N-Benzyl­tetra­hydro­pyrido-anellated thio­phene derivatives: new anti­cholinesterases

The title compounds, tert-butyl 6-benzyl-2-(3,3-diethyl­ureido)-4,5,6,7-tetra­hydro­thieno[2,3-c]pyridine-3-carboxyl­ate, C₂₄H₃₃N₃O₃S, (I), 7-benzyl-2-diethyl­amino-5,6,7,8-tetra­hydro-3-oxa-9-thia-1,7-diaza­fluoren-4-one, C₂₀H₂₃N₃O₂S, (II), and N-(7-benzyl-4-oxo-5,6,7,8-tetra­hydro-4H-3,9-dithia-1,7-diaza­fluoren-2-yl)benzamide, C₂₃H₁₉N₃O₂S₂, (III), form monoclinic crystal systems. In (I) and (II), the mol­ecules are linked into a three-dimensional framework by weak inter­molecular C-H...O=C hydrogen bonds, whereas in (III) stronger inter­molecular N-H...O=C inter­actions are observed. The conformation of (I) is further stabilized by an intra­molecular N-H...O=C hydrogen bond, which effects the planarity of the ureido­thio­phene­carboxyl­ate moiety.

S1. Comment

As part of our search for new structures exhibiting an inhibitory potency towards members of the α/β-hydrolase family, we performed the present structure determinations. In this context, we were especially interested in inhibitors of the enzyme acetylcholinesterase (AChE) being currently used as major therapeutic agents to alleviate the symptoms of Morbus Alzheimer (Colombres et al., 2004; Muñoz-Torrero & Camps, 2006). This disease is characterized by a selective neuronal cell death probably caused by amyloid fibrils, as well as a loss of cholinergic transmission. AChE was found to be associated with such amyloid species and may contribute to their development (Alvarez et al., 1997, 1998; Inestrosa & Alarcon, 1998). In addition, the enzyme catalyzes the hydrolytic destruction of the neurotransmitter acetylcholine at cholinergic synapses (Cartaud et al., 2004; Silman & Sussman, 2005). A reduction of the activity of AChE leads to an increased bioavailability of acetylcholine at the synaptic cleft and an improvement of the cholinergic neurotransmission as well as the cognitive functions (Colombres et al., 2004; Muñoz-Torrero & Camps, 2006). Beside its central role in the therapy of Alzheimer's disease, AChE has been targeted in treatments for myasthenia gravis, glaucoma, obstipation and spasmolysis and to antagonize muscle relaxation in anesthesiology (Ibach & Haen, 2004). Compounds of several classes bearing a benzyl substituted piperidine moiety including donepezil (Aricept) have been characterized as inhibitors of AChE (Muñoz-Torrero & Camps, 2006). These findings resulted in the investigation and X-ray crystal structures of the N-benzyl-tetrahydropyrido-anellated thiophene derivatives (I)–(III), at 123 (2) K, that are reported here. Compounds (II) and (III) are potent inhibitors of AChE (IC₅₀ values of 2.1 µM and 5.2 µM, respectively), whereas the enzyme is less affected by (I), i.e. the educt of (II) (IC₅₀ = 10 µM). Full details of the synthesis and characterization of these compounds as well as their biological activity were published elsewhere (Pietsch & Gütschow, 2005).

The structure of (I) with the atomic numbering scheme is shown in Fig. 1. Selected parameters characterizing the geometry of the ureidothiophenecarboxylic ester unit of the two independent molecules are given in Table 1. This unit is planar with the ester group and the ureido group situated in the plane of the thiophene ring system, and torsion angles C2—C3—C31—O32 (C2'—C3'—C31'—O32') and C2—N2—C21—N21 (C2'—N2'—C21'—N21') of 177.93 (16)° [–175.24 (16)°] and -173.60 (17)° [174.37 (17)°], respectively. The mean deviation of the atoms from N21/C21/O21/N2/C2/S1/C7A/C7/C4/C3A/C3/C31/O31/O32/C32 (N21'/C21'/O21'/N2'/C2'/S1'/C7A'/C7'/C4'/C3A'/C3'/C31'/O31'/O32'/C32') plane is 0.044 Å (0.053 Å). The dihedral angles between the planes delineated by the above-mentioned atoms and all the non-H atoms of the phenyl moieties are 68.11 (5) and 67.11 (5)° in the two independent molecules of (I). The ester carbonyl group has a cis orientation with respect to the C2═C3 double bond. This leads to an intramolecular, resonance-assisted N2—H2···O31 hydrogen bond (Table 2), which locks the molecular conformation by forming a pseudo-six-membered ring and eliminates conformational flexibility (Gilli et al., 2000). The values of the H—A and D···A distances and the D—H···A angle (Table 2) characterize this bond as a strong hydrogen bond (Desiraju & Steiner, 1999; Steiner, 2002), and agree with relevant data (average values) for 11 β-enaminoesters forming intramolecular N—H···O hydrogen bonds [D···A = 2.70 (2) Å and D—H···A = 132 (4)°; Gilli et al., 2000]. In addition, the O31═C31 distance of 1.225 (2) Å [O31'═C31' = 1.222 (2) Å] in (I) is in accordance with the average value of C═O [1.221 (6) Å] for the above-mentioned β-enaminoesters, and can be calculated from the distance D···A by the equation C═O = a + b(D···A), with a = 2.14 (5) and b = -0.34 (2) (Gilli et al., 2000). This calculation yielded values of 1.227 and 1.231 Å for O31═C31 and O31'═C31', respectively, and agreed with the experimentally found data. The intramolecular hydrogen bond is weakened by the electron-attracting tert-butoxy group, which decreases the charge density and thus the proton affinity of the carbonyl O atom. This effect has been confirmed by calculations showing that the resonance assistance of hydrogen bonds in β-enaminoesters has become so weak that such hydrogen bonds are barely distinguishable from non-resonant ones (Gilli et al., 2000). The weakening of the intramolecular hydrogen bond in (I) is further supported by IR and NMR spectroscopic data. The band of the isolated N—H stretching vibration, ν NH, is only marginally shifted to a lower frequency from approximately 3400 cm^-1 (Gilli et al., 2000) to 3247 cm^-1 (Pietsch & Gütschow, 2005). Likewise, the σ N—H chemical shift obtained from an NMR measurement shows only a minor downfield shift from approximatately 7 p.p.m. (Gilli et al., 2000) to 11.09 p.p.m. (Pietsch & Gütschow, 2005). In contrast, very strong hydrogen bonds are characterized by the values 2.65 ≥ D···A ≥ 2.48 Å, 3200 ≥ ν NH ≥ 2340 cm^-1 and 13 ≤ σ N—H ≤ 18 p.p.m. The latter value, obtained in solution (CDCl₃), can be correlated with the solid-state D···A distance using the equation σ N—H = 91 (6) - 30 (2)(D···A) (Gilli et al., 2000), with the calculated values, i.e. 10.48 and 10.78 p.p.m., being in accordance with the experimental one. Molecules of (I) are interconnected by a framework of intermolecular C—H···O═C hydrogen bonds, C66—H66···O21' and C64'—H64'···O21, respectively, as shown in Fig. 2 and detailed in Table 2. The values of the H—A and D···A distances, as well as the D—H···A angle, characterize these nearly linear hydrogen bonds (D—H···A = 159 and 160°) as weak ones (Desiraju, 1996; Desiraju & Steiner, 1999; Steiner, 2002) and agree with data described in the literature (Cox, 2002; Pigge et al., 1999; Schulze et al., 2005; Vasu et al., 2004).

Compound (II) is the first thieno[1,3]oxazin-4-one that has been characterized by X-ray crystallography. The synthesis of (II) was performed by treating (I) with trifluoroacetic acid and trifluoroacetic anhydride, resulting in deesterification and cyclocondenstaion (Pietsch & Gütschow, 2005). The structure of (II) with the atomic numbering scheme and the arrangement of the molecules in the asymmetric unit are shown in Figs. 3 and 4, respectively; selected bond distances and angles are given in Table 3. The thienoxazinone system in (II) is essentially planar, in agreement with earlier experimental data of bioisosteric benzoxazinones (Crane & Rogerson, 2004; Gütschow et al., 1998; Kovalevsky & Ponomarev, 2000; Kovalevsky et al., 2000; Yadav et al., 2002). The mean deviation of the atoms from the plane formed by this heterocyclic moiety and the atoms N2, C5 and C8 is 0.015 Å, with C8 deviating by a maximum of 0.041 Å. The aforementioned plane and the phenyl ring of the benzyl group in (II) are virtually perpendicular to each other, as shown by the dihedral angle of 75.50 (3)°. In compound (II), the O3—C2 bond is shorter than the O3—C4 bond. Moreover, the bond angles at C2 and C4 are distorted from their ideal values of 120°. Such observations were explained as a result of the concerted electronic effects of adjactent substituents (Kovalevsky & Ponomarev, 2000). Similarly to the molecules of (I), the crystal structure of (II) is stabilized by weak intermolecular C—H···O═C hydrogen bonds formed by C73, H73 and O4 (Table 4 and Fig. 4).

In contrast to the thieno[1,3]oxazin-4-one heterocycle in compound (II), the isosteric thieno[1,3]thiazin-4-one system in (III) (Table 5 and Fig. 5) is less planar. This is reflected in a mean deviation of the atoms from the plane formed by this system and atoms N21, C5 and C8, taking a value of 0.085 Å, with O4 deviating by a maximum of 0.229 Å. The dihedral angles between this plane and the phenyl rings of the benzyl and benzoyl groups are 55.69 (4) and 53.90 (4)°, respectively. The replacement of the ring O atom in the oxazinone (II) by an S atom in the thiazinone (III) results in a significant distortion of the bond angles at C2, C4 and C9A from 120° (Table 5), with the obtained values agreeing with reported data (Evain et al., 2002; Lamiot et al., 1992). As N21, and not N1, was found to be hydrogen-substituted, the structure of the tautomeric form (III) based on IR and NMR data (Pietsch & Gütschow, 2005) has been proved true. The tautomer containing an exocyclic C2═N21 double bond is not observed and thus an intramolecular N1—H1···O22 hydrogen bond cannot be formed. Instead, a non-binding intramolecular interaction between atoms S3 and O22 has been taken into account as already shown for 4-acylimino-2-aminothieno[2,3-d][1,3]thiazines (Gütschow et al., 1992). Such interaction was not found as the S3···O22 distance exceeds the described value, and the system formed by atoms S3, C2, N21, C22 and O22 is less planar, with C2 deviating by a maximum of 0.176 Å. In contrast to compounds (I) and (II), molecules of (III) are linked via intermolecular N—H···O═C hydrogen bonds originating from N21, H21 and O4 (Table 6 and Fig. 6). The values of the N···O contact distance as a measure of the hydrogen-bond strength, and the C4═O4 bond length, taken as an indicator of π-delocalization in an ···O═R_n—N—H··· heteroconjugated system (Tables 5 and 6), characterize this intermolecular interaction as not assisted by resonance (Bertolasi et al., 1995, 1998).

