 (5)	1.0200 (7)	0.1991 (8)	0.099 (6)	0.760 (6)
C12	1.5993 (7)	1.1320 (6)	0.2411 (6)	0.086 (5)	0.760 (6)
C13	1.4450 (7)	1.1631 (5)	0.1977 (7)	0.067 (3)	0.760 (6)
C15	1.0001 (7)	0.9035 (9)	−0.0857 (10)	0.077 (4)	0.760 (6)
C21	0.9528 (5)	0.9190 (4)	−0.3268 (4)	0.121 (6)	0.760 (6)
C16	0.9868 (4)	0.8444 (4)	−0.2135 (3)	0.075 (3)	0.760 (6)
C17	0.9872 (5)	0.7131 (4)	−0.2244 (4)	0.084 (5)	0.760 (6)
C18	0.9534 (6)	0.6564 (4)	−0.3486 (5)	0.083 (5)	0.760 (6)
C19	0.9193 (7)	0.7310 (5)	−0.4620 (4)	0.098 (5)	0.760 (6)
C20	0.9190 (7)	0.8623 (5)	−0.4511 (3)	0.145 (7)	0.760 (6)
D8A	1.2702 (4)	0.9238 (4)	−0.1160 (4)	0.101 (4)	0.760 (6)
D8B	1.3588 (5)	0.7909 (5)	−0.0224 (5)	0.104 (5)	0.760 (6)
D10	1.5991 (5)	0.8496 (7)	0.0825 (7)	0.120 (6)	0.760 (6)
D11	1.7759 (6)	0.9940 (9)	0.2368 (9)	0.181 (11)	0.760 (6)
D12	1.6626 (8)	1.1998 (8)	0.3123 (9)	0.179 (11)	0.760 (6)
D13	1.3964 (8)	1.2438 (7)	0.2379 (7)	0.220 (19)	0.760 (6)
D14	1.2262 (6)	1.1057 (5)	0.0828 (5)	0.114 (6)	0.760 (6)
D15A	0.9062 (5)	0.8974 (6)	−0.0323 (4)	0.101 (5)	0.760 (6)
D15B	1.0331 (5)	1.0027 (4)	−0.0848 (4)	0.094 (5)	0.760 (6)
D17	1.0281 (6)	0.6510 (4)	−0.1401 (5)	0.134 (6)	0.760 (6)
D18	0.9455 (7)	0.5527 (4)	−0.3506 (6)	0.109 (5)	0.760 (6)
D19	0.8936 (8)	0.6766 (6)	−0.5532 (5)	0.222 (17)	0.760 (6)
D20	0.9051 (8)	0.9014 (6)	−0.5437 (3)	0.27 (2)	0.760 (6)
D21	0.9628 (6)	1.0216 (4)	−0.3198 (4)	0.26 (2)	0.760 (6)
H3	1.2905	0.6012	0.0672	0.135 (15)*	0.760 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.057 (4)	0.090 (6)	0.055 (4)	0.002 (4)	0.008 (3)	0.001 (4)
C1	0.046 (4)	0.066 (7)	0.041 (5)	0.008 (5)	−0.006 (4)	−0.006 (5)
C2	0.063 (6)	0.028 (6)	0.044 (6)	−0.004 (4)	−0.010 (4)	−0.001 (4)
C3	0.108 (9)	0.056 (8)	0.097 (9)	0.028 (8)	−0.042 (8)	−0.009 (8)
C4	0.090 (9)	0.048 (7)	0.193 (19)	0.048 (7)	−0.027 (9)	−0.027 (9)
C5	0.144 (15)	0.075 (10)	0.065 (8)	−0.006 (8)	−0.046 (8)	0.023 (7)
C6	0.102 (9)	0.044 (7)	0.102 (11)	−0.022 (6)	−0.042 (7)	0.014 (7)
C7	0.090 (10)	0.128 (16)	0.036 (6)	−0.008 (8)	0.000 (5)	−0.007 (7)
C8	0.081 (8)	0.094 (10)	0.054 (6)	0.006 (6)	−0.010 (6)	0.016 (7)
C14	0.057 (6)	0.064 (8)	0.168 (13)	0.010 (6)	0.026 (7)	−0.030 (10)
C9	0.048 (5)	0.078 (8)	0.080 (7)	−0.022 (5)	−0.009 (5)	0.020 (7)