Related literature

For related literature, see: Alvarez et al. (1997, 1998); Bertolasi et al. (1995, 1998); Cartaud et al. (2004); Colombres et al. (2004); Cox (2002); Crane & Rogerson (2004); Desiraju (1996); Desiraju & Steiner (1999); Ellman et al. (1961); Evain et al. (2002); Gütschow et al. (1992, 1998); Gilli et al. (2000); Ibach & Haen (2004); Inestrosa & Alarcon (1998); Kovalevsky & Ponomarev (2000); Kovalevsky, Ponomarev & Baranova (2000); Lamiot et al. (1992); Muñoz-Torrero & Camps (2006); Pietsch & Gütschow (2005); Pigge et al. (1999); Schulze et al. (2005); Silman & Sussman (2005); Steiner (2002); Vasu, Nirmala, Chopra, Mohan & Saravanan (2004); Yadav et al. (2002).

S2. Experimental

The preparation of compounds (I)–(III) was carried out as described previously (Pietsch & Gütschow, 2005). Yellow crystals of (I) suitable for X-ray analysis were grown from methanol; yellow crystals of (II) and (III) were obtained upon recrystallization from hexane and ethyl acetate, respectively. AChE inhibition by compound (I) was assayed spectrophometrically in two separate experiments (each in duplicate) at a single concentration (10 µM) according to the method of Ellman et al. (1961) as described elsewhere (Pietsch & Gütschow, 2005).

S3. Refinement

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.98 Å and U_iso(H) = 1.5U_eq(C). The H atoms bound to an N atom were refined freely with N—H distances in the range 0.86–0.88 Å and U_iso(H) = 1.2U_eq(N). All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95–0.99 Å and U_iso(H) = 1.2U_eq(C).

Computing details

For all compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001). Software used to prepare material for publication: SHELXL97 (Sheldrick, 1997); calculation of dihedral angels between planes and mean deviation of atoms from the plane: DIAMOND 3.1d (Brandenburg, 2006) for (I), (III); SHELXL97 (Sheldrick, 1997) for (II).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labeling scheme and displacement ellipsoids at the 50% probability level for non-H atoms of two independent molecules from the asymmetric unit. H atoms are depicted as small circles of arbitrary radii; dashed lines represent hydrogen bonds.
	Fig. 2. The arrangement of the molecules of (I) in the unit cell. The intramolecular N—H···O interactions and intermolecular C—H···O interactions are represented by dashed lines.
	Fig. 3. The molecular structure of (II), showing the atom-labeling scheme and displacement ellipsoids at the 50% probability level for non-H atoms. H atoms are depicted as small circles of arbitrary radii.
	Fig. 4. The arrangement of the molecules of (II) in the unit cell. The intermolecular C—H···O interactions are represented by dashed lines.
	Fig. 5. The molecular structure of (III), showing the atom-labeling scheme and displacement ellipsoids at the 50% probability level for non-H atoms. H atoms are depicted as small circles of arbitrary radii.
	Fig. 6. The arrangement of the molecules of (III) in the unit cell. The intermolecular N—H···O interactions are represented by dashed lines.

(I) tert-butyl 6_benzyl-2-(3,3-diethylureido)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine- 3-carboxylate

Crystal data

C24H33N3O3S	F(000) = 1904
Mr = 443.59	Dx = 1.254 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9222 reflections
a = 9.7735 (2) Å	θ = 1–27.5°
b = 24.4098 (5) Å	µ = 0.17 mm^−1
c = 19.7439 (5) Å	T = 123 K
β = 93.865 (1)°	Plate, yellow
V = 4699.57 (18) Å^3	0.50 × 0.40 × 0.20 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	6646 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 27.5°, θmin = 2.9°
rotation in phi and ω, 1 deg. scans	h = −12→10
28911 measured reflections	k = −31→29
10616 independent reflections	l = −25→22

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0609P)^2] where P = (Fo^2 + 2Fc^2)/3
10616 reflections	(Δ/σ)max = 0.001
565 parameters	Δρmax = 0.51 e Å^−3
2 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. dx = 40 mm, 40 sec./°., 1 °., 3 sets, 259 frames, mos.= 0.624 (2) °.

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	0.22311 (5)	0.50862 (2)	0.38653 (2)	0.02217 (13)
C2	0.12730 (18)	0.49062 (8)	0.31313 (9)	0.0188 (4)
N2	0.09788 (16)	0.43718 (7)	0.29608 (8)	0.0221 (4)
H2	0.0534 (18)	0.4349 (9)	0.2559 (8)	0.027*
C21	0.14393 (18)	0.39301 (9)	0.33441 (10)	0.0220 (5)
O21	0.20740 (13)	0.40003 (6)	0.38997 (7)	0.0279 (4)
N21	0.11828 (16)	0.34242 (7)	0.30793 (8)	0.0245 (4)
C22	0.03758 (19)	0.33253 (9)	0.24385 (10)	0.0253 (5)
H22A	0.0644	0.2966	0.2256	0.030*
H22B	0.0607	0.3610	0.2108	0.030*
C23	−0.11590 (19)	0.33277 (10)	0.24981 (11)	0.0329 (6)
H23A	−0.1626	0.3258	0.2051	0.049*
H23B	−0.1442	0.3685	0.2665	0.049*
H23C	−0.1404	0.3041	0.2816	0.049*
C24	0.1628 (2)	0.29592 (9)	0.35058 (11)	0.0285 (5)
H24A	0.2574	0.3028	0.3698	0.034*
H24B	0.1650	0.2628	0.3218	0.034*
C25	0.0720 (2)	0.28478 (9)	0.40837 (11)	0.0315 (5)
H25A	0.1080	0.2533	0.4348	0.047*
H25B	−0.0214	0.2767	0.3899	0.047*
H25C	0.0708	0.3171	0.4378	0.047*
C3	0.08733 (18)	0.53602 (8)	0.27429 (9)	0.0184 (4)
C31	0.00558 (18)	0.52884 (9)	0.21049 (10)	0.0210 (5)
O31	−0.02886 (14)	0.48435 (6)	0.18620 (7)	0.0275 (3)
O32	−0.02791 (13)	0.57687 (6)	0.18056 (6)	0.0229 (3)
C32	−0.10338 (19)	0.57932 (9)	0.11324 (10)	0.0224 (5)
C33	−0.0192 (2)	0.55384 (10)	0.06002 (10)	0.0323 (5)
H33A	−0.0103	0.5144	0.0684	0.049*
H33B	0.0720	0.5706	0.0622	0.049*
H33C	−0.0648	0.5600	0.0149	0.049*
C34	−0.1183 (2)	0.64031 (9)	0.10211 (11)	0.0348 (6)
H34A	−0.1727	0.6560	0.1373	0.052*
H34B	−0.1645	0.6472	0.0573	0.052*
H34C	−0.0273	0.6574	0.1046	0.052*
C35	−0.24315 (19)	0.55211 (10)	0.11548 (11)	0.0316 (5)
H35A	−0.2310	0.5127	0.1229	0.047*
H35B	−0.2965	0.5583	0.0723	0.047*
H35C	−0.2919	0.5679	0.1526	0.047*
C3A	0.13883 (18)	0.58655 (8)	0.30497 (9)	0.0184 (4)
C4	0.12217 (19)	0.64456 (8)	0.27978 (10)	0.0224 (5)
H4A	0.0287	0.6578	0.2875	0.027*
H4B	0.1339	0.6457	0.2304	0.027*
C5	0.22819 (19)	0.68184 (9)	0.31692 (10)	0.0230 (5)
H5A	0.3203	0.6736	0.3015	0.028*
H5B	0.2065	0.7205	0.3057	0.028*
N6	0.22943 (15)	0.67409 (7)	0.39068 (8)	0.0210 (4)
C61	0.31554 (19)	0.71516 (8)	0.42705 (10)	0.0241 (5)
H61A	0.4064	0.7158	0.4077	0.029*
H61B	0.3297	0.7040	0.4752	0.029*
C62	0.25617 (19)	0.77208 (9)	0.42382 (9)	0.0207 (4)
C63	0.33997 (19)	0.81726 (9)	0.41611 (10)	0.0228 (5)
H63	0.4347	0.8118	0.4102	0.027*
C64	0.2882 (2)	0.87014 (9)	0.41688 (10)	0.0275 (5)
H64	0.3476	0.9005	0.4121	0.033*
C65	0.1506 (2)	0.87856 (9)	0.42453 (10)	0.0295 (5)
H65	0.1145	0.9147	0.4243	0.035*
C66	0.0654 (2)	0.83407 (10)	0.43247 (10)	0.0287 (5)
H66	−0.0293	0.8397	0.4381	0.034*
C67	0.11771 (19)	0.78111 (9)	0.43224 (10)	0.0240 (5)
H67	0.0585	0.7508	0.4379	0.029*
C7	0.28340 (19)	0.61963 (8)	0.40883 (10)	0.0241 (5)
H7A	0.2688	0.6118	0.4570	0.029*
H7B	0.3832	0.6186	0.4031	0.029*
C7A	0.21248 (18)	0.57710 (9)	0.36460 (10)	0.0213 (5)
S1'	0.26646 (5)	0.25753 (2)	0.09285 (3)	0.02383 (14)
C2'	0.35061 (18)	0.27771 (9)	0.16840 (10)	0.0203 (4)
N2'	0.37412 (16)	0.33189 (7)	0.18532 (9)	0.0221 (4)
H2'	0.4126 (18)	0.3366 (9)	0.2259 (8)	0.027*
C21'	0.33013 (19)	0.37565 (9)	0.14570 (11)	0.0246 (5)
O21'	0.27215 (13)	0.36837 (6)	0.08921 (7)	0.0305 (4)
N21'	0.35199 (16)	0.42622 (7)	0.17308 (9)	0.0262 (4)
C22'	0.4264 (2)	0.43664 (9)	0.23938 (10)	0.0280 (5)
H22C	0.4064	0.4065	0.2708	0.034*
H22D	0.3916	0.4710	0.2585	0.034*
C23'	0.5795 (2)	0.44123 (11)	0.23601 (11)	0.0411 (6)
H23D	0.6221	0.4481	0.2816	0.062*
H23E	0.6007	0.4716	0.2060	0.062*
H23F	0.6155	0.4070	0.2183	0.062*
C24'	0.3040 (2)	0.47287 (9)	0.13086 (11)	0.0322 (5)
H24C	0.2970	0.5055	0.1602	0.039*
H24D	0.2109	0.4646	0.1105	0.039*
C25'	0.3957 (2)	0.48634 (10)	0.07482 (11)	0.0371 (6)
H25D	0.3583	0.5179	0.0490	0.056*
H25E	0.4007	0.4547	0.0445	0.056*
H25F	0.4878	0.4952	0.0945	0.056*
C3'	0.39015 (18)	0.23366 (9)	0.20913 (10)	0.0209 (5)
C31'	0.46682 (19)	0.24265 (9)	0.27454 (10)	0.0234 (5)
O31'	0.49274 (13)	0.28790 (6)	0.29859 (7)	0.0287 (4)
O32'	0.50591 (13)	0.19556 (6)	0.30506 (7)	0.0264 (3)
C32'	0.57434 (19)	0.19510 (9)	0.37424 (10)	0.0258 (5)
C33'	0.70977 (18)	0.22647 (9)	0.37673 (10)	0.0277 (5)
H33D	0.6914	0.2655	0.3688	0.042*
H33E	0.7666	0.2124	0.3416	0.042*
H33F	0.7582	0.2216	0.4214	0.042*
C34'	0.4774 (2)	0.21862 (10)	0.42415 (10)	0.0349 (6)
H34D	0.4630	0.2577	0.4148	0.052*
H34E	0.5177	0.2139	0.4706	0.052*
H34F	0.3894	0.1994	0.4191	0.052*
C35'	0.6000 (2)	0.13466 (10)	0.38634 (12)	0.0392 (6)
H35D	0.5122	0.1151	0.3843	0.059*
H35E	0.6473	0.1294	0.4312	0.059*
H35F	0.6569	0.1203	0.3514	0.059*
C3A'	0.34624 (18)	0.18201 (8)	0.17856 (10)	0.0203 (4)
C4'	0.3600 (2)	0.12545 (8)	0.20794 (10)	0.0236 (5)
H4'1	0.3416	0.1264	0.2566	0.028*
H4'2	0.4547	0.1120	0.2042	0.028*
C5'	0.25900 (19)	0.08669 (9)	0.17014 (10)	0.0238 (5)
H5'1	0.2791	0.0485	0.1846	0.029*
H5'2	0.1645	0.0956	0.1817	0.029*
N6'	0.26842 (15)	0.09128 (7)	0.09670 (8)	0.0223 (4)
C61'	0.19034 (19)	0.04783 (9)	0.06019 (10)	0.0251 (5)
H61C	0.1850	0.0561	0.0110	0.030*
H61D	0.0957	0.0475	0.0751	0.030*
C62'	0.25277 (19)	−0.00810 (9)	0.07156 (10)	0.0219 (5)
C63'	0.39345 (19)	−0.01599 (9)	0.06918 (10)	0.0243 (5)
H63'	0.4507	0.0144	0.0610	0.029*
C64'	0.4511 (2)	−0.06727 (9)	0.07842 (10)	0.0266 (5)
H64'	0.5472	−0.0719	0.0762	0.032*
C65'	0.3693 (2)	−0.11202 (9)	0.09088 (10)	0.0287 (5)
H65'	0.4091	−0.1472	0.0982	0.034*
C66'	0.2296 (2)	−0.10496 (10)	0.09253 (10)	0.0308 (5)
H66'	0.1727	−0.1356	0.1003	0.037*
C67'	0.1715 (2)	−0.05340 (9)	0.08288 (10)	0.0267 (5)
H67'	0.0750	−0.0491	0.0840	0.032*
C7'	0.2178 (2)	0.14467 (9)	0.07285 (10)	0.0255 (5)
H7'1	0.1168	0.1458	0.0739	0.031*
H7'2	0.2412	0.1503	0.0253	0.031*
C7A'	0.28013 (18)	0.18939 (9)	0.11657 (10)	0.0215 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0260 (3)	0.0176 (3)	0.0223 (3)	−0.0004 (2)	−0.0030 (2)	0.0013 (2)
C2	0.0175 (9)	0.0165 (11)	0.0225 (11)	−0.0016 (8)	0.0023 (8)	0.0000 (9)
N2	0.0272 (9)	0.0162 (10)	0.0225 (9)	−0.0011 (8)	−0.0021 (7)	−0.0002 (8)
C21	0.0179 (10)	0.0201 (13)	0.0281 (12)	0.0003 (9)	0.0016 (8)	0.0012 (10)
O21	0.0298 (8)	0.0236 (9)	0.0293 (8)	−0.0015 (6)	−0.0070 (6)	0.0021 (7)
N21	0.0294 (9)	0.0160 (10)	0.0275 (10)	−0.0002 (8)	−0.0017 (7)	−0.0009 (8)
C22	0.0331 (11)	0.0196 (13)	0.0232 (11)	0.0003 (9)	0.0009 (9)	−0.0042 (9)
C23	0.0331 (12)	0.0409 (16)	0.0241 (12)	−0.0063 (11)	−0.0020 (9)	0.0003 (11)
C24	0.0312 (11)	0.0147 (12)	0.0387 (13)	0.0057 (9)	−0.0038 (10)	0.0013 (10)
C25	0.0351 (12)	0.0221 (14)	0.0360 (13)	−0.0024 (10)	−0.0066 (10)	0.0031 (11)
C3	0.0198 (9)	0.0173 (12)	0.0179 (10)	0.0004 (8)	0.0012 (8)	−0.0001 (9)
C31	0.0229 (10)	0.0187 (12)	0.0217 (11)	0.0006 (9)	0.0031 (8)	0.0001 (9)
O31	0.0403 (8)	0.0154 (9)	0.0255 (8)	−0.0026 (7)	−0.0063 (6)	−0.0007 (7)
O32	0.0296 (7)	0.0165 (8)	0.0214 (7)	0.0006 (6)	−0.0076 (6)	0.0005 (6)
C32	0.0261 (10)	0.0203 (12)	0.0199 (10)	0.0012 (9)	−0.0057 (8)	−0.0004 (9)
C33	0.0397 (12)	0.0325 (15)	0.0251 (12)	0.0045 (11)	0.0040 (9)	0.0036 (10)
C34	0.0434 (13)	0.0250 (14)	0.0340 (13)	0.0050 (11)	−0.0121 (10)	0.0037 (11)
C35	0.0280 (11)	0.0377 (16)	0.0283 (12)	0.0019 (10)	−0.0030 (9)	−0.0026 (11)
C3A	0.0199 (10)	0.0155 (11)	0.0198 (10)	0.0000 (8)	0.0022 (8)	−0.0006 (9)
C4	0.0289 (11)	0.0180 (12)	0.0198 (10)	−0.0023 (9)	−0.0025 (8)	0.0027 (9)
C5	0.0271 (10)	0.0196 (12)	0.0220 (11)	−0.0028 (9)	0.0003 (8)	0.0012 (9)
N6	0.0261 (9)	0.0166 (10)	0.0196 (9)	−0.0022 (7)	−0.0028 (7)	−0.0012 (7)
C61	0.0252 (10)	0.0200 (13)	0.0263 (11)	−0.0002 (9)	−0.0031 (8)	−0.0031 (10)
C62	0.0253 (10)	0.0203 (12)	0.0161 (10)	−0.0001 (9)	−0.0013 (8)	−0.0009 (9)
C63	0.0240 (10)	0.0231 (13)	0.0212 (11)	−0.0018 (9)	0.0013 (8)	−0.0017 (9)
C64	0.0375 (12)	0.0203 (13)	0.0247 (11)	−0.0047 (10)	0.0032 (9)	−0.0010 (10)
C65	0.0401 (13)	0.0229 (13)	0.0253 (11)	0.0073 (10)	0.0010 (9)	−0.0014 (10)
C66	0.0272 (11)	0.0316 (15)	0.0272 (12)	0.0042 (10)	0.0012 (9)	−0.0042 (10)
C67	0.0275 (11)	0.0221 (13)	0.0224 (11)	−0.0031 (9)	0.0000 (8)	0.0003 (10)
C7	0.0279 (11)	0.0196 (12)	0.0242 (11)	−0.0004 (9)	−0.0035 (8)	−0.0001 (9)
C7A	0.0232 (10)	0.0177 (12)	0.0230 (11)	−0.0004 (9)	0.0007 (8)	0.0014 (9)
S1'	0.0251 (3)	0.0198 (3)	0.0257 (3)	−0.0006 (2)	−0.0045 (2)	−0.0002 (2)
C2'	0.0191 (10)	0.0190 (12)	0.0231 (11)	−0.0028 (9)	0.0025 (8)	−0.0025 (9)
N2'	0.0259 (9)	0.0164 (10)	0.0238 (9)	−0.0025 (8)	−0.0007 (7)	−0.0003 (8)
C21'	0.0212 (10)	0.0196 (13)	0.0334 (12)	−0.0028 (9)	0.0042 (9)	0.0001 (10)
O21'	0.0319 (8)	0.0274 (10)	0.0309 (8)	−0.0038 (7)	−0.0078 (6)	0.0010 (7)
N21'	0.0310 (9)	0.0168 (10)	0.0306 (10)	0.0005 (8)	0.0008 (7)	−0.0005 (8)
C22'	0.0348 (12)	0.0224 (13)	0.0274 (12)	−0.0018 (10)	0.0064 (9)	−0.0059 (10)
C23'	0.0373 (13)	0.0572 (19)	0.0284 (13)	−0.0051 (12)	0.0000 (10)	−0.0019 (12)
C24'	0.0337 (12)	0.0192 (13)	0.0430 (14)	0.0041 (10)	−0.0018 (10)	−0.0008 (11)
C25'	0.0467 (14)	0.0287 (15)	0.0348 (13)	−0.0030 (11)	−0.0056 (11)	0.0052 (11)
C3'	0.0217 (10)	0.0190 (12)	0.0219 (11)	−0.0010 (9)	0.0022 (8)	−0.0017 (9)
C31'	0.0241 (10)	0.0238 (13)	0.0226 (11)	−0.0031 (9)	0.0028 (8)	−0.0002 (10)
O31'	0.0374 (8)	0.0207 (9)	0.0271 (8)	−0.0040 (7)	−0.0047 (6)	−0.0049 (7)
O32'	0.0317 (8)	0.0222 (9)	0.0239 (8)	−0.0042 (7)	−0.0083 (6)	−0.0008 (7)
C32'	0.0278 (11)	0.0270 (13)	0.0213 (11)	−0.0030 (10)	−0.0090 (8)	0.0002 (10)
C33'	0.0234 (10)	0.0328 (14)	0.0266 (11)	−0.0028 (10)	−0.0001 (9)	−0.0017 (10)
C34'	0.0275 (11)	0.0522 (18)	0.0245 (12)	−0.0051 (11)	−0.0016 (9)	0.0060 (11)
C35'	0.0443 (14)	0.0296 (15)	0.0410 (14)	−0.0066 (11)	−0.0168 (11)	0.0072 (12)
C3A'	0.0206 (10)	0.0169 (12)	0.0233 (11)	−0.0028 (9)	0.0016 (8)	−0.0017 (9)
C4'	0.0292 (11)	0.0195 (12)	0.0219 (11)	−0.0036 (9)	−0.0003 (8)	−0.0007 (9)
C5'	0.0271 (11)	0.0209 (12)	0.0235 (11)	−0.0029 (9)	0.0022 (8)	−0.0008 (9)
N6'	0.0254 (9)	0.0194 (10)	0.0216 (9)	−0.0009 (7)	−0.0016 (7)	−0.0028 (8)
C61'	0.0250 (10)	0.0215 (13)	0.0280 (12)	−0.0012 (9)	−0.0042 (9)	−0.0039 (10)
C62'	0.0259 (10)	0.0214 (12)	0.0183 (10)	−0.0031 (9)	0.0005 (8)	−0.0022 (9)
C63'	0.0254 (11)	0.0218 (13)	0.0256 (11)	−0.0061 (9)	0.0004 (8)	−0.0014 (10)
C64'	0.0233 (11)	0.0272 (14)	0.0287 (12)	0.0025 (10)	−0.0031 (9)	−0.0005 (10)
C65'	0.0420 (13)	0.0200 (13)	0.0234 (11)	0.0044 (10)	−0.0036 (9)	−0.0001 (10)
C66'	0.0400 (13)	0.0271 (14)	0.0257 (12)	−0.0088 (11)	0.0044 (9)	−0.0001 (10)
C67'	0.0252 (11)	0.0280 (14)	0.0273 (12)	−0.0050 (10)	0.0041 (9)	−0.0057 (10)
C7'	0.0268 (11)	0.0212 (13)	0.0277 (11)	0.0012 (9)	−0.0039 (9)	−0.0015 (10)
C7A'	0.0242 (10)	0.0161 (12)	0.0241 (11)	0.0000 (9)	0.0012 (8)	0.0001 (9)