C11	0.083 (8)	0.108 (13)	0.109 (11)	0.007 (8)	0.029 (7)	−0.018 (9)
C12	0.082 (9)	0.103 (12)	0.058 (7)	−0.032 (8)	−0.018 (6)	−0.001 (7)
C13	0.106 (8)	0.049 (6)	0.049 (5)	−0.033 (7)	0.024 (5)	−0.043 (6)
C15	0.125 (11)	0.023 (6)	0.079 (9)	−0.012 (6)	0.011 (7)	0.016 (7)
C21	0.201 (16)	0.142 (14)	0.005 (5)	−0.041 (12)	−0.013 (6)	−0.019 (7)
C16	0.094 (7)	0.099 (10)	0.021 (5)	−0.017 (7)	−0.009 (4)	0.006 (6)
C17	0.075 (7)	0.064 (9)	0.120 (12)	0.000 (6)	0.033 (7)	0.022 (9)
C18	0.089 (8)	0.089 (10)	0.066 (7)	−0.015 (7)	0.009 (5)	−0.052 (9)
C19	0.123 (10)	0.090 (12)	0.071 (9)	0.001 (8)	0.000 (7)	0.008 (9)
C20	0.201 (19)	0.123 (15)	0.088 (11)	−0.055 (14)	−0.021 (10)	0.060 (12)
D8A	0.114 (9)	0.109 (11)	0.078 (7)	−0.055 (8)	0.019 (7)	−0.009 (8)
D8B	0.060 (7)	0.152 (14)	0.111 (10)	−0.038 (8)	0.040 (6)	−0.050 (11)
D10	0.095 (9)	0.099 (11)	0.163 (14)	0.035 (9)	0.019 (9)	0.034 (12)
D11	0.093 (10)	0.158 (19)	0.26 (3)	0.051 (11)	−0.032 (14)	−0.047 (17)
D12	0.148 (15)	0.27 (3)	0.116 (14)	−0.068 (18)	0.018 (12)	−0.004 (16)
D13	0.26 (3)	0.26 (4)	0.106 (15)	−0.03 (3)	−0.018 (16)	−0.081 (19)
D14	0.084 (8)	0.076 (9)	0.169 (15)	0.045 (7)	0.000 (8)	−0.030 (10)
D15A	0.096 (8)	0.137 (14)	0.076 (7)	−0.017 (8)	0.030 (6)	0.022 (8)
D15B	0.080 (7)	0.151 (16)	0.052 (6)	−0.011 (9)	0.018 (5)	0.009 (8)
D17	0.179 (16)	0.084 (12)	0.129 (13)	0.048 (12)	0.008 (12)	−0.008 (10)
D18	0.129 (10)	0.076 (9)	0.109 (10)	−0.007 (9)	−0.005 (8)	−0.065 (10)
D19	0.177 (17)	0.41 (5)	0.070 (10)	0.00 (2)	0.009 (10)	−0.133 (18)
D20	0.54 (7)	0.15 (2)	0.066 (10)	−0.01 (3)	−0.046 (19)	0.040 (12)
D21	0.58 (7)	0.057 (11)	0.101 (14)	−0.02 (2)	0.00 (2)	−0.003 (12)

Geometric parameters (Å, º)

S1'—C1'	1.6237	D3'—H3	0.4856
N1'—C1'	1.3343	S1—C1	1.7323
N1'—C8'	1.4519	N1—C1	1.3460
N1'—C15'	1.4846	N1—C8	1.3877
C1'—C2'	1.4912	N1—C15	1.560 (8)
C2'—C8'	1.5322	C1—C2	1.5183
C2'—C7'	1.5476	C2—C3	1.3248
C2'—C3'	1.5537	C2—C7	1.5269
C3'—D3'	1.00 (3)	C3—C4	1.5382
C3'—C4'	1.5117	C3—H3	1.0765
C3'—H3'	1.04 (4)	C4—C5	1.5605
C3'—H3	1.2935	C4—H4A	1.0920
C4'—C5'	1.5375	C4—H4B	1.0920
C4'—H4A'	1.0920	C5—C6	1.5199
C4'—H4B'	1.0920	C5—H5A	1.0920
C5'—C6'	1.4861	C5—H5B	1.0920
C5'—H5A'	1.0920	C6—C7	1.5486