Geometric parameters (Å, º)

S1—C7A	1.728 (2)	S1'—C2'	1.7258 (19)
S1—C2	1.7284 (19)	S1'—C7A'	1.731 (2)
C2—N2	1.373 (2)	C2'—N2'	1.380 (2)
C2—C3	1.389 (3)	C2'—C3'	1.382 (3)
N2—C21	1.376 (3)	N2'—C21'	1.376 (3)
N2—H2	0.881 (14)	N2'—H2'	0.870 (14)
C21—O21	1.235 (2)	C21'—O21'	1.229 (2)
C21—N21	1.358 (2)	C21'—N21'	1.359 (3)
N21—C24	1.462 (2)	N21'—C24'	1.469 (3)
N21—C22	1.465 (2)	N21'—C22'	1.476 (2)
C22—C23	1.512 (3)	C22'—C23'	1.506 (3)
C22—H22A	0.9900	C22'—H22C	0.9900
C22—H22B	0.9900	C22'—H22D	0.9900
C23—H23A	0.9800	C23'—H23D	0.9800
C23—H23B	0.9800	C23'—H23E	0.9800
C23—H23C	0.9800	C23'—H23F	0.9800
C24—C25	1.516 (3)	C24'—C25'	1.507 (3)
C24—H24A	0.9900	C24'—H24C	0.9900
C24—H24B	0.9900	C24'—H24D	0.9900
C25—H25A	0.9800	C25'—H25D	0.9800
C25—H25B	0.9800	C25'—H25E	0.9800
C25—H25C	0.9800	C25'—H25F	0.9800
C3—C3A	1.449 (3)	C3'—C3A'	1.450 (3)
C3—C31	1.456 (3)	C3'—C31'	1.465 (3)
C31—O31	1.225 (2)	C31'—O31'	1.222 (2)
C31—O32	1.343 (2)	C31'—O32'	1.341 (2)
O32—C32	1.477 (2)	O32'—C32'	1.480 (2)
C32—C34	1.510 (3)	C32'—C35'	1.513 (3)
C32—C33	1.511 (3)	C32'—C34'	1.524 (3)
C32—C35	1.522 (3)	C32'—C33'	1.527 (3)
C33—H33A	0.9800	C33'—H33D	0.9800
C33—H33B	0.9800	C33'—H33E	0.9800
C33—H33C	0.9800	C33'—H33F	0.9800
C34—H34A	0.9800	C34'—H34D	0.9800
C34—H34B	0.9800	C34'—H34E	0.9800
C34—H34C	0.9800	C34'—H34F	0.9800
C35—H35A	0.9800	C35'—H35D	0.9800
C35—H35B	0.9800	C35'—H35E	0.9800
C35—H35C	0.9800	C35'—H35F	0.9800
C3A—C7A	1.358 (2)	C3A'—C7A'	1.357 (3)
C3A—C4	1.506 (3)	C3A'—C4'	1.500 (3)
C4—C5	1.529 (3)	C4'—C5'	1.525 (3)
C4—H4A	0.9900	C4'—H4'1	0.9900
C4—H4B	0.9900	C4'—H4'2	0.9900
C5—N6	1.468 (2)	C5'—N6'	1.463 (2)
C5—H5A	0.9900	C5'—H5'1	0.9900
C5—H5B	0.9900	C5'—H5'2	0.9900
N6—C61	1.465 (2)	N6'—C7'	1.461 (2)
N6—C7	1.466 (2)	N6'—C61'	1.467 (2)
C61—C62	1.506 (3)	C61'—C62'	1.506 (3)
C61—H61A	0.9900	C61'—H61C	0.9900
C61—H61B	0.9900	C61'—H61D	0.9900
C62—C63	1.388 (3)	C62'—C67'	1.389 (3)
C62—C67	1.392 (3)	C62'—C63'	1.392 (3)
C63—C64	1.387 (3)	C63'—C64'	1.380 (3)
C63—H63	0.9500	C63'—H63'	0.9500
C64—C65	1.379 (3)	C64'—C65'	1.385 (3)
C64—H64	0.9500	C64'—H64'	0.9500
C65—C66	1.384 (3)	C65'—C66'	1.379 (3)
C65—H65	0.9500	C65'—H65'	0.9500
C66—C67	1.390 (3)	C66'—C67'	1.389 (3)
C66—H66	0.9500	C66'—H66'	0.9500
C67—H67	0.9500	C67'—H67'	0.9500
C7—C7A	1.496 (3)	C7'—C7A'	1.495 (3)
C7—H7A	0.9900	C7'—H7'1	0.9900
C7—H7B	0.9900	C7'—H7'2	0.9900
C7A—S1—C2	90.91 (9)	C2'—S1'—C7A'	90.97 (10)
N2—C2—C3	125.19 (17)	N2'—C2'—C3'	124.70 (18)
N2—C2—S1	122.69 (15)	N2'—C2'—S1'	123.01 (15)
C3—C2—S1	112.11 (15)	C3'—C2'—S1'	112.28 (15)
C2—N2—C21	123.67 (17)	C21'—N2'—C2'	124.48 (17)
C2—N2—H2	111.3 (14)	C21'—N2'—H2'	121.4 (14)
C21—N2—H2	124.8 (14)	C2'—N2'—H2'	113.8 (14)
O21—C21—N21	122.46 (19)	O21'—C21'—N21'	122.9 (2)
O21—C21—N2	120.40 (19)	O21'—C21'—N2'	120.7 (2)
N21—C21—N2	117.13 (17)	N21'—C21'—N2'	116.39 (18)
C21—N21—C24	116.39 (16)	C21'—N21'—C24'	116.27 (17)
C21—N21—C22	123.85 (17)	C21'—N21'—C22'	124.35 (18)
C24—N21—C22	119.43 (17)	C24'—N21'—C22'	119.28 (17)
N21—C22—C23	114.28 (17)	N21'—C22'—C23'	113.91 (17)
N21—C22—H22A	108.7	N21'—C22'—H22C	108.8
C23—C22—H22A	108.7	C23'—C22'—H22C	108.8
N21—C22—H22B	108.7	N21'—C22'—H22D	108.8
C23—C22—H22B	108.7	C23'—C22'—H22D	108.8
H22A—C22—H22B	107.6	H22C—C22'—H22D	107.7
C22—C23—H23A	109.5	C22'—C23'—H23D	109.5
C22—C23—H23B	109.5	C22'—C23'—H23E	109.5
H23A—C23—H23B	109.5	H23D—C23'—H23E	109.5
C22—C23—H23C	109.5	C22'—C23'—H23F	109.5
H23A—C23—H23C	109.5	H23D—C23'—H23F	109.5
H23B—C23—H23C	109.5	H23E—C23'—H23F	109.5
N21—C24—C25	113.98 (17)	N21'—C24'—C25'	113.74 (17)
N21—C24—H24A	108.8	N21'—C24'—H24C	108.8
C25—C24—H24A	108.8	C25'—C24'—H24C	108.8
N21—C24—H24B	108.8	N21'—C24'—H24D	108.8
C25—C24—H24B	108.8	C25'—C24'—H24D	108.8
H24A—C24—H24B	107.7	H24C—C24'—H24D	107.7
C24—C25—H25A	109.5	C24'—C25'—H25D	109.5
C24—C25—H25B	109.5	C24'—C25'—H25E	109.5
H25A—C25—H25B	109.5	H25D—C25'—H25E	109.5
C24—C25—H25C	109.5	C24'—C25'—H25F	109.5
H25A—C25—H25C	109.5	H25D—C25'—H25F	109.5
H25B—C25—H25C	109.5	H25E—C25'—H25F	109.5
C2—C3—C3A	111.81 (16)	C2'—C3'—C3A'	111.77 (17)
C2—C3—C31	119.94 (18)	C2'—C3'—C31'	120.17 (19)
C3A—C3—C31	128.24 (18)	C3A'—C3'—C31'	128.06 (19)
O31—C31—O32	123.30 (17)	O31'—C31'—O32'	123.68 (18)
O31—C31—C3	124.45 (19)	O31'—C31'—C3'	123.9 (2)
O32—C31—C3	112.25 (17)	O32'—C31'—C3'	112.38 (18)
C31—O32—C32	121.55 (15)	C31'—O32'—C32'	121.24 (16)
O32—C32—C34	102.01 (15)	O32'—C32'—C35'	102.30 (16)
O32—C32—C33	110.30 (15)	O32'—C32'—C34'	109.39 (15)
C34—C32—C33	110.86 (18)	C35'—C32'—C34'	111.64 (19)
O32—C32—C35	110.54 (16)	O32'—C32'—C33'	111.27 (16)
C34—C32—C35	110.88 (17)	C35'—C32'—C33'	110.49 (17)
C33—C32—C35	111.85 (18)	C34'—C32'—C33'	111.41 (18)
C32—C33—H33A	109.5	C32'—C33'—H33D	109.5
C32—C33—H33B	109.5	C32'—C33'—H33E	109.5
H33A—C33—H33B	109.5	H33D—C33'—H33E	109.5
C32—C33—H33C	109.5	C32'—C33'—H33F	109.5
H33A—C33—H33C	109.5	H33D—C33'—H33F	109.5
H33B—C33—H33C	109.5	H33E—C33'—H33F	109.5
C32—C34—H34A	109.5	C32'—C34'—H34D	109.5
C32—C34—H34B	109.5	C32'—C34'—H34E	109.5
H34A—C34—H34B	109.5	H34D—C34'—H34E	109.5
C32—C34—H34C	109.5	C32'—C34'—H34F	109.5
H34A—C34—H34C	109.5	H34D—C34'—H34F	109.5
H34B—C34—H34C	109.5	H34E—C34'—H34F	109.5
C32—C35—H35A	109.5	C32'—C35'—H35D	109.5
C32—C35—H35B	109.5	C32'—C35'—H35E	109.5
H35A—C35—H35B	109.5	H35D—C35'—H35E	109.5
C32—C35—H35C	109.5	C32'—C35'—H35F	109.5
H35A—C35—H35C	109.5	H35D—C35'—H35F	109.5
H35B—C35—H35C	109.5	H35E—C35'—H35F	109.5
C7A—C3A—C3	111.52 (18)	C7A'—C3A'—C3'	111.70 (18)
C7A—C3A—C4	119.03 (17)	C7A'—C3A'—C4'	119.71 (18)