C5'—H5B'	1.0920	C6—H6A	1.0920
C6'—C7'	1.5506	C6—H6B	1.0920
C6'—H6A'	1.0920	C7—H7A	1.0920
C6'—H6B'	1.0920	C7—H7B	1.0920
C7'—H7A'	1.0920	C8—D8A	1.088 (6)
C7'—H7B'	1.0920	C8—D8B	1.100 (6)
C8'—D8'	0.9837	C8—C9	1.571 (8)
C8'—C9'	1.5088	C14—D14	1.083 (5)
C9'—C10'	1.3900	C14—C9	1.3900
C9'—C14'	1.3982	C14—C13	1.3900
C10'—D10'	1.0893	C9—C10	1.3900
C10'—C11'	1.3961	C10—D10	1.089 (5)
C11'—D11'	1.0829	C10—C11	1.3900
C11'—C12'	1.3982	C11—D11	1.092 (5)
C12'—D12'	1.0876	C11—C12	1.3900
C12'—C13'	1.3903	C12—D12	1.092 (5)
C13'—D13'	1.0891	C12—C13	1.3900
C13'—C14'	1.3955	C13—D13	1.079 (5)
C14'—D14'	1.0831	C15—D15B	1.087 (9)
C15'—D15C	1.0932	C15—D15A	1.101 (11)
C15'—D15D	1.0979	C15—C16	1.443 (11)
C15'—C16'	1.5338	C21—D21	1.0873
C16'—C21'	1.3934	C21—C16	1.3900
C16'—C17'	1.3990	C21—C20	1.3900
C17'—D17'	1.0860	C16—C17	1.3900
C17'—C18'	1.3925	C17—D17	1.0884
C18'—D18'	1.0902	C17—C18	1.3900
C18'—C19'	1.3939	C18—D18	1.0964
C19'—D19'	1.0850	C18—C19	1.3900
C19'—C20'	1.3993	C19—D19	1.0856
C20'—D20'	1.0860	C19—C20	1.3900
C20'—C21'	1.3931	C20—D20	1.0254
C21'—D21'	1.0902
C1'—N1'—C8'	98.1	D21'—C21'—C20'	120.1
C1'—N1'—C15'	128.0	D21'—C21'—C16'	120.2
C8'—N1'—C15'	133.5	C20'—C21'—C16'	119.7
N1'—C1'—C2'	89.6	C1—N1—C8	124.5
N1'—C1'—S1'	130.9	C1—N1—C15	116.7 (5)
C2'—C1'—S1'	139.5	C8—N1—C15	118.5 (5)
C1'—C2'—C8'	88.3	N1—C1—C2	114.1
C1'—C2'—C7'	111.4	N1—C1—S1	126.7
C8'—C2'—C7'	113.7	C2—C1—S1	119.0
C1'—C2'—C3'	113.5	C3—C2—C1	119.6
C8'—C2'—C3'	115.7	C3—C2—C7	121.2
C7'—C2'—C3'	112.2	C1—C2—C7	116.0
D3'—C3'—C4'	104.3 (18)	C2—C3—C4	121.8
D3'—C3'—C2'	108 (2)	C2—C3—H3	117.3
C4'—C3'—C2'	111.2	C4—C3—H3	118.5
D3'—C3'—H3'	102 (4)	C3—C4—C5	112.8
C4'—C3'—H3'	95 (2)	C3—C4—H4A	109.0
C2'—C3'—H3'	134 (3)	C5—C4—H4A	109.0
C3'—C4'—C5'	111.2	C3—C4—H4B	109.0
C3'—C4'—H4A'	109.4	C5—C4—H4B	109.0
C5'—C4'—H4A'	109.4	H4A—C4—H4B	107.8
C3'—C4'—H4B'	109.4	C6—C5—C4	110.8
C5'—C4'—H4B'	109.4	C6—C5—H5A	109.5
H4A'—C4'—H4B'	108.0	C4—C5—H5A	109.5
C6'—C5'—C4'	111.0	C6—C5—H5B	109.5
C6'—C5'—H5A'	109.4	C4—C5—H5B	109.5
C4'—C5'—H5A'	109.4	H5A—C5—H5B	108.1
C6'—C5'—H5B'	109.4	C5—C6—C7	107.9
C4'—C5'—H5B'	109.4	C5—C6—H6A	110.1
H5A'—C5'—H5B'	108.0	C7—C6—H6A	110.1
C5'—C6'—C7'	116.6	C5—C6—H6B	110.1
C5'—C6'—H6A'	108.1	C7—C6—H6B	110.1
C7'—C6'—H6A'	108.1	H6A—C6—H6B	108.4
C5'—C6'—H6B'	108.1	C2—C7—C6	112.1
C7'—C6'—H6B'	108.1	C2—C7—H7A	109.2
H6A'—C6'—H6B'	107.3	C6—C7—H7A	109.2
C2'—C7'—C6'	111.8	C2—C7—H7B	109.2
C2'—C7'—H7A'	109.3	C6—C7—H7B	109.2
C6'—C7'—H7A'	109.3	H7A—C7—H7B	107.9
C2'—C7'—H7B'	109.3	D8A—C8—D8B	109.5 (5)
C6'—C7'—H7B'	109.3	D8A—C8—N1	108.4 (4)
H7A'—C7'—H7B'	107.9	D8B—C8—N1	113.0 (4)
D8'—C8'—N1'	111.6	D8A—C8—C9	102.1 (5)
D8'—C8'—C9'	111.8	D8B—C8—C9	103.7 (4)
N1'—C8'—C9'	114.9	N1—C8—C9	119.3 (3)
D8'—C8'—C2'	111.3	D14—C14—C9	120.8 (4)
N1'—C8'—C2'	83.8	D14—C14—C13	119.2 (4)
C9'—C8'—C2'	120.6	C9—C14—C13	120.0
C10'—C9'—C14'	119.9	C14—C9—C10	120.0
C10'—C9'—C8'	118.5	C14—C9—C8	119.2 (3)
C14'—C9'—C8'	121.4	C10—C9—C8	120.7 (3)
D10'—C10'—C9'	119.9	D10—C10—C11	121.1 (4)
D10'—C10'—C11'	120.3	D10—C10—C9	118.9 (4)
C9'—C10'—C11'	119.8	C11—C10—C9	120.0
D11'—C11'—C10'	119.8	D11—C11—C10	120.2 (5)
D11'—C11'—C12'	119.9	D11—C11—C12	119.7 (5)
C10'—C11'—C12'	120.3	C10—C11—C12	120.0
D12'—C12'—C13'	119.8	D12—C12—C13	113.1 (5)
D12'—C12'—C11'	120.3	D12—C12—C11	126.8 (5)
C13'—C12'—C11'	119.9	C13—C12—C11	120.0
D13'—C13'—C12'	119.9	D13—C13—C12	120.9 (4)
D13'—C13'—C14'	120.3	D13—C13—C14	118.7 (4)
C12'—C13'—C14'	119.8	C12—C13—C14	120.0
D14'—C14'—C13'	119.8	D15B—C15—D15A	106.6 (10)
D14'—C14'—C9'	119.9	D15B—C15—C16	113.1 (9)
C13'—C14'—C9'	120.3	D15A—C15—C16	121.0 (4)
D15C—C15'—D15D	107.7	D15B—C15—N1	98.1 (4)
D15C—C15'—N1'	109.4	D15A—C15—N1	107.0 (8)
D15D—C15'—N1'	109.7	C16—C15—N1	108.5 (7)
D15C—C15'—C16'	109.5	D21—C21—C16	120.5
D15D—C15'—C16'	109.5	D21—C21—C20	119.2
N1'—C15'—C16'	111.0	C16—C21—C20	120.0
C21'—C16'—C17'	120.2	C21—C16—C17	120.0
C21'—C16'—C15'	120.5	C21—C16—C15	119.2 (4)
C17'—C16'—C15'	119.2	C17—C16—C15	120.2 (4)
D17'—C17'—C18'	119.7	D17—C17—C18	116.7
D17'—C17'—C16'	120.2	D17—C17—C16	122.8
C18'—C17'—C16'	120.1	C18—C17—C16	120.0
D18'—C18'—C17'	120.2	D18—C18—C17	116.5
D18'—C18'—C19'	120.1	D18—C18—C19	123.3
C17'—C18'—C19'	119.7	C17—C18—C19	120.0
D19'—C19'—C18'	119.7	D19—C19—C20	126.4
D19'—C19'—C20'	120.1	D19—C19—C18	113.6
C18'—C19'—C20'	120.2	C20—C19—C18	120.0
D20'—C20'—C21'	119.7	D20—C20—C19	109.1
D20'—C20'—C19'	120.1	D20—C20—C21	130.4
C21'—C20'—C19'	120.1	C19—C20—C21	120.0