C3—C3A—C4	129.44 (16)	C3'—C3A'—C4'	128.54 (17)
C3A—C4—C5	110.27 (15)	C3A'—C4'—C5'	110.10 (16)
C3A—C4—H4A	109.6	C3A'—C4'—H4'1	109.6
C5—C4—H4A	109.6	C5'—C4'—H4'1	109.6
C3A—C4—H4B	109.6	C3A'—C4'—H4'2	109.6
C5—C4—H4B	109.6	C5'—C4'—H4'2	109.6
H4A—C4—H4B	108.1	H4'1—C4'—H4'2	108.2
N6—C5—C4	111.06 (16)	N6'—C5'—C4'	110.82 (16)
N6—C5—H5A	109.4	N6'—C5'—H5'1	109.5
C4—C5—H5A	109.4	C4'—C5'—H5'1	109.5
N6—C5—H5B	109.4	N6'—C5'—H5'2	109.5
C4—C5—H5B	109.4	C4'—C5'—H5'2	109.5
H5A—C5—H5B	108.0	H5'1—C5'—H5'2	108.1
C61—N6—C7	108.38 (14)	C7'—N6'—C5'	110.19 (16)
C61—N6—C5	111.36 (15)	C7'—N6'—C61'	109.45 (14)
C7—N6—C5	109.77 (16)	C5'—N6'—C61'	111.48 (16)
N6—C61—C62	113.81 (15)	N6'—C61'—C62'	112.95 (15)
N6—C61—H61A	108.8	N6'—C61'—H61C	109.0
C62—C61—H61A	108.8	C62'—C61'—H61C	109.0
N6—C61—H61B	108.8	N6'—C61'—H61D	109.0
C62—C61—H61B	108.8	C62'—C61'—H61D	109.0
H61A—C61—H61B	107.7	H61C—C61'—H61D	107.8
C63—C62—C67	118.22 (19)	C67'—C62'—C63'	118.2 (2)
C63—C62—C61	120.61 (17)	C67'—C62'—C61'	121.03 (17)
C67—C62—C61	121.07 (18)	C63'—C62'—C61'	120.76 (18)
C64—C63—C62	121.34 (19)	C64'—C63'—C62'	121.10 (19)
C64—C63—H63	119.3	C64'—C63'—H63'	119.5
C62—C63—H63	119.3	C62'—C63'—H63'	119.5
C65—C64—C63	119.9 (2)	C63'—C64'—C65'	120.23 (19)
C65—C64—H64	120.0	C63'—C64'—H64'	119.9
C63—C64—H64	120.0	C65'—C64'—H64'	119.9
C64—C65—C66	119.6 (2)	C66'—C65'—C64'	119.3 (2)
C64—C65—H65	120.2	C66'—C65'—H65'	120.3
C66—C65—H65	120.2	C64'—C65'—H65'	120.3
C65—C66—C67	120.35 (19)	C65'—C66'—C67'	120.4 (2)
C65—C66—H66	119.8	C65'—C66'—H66'	119.8
C67—C66—H66	119.8	C67'—C66'—H66'	119.8
C66—C67—C62	120.5 (2)	C66'—C67'—C62'	120.71 (19)
C66—C67—H67	119.7	C66'—C67'—H67'	119.6
C62—C67—H67	119.7	C62'—C67'—H67'	119.6
N6—C7—C7A	109.97 (15)	N6'—C7'—C7A'	110.45 (16)
N6—C7—H7A	109.7	N6'—C7'—H7'1	109.6
C7A—C7—H7A	109.7	C7A'—C7'—H7'1	109.6
N6—C7—H7B	109.7	N6'—C7'—H7'2	109.6
C7A—C7—H7B	109.7	C7A'—C7'—H7'2	109.6
H7A—C7—H7B	108.2	H7'1—C7'—H7'2	108.1
C3A—C7A—C7	125.87 (19)	C3A'—C7A'—C7'	125.06 (19)
C3A—C7A—S1	113.64 (15)	C3A'—C7A'—S1'	113.26 (16)
C7—C7A—S1	120.47 (14)	C7'—C7A'—S1'	121.63 (14)
C7A—S1—C2—N2	177.95 (16)	C7A'—S1'—C2'—N2'	−178.31 (16)
C7A—S1—C2—C3	−1.01 (15)	C7A'—S1'—C2'—C3'	1.41 (15)
C3—C2—N2—C21	177.20 (18)	C3'—C2'—N2'—C21'	−177.49 (18)
S1—C2—N2—C21	−1.6 (3)	S1'—C2'—N2'—C21'	2.2 (3)
C2—N2—C21—O21	5.4 (3)	C2'—N2'—C21'—O21'	−4.3 (3)
C2—N2—C21—N21	−173.60 (17)	C2'—N2'—C21'—N21'	174.37 (17)
O21—C21—N21—C24	3.5 (3)	O21'—C21'—N21'—C24'	−0.9 (3)
N2—C21—N21—C24	−177.48 (16)	N2'—C21'—N21'—C24'	−179.55 (16)
O21—C21—N21—C22	176.85 (17)	O21'—C21'—N21'—C22'	−177.22 (18)
N2—C21—N21—C22	−4.2 (3)	N2'—C21'—N21'—C22'	4.1 (3)
C21—N21—C22—C23	−82.1 (2)	C21'—N21'—C22'—C23'	86.3 (2)
C24—N21—C22—C23	91.0 (2)	C24'—N21'—C22'—C23'	−90.0 (2)
C21—N21—C24—C25	75.5 (2)	C21'—N21'—C24'—C25'	−76.9 (2)
C22—N21—C24—C25	−98.1 (2)	C22'—N21'—C24'—C25'	99.7 (2)
N2—C2—C3—C3A	−177.82 (17)	N2'—C2'—C3'—C3A'	177.75 (17)
S1—C2—C3—C3A	1.1 (2)	S1'—C2'—C3'—C3A'	−2.0 (2)
N2—C2—C3—C31	1.1 (3)	N2'—C2'—C3'—C31'	−2.2 (3)
S1—C2—C3—C31	−179.95 (14)	S1'—C2'—C3'—C31'	178.12 (14)
C2—C3—C31—O31	−2.4 (3)	C2'—C3'—C31'—O31'	4.5 (3)
C3A—C3—C31—O31	176.38 (18)	C3A'—C3'—C31'—O31'	−175.36 (18)
C2—C3—C31—O32	177.93 (16)	C2'—C3'—C31'—O32'	−175.24 (16)
C3A—C3—C31—O32	−3.3 (3)	C3A'—C3'—C31'—O32'	4.9 (3)
O31—C31—O32—C32	−3.5 (3)	O31'—C31'—O32'—C32'	5.5 (3)
C3—C31—O32—C32	176.18 (15)	C3'—C31'—O32'—C32'	−174.77 (15)
C31—O32—C32—C34	179.15 (16)	C31'—O32'—C32'—C35'	−179.24 (16)
C31—O32—C32—C33	−63.0 (2)	C31'—O32'—C32'—C34'	62.3 (2)
C31—O32—C32—C35	61.2 (2)	C31'—O32'—C32'—C33'	−61.2 (2)
C2—C3—C3A—C7A	−0.6 (2)	C2'—C3'—C3A'—C7A'	1.6 (2)
C31—C3—C3A—C7A	−179.45 (18)	C31'—C3'—C3A'—C7A'	−178.47 (18)
C2—C3—C3A—C4	178.89 (18)	C2'—C3'—C3A'—C4'	−175.48 (18)
C31—C3—C3A—C4	0.1 (3)	C31'—C3'—C3A'—C4'	4.4 (3)
C7A—C3A—C4—C5	16.7 (2)	C7A'—C3A'—C4'—C5'	−16.4 (3)
C3—C3A—C4—C5	−162.80 (18)	C3'—C3A'—C4'—C5'	160.47 (18)
C3A—C4—C5—N6	−49.7 (2)	C3A'—C4'—C5'—N6'	49.9 (2)
C4—C5—N6—C61	−171.56 (16)	C4'—C5'—N6'—C7'	−68.3 (2)
C4—C5—N6—C7	68.4 (2)	C4'—C5'—N6'—C61'	169.99 (16)
C7—N6—C61—C62	−168.72 (16)	C7'—N6'—C61'—C62'	168.89 (16)
C5—N6—C61—C62	70.4 (2)	C5'—N6'—C61'—C62'	−68.9 (2)
N6—C61—C62—C63	−140.51 (18)	N6'—C61'—C62'—C67'	137.29 (19)
N6—C61—C62—C67	43.1 (3)	N6'—C61'—C62'—C63'	−44.4 (3)
C67—C62—C63—C64	0.2 (3)	C67'—C62'—C63'—C64'	−0.6 (3)
C61—C62—C63—C64	−176.32 (17)	C61'—C62'—C63'—C64'	−178.91 (19)
C62—C63—C64—C65	−0.9 (3)	C62'—C63'—C64'—C65'	−0.5 (3)
C63—C64—C65—C66	1.0 (3)	C63'—C64'—C65'—C66'	1.3 (3)
C64—C65—C66—C67	−0.5 (3)	C64'—C65'—C66'—C67'	−1.0 (3)
C65—C66—C67—C62	−0.2 (3)	C65'—C66'—C67'—C62'	−0.1 (3)
C63—C62—C67—C66	0.4 (3)	C63'—C62'—C67'—C66'	0.9 (3)
C61—C62—C67—C66	176.83 (18)	C61'—C62'—C67'—C66'	179.23 (18)
C61—N6—C7—C7A	−171.03 (16)	C5'—N6'—C7'—C7A'	48.2 (2)
C5—N6—C7—C7A	−49.2 (2)	C61'—N6'—C7'—C7A'	171.12 (16)
C3—C3A—C7A—C7	178.35 (17)	C3'—C3A'—C7A'—C7'	−177.75 (17)
C4—C3A—C7A—C7	−1.2 (3)	C4'—C3A'—C7A'—C7'	−0.4 (3)
C3—C3A—C7A—S1	−0.1 (2)	C3'—C3A'—C7A'—S1'	−0.6 (2)
C4—C3A—C7A—S1	−179.71 (13)	C4'—C3A'—C7A'—S1'	176.83 (14)
N6—C7—C7A—C3A	17.3 (3)	N6'—C7'—C7A'—C3A'	−15.2 (3)
N6—C7—C7A—S1	−164.33 (13)	N6'—C7'—C7A'—S1'	167.81 (13)
C2—S1—C7A—C3A	0.66 (16)	C2'—S1'—C7A'—C3A'	−0.47 (16)
C2—S1—C7A—C7	−177.93 (16)	C2'—S1'—C7A'—C7'	176.84 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O31	0.88 (1)	1.96 (2)	2.684 (2)	138 (2)
N2′—H2′···O31′	0.87 (1)	1.98 (2)	2.674 (2)	136 (2)
C64′—H64′···O21^i	0.95	2.54	3.448 (2)	160
C66—H66···O21′^ii	0.95	2.50	3.403 (2)	159

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

(II) 7-Benzyl-2-diethylamino-5,6,7,8-tetrahydro-3-oxa-9-thia-1,7-diazafluoren-4-one

Crystal data

C20H23N3O2S	F(000) = 784
Mr = 369.47	Dx = 1.308 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3312 reflections
a = 12.0595 (4) Å	θ = 1–27.5°
b = 8.9892 (3) Å	µ = 0.19 mm^−1
c = 18.0483 (6) Å	T = 123 K
β = 106.503 (1)°	Block, yellow
V = 1875.93 (11) Å^3	0.60 × 0.50 × 0.30 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3374 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
rotation in phi and ω, 1 deg. scans	h = −15→15
10069 measured reflections	k = −11→10
4092 independent reflections	l = −16→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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0465P)^2 + 0.1983P] where P = (Fo^2 + 2Fc^2)/3
4092 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. dx = 40 mm, 40 sec./°., 1 °., 2 sets, 244 frames, mos.= 1.116 (2) °.

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
N1	0.55658 (8)	0.51507 (11)	0.11573 (5)	0.0192 (2)
C2	0.53789 (10)	0.65549 (13)	0.12727 (6)	0.0186 (2)
N2	0.62200 (8)	0.74882 (11)	0.16308 (6)	0.0200 (2)
C21	0.60018 (11)	0.90816 (14)	0.16977 (7)	0.0247 (3)
H21A	0.5481	0.9434	0.1200	0.030*
H21B	0.6743	0.9624	0.1788	0.030*
C22	0.54676 (13)	0.94707 (17)	0.23377 (8)	0.0364 (3)
H22A	0.5349	1.0549	0.2345	0.055*
H22B	0.5986	0.9154	0.2836	0.055*
H22C	0.4722	0.8962	0.2247	0.055*
C23	0.73978 (10)	0.69133 (15)	0.19616 (7)	0.0244 (3)
H23A	0.7959	0.7644	0.1871	0.029*
H23B	0.7488	0.5980	0.1693	0.029*
C24	0.76704 (13)	0.6615 (2)	0.28142 (9)	0.0472 (4)
H24A	0.8461	0.6231	0.3007	0.071*
H24B	0.7126	0.5879	0.2907	0.071*
H24C	0.7603	0.7541	0.3085	0.071*
O3	0.43242 (7)	0.72369 (9)	0.10560 (5)	0.02098 (19)
C4	0.32978 (9)	0.64628 (14)	0.06735 (7)	0.0203 (3)
O4	0.24172 (7)	0.71914 (10)	0.05296 (5)	0.0275 (2)
C4A	0.34812 (9)	0.49406 (13)	0.05284 (6)	0.0189 (3)
C4B	0.26436 (9)	0.38243 (14)	0.01737 (7)	0.0206 (3)
C5	0.13585 (10)	0.40177 (15)	−0.01428 (8)	0.0263 (3)
H5A	0.1176	0.4524	−0.0650	0.032*
H5B	0.1066	0.4641	0.0213	0.032*
C6	0.07766 (11)	0.24990 (15)	−0.02333 (8)	0.0273 (3)
H6A	0.0824	0.2083	0.0283	0.033*
H6B	−0.0051	0.2604	−0.0522	0.033*
N7	0.13420 (9)	0.14833 (12)	−0.06494 (6)	0.0256 (2)
C71	0.06566 (11)	0.01351 (16)	−0.09180 (8)	0.0324 (3)
H71A	−0.0171	0.0407	−0.1117	0.039*
H71B	0.0741	−0.0553	−0.0477	0.039*
C72	0.10345 (10)	−0.06459 (15)	−0.15479 (7)	0.0263 (3)
C73	0.17449 (12)	−0.18859 (15)	−0.13935 (8)	0.0319 (3)
H73	0.1965	−0.2293	−0.0887	0.038*
C74	0.21427 (12)	−0.25465 (15)	−0.19670 (9)	0.0350 (3)
H74	0.2647	−0.3380	−0.1847	0.042*
C75	0.18032 (12)	−0.19873 (17)	−0.27112 (8)	0.0350 (3)
H75	0.2065	−0.2440	−0.3106	0.042*
C76	0.10778 (12)	−0.07623 (16)	−0.28757 (8)	0.0333 (3)
H76	0.0840	−0.0377	−0.3387	0.040*
C77	0.06958 (10)	−0.00936 (16)	−0.23017 (7)	0.0285 (3)
H77	0.0200	0.0747	−0.2422	0.034*
C8	0.25010 (10)	0.10833 (15)	−0.01587 (7)	0.0253 (3)
H8A	0.2929	0.0537	−0.0467	0.030*
H8B	0.2435	0.0431	0.0269	0.030*
C8A	0.31368 (10)	0.24800 (13)	0.01616 (7)	0.0215 (3)
S9	0.46362 (2)	0.25101 (3)	0.058234 (17)	0.02160 (10)
C9A	0.45968 (9)	0.43939 (13)	0.07814 (6)	0.0193 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0188 (5)	0.0187 (5)	0.0187 (5)	−0.0006 (4)	0.0031 (4)	0.0001 (4)
C2	0.0194 (5)	0.0218 (6)	0.0145 (5)	0.0009 (5)	0.0048 (4)	0.0023 (5)
N2	0.0212 (5)	0.0178 (5)	0.0202 (5)	−0.0019 (4)	0.0043 (4)	−0.0013 (4)
C21	0.0295 (6)	0.0188 (6)	0.0252 (6)	−0.0022 (5)	0.0071 (5)	−0.0020 (5)
C22	0.0438 (8)	0.0348 (8)	0.0331 (8)	0.0026 (7)	0.0149 (6)	−0.0074 (6)
C23	0.0187 (6)	0.0231 (7)	0.0298 (7)	−0.0027 (5)	0.0046 (5)	−0.0004 (5)
C24	0.0339 (8)	0.0697 (12)	0.0338 (8)	0.0166 (8)	0.0027 (6)	0.0149 (8)
O3	0.0199 (4)	0.0202 (5)	0.0207 (4)	0.0025 (3)	0.0024 (3)	−0.0003 (3)
C4	0.0194 (6)	0.0244 (7)	0.0161 (6)	−0.0005 (5)	0.0033 (4)	0.0015 (5)
O4	0.0225 (4)	0.0292 (5)	0.0281 (5)	0.0063 (4)	0.0029 (4)	0.0010 (4)
C4A	0.0191 (5)	0.0225 (6)	0.0145 (5)	0.0003 (5)	0.0039 (4)	0.0010 (5)
C4B	0.0197 (5)	0.0250 (7)	0.0167 (6)	−0.0023 (5)	0.0043 (4)	0.0003 (5)
C5	0.0191 (6)	0.0316 (8)	0.0269 (7)	−0.0015 (5)	0.0043 (5)	−0.0024 (6)
C6	0.0205 (6)	0.0356 (8)	0.0260 (7)	−0.0065 (5)	0.0067 (5)	−0.0025 (6)
N7	0.0218 (5)	0.0310 (6)	0.0233 (5)	−0.0094 (4)	0.0055 (4)	−0.0050 (5)
C71	0.0309 (7)	0.0381 (8)	0.0295 (7)	−0.0168 (6)	0.0109 (6)	−0.0060 (6)
C72	0.0247 (6)	0.0276 (7)	0.0243 (6)	−0.0137 (5)	0.0031 (5)	−0.0032 (5)
C73	0.0359 (7)	0.0270 (7)	0.0266 (7)	−0.0112 (6)	−0.0008 (6)	0.0026 (6)
C74	0.0345 (7)	0.0232 (8)	0.0422 (8)	−0.0046 (6)	0.0027 (6)	−0.0034 (6)
C75	0.0362 (7)	0.0357 (8)	0.0330 (8)	−0.0111 (7)	0.0097 (6)	−0.0121 (6)
C76	0.0342 (7)	0.0399 (9)	0.0212 (6)	−0.0120 (6)	0.0006 (5)	−0.0009 (6)
C77	0.0234 (6)	0.0302 (8)	0.0275 (7)	−0.0056 (5)	0.0001 (5)	−0.0007 (6)
C8	0.0260 (6)	0.0238 (7)	0.0252 (6)	−0.0049 (5)	0.0059 (5)	−0.0019 (5)
C8A	0.0214 (6)	0.0245 (7)	0.0176 (6)	−0.0036 (5)	0.0042 (5)	−0.0005 (5)
S9	0.02096 (16)	0.01875 (17)	0.02313 (17)	−0.00013 (12)	0.00312 (12)	−0.00123 (12)
C9A	0.0216 (6)	0.0204 (6)	0.0158 (5)	−0.0010 (5)	0.0052 (4)	0.0008 (5)

Geometric parameters (Å, º)

N1—C2	1.3093 (16)	C5—H5A	0.9900
N1—C9A	1.3558 (14)	C5—H5B	0.9900
C2—N2	1.3334 (15)	C6—N7	1.4675 (17)
C2—O3	1.3654 (13)	C6—H6A	0.9900
N2—C21	1.4674 (16)	C6—H6B	0.9900
N2—C23	1.4695 (15)	N7—C71	1.4695 (16)
C21—C22	1.5148 (18)	N7—C8	1.4710 (15)
C21—H21A	0.9900	C71—C72	1.5125 (19)
C21—H21B	0.9900	C71—H71A	0.9900
C22—H22A	0.9800	C71—H71B	0.9900
C22—H22B	0.9800	C72—C73	1.385 (2)
C22—H22C	0.9800	C72—C77	1.3959 (18)
C23—C24	1.5035 (19)	C73—C74	1.391 (2)
C23—H23A	0.9900	C73—H73	0.9500
C23—H23B	0.9900	C74—C75	1.383 (2)
C24—H24A	0.9800	C74—H74	0.9500
C24—H24B	0.9800	C75—C76	1.385 (2)
C24—H24C	0.9800	C75—H75	0.9500
O3—C4	1.4169 (14)	C76—C77	1.3849 (19)
C4—O4	1.2114 (14)	C76—H76	0.9500
C4—C4A	1.4222 (17)	C77—H77	0.9500
C4A—C9A	1.3824 (15)	C8—C8A	1.4989 (17)
C4A—C4B	1.4386 (16)	C8—H8A	0.9900
C4B—C8A	1.3498 (17)	C8—H8B	0.9900
C4B—C5	1.5018 (15)	C8A—S9	1.7512 (12)
C5—C6	1.5225 (18)	S9—C9A	1.7345 (13)
C2—N1—C9A	113.61 (10)	N7—C6—C5	110.23 (10)
N1—C2—N2	122.83 (10)	N7—C6—H6A	109.6
N1—C2—O3	125.16 (10)	C5—C6—H6A	109.6
N2—C2—O3	112.01 (10)	N7—C6—H6B	109.6
C2—N2—C21	121.64 (10)	C5—C6—H6B	109.6
C2—N2—C23	119.34 (10)	H6A—C6—H6B	108.1
C21—N2—C23	119.02 (10)	C6—N7—C71	112.48 (10)
N2—C21—C22	114.40 (11)	C6—N7—C8	110.13 (10)
N2—C21—H21A	108.7	C71—N7—C8	110.25 (10)
C22—C21—H21A	108.7	N7—C71—C72	111.68 (10)
N2—C21—H21B	108.7	N7—C71—H71A	109.3
C22—C21—H21B	108.7	C72—C71—H71A	109.3
H21A—C21—H21B	107.6	N7—C71—H71B	109.3
C21—C22—H22A	109.5	C72—C71—H71B	109.3
C21—C22—H22B	109.5	H71A—C71—H71B	107.9
H22A—C22—H22B	109.5	C73—C72—C77	118.38 (13)
C21—C22—H22C	109.5	C73—C72—C71	121.57 (12)
H22A—C22—H22C	109.5	C77—C72—C71	120.02 (13)
H22B—C22—H22C	109.5	C72—C73—C74	121.20 (13)
N2—C23—C24	112.56 (10)	C72—C73—H73	119.4
N2—C23—H23A	109.1	C74—C73—H73	119.4
C24—C23—H23A	109.1	C75—C74—C73	119.86 (14)
N2—C23—H23B	109.1	C75—C74—H74	120.1
C24—C23—H23B	109.1	C73—C74—H74	120.1
H23A—C23—H23B	107.8	C74—C75—C76	119.47 (14)
C23—C24—H24A	109.5	C74—C75—H75	120.3
C23—C24—H24B	109.5	C76—C75—H75	120.3
H24A—C24—H24B	109.5	C77—C76—C75	120.58 (13)
C23—C24—H24C	109.5	C77—C76—H76	119.7
H24A—C24—H24C	109.5	C75—C76—H76	119.7
H24B—C24—H24C	109.5	C76—C77—C72	120.48 (13)
C2—O3—C4	122.20 (9)	C76—C77—H77	119.8
O4—C4—O3	115.48 (11)	C72—C77—H77	119.8
O4—C4—C4A	130.80 (11)	N7—C8—C8A	108.78 (10)
O3—C4—C4A	113.72 (10)	N7—C8—H8A	109.9
C9A—C4A—C4	117.96 (10)	C8A—C8—H8A	109.9
C9A—C4A—C4B	113.17 (11)	N7—C8—H8B	109.9
C4—C4A—C4B	128.81 (10)	C8A—C8—H8B	109.9
C8A—C4B—C4A	112.01 (10)	H8A—C8—H8B	108.3
C8A—C4B—C5	120.62 (11)	C4B—C8A—C8	125.22 (11)
C4A—C4B—C5	127.35 (11)	C4B—C8A—S9	112.62 (9)
C4B—C5—C6	109.36 (11)	C8—C8A—S9	122.16 (9)
C4B—C5—H5A	109.8	C9A—S9—C8A	91.10 (5)
C6—C5—H5A	109.8	N1—C9A—C4A	127.34 (11)
C4B—C5—H5B	109.8	N1—C9A—S9	121.54 (9)
C6—C5—H5B	109.8	C4A—C9A—S9	111.10 (9)
H5A—C5—H5B	108.3
C9A—N1—C2—N2	−179.86 (10)	N7—C71—C72—C73	100.64 (15)
C9A—N1—C2—O3	0.89 (16)	N7—C71—C72—C77	−77.42 (14)
N1—C2—N2—C21	175.05 (11)	C77—C72—C73—C74	1.84 (19)
O3—C2—N2—C21	−5.62 (15)	C71—C72—C73—C74	−176.25 (11)
N1—C2—N2—C23	−4.42 (17)	C72—C73—C74—C75	−1.7 (2)
O3—C2—N2—C23	174.92 (9)	C73—C74—C75—C76	0.7 (2)
C2—N2—C21—C22	80.24 (14)	C74—C75—C76—C77	0.3 (2)
C23—N2—C21—C22	−100.29 (13)	C75—C76—C77—C72	−0.12 (19)
C2—N2—C23—C24	−97.92 (14)	C73—C72—C77—C76	−0.91 (18)
C21—N2—C23—C24	82.60 (15)	C71—C72—C77—C76	177.20 (11)
N1—C2—O3—C4	0.04 (17)	C6—N7—C8—C8A	−50.28 (13)
N2—C2—O3—C4	−179.28 (9)	C71—N7—C8—C8A	−174.97 (10)
C2—O3—C4—O4	178.37 (10)	C4A—C4B—C8A—C8	179.21 (11)
C2—O3—C4—C4A	−1.15 (15)	C5—C4B—C8A—C8	0.56 (19)
O4—C4—C4A—C9A	−178.16 (12)	C4A—C4B—C8A—S9	0.18 (13)
O3—C4—C4A—C9A	1.27 (15)	C5—C4B—C8A—S9	−178.47 (9)
O4—C4—C4A—C4B	−1.2 (2)	N7—C8—C8A—C4B	16.29 (17)
O3—C4—C4A—C4B	178.25 (10)	N7—C8—C8A—S9	−164.77 (8)
C9A—C4A—C4B—C8A	−0.39 (15)	C4B—C8A—S9—C9A	0.04 (10)
C4—C4A—C4B—C8A	−177.49 (11)	C8—C8A—S9—C9A	−179.02 (11)
C9A—C4A—C4B—C5	178.15 (11)	C2—N1—C9A—C4A	−0.71 (17)
C4—C4A—C4B—C5	1.0 (2)	C2—N1—C9A—S9	−178.81 (9)
C8A—C4B—C5—C6	15.71 (16)	C4—C4A—C9A—N1	−0.41 (18)
C4A—C4B—C5—C6	−162.71 (11)	C4B—C4A—C9A—N1	−177.85 (11)
C4B—C5—C6—N7	−49.80 (13)	C4—C4A—C9A—S9	177.86 (9)
C5—C6—N7—C71	−166.12 (11)	C4B—C4A—C9A—S9	0.42 (13)
C5—C6—N7—C8	70.47 (13)	C8A—S9—C9A—N1	178.12 (10)
C6—N7—C71—C72	161.71 (11)	C8A—S9—C9A—C4A	−0.27 (9)
C8—N7—C71—C72	−74.95 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C73—H73···O4^i	0.95	2.50	3.4341 (16)	167

Symmetry code: (i) x, y−1, z.

(III) N-(7-Benzyl-4-oxo-5,6,7,8-tetrahydro-4H-3,9-dithia-1,7-diazafluoren- 2-yl)benzamide

Crystal data

C23H19N3O2S2	F(000) = 904
Mr = 433.53	Dx = 1.453 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3743 reflections
a = 9.2927 (2) Å	θ = 1–27.5°
b = 29.3299 (6) Å	µ = 0.30 mm^−1
c = 7.5645 (1) Å	T = 123 K
β = 106.015 (1)°	Plate, yellow
V = 1981.72 (7) Å^3	0.50 × 0.30 × 0.20 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3832 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
rotation in phi and ω, 1 deg. scans	h = −11→12
11671 measured reflections	k = −34→38
4398 independent reflections	l = −9→5

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 0.6981P] where P = (Fo^2 + 2Fc^2)/3
4398 reflections	(Δ/σ)max = 0.001
274 parameters	Δρmax = 0.46 e Å^−3
1 restraint	Δρmin = −0.37 e Å^−3

Special details

Experimental. dx = 40 mm, 30 sec./°., 1 °., 2 sets, 250 frames, mos.= 0.570 (2) °.

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
N1	0.79682 (14)	0.52023 (4)	0.51254 (17)	0.0218 (3)
C2	0.86955 (15)	0.55670 (5)	0.57969 (19)	0.0199 (3)
N21	0.92148 (14)	0.58309 (4)	0.45708 (17)	0.0206 (2)
H21	0.9122 (19)	0.5703 (6)	0.353 (2)	0.025*
C22	0.96165 (15)	0.62857 (5)	0.48298 (19)	0.0214 (3)
O22	0.96154 (14)	0.64889 (4)	0.62344 (15)	0.0324 (3)
C23	1.00622 (15)	0.65129 (5)	0.32982 (19)	0.0190 (3)
C24	0.97997 (16)	0.69825 (5)	0.30824 (19)	0.0221 (3)
H24	0.9246	0.7135	0.3791	0.027*
C25	1.03471 (17)	0.72253 (5)	0.1836 (2)	0.0247 (3)
H25	1.0165	0.7543	0.1684	0.030*
C26	1.11642 (17)	0.70023 (5)	0.0810 (2)	0.0252 (3)
H26	1.1565	0.7170	−0.0019	0.030*
C27	1.13946 (16)	0.65344 (5)	0.0994 (2)	0.0243 (3)
H27	1.1936	0.6382	0.0273	0.029*
C28	1.08349 (15)	0.62903 (5)	0.22295 (19)	0.0212 (3)
H28	1.0982	0.5970	0.2342	0.025*
S3	0.91078 (4)	0.575481 (12)	0.80867 (5)	0.02223 (10)
C4	0.84117 (15)	0.53040 (5)	0.9229 (2)	0.0196 (3)
O4	0.87017 (11)	0.53391 (4)	1.09107 (14)	0.0239 (2)
C4A	0.75219 (14)	0.49553 (5)	0.81052 (19)	0.0180 (3)
C4B	0.66690 (15)	0.46052 (5)	0.87018 (19)	0.0184 (3)
C5	0.64746 (16)	0.45338 (5)	1.05904 (19)	0.0196 (3)
H5A	0.6341	0.4831	1.1144	0.023*
H5B	0.7375	0.4384	1.1392	0.023*
C6	0.51020 (15)	0.42346 (5)	1.0431 (2)	0.0201 (3)
H6A	0.5042	0.4150	1.1675	0.024*
H6B	0.4186	0.4407	0.9812	0.024*
N7	0.51883 (13)	0.38210 (4)	0.93779 (16)	0.0189 (2)
C71	0.40820 (16)	0.34831 (5)	0.9556 (2)	0.0226 (3)
H71A	0.4038	0.3237	0.8645	0.027*
H71B	0.3084	0.3630	0.9265	0.027*
C72	0.44223 (15)	0.32742 (5)	1.14584 (19)	0.0199 (3)
C73	0.58852 (16)	0.32254 (5)	1.2559 (2)	0.0237 (3)
H73	0.6692	0.3340	1.2145	0.028*
C74	0.61748 (17)	0.30106 (5)	1.4256 (2)	0.0260 (3)
H74	0.7177	0.2982	1.5000	0.031*
C75	0.50135 (18)	0.28381 (5)	1.4873 (2)	0.0277 (3)
H75	0.5217	0.2687	1.6026	0.033*
C76	0.35499 (18)	0.28879 (5)	1.3794 (2)	0.0297 (3)
H76	0.2747	0.2770	1.4207	0.036*
C77	0.32585 (16)	0.31101 (5)	1.2109 (2)	0.0249 (3)
H77	0.2252	0.3150	1.1392	0.030*
C8	0.49702 (16)	0.39339 (5)	0.7437 (2)	0.0226 (3)
H8A	0.3908	0.4013	0.6862	0.027*
H8B	0.5227	0.3667	0.6780	0.027*
C8A	0.59499 (15)	0.43299 (5)	0.7290 (2)	0.0205 (3)
S9	0.62725 (4)	0.447965 (13)	0.52184 (5)	0.02424 (11)
C9A	0.73944 (15)	0.49314 (5)	0.62306 (19)	0.0204 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0270 (6)	0.0212 (6)	0.0186 (6)	−0.0054 (5)	0.0088 (5)	−0.0005 (5)
C2	0.0215 (6)	0.0212 (7)	0.0181 (7)	−0.0009 (5)	0.0073 (5)	0.0011 (5)
N21	0.0263 (6)	0.0203 (6)	0.0173 (6)	−0.0049 (5)	0.0094 (5)	−0.0012 (5)
C22	0.0225 (7)	0.0214 (7)	0.0211 (7)	−0.0026 (5)	0.0075 (5)	−0.0001 (6)
O22	0.0521 (7)	0.0248 (6)	0.0258 (6)	−0.0084 (5)	0.0201 (5)	−0.0048 (4)
C23	0.0182 (6)	0.0196 (7)	0.0179 (7)	−0.0036 (5)	0.0028 (5)	0.0001 (5)
C24	0.0241 (7)	0.0214 (7)	0.0191 (7)	−0.0002 (6)	0.0032 (5)	−0.0030 (5)
C25	0.0301 (7)	0.0195 (7)	0.0214 (7)	−0.0017 (6)	0.0019 (6)	0.0023 (6)
C26	0.0287 (7)	0.0245 (7)	0.0221 (7)	−0.0054 (6)	0.0063 (6)	0.0046 (6)
C27	0.0256 (7)	0.0257 (7)	0.0235 (7)	−0.0033 (6)	0.0100 (6)	−0.0008 (6)
C28	0.0222 (7)	0.0187 (7)	0.0226 (7)	−0.0025 (5)	0.0061 (5)	0.0001 (6)
S3	0.02805 (19)	0.02204 (19)	0.01761 (18)	−0.00751 (14)	0.00801 (14)	−0.00200 (13)
C4	0.0195 (6)	0.0208 (7)	0.0194 (7)	−0.0004 (5)	0.0068 (5)	0.0003 (5)
O4	0.0289 (5)	0.0262 (5)	0.0172 (5)	−0.0061 (4)	0.0073 (4)	−0.0019 (4)
C4A	0.0192 (6)	0.0184 (6)	0.0172 (6)	0.0008 (5)	0.0065 (5)	0.0009 (5)
C4B	0.0190 (6)	0.0180 (7)	0.0185 (7)	0.0007 (5)	0.0058 (5)	−0.0001 (5)
C5	0.0242 (7)	0.0184 (7)	0.0171 (7)	−0.0031 (5)	0.0073 (5)	−0.0012 (5)
C6	0.0225 (6)	0.0189 (7)	0.0203 (7)	−0.0021 (5)	0.0084 (5)	−0.0018 (5)
N7	0.0222 (6)	0.0177 (6)	0.0173 (6)	−0.0043 (4)	0.0062 (4)	−0.0007 (4)
C71	0.0236 (7)	0.0226 (7)	0.0206 (7)	−0.0066 (6)	0.0041 (6)	0.0008 (5)
C72	0.0243 (7)	0.0147 (6)	0.0202 (7)	−0.0029 (5)	0.0055 (5)	−0.0005 (5)
C73	0.0228 (7)	0.0219 (7)	0.0263 (7)	−0.0033 (6)	0.0065 (6)	−0.0001 (6)
C74	0.0278 (7)	0.0205 (7)	0.0257 (8)	0.0003 (6)	0.0005 (6)	0.0006 (6)
C75	0.0408 (8)	0.0186 (7)	0.0225 (7)	−0.0017 (6)	0.0067 (6)	0.0026 (6)
C76	0.0327 (8)	0.0295 (8)	0.0297 (8)	−0.0070 (7)	0.0132 (7)	0.0030 (7)
C77	0.0231 (7)	0.0253 (7)	0.0259 (8)	−0.0022 (6)	0.0063 (6)	0.0008 (6)
C8	0.0281 (7)	0.0224 (7)	0.0171 (7)	−0.0067 (6)	0.0057 (6)	−0.0010 (5)
C8A	0.0234 (7)	0.0198 (7)	0.0187 (7)	−0.0021 (5)	0.0066 (5)	0.0007 (5)
S9	0.0337 (2)	0.0241 (2)	0.01515 (18)	−0.00952 (15)	0.00706 (15)	−0.00207 (13)
C9A	0.0234 (6)	0.0199 (7)	0.0183 (7)	−0.0016 (5)	0.0062 (5)	−0.0007 (5)

Geometric parameters (Å, º)

N1—C2	1.2920 (19)	C5—H5A	0.9900
N1—C9A	1.3640 (18)	C5—H5B	0.9900
C2—N21	1.3927 (17)	C6—N7	1.4655 (18)
C2—S3	1.7562 (14)	C6—H6A	0.9900
N21—C22	1.3844 (18)	C6—H6B	0.9900
N21—H21	0.855 (14)	N7—C71	1.4608 (17)
C22—O22	1.2185 (17)	N7—C8	1.4637 (18)
C22—C23	1.4908 (19)	C71—C72	1.515 (2)
C23—C28	1.384 (2)	C71—H71A	0.9900
C23—C24	1.400 (2)	C71—H71B	0.9900
C24—C25	1.385 (2)	C72—C77	1.392 (2)
C24—H24	0.9500	C72—C73	1.392 (2)
C25—C26	1.390 (2)	C73—C74	1.388 (2)
C25—H25	0.9500	C73—H73	0.9500
C26—C27	1.390 (2)	C74—C75	1.384 (2)
C26—H26	0.9500	C74—H74	0.9500
C27—C28	1.387 (2)	C75—C76	1.387 (2)
C27—H27	0.9500	C75—H75	0.9500
C28—H28	0.9500	C76—C77	1.390 (2)
S3—C4	1.7948 (14)	C76—H76	0.9500
C4—O4	1.2299 (17)	C77—H77	0.9500
C4—C4A	1.4368 (19)	C8—C8A	1.4986 (19)
C4A—C9A	1.3918 (19)	C8—H8A	0.9900
C4A—C4B	1.4435 (18)	C8—H8B	0.9900
C4B—C8A	1.359 (2)	C8A—S9	1.7314 (14)
C4B—C5	1.5032 (19)	S9—C9A	1.7287 (14)
C5—C6	1.5253 (19)
C2—N1—C9A	119.46 (12)	N7—C6—H6A	109.6
N1—C2—N21	115.99 (13)	C5—C6—H6A	109.6
N1—C2—S3	126.56 (11)	N7—C6—H6B	109.6
N21—C2—S3	117.45 (10)	C5—C6—H6B	109.6
C22—N21—C2	124.81 (12)	H6A—C6—H6B	108.1
C22—N21—H21	120.6 (12)	C71—N7—C8	109.88 (11)
C2—N21—H21	113.8 (12)	C71—N7—C6	111.46 (11)
O22—C22—N21	121.98 (13)	C8—N7—C6	110.17 (11)
O22—C22—C23	121.75 (13)	N7—C71—C72	113.23 (11)
N21—C22—C23	116.27 (12)	N7—C71—H71A	108.9
C28—C23—C24	119.84 (13)	C72—C71—H71A	108.9
C28—C23—C22	122.90 (13)	N7—C71—H71B	108.9
C24—C23—C22	116.96 (12)	C72—C71—H71B	108.9
C25—C24—C23	120.00 (13)	H71A—C71—H71B	107.7
C25—C24—H24	120.0	C77—C72—C73	118.62 (13)
C23—C24—H24	120.0	C77—C72—C71	119.78 (13)
C24—C25—C26	119.87 (14)	C73—C72—C71	121.55 (13)
C24—C25—H25	120.1	C74—C73—C72	120.53 (13)
C26—C25—H25	120.1	C74—C73—H73	119.7
C27—C26—C25	120.08 (14)	C72—C73—H73	119.7
C27—C26—H26	120.0	C75—C74—C73	120.50 (14)
C25—C26—H26	120.0	C75—C74—H74	119.8
C28—C27—C26	120.07 (14)	C73—C74—H74	119.8
C28—C27—H27	120.0	C74—C75—C76	119.47 (14)
C26—C27—H27	120.0	C74—C75—H75	120.3
C23—C28—C27	120.09 (13)	C76—C75—H75	120.3
C23—C28—H28	120.0	C75—C76—C77	120.01 (14)
C27—C28—H28	120.0	C75—C76—H76	120.0
C2—S3—C4	103.54 (7)	C77—C76—H76	120.0
O4—C4—C4A	126.70 (13)	C76—C77—C72	120.83 (14)
O4—C4—S3	115.54 (11)	C76—C77—H77	119.6
C4A—C4—S3	117.69 (10)	C72—C77—H77	119.6
C9A—C4A—C4	120.79 (12)	N7—C8—C8A	109.32 (11)
C9A—C4A—C4B	112.52 (12)	N7—C8—H8A	109.8
C4—C4A—C4B	126.69 (12)	C8A—C8—H8A	109.8
C8A—C4B—C4A	111.74 (12)	N7—C8—H8B	109.8
C8A—C4B—C5	120.15 (12)	C8A—C8—H8B	109.8
C4A—C4B—C5	128.07 (12)	H8A—C8—H8B	108.3
C4B—C5—C6	108.79 (11)	C4B—C8A—C8	125.41 (13)
C4B—C5—H5A	109.9	C4B—C8A—S9	112.97 (10)
C6—C5—H5A	109.9	C8—C8A—S9	121.61 (11)
C4B—C5—H5B	109.9	C9A—S9—C8A	91.57 (7)
C6—C5—H5B	109.9	N1—C9A—C4A	131.10 (13)
H5A—C5—H5B	108.3	N1—C9A—S9	117.71 (10)
N7—C6—C5	110.43 (11)	C4A—C9A—S9	111.18 (10)
C9A—N1—C2—N21	−178.52 (12)	C5—C6—N7—C71	166.99 (11)
C9A—N1—C2—S3	2.4 (2)	C5—C6—N7—C8	−70.76 (14)
N1—C2—N21—C22	160.22 (14)	C8—N7—C71—C72	167.93 (12)
S3—C2—N21—C22	−20.61 (18)	C6—N7—C71—C72	−69.66 (15)
C2—N21—C22—O22	3.8 (2)	N7—C71—C72—C77	152.40 (13)
C2—N21—C22—C23	−176.63 (12)	N7—C71—C72—C73	−30.10 (19)
O22—C22—C23—C28	144.27 (15)	C77—C72—C73—C74	1.0 (2)
N21—C22—C23—C28	−35.30 (19)	C71—C72—C73—C74	−176.50 (13)
O22—C22—C23—C24	−29.4 (2)	C72—C73—C74—C75	0.6 (2)
N21—C22—C23—C24	150.98 (13)	C73—C74—C75—C76	−1.1 (2)
C28—C23—C24—C25	−1.7 (2)	C74—C75—C76—C77	−0.1 (2)
C22—C23—C24—C25	172.21 (13)	C75—C76—C77—C72	1.7 (2)
C23—C24—C25—C26	−0.4 (2)	C73—C72—C77—C76	−2.2 (2)
C24—C25—C26—C27	1.9 (2)	C71—C72—C77—C76	175.39 (14)
C25—C26—C27—C28	−1.3 (2)	C71—N7—C8—C8A	171.43 (12)
C24—C23—C28—C27	2.3 (2)	C6—N7—C8—C8A	48.26 (15)
C22—C23—C28—C27	−171.24 (13)	C4A—C4B—C8A—C8	−179.95 (13)
C26—C27—C28—C23	−0.8 (2)	C5—C4B—C8A—C8	−2.0 (2)
N1—C2—S3—C4	4.18 (15)	C4A—C4B—C8A—S9	0.11 (15)
N21—C2—S3—C4	−174.90 (11)	C5—C4B—C8A—S9	178.04 (10)
C2—S3—C4—O4	173.43 (11)	N7—C8—C8A—C4B	−13.5 (2)
C2—S3—C4—C4A	−9.59 (12)	N7—C8—C8A—S9	166.44 (10)
O4—C4—C4A—C9A	−174.01 (14)	C4B—C8A—S9—C9A	−0.63 (12)
S3—C4—C4A—C9A	9.39 (18)	C8—C8A—S9—C9A	179.43 (12)
O4—C4—C4A—C4B	6.8 (2)	C2—N1—C9A—C4A	−4.9 (2)
S3—C4—C4A—C4B	−169.78 (11)	C2—N1—C9A—S9	173.64 (11)
C9A—C4A—C4B—C8A	0.64 (17)	C4—C4A—C9A—N1	−1.8 (2)
C4—C4A—C4B—C8A	179.87 (13)	C4B—C4A—C9A—N1	177.49 (14)
C9A—C4A—C4B—C5	−177.08 (13)	C4—C4A—C9A—S9	179.62 (11)
C4—C4A—C4B—C5	2.1 (2)	C4B—C4A—C9A—S9	−1.10 (15)
C8A—C4B—C5—C6	−16.44 (18)	C8A—S9—C9A—N1	−177.82 (12)
C4A—C4B—C5—C6	161.11 (13)	C8A—S9—C9A—C4A	0.98 (11)
C4B—C5—C6—N7	51.47 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O4^i	0.86 (1)	2.19 (1)	3.0406 (16)	175 (2)

Symmetry code: (i) x, y, z−1